EP0628625A1

EP0628625A1 - Protease compatible with lipase in dry, concentrated bleach compositions

Info

Publication number: EP0628625A1
Application number: EP93870099A
Authority: EP
Inventors: Marina Trani; Carlo Ricci
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1993-06-07
Filing date: 1993-06-07
Publication date: 1994-12-14
Anticipated expiration: 2013-06-07
Also published as: DE69324802D1; AU678027B2; JPH09501451A; WO1994029423A1; CN1127522A; BR9406791A; EP0628625B1; DE69324802T2; AU7050794A; CA2164587A1; ZA943979B; CN1066193C; GR3030162T3; ES2131103T3

Abstract

The application relates to a detergent composition or additive comprising a high level of bleach, a lipase and a double coated protease (e.g. Savinase 4.0 CT +).

Also the use of said composition or additive wherein the lipolytic activity in the presence of protease remains unchanged is described.

Description

In order to enhance the overall cleaning of clothes bleaching agents have long been used in laundry detergents.
Using the 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.
Addition 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.
Performance on greasy and enzymatic soils is however limited and therefore generating a non-optimum consumers satisfaction. Thus there is still a need for improvement of such bleach compositions.
Enzymes represent an opportunity in this case having a specific advantage to remove for instance grease in a very efficient way.
Although lipase shows a good activity, also in dry matrixes containing a high bleach level, it appears however that when a protease (for instance Savinase ^R 4.0 T, ex Novo) is added the lipase activity becomes much more prone to the attack by the protease.
The result thereof is a dramatic loss of lipase activity in the wash solution.
It is also known that enzyme stability in detergent compositions or additive is reduced at certain storage conditions.
In order to overcome these above-mentioned problems, Novo Industri A/S presented a solution in the patent application WO 87/07292 which is herewith incorporated by reference by coating the enzymatic material showing an improved stability at adverse conditions without any accompanying unwanted side effects.
However adding standard protease (Savinase 4.0 T, ex Novo) to the composition still causes a dramatic drop in the lipase activity in the wash solution.
Probably in solutions containing a high bleach level the active site of lipase is not directly attacked by protease and can continue to work. However it is possible that part or the whole quaternary structure of the lipase can be partially or totally denatured causing a higher exposure of the active site of lipase to the attack of protease.
Adding a protease (Savinase 4.0 T, ex Novo) to a composition having a high bleach level, it is observed that lipase both in performance and in analytical tests shows a significant drop of lipolytic activity in the wash solution.
It is our invention that detergent compositions or additives with a high level of bleach, a lipase and a double coated protease (for instance Savinase ^R 4.0 CT +, ex Novo) deliver an excellent performance profile with respect to lipolytic activity. Surprisingly it appears that 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.
Consequently there exists in such compositions or additives an excellent compatibility between lipase and protease in an environment coming from the dissolution of a highly concentrated (dry) bleach.
The use in dry, concentrated bleaches of double coated protease (Savinase ^R 4.0 CT +, ex Novo) instead of other more commonly used proteases (e.g. Savinase 4.0 T, ex Novo) allows an excellent stability of the lipase which in our invention, not strongly attacked by the protease, can perform at its highest potential.
Therefore it is even satisfactory to use relatively low levels of lipase for dingy cleaning and/or triglyceridic stains removal and thus there is no need of compensating for the enzyme activity loss due to incompatibility with protease. This clearly ensures a cost saving, better industrial hygienic conditions during product production and lower risks from a human safety point of view during product usage.
Also the 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.) or 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)	0-20%
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%

Specific examples to illustrate the present invention are typical laundry bleach formulations (A1) and (A2)

	A1 %	A2 %
Anhydrous sodium percarbonate	46.00	46.00
TAED	10.22	10.22
Savinase 4.0 T (4.0 KNPU/g)	0.5	--
Savinase 4.0 CT + (5.1 KNPU/g)	--	0.4
Maleic acrylic co polymer (Sokalan CP5)	4.00	4.00
Lipolase 100T (100 LU/g)	0.50	0.50
Anhydrous Citric Acid	7.00	7.00
Anhydrous sodium bicarbonate	13.00	13.00
Brightener 49, BH base, Perfume	up to 100%	up to 100%

Further examples to illustrate the present invention are typical automatic dishwashing formulations having a high level of bleach.
The lipase used in the present invention is included in the detergent and bleaching composition 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.
A Lipase Unit (LU) is that amount of lipase which produces 1/micromol of titratable fatty acid per minute in a pH stat. under the following conditions : temperature 30 °C; pH = 9.0; substrate is an emulsion of 3.3 wt% of olive oil and 3.3% gum arabic, in the presence of 13 mmol/l Ca ++; and 20 mmol/l NaCl in 5 mmol/l Tris-Buffer. An alternative definition of the lipase unit is given in EP 0 258 068 (Novo), which mentions (inter alia) lipases suitable for use in the practice of this invention and is hereby incorporated by reference.
Naturally, mixtures of the above lipase with other known lipases can be used. 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.
The 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.
The 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. In more detail, such 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. By 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^oC to 65^oC 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.
Additionally detergent compositions comprise surfactants which may be of the anionic, non-ionic,amphoteric, cationic or zwitteronic type as well as mixtures of these types.
A typical listing of these surfactants is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Mixtures of 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 C₁₂-C₁₈ fatty source preferably from a C₁₆-C₁₈ fatty source. In each instance 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. Examples of preferred alkyl sulphates herein are tallow alkyl sulphate, coconut alkyl sulphate, and C₁₄₋₁₅ alkyl sulphates. An example of a preferred ethoxy sulphate is the so-called AE3S (C₁₂₋₁₅ alkyl 3 times ethoxylated sulphate). The cation in each instance is again an alkali metal cation, preferably sodium.
One class of 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. In order to maximize the lipase activity preferably a so-called nil-LAS containing detergent composition or additive is used according to the invention.
Especially preferred nonionic surfactants of this type are the C₉-C₁₅ primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C₁₄-C₁₅ primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol and the C₁₂-C₁₄ primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula

RO (C_nH_2nO)_tZ_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.
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula

wherein R¹ is H, C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R₂ is C₅₋₃₁ 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. Preferably, R₁ is methyl, R₂ is a straight C₁₁₋₁₇ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
According to the invention 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 C₈-C₂₀, preferably C₁₀-C₁₄ 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.
Another class of surfactants are 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 C₈-C₁₆, preferably C₁₀-C₁₄ N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Mixtures of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic-cationic mixtures. Particularly preferred mixtures are described in British Patent No. 2040987 and European Published Application No. 0 087 914. 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

Builder materials will typically be present at from 0% to 90% preferably up to 30% of the detergent compositions herein.
The 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 [(A10₂)_z (SiO₂)_y] xH₂O

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. The term "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 CaCO₃ 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-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. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula

Na₁₂[(A10₂)₁₂ (SiO₂)₁₂] xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X of formula Na₈₆ [(A10₂)₈₆(SiO₂)₁₀₆] - 10
.276H₂O is also suitable, as well as Zeolite HS of formula Na₆ [(A10₂)₆(SiO₂)₆] 7.5 H₂O).
Another suitable water-insoluble, inorganic builder material is layered silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na₂Si₂O₅). 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.
Of the above, 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.
Other 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.
Other 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.
The 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 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. Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na₂EDDS and Na₄EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg₂EDDS. The magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
Other 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. Preferably, 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.

OPTIONAL INGREDIENTS

The present compositions will typically include optional ingredients that normally form part of detergent compositions like antiredeposition and soil suspension agents, optical brighteners, bleaches, bleach activators, suds suppressors, anticacking agents, dyes and pigments are examples of such optional ingredients and 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 4,4¹-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2¹ disulphonate, disodium 4, - 4¹-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2¹ - disulphonate, disodium 4,4¹ - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2¹ - disulphonate, monosodium 4¹,4¹¹ -bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2-sulphonate, disodium 4,4¹ -bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹ - disulphonate, disodium 4,4¹ -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2¹ disulphonate, disodium 4,4¹bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2¹disulphonate and sodium 2(stilbyl-4¹¹-(naphtho-1¹,2¹:4,5)-1,2,3 - triazole-2¹¹-sulphonate.
Any particulate inorganic perhydrate bleach can be used. If used for a bleach additive, the inorganic perhydrate can be 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 preferably 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). Examples of 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 4 818 425 and nonylamide of peroxyadipic acid as described for instance in US 4 259 201 and n-nonanoyloxybenzenesulphonate (NOBS), and acetyl triethyl citrate (ATC) such as described in European Patent application 91870207.7.
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.
Another optional ingredient is 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. Alternatively 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.
As mentioned above, 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 m²/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.
Other useful polymeric materials are the 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

(CH₃(PEG)₄₃)_0.75(POH)_0.25[T-PO)_2.8(T-PEG)_0.4]T(PO H)_0.25((PEG)₄₃CH₃)_0.75

where PEG is -(OC₂H₄)O-,PO is (OC₃H₆O) and T is (pcOC₆H₄CO).
Also very useful are 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. However, 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.

MAKING PROCESS

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).

Examples

Example 1

Tests were conducted in a European washing machine at 40C° with medium water hardness (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 A1 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).

According to this test method, 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.

Washing performance test results of formulations with enzymes vs Ace Color (Detergent composition used for this test is powder Regular Dash).
	Ace Color	A*	A1	A2
		Lipase	Lipase and savinase (4.0T)	Lipase and savinase double coated (4.0 CT+)
Cleaning	ref.	+1.1	+0.5	+1.0
Bleachable stains	ref.	+1.3	-0.1	+1.5
Enzymatic stains	ref.	+0.3	+1.3	+1.4

* [formulation A means the same formulation as A1 and A2, however without Savinase (4.0 T) and Savinase double coated (4.0 CT +) resp.]

Washing performance test results of formulations with enzymes vs. Ace Color (Detergent composition used in this test is liquid Regular Dash).
	Ace Color	A *	A1	A2
Cleaning	ref	+1.1	+0.4	+0.9
Bleachable stains	ref	+1.0	+0.1	+0.9
Enzymatic stains	ref	-0.3	+0.7	+1.1

These results show that adding standard savinase 4.0T to the product causes a drop in the lipolase activity. This is clearly evidenced by the drop in the overall dingy cleaning (evaluated on soiled items coming from consumers houses including triglycerides based stains e.g. body soils) and bleachable stain removal results. The latter effect is due to the undesired elimination of any bleach activiation through lipase and maleic acrylic copolymer . Both dingy cleaning and bleachable stain removal performances are recuparated using savinase 4.0 CT +, while the significant advantage for enzymatic stain removal delivered by the protolytic enzyme is maintened.

Example 2

We added 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 A1 or A2. Results are as follows :

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
These results are an average of three consistent measures for each sample and confirm that the lipolytic activity is heavily affected by savinase 4.0 T when matrixes containing a high level of bleach are dissolved. The lipolytic activity is however maintained at very high levels using savinase 4.0 CT +, also in matrixes with high bleach levels.
It is feasible that the very clear and good compatibility between savinase 4.0 CT +, and lipolase is strictly linked to the type of coating material and to its concentration in the granulated enzyme. 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. Na₂SO₄,CaCO₃,NaCl, talc, TiO₂, magnesium silicate, sorbitol, copolymers of acrylic acid or metacrylic acid and other units, etc).
The very good compatibility between savinase 4.0 CT +, and lipolase is may be due to the high level of PEG and/or PVP included in the coating. To note that both 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.
Also the effects on 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.

Claims

Detergent composition or additive comprising a high level of bleach, a lipase and a double coated protease.
Detergent composition or additive according to claim 1 wherein the available active oxygen in the composition is 3.0-11% by weight.
Detergent composition or additive according to claim 1 or 2 wherein the bleach is anhydrous sodium percarbonate.
Detergent composition or additive according to claim 3 wherein the composition also contains a bleach activator.
Detergent composition or additive according to any of the claims 1 - 4 wherein the double coated protease is coated with polyethyleneglycol and/or polyvinylpyrrolidone and a cellulose derivative.
Detergent composition or additive according to claim 5 wherein the protease is Savinase 4.0 CT + .
Use of detergent composition or additive according to claim 1 wherein the lipolytic activity remains unchanged in the wash solution.
Use of detergent composition or additive according to claim 7 for grease and/or bleachable and/or proteineous soil removal in the wash solution.