EP0934384A1 - Enzymhaltige zusammensetzungen - Google Patents

Enzymhaltige zusammensetzungen

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Publication number
EP0934384A1
EP0934384A1 EP97945848A EP97945848A EP0934384A1 EP 0934384 A1 EP0934384 A1 EP 0934384A1 EP 97945848 A EP97945848 A EP 97945848A EP 97945848 A EP97945848 A EP 97945848A EP 0934384 A1 EP0934384 A1 EP 0934384A1
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EP
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Prior art keywords
composition
enzyme
weight
iii
water
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EP97945848A
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English (en)
French (fr)
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EP0934384B1 (de
Inventor
Johannes Cornelis van de Unilever Res lab PAS
Willem R. Van Dijk
Marja Unilever Res Vlaardingen Lab OUWENDIJK
David Alan Unilever Research Lab. REED
Lisa Jane Unilever Research Lab. THOMAS
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38663Stabilised liquid enzyme compositions
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase

Definitions

  • the present invention relates to aqueous detergent compositions which contain enzymes.
  • enzymes can lose their activity with time when included in an aqueous liquid detergent composition, and various proposals have already been made to retard that loss of activity by including in such compositions an enzyme-stabilising system.
  • Various enzyme stabilisers have been suggested in the art for inclusion in liquid detergent compositions, e.g. polyols (e.g. glycerol) , borax (preferably in combination with glycerol) , calcium ions, alcohols, low molecular weight carboxylates (formate, acetate, propionate, etc.) and polymers (e.g. poly-vinyl-pyrollidone) .
  • Borax usually in the presence of glycerol, is a very commonly used enzyme stabiliser and is very effective.
  • concerns about the negative environmental impact of boron mean that there is a need to formulate substantially without use of boron-containing compounds yet to achieve comparable enzyme stability.
  • structured aqueous liquid detergent compositions by a combination of two or more formulation steps.
  • structured aqueous liquid detergent composition is meant those compositions which contain sufficient detergent-active material and, optionally, sufficiently dissolved electrolyte to result in a structure of lamellar droplets dispersed in a continuous aqueous phase.
  • Lamellar droplets are a particular class of surfactant structures which, inter alia, are already known from a variety of references, e.g. H.A. Barnes, "Detergents", Ch. 2, in K. Walters (Ed) , “Rheometry: Industrial Applications”, J. Wiley & Sons, Letchworth 1980.
  • Such lamellar dispersions are used to endow properties such as consumer-preferred flow behaviour and/or turbid appearance. Many are also capable of suspending particulate solids such as detergency builders or abrasive particles. Examples of such structured liquids without suspended solids are given in US patent 4 244 840, whilst examples where solid particles are suspended are disclosed in specifications EP-A-160 342; EP-A-38 101; EP-A-104 452 and also in the aforementioned US 4 244 840. Others are disclosed in European Patent Specification EP-A-151 884, where the lamellar droplet are called ⁇ spherulites' .
  • lamellar droplets in a liquid detergent product may be detected by means known to those skilled in the art, for example optical techniques, various rheometrical measurements, X-ray or neutron diffraction, and electron microscopy.
  • the droplets consist of an onion-like configuration of concentric bi-layers of surfactant molecules, between which is trapped water or electrolyte solution (aqueous phase) .
  • Systems in which such droplets are close-packed provide a very desirable combination of physical stability and solid- suspending properties with useful flow properties.
  • UK patent specification GB-A-2 245 280 discloses examples of structured aqueous liquid detergents in which the ratio of water-soluble salt to water is more than 0.25:1 and containing an enzyme of undefined solubility.
  • the compositions contain 0.1% by weight of calcium acetate.
  • boron- containing enzyme stabilisers which provides a liquid detergent composition comprising a dispersion of lamellar droplets in an aqueous continuous phase, the composition further comprising an enzyme and being characterised by at least two of the following three features (i) - (iii):-
  • the weight ratio of total water-soluble salt to water in the total composition is at least 0.25:1;
  • the composition further comprises at least one non- Boron-containing enzyme stabiliser at a level of at least 0.01% by weight; wherein the enzyme has a residual activity of at least 10% after storage of the composition at 37C for 4 weeks from the time of making; and wherein the composition contains no more than 0.01% by weight of Boron; provided that if only features (i) and (iii) are present and the non-Boron containing enzyme stabiliser comprises a water-soluble calcium salt, then the total amount of water-soluble calcium salt is at least 0.3% by weight of the total composition; and if all of features (i), (ii) and (iii) are present, then the non-Boron containing enzyme stabiliser comprises at least one material other than a lignin compound.
  • the solubility of the enzyme is defined as the percentage of total enzyme activity present in the supernatant after centrifuging for 15 minutes at 16,000g a solution of deionised water comprising of sodium citrate (25% by weight) and enzyme.
  • a typical enzyme dosage for this solubility test is 0.4% by weight of a (commercial) liquid enzyme preparation containing typically 4% enzyme protein.
  • proteases the activities before and after centrifugation are determined at 40°C and pH 9.0 using acetylated caseine as a substrate and reacting quantitatively the formed amine-groups with 2,4,6- trinitrobenzene sulphonic acid. The change in absorbance at 405nm is used a measure for activity.
  • the pH of compositions according to the present invention is preferably greater than 6, more preferably greater than 7 and most preferably greater than 7.5. On the other hand, the pH is preferably less than 11, more preferably less than 10 and most preferably less than 9.5.
  • compositions which combine all of features (i) - (iii) .
  • the amount of the non-Boron- containing enzyme stabiliser in the composition is at least 0.01% by weight but more preferably, this minimum is 0.03%, especially 0.05%. In ascending order, still more preferred minima for this amount (by weight) are 0.1%, 0.2% and 0.5%.
  • the non-Boron-containing enzyme stabiliser may for example be selected from lignin compounds, alkali metal mono- or dicarboxylates, sources of calcium ions preferably in the presence of sequestrants and enzyme stabilising polymers.
  • Suitable lignin compounds are those described in our co- pending European Patent Application No. 95304401.3, filed 22 June 1995 (unpublished at the priority date of the present application but subsequently published in the form of an International Patent Application No. WO 97/00932) .
  • the latter document exemplifies compositions exemplifying all of features (i), (ii) and (iii) of the present invention wherein a lignin compound is used as a non-Boron containing enzyme stabiliser. These compositions are thus disclaimed from the scope of the present invention.
  • the lignin compounds are mixtures of components and are usually referred to as a polymer which contains, amongst others, phenylpropane units.
  • Lignin compounds can be prepared from the chemical pulping of hard- and softwoods. Lignin compounds have been found to be very effective compounds according to the present invention. There are various lignin compounds which are preferred enzyme stabilisers according to the invention, including lignosulphonates, Kraft lignins and oxylignins. All these compounds are considered lignin compounds. These compounds may be prepared from Lignin by various ways, including:
  • Lignin or any of its derivatives may be made by varying the kind of cation (Na + , K + , Ca 2+ , Mg 2+ , NH + , the degree of sulphonation and/or the average molecular size) .
  • lignin derivatives that have been found useful are Borresperse NA, Borresperse CA, Kelig FS, Maracarb N-l, Marasperse N-22, Marasperse N-3, Norlig BD, Norlig 415, Ufoxane 2, Ufoxane 3A, Maracell 3A, Vanisperse CB, Ultrazine NA, Ultrazine CA (all ex Borregaard) and lignosulphonates ex Aldrich and ex Sigma as well as ex a number of pharmaceutical companies.
  • lignin compounds significantly retards the enzyme deactivation, and most surprisingly, lignin compounds are effective as stabiliser at low concentration. Consequently, lignin compounds are included in effective amounts in the composition, in particular in the range of 0.0001 to 10%, preferably 0.001 to 5%, more preferably at least 0.01 and more preferably at most 3% by weight of the composition.
  • the weight ratio between lignin compound and enzyme (as defined as the weight of the active enzyme protein material, which does not include any additives that for example may be present in the enzyme preparations as supplied by the enzyme manufacturers) may be varied widely, as long as the enzyme is effectively stabilised, a weight ratio between 1000:1 and 1:10 has been found to be preferred, more preferably lower than 500:1, most preferably lower than 100:1, in particular lower than 50:1, whereas it is more preferred to have a weight ratio of higher than 1:5, most preferably higher than 1:3, in particular 1:2, more in particular 1:1.
  • the molar ratio between the total lignin compound and total enzyme is from 0.1 to 10,000, more preferably at least 1 and at most 5,000, most preferably at least 2.
  • Suitable enzyme stabilising alkali metal mono- or di- carboxylate include alkali metal formates, e.g. sodium formate and acetate and propionate, as well as sodium succinate, sodium maleate, sodium glutamate and sodium aspartate .
  • Suitable enzyme-stabilising sources of calcium ions include any water-soluble calcium salt, such as calcium chloride, as well as calcium formate and calcium acetate.
  • sequestants are present when calcium is present, for example, phosphorous containing Dequest (Trade mark of Monsanto) and non-phosphorous containing sequestrants, for example the amino (poly) carboxylates, e.g. salts of glutamic acid N,N-diacetic acid, beta-alanine diacetic acid, ethylenediamine triaceticacid, methyl glycine diacetic acid, diethylenetriamine penta-acetic acid, ethylenediamine-N,N-disuccinic acid and ethylenediamine di (sulfosuccinate)
  • amino (poly) carboxylates e.g. salts of glutamic acid N,N-diacetic acid, beta-alanine diacetic acid, ethylenediamine triaceticacid, methyl glycine diacetic acid, diethylenetriamine penta-acetic acid, ethylenediamine-N,N-disuccinic acid and ethylenediamine di (sul
  • Suitable enzyme-stabilising polymers include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyvinyl immidazole, as well as copolymers thereof.
  • More than one non-boron containing enzyme stabiliser may be utilised in the same formulation.
  • composition must contain no more than 0.01% by weight of Boron.
  • composition is substantially
  • the maximum Boron content by weight of the total composition is 0.005%, still more preferably 0.003 and especially 0.001%.
  • feature (ii) of the present invention is utilised, then one suitable class of enzymes which meet the solubility criterion defined by feature (ii) is that described in our co-pending European Patent Application No. 95201161.7, filed 5 May 1995 (unpublished at the priority date of the present application) .
  • These enzymes are subtilase variants wherein one or more amino acid residues situated in or in the vicinity of a hydrophobic domain of the parent subtilase have been substituted for an amino acid residue more hydrophobic than the original residue, said hydrophobic domain comprising the residues P129, P131,
  • the original amino acid residue has been substituted for a residue selected from the group comprising Val (V), lie (I), Leu (L) , Met (M) , Phe (F), and Trp (W) , preferably Val, lie or Leu.
  • a residue selected from the group comprising Val (V), lie (I), Leu (L) , Met (M) , Phe (F), and Trp (W) preferably Val, lie or Leu.
  • the parent subtilase is preferably chosen from the subgroup I-SI or I-S2.
  • wild-type enzymes can meet the solubility criterion of feature (ii).
  • Enzymes can be available in various forms, such as:
  • Liquids, slurries and encapsulates may contain a mixture of enzymes selected from protease, lip(ol)ase, amylase, cellulase, etc. All these enzyme forms can be used in the present invention.
  • the residual activity of the enzyme is at least 10% as determined as hereinbefore described. Preferably though, this minimum is at least 25%, more preferably 40%, still more preferably 50% and most preferably 75%.
  • the enzyme solubility when determined as hereinbefore described in respect of feature (ii) is at most 50% by weight of the total added enzyme. Preferably though, this maximum is 25%, more preferably 10%, still more preferably 5% and especially 2%.
  • the enzyme may be chosen from any of those known in the art of formulating enzyme-containing detergent compositions and even if feature (ii) is utilised the composition may additionally contain one or more additional enzymes selected from such known enzymes.
  • additional enzymes selected from such known enzymes.
  • such enzymes may be selected from proteases, amylases, upases, cellulases and mixtures of one or more of these enzymes.
  • Proteases are preferred enzymes for use in the present invention, as we have seen the best results with protease stabilisation.
  • the enzyme (s) preferably provide (as appropriate) a proteolytic activity between 0.1 and 50 GU/mg, a lipolytic activity between 0.005-100 LU/mg and an amylolytic activity between 10 3 and 10 7 MU/kg, wherein GU, LU and MU units are well known in the art and have e.g. been defined in lines 8-14 of column 3 and lines 8-12 and 21-24 of column 4 of US 5,112,518.
  • the level of active enzyme protein will be higher (up to 10%, preferably up to 5% by weight for concentrated enzyme preparations, e.g. as supplied by enzyme manufacturers) or lower (up to 3%, preferably up to 1.0%, although levels up to 0.5% or up to 0.1% or even as low as up to 0.05% are also suitable for more dilute systems, e.g. commercial liquid detergent compositions in which the concentrated enzyme preparations are used during production) .
  • the active enzyme protein level may be as low as 0.0001%, preferably at least 0.01% by weight of the composition. Again in more concentrated enzyme preparations, the lower level will be higher, e.g. at least 0.5% by weight.
  • the weight ratio of the total water-soluble salt (electrolyte) to water in the total composition is at least 0.25:1 but preferably it is of at least 0.35:1, more preferably at least 0.40:1, still more preferred minima for this weight ratio are, in ascending order: 0.45:1, 0.50:1, 0.55:1, 0.60:1 and 0.65:1.
  • the maximum value of this weight ratio is 1.0.
  • water-soluble salt includes both the salt(s) from the formulation that totally dissolves and the dissolved part of the salt(s) that does not totally dissolve, expressed as anhydrous salts.
  • compositions of the present invention are aqueous dispersions of lamellar droplets. Although it is possible to form lamellar dispersions of surfactant in water alone, in many cases it is preferred for the aqueous continuous phase to contain dissolved electrolyte.
  • electrolyte means any ionic water-soluble material. However, in lamellar dispersions, not all the electrolyte is necessarily dissolved but may be suspended as particles of solid because the total electrolyte concentration of the liquid is higher than the solubility limit of the electrolyte. Mixtures of electrolytes also may be used, with one or more of the electrolytes being in the dissolved aqueous phase and one or more being substantially only in the suspended solid phase.
  • v salts' includes all organic and inorganic materials which may be included, other than surfactants and water, whether or not they are ionic, and this term encompasses the sub-set of the electrolytes (water-soluble materials) .
  • compositions of the invention The only restriction on the total amount of detergent- active material and electrolyte (if any) is that in the compositions of the invention, together they must result in formation of an aqueous lamellar dispersion.
  • a very wide variation in surfactant types and levels is possible.
  • the selection of surfactant types and their proportions, in order to obtain a stable liquid with the required structure will be fully within the capability of those skilled in the art.
  • an important sub-class of useful compositions is those where the detergent-active material comprises blends of different surfactant types.
  • Typical blends useful for fabric washing compositions include those where the primary surfactant (s) comprise nonionic and/or a non-alkoxylated anionic and/or an alkoxylated anionic surfactant.
  • compositions of the present invention may be enhanced, or the rheology of such compositions may be controlled by incorporation of a deflocculating polymer such as any described in EP-A-346 995 or in any of WO91/06622; WO91/06623; GB-A-2,237, 813; WO91/09109; US-A-5, 494 , 602 ; EP-A-623, 670 ; US-A-5,489,397; and EP-A-691, 399.
  • a deflocculating polymer such as any described in EP-A-346 995 or in any of WO91/06622; WO91/06623; GB-A-2,237, 813; WO91/09109; US-A-5, 494 , 602 ; EP-A-623, 670 ; US-A-5,489,397; and EP-A-691, 399.
  • the total detergent-active material may be present at from 2% to 60% by weight of the total composition, for example from 5% to 40% and typically from 10% to 30% by weight.
  • one preferred class of compositions comprises at least 20%, most preferably at least 25%, and especially at least 30% of detergent-active material based on the weight of the total composition.
  • the precise proportions of each component which will result in such stability and viscosity will depend on the type(s) and amount (s) of the electrolytes, as in the case with conventional structured liquids .
  • the detergent-active material in general, may comprise one or more surfactants, and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric species, and (provided mutually compatible) mixtures thereof.
  • surfactants may be selected from any of the classes, sub-classes and specific materials described in ⁇ Surface Active Agents' Vol. 1. By Schwartz & Perry, Interscience 1949 and ⁇ Surface Active Agents' Vol.
  • Suitable nonionic surfactants include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide, either alone or with propylene oxide.
  • nonionic detergent compounds are alkyl (C 6 -C ⁇ 8 ) primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine.
  • Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long-chain tertiary phospine oxides and dialkyl sulphoxides .
  • Suitable anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals.
  • suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C 8 -C ⁇ 8 ) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C 9 - C 2 o) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8 - Cis) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts of fatty acid amides of
  • part or all of the detergent active material is a stabilising surfactant, which has an average alkyl chain length greater than 6 C-atoms, and which has a salting out resistance, greater than, or equal to 6.4.
  • stabilising surfactants are disclosed in our European patent application EP-A-328, 177. Examples of these materials are alkyl polyalkyloxated carboxylates, alkyl polyalkoxylated phosphates, alkyl polyalkoxylated sulphosuccinates; dialkyl diphenyloxide disulphonates; alkyl polysacccharides and mixtures thereof.
  • an alkali metal soap of a long chain mono- or dicarboxylic acid for example one having from 12 to 18 carbon atoms.
  • Typical acids of this kind are oleic acid, ricinoleic acid, and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palm kernel oil or mixtures thereof.
  • the sodium or potassium soaps of these acids can be used.
  • the amount of water in the composition is from 5 to 95%, more preferred from 25 to 75%, most preferred from 30 to 50%. Especially preferred less than 45% by weight.
  • compositions optionally also contain electrolyte in an amount sufficient to bring about structuring of the detergent-active material.
  • the compositions contain from 1% to 60%, especially from 10 to 45% of a salting-out electrolyte.
  • Salting-out electrolyte has the meaning ascribed to in specification EP-A-79 646.
  • some salting-in electrolyte (as defined in the latter specification) may also be included, provided if of a kind and in an amount compatible with the other components and the composition is still in accordance with the definition of the invention claimed herein.
  • Some or all of the electrolyte may have detergency builder properties.
  • compositions according to the present invention include detergency builder material, some or all of which may be electrolyte.
  • the builder material is any capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, the suspension of soil removed from the fabric and the dispersion of the fabric softening clay material.
  • Examples of phosphorous-containing inorganic detergency builders when present, include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates .
  • Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates . Phosphonate sequestrant builders may also be used.
  • non-phosphorus-containing inorganic detergency builders when present, include water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates .
  • Specific examples include sodium carbonate (with or without calcite seeds) , potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites.
  • electrolytes which promote the solubility of other electrolytes, for example use of potassium salts to promote the solubility of sodium salts.
  • electrolytes which promote the solubility of other electrolytes
  • potassium salts to promote the solubility of sodium salts.
  • organic detergency builders when present, include the alkaline metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates, carboxymethyloxysuccinates, carboxymethyloxymalonates, ethylene diamine-N,N, disuccinic acid salts, polyepoxysuccinates, oxydiacetates, triethylene tetramine hexacetic acid salts, N-alkyl imino diacetates or dipropionates, alpha sulpho- fatty acid salts, dipicolinic acid salts, oxidised polysaccharides, polyhydroxysulphonates and mixtures thereof.
  • Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilitriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acids and citric acid, tartrate mono succinate and tartrate di succinate.
  • partly dissolved polymers include many of the polymer and co-polymers salts already known as detergency builders. For example, may be used (including building and non-building polymers) polyethylene glycols, polyacrylates, polymaleates, polysugars, polysugarsulphonates and co- polymers of any of these.
  • the partly dissolved polymer comprises a co-polymer which includes an alkali metal salt of a polyacrylic, polymethacrylic or maleic acid or anhydride.
  • compositions with these co- polymers have a pH of above 8.0.
  • the amount of viscosity-reducing polymer can vary widely according to the formulation of the rest of the composition. However, typical amounts are from 0.5 to 4.5% by weight.
  • compositions of the present invention alternatively, or in addition to the partly dissolved polymer, yet another polymer which is substantially totally soluble in the aqueous phase and has an electrolyte resistance of more than 5 grams sodium nitrilotriacetate in 100 ml of a 5% by weight aqueous solution of the polymer, said second polymer also having a vapour pressure in 20% aqueous solution, equal to or less than the vapour pressure of a reference 2% by weight or greater aqueous solution of polyethylene glycol having an average molecular weight of 6,000; said second polymer having a molecular weight of at least 1,000.
  • the incorporation of the soluble polymer permits formulation with improved stability at the same viscosity (relative to the composition without the soluble polymer) or lower viscosity with the same stability.
  • the soluble polymer can also reduce viscosity drift, even when it also brings about a viscosity reduction.
  • improved stability and lower viscosity mean over and above any such effects brought about by the deflocculating polymer.
  • the soluble polymer is especially preferred to incorporate with a partly dissolved polymer which has a large insoluble component. That is because although the building capacity of the partly dissolved polymer will be good (since relatively high quantities can be stably incorporated) , the viscosity reduction will not be optimum (since little will be dissolved) . Thus, the soluble polymer can usefully function to reduce the viscosity further, to an ideal level.
  • the soluble polymer can, for example, be incorporated at from 0.05 to 20% by weight, although usually, from 0.1 to 10% by weight of the total composition is sufficient, and especially from 0.2 to 3.5 - 4.5% by weight. It has been found that the presence of deflocculating polymer increase the tolerance for higher levels of soluble polymer without stability problems.
  • a large number of different polymers may be used as such a soluble polymer, provided the electrolyte resistance and vapour pressure requirements are met.
  • the former is measured as the amount of sodium nitrilotriacetate (NaNTA) solution necessary to reach the cloud point of 100 ml of a 5% solution of the polymer in water at 25°C, with the system adjusted to neutral pH, i.e. about 7.
  • the electrolyte resistance is 10 g NaNTA, especially 15 g.
  • the latter indicates a vapour pressure low enough to have sufficient water binding capability, as generally explained in the Applicants' specification GB-A-2 053 249.
  • the measurement is effected with a reference solution at 10% by weight aqueous concentration, especially 18%.
  • Typical classes of polymers which may be used as the soluble polymer include polyethylene glycols, Dextran, Dextran sulphonates, polyacrylates and polyacrylate/maleic acid co-polymers.
  • the soluble polymer must have an average molecular weight of at least 1,000 but a minimum average molecular weight of 2,000 is preferred.
  • compositions of the present invention are substantially free from hydrotropes.
  • hydrotrope any water soluble agent which tends to enhance the solubility of surfactants in aqueous solution.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, fabric softeners such as clays, amines and amine oxides, lather depressants, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in minor amounts, oily-soil release polymers, e.g. those described in our copending European patent application EP 95300175.7 and EP 95308630.3 and EP 95308629.5 and those sold under Trademarks Permalose, Aquaperle and Gerol, fluorescent agents, perfumes, germicides and colorants.
  • lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids
  • fabric softeners such as clays, amines and amine oxides
  • Oleic acid (Priolene 6907) 4.5
  • Nonionic Dobanol 25- 7.5
  • Tinopal CBS-X 0.09%
  • Nonionic Dobanol 25- 7.5

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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)
  • Crystallography & Structural Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
EP97945848A 1996-10-15 1997-10-14 Enzymhaltige zusammensetzungen Revoked EP0934384B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9621436 1996-10-15
GBGB9621436.6A GB9621436D0 (en) 1996-10-15 1996-10-15 Enzymatic compositions
PCT/EP1997/005711 WO1998016607A2 (en) 1996-10-15 1997-10-14 Enzymatic compositions

Publications (2)

Publication Number Publication Date
EP0934384A1 true EP0934384A1 (de) 1999-08-11
EP0934384B1 EP0934384B1 (de) 2003-02-12

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EP97945848A Revoked EP0934384B1 (de) 1996-10-15 1997-10-14 Enzymhaltige zusammensetzungen

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AR (1) AR009116A1 (de)
AU (1) AU734832B2 (de)
BR (1) BR9711927A (de)
CA (1) CA2268788A1 (de)
DE (1) DE69719050T2 (de)
ES (1) ES2191859T3 (de)
GB (1) GB9621436D0 (de)
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ZA (1) ZA979227B (de)

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DE19859808A1 (de) * 1998-12-23 2000-06-29 Henkel Kgaa Mehrphasiges Reinigungsmittel mit Ligninsulfonat
EP1700904A1 (de) * 2005-03-11 2006-09-13 Unilever N.V. Flüssige Waschmittelzusammensetzung
US20220403298A1 (en) * 2019-07-12 2022-12-22 Novozymes A/S Enzymatic emulsions for detergents

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EG18543A (en) * 1986-02-20 1993-07-30 Albright & Wilson Protected enzyme systems
GB8813978D0 (en) * 1988-06-13 1988-07-20 Unilever Plc Liquid detergents
GB8928022D0 (en) * 1989-12-12 1990-02-14 Unilever Plc Enzymatic liquid detergent compositions and their use
EP0450702A3 (en) * 1990-04-06 1993-06-02 Unilever N.V. Process for preparing liquid enzymatic detergent compositions
IL97805A (en) * 1990-04-10 1995-01-24 Albright & Wilson Concentrated surfactants
SK53294A3 (en) * 1993-05-07 1995-04-12 Albright & Wilson Concentrated aqueous mixture containing surface active matter and its use
SK284609B6 (sk) * 1995-05-05 2005-07-01 Unilever Nv Detergentná zmes obsahujúca subtilázový BLS309 variant

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WO1998016607A3 (en) 1998-05-22
CA2268788A1 (en) 1998-04-23
AU734832B2 (en) 2001-06-21
DE69719050D1 (de) 2003-03-20
EP0934384B1 (de) 2003-02-12
ES2191859T3 (es) 2003-09-16
WO1998016607A2 (en) 1998-04-23
DE69719050T2 (de) 2003-07-24
AR009116A1 (es) 2000-03-08
GB9621436D0 (en) 1996-12-04
AU5119898A (en) 1998-05-11
BR9711927A (pt) 1999-08-24
ZA979227B (en) 1999-04-15

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