Abstract:
The present invention provides a detergent composition comprising a quaternary ammonium compound of formula: R 1  R 2  R 3  R 4  N +  X - ,wherein R 1  is C 8  -C 16  alkyl, each of R 2 , R 3  and R 4  is independently C 1  -C 4  alkyl or hydroxy alkyl, benzyl or --(C 2  H 40 ) x  H where x has a value from 2 to 5, not more of R 2 , R 3  or R 4  being benzyl, and X is an anion, and a cellulase characterized in that said cellulase provides at least 10% removal of immobilized radio-active labelled carboxymethylcellulose according to the CMC-method at 25×10 -6  % by weight of cellulase protein in the laundry test solution. According to the present invention, a preferred cellulase consists of a homogeneous endoglucanase component which is immunoreactive with a monoclonal antibody raised against a partially purified=43 kD cellulase derived from Humicola insolens DM 1800.

Description:
This is a continuation of application Ser. No. 08/290,712, filed as PCT/US92/01179 Feb. 15, 1992, published as WO93/16158 Aug. 19, 1993. 
    
    
     TECHNICAL FIELD 
     The present invention relates to detergent compositions having cleaning and softening benefits. 
     BACKGROUND OF THE INVENTION 
     The need for detergent compositions which exhibit not only good cleaning properties, but also good fabric-softening performance, and other fabric care benefits, is well-established in the art. 
     EP 0 026 529 describes detergent compositions containing smectite-type clays and certain cationic compounds having cleaning and textile softening performance. 
     The efficiency of cellulolytic enzymes, i.e. cellulases, in terms of textile cleaning and harshness-reducing agent for fabrics has been recognized for some time; GB-A-2,075,028, GB-A-2,095,275 and GB-A-2,094,826, disclose detergent compositions with cellulase for improved cleaning performance; GB-A-1,368,599 discloses the use of cellulase for reducing the harshness of cotton-containing fabrics; U.S. Pat. No. 4,435,307 teaches the use of a cellulolytic enzyme derived from Humicola insolens as well as a fraction thereof, designated ACXI, as a harshness-reducing detergent additive. 
     EP-A-0 269 168 discloses optimized detergent compositions containing cellulase, which are formulated at a mild alkaline pH range and provide combined fabric cleaning, fabric softening, and fabric care performance. EP-B-0 125 122 discloses a detergent composition which combines cleaning and textile softening performance by using a synergetic mixture of a long-chain tertiary amine and cellulase. 
     In WO 89109259 have been disclosed cellulase preparations useful for reducing the harshness of cotton-containing fabrics, comprising an endoglucanase component with a high endoase activity and affinity towards cellulose. 
     The practical exploitation of cellulases has however, been set back by the fact that cellulase preparations such as those disclosed in the above-mentioned prior art documents, are complex mixtures, of which only a certain fraction is effective in the fabric-care context; it was thus difficult to implement cost effective industrial production of cellulase for the detergent industry; and large quantities of such cellulase preparations would need to be applied, in order to obtain the desired effect on fabrics. 
     Improvements in cellulase production also often have not proven to be sufficiently identifiable in terms of applicability in detergents. Defining a cellulase selection criterium relevant for detergent application of cellulase was made possible by the C14CMC-method disclosed in EP-A-350 098. A minimum of 10% removal of immobilized radioactive labelled carboxymethylcellulose at 25×10 -6  % by weight of cellulase protein in the laundry test solution has been found to provide high activity cellulase. A preferred group of cellulase falling under the high activity definition according to the present invention has been disclosed in copending Danish Patent Application No. : 1159/90 filed May 5, 1990. There is disclosed a cellulase preparation consisting essentially of a homogeneous endoglucanase component which is immunoreactive with a monoclonal antibody raised against a partially purified 43 kD cellulase derived from Humicola insolens DM1800. 
     The finding that this particular endoglucanase component of cellulase is advantageous for the treatment of cellulose-containing materials now permits to produce the cellulase cost-effectively, e.g. by employing recombinant DNA techniques, and allows to apply only a small quantity of the cellulase preparation, and obtain the desired effect on fabrics. 
     It has surprisingly been found that an improved detergent composition can be formulated which combine superior cleaning and softening performance by using a synergestic mixture of water soluble quaternary ammonium compounds and high active cellulase. Said cellulase having at least 10% CMC removal at 25×10 -6  % by weight of cellulase protein in the laundry test solution. 
     It is another object of the present invention to provide a method for treating fabrics in a washing machine, comprising the utilization of the present detergent compositions, for the main wash cycle. 
     SUMMARY OF THE INVENTION 
     The present invention provides a detergent composition comprising a quaternary ammonium compound of formula 
     
         R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.- 
    
     wherein R 1  is C 8  -C 16  alkyl, each of R 2 , R 3  and R 4  is independently C 1  -C 4  alkyl or hydroxy alkyl, benzyl, or --(C 2  H 40 ) x  H where x has a value from 2 to 5, not more than one of R 2 , R 3  or R 4  being benzyl, and X is an anion, and a cellulase characterized in that said cellulase provides at least 10% removal of immobilized radio-active labelled carboxymethylcellulose according to the C14 CMC-method at 25×10 -6  % by weight of cellulase protein in the laundry test solution. 
     According to the present invention, a preferred cellulase consists of a homogeneous endoglucanase component which is immunoreactive with a monoclonal antibody raised against a partially purified=43 kD cellulase derived from Humicola insolens DM 1800. 
     DETAILED DESCRIPTION OF THE INVENTION 
     Cellulase 
     The activity of enzymes and particularly the activity of cellulase enzyme has been defined for various applications by different analytical methods. These methods all attempt to provide a realistic assessment of the expected in use performance or at least a measurement correlating with the in use performance. As has been detailed in European Patent Application EP-A-350098, many of the methods, particularly these frequently used by cellulase manufacturers, are not sufficiently correlated with the in use performance of cellulase in laundry detergent compositions. This is due to the various other usage conditions for which these activity measurement methods have been developed. 
     The method described in EP-A-350098, has been developed to be and to have a predictive correlation for the ranking of cellulase activity in laundry detergent compositions. 
     The present invention therefore uses the method disclosed in EP-A-350098 to screen cellulases in order to distinguish cellulases which are useful in the present invention and those which would not provide the objectives of the present invention. The screening method, hereinafter referred to as C14CMC-Method, which has been adopted from the method disclosed in EP-A-350098, can be described as follows: 
     Principle 
     The principle of the C14CMC-Method for screening is to measure at a defined cellulase concentration in a wash solution the removal of immobilized carboxy methyl cellulose (CMC) from a cloth substrate. The removal of CMC is measured by radio-active labelling of some of the CMC by using C14 radio-active carbon. Simple counting of the amount of radio-active C14 on the cloth substrate before and after the cellulase treatment allows the evaluation of the cellulase activity. 
     Sample Preparation 
     CMC preparation: The radio-active CMC stock solution is prepared according to Table I. The radio-active CMC can be obtained by methods referred to in EP-A-350098. 
     Fabric substrates: The fabric substrates are muslin cotton swatches having a size of 5 cm×5 cm. They are inocculated with 0.35 ml of the radio-active labelled CMC stock solution in their center. The muslin cotton swatches are then airdried. 
     Immobilization of CMC: To immobilize the radio-active labelled CMC on the muslin cotton swatches, laundero-meter equipment &#34;Linitest Original Haunau&#34; made by Original Haunau, Germany, is used. A metal jar of the laundero-meter is filled with 400 ml of hard water (4 mmol/liter of Ca ++   ions). A maximum number of 13 swatches can be used per jar. The jar is then incubated in a heat-up cycle from 20° C. to 60° C. over 40 minutes in the laundero-meter equipment. After incubation the swatches are rinsed under running city water for 1 minute. They are squeezed and allowed to airdry for at least 30 minutes. 
     According to EP-A-350098 samples of the swatches with immobilized radio-active CMC can also be measured as &#34;blank samples&#34; without washing. 
     Sample Treatment 
     Laundry test solution: The laundry test solution is prepared according to the composition of Table II. It is balanced to pH 7.5. The laundry test solution is the basis to which a cellulase test sample is added. Care should be taken to not dilute the laundry test solution by adding water to a 100% balance prior to having determined the amount of cellulase to be added. The amount of cellulase which is used in this screening test should be added to provide 25×10 -6  weight percent of cellulase protein in the laundry test solution (equivalent to 0.25 milligram/liter at 14.5° C.). 
     Wash procedure: The swatches thus inocculated with radio-active labelled CMC are then treated in a laundry simulation process. The laundry process is simulated in the laundero-meter type equipment, &#34;Linitest, Original Haunau&#34;, by Original Haunau, Haunau Germany. An individual swatch is put into a 20 cm 3  glass vial. The vial is filled with 10 ml of the laundry test solution and then sealed liquid tight. Up to 5 vials are put into each laundero-meter jar. The jar is filled with water as a heat tranfer medium for the laundering simulation. The laundering simulation is conducted as a heat-up cycle from 20° C. to 60° C. over 40 minutes. 
     After the processing of the samples the vials are submerged in cold water and subsequently each swatch is taken out of its vial, rinsed in a beaker under running soft water, squeezed and allowed to airdry for at least 30 minutes. 
     Measurement 
     In order to measure radio-active labelled CMC removal, a scintillation counter, for example, a LKB 1210 Ultrabeta Scintillation Counter, is used. In order to obtain most accurate results, the instruction manual for optimum operation of the particular scintillation counter should be followed. For example, for the LKB 1210 Ultrabeta Scintillation Counter, the following procedure should be followed. The swatch to be measured is put into a plastic vial filled with 12 ml of scintillator liquid (e.g. scintillator 299 from Packard). The swatch is then allowed to stabilize for at least 30 minutes. The vial is then put into the LKB 1210 Ultrabeta Scintillation Counter and the respective radio-activity counts for the swatch is obtained. 
     In order to measure the amount of CMC removal due only to the cellulase, a measurement of a swatch which has been inocculated at the same time but has been treated in the laundry test solution without cellulase, is necessary. The activity of the cellulase is then expressed as percent of radio-active labelled CMC removal. This percentage is calculated by the following formula: ##EQU1## Wherein XO is the radioactivity scintillation count of a swatch treated with the laundry test solution without cellulase 
     XC is the radioactivity scintillation count of a swatch treated with the laundry test solution containing the cellulase to be evaluated 
     Statistical Considerations, Procedure Confirmation 
     In order to provide statistically sound results, standard statistical analysis should be employed. For the given example, using the LKB 1210 Ultrabeta Scintillation Counter, it has been found that a sample size of 3 swatches for each radioactivity scintillation count can be used. 
     In order to confirm the procedure by internal crosschecking, measurement and calculation of the &#34;blank sample&#34; according to EP-A-350098 are recommended. This will allow to detect and eliminate errors. 
     Interpretation of results 
     The described screening test does provide a fast, unique and reliable method to identify cellulases which satisfy the activity criteria of the present invention versus cellulases which are not part of the present invention. 
     It has been found that a removal of 10% or more of the immobilized radioactive labelled CMC according to the above C14CMC-method, indicates that the respective cellulase satisfies the requirements of the invention. 
     It will be obvious to those skilled in the art that removal percentages above 10% indicate a higher activity for the respective cellulase. It therefore is contemplated that cellulase providing above 25% or preferably above 50% removal of radioactive labelled CMC, at the protein concentration in the laundry test solution according to the C14CMC-method, would provide indication of an even better performance of the cellulase for use in laundry detergents. 
     It also has been contemplated that usage of higher concentrations of cellulase for C14CMC-method, would provide higher removal percentages. However, there exists no linear proven correlation between cellulase concentration and removal percentage obtained by it. 
     It also has been contemplated that usage of higher concentrations of cellulase for C14CMC-method, would provide higher removal percentages. 
     
                       TABLE I______________________________________Radioactive C.sub.14 labelled CMC stock solution(all percentages by weight of total solution)______________________________________Total CMC*        99.2 × 10.sup.-3 %(CMC should bedetergent grade CMCwith a degree ofsubstitution from about0.47 to about 0.7)Ethanol           14985.12 × 10.sup.-3 %Deionized Water   84915.68 × 10.sup.-3 %Total:            100%______________________________________ *Total CMC contains nonradio-active and radioactive CMC to provide a radioactivity which allows sufficiently clear readings on the scintillation counter used. For example, the radioactive CMC can have an activity of 0.7 millicurie/g and be mixed with nonradio-active CMC at a ratio of 1:6.7. 
    
     
                       TABLE II______________________________________Laundry test solution(all percentages by weight of total solution)______________________________________Linear C.sub.12 alkyl           0.110%benzene sulphonicacidCoconut alkyl   0.040%sulphate (TEA salt)C.sub.12-15 alcohol           0.100%ethoxylate (E07)Coconut fatty acid           0.100%Oleic acid      0.050%Citric acid     0.010%Triethanolamine 0.040%Ethanol         0.060%Propanediol     0.015%Sodium hydroxide           0.030%Sodium formate  0.010%Protease        0.006%Water (2.5      balance to 100%mmol/liter Ca.sup.++), pHadjustment agent(HCL or NAOHsolutions) andcellulase______________________________________ 
    
     The Water-Soluble Quaternary Ammonium Compound 
     The water-soluble soluble quaternary ammonium compound has the formula: 
     
         R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.- 
    
     wherein R 1  is C 8  -C 16  alkyl, each of R 2 , R 3  and R 4  is independently C 1  -C 4  alkyl, C 1  -C 4  hydroxy alkyl, benzyl, and --(C 2  H 40 ) x  H where x has a value from 2 to 5, and X is an anion. Not more than one of R 2 , R 3  or R 4  should be benzyl. 
     The preferred alkyl chain length for R 1  is C 12  -C 15  particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R 2  R 3  and R 4  are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions. Examples of suitable quaternary ammonium compounds are 
     coconut trimethyl ammonium bromide 
     coconut methyl dihydroxyethyl ammonium bromide 
     decyl triethyl ammonium chloride 
     decyl dimethyl hydroxyethyl ammonium bromide 
     myristyl trimethyl ammonium methyl sulphate 
     lauryl dimethyl benzyl ammonium bromide 
     lauryl methyl (ethenoxy) 4  ammonium bromide 
     The water-soluble cationic component of the compositions of the present invention is capable of existing in cationic form in a 0.1% aqueous solution at pH 10. The water-soluble cationic compound will normally be present in an amount of from 0.2% to 10% by weight of the detergent composition. 
     Detergent Adjuncts 
     The detergent compositions of the present invention include components that are usually found in laundry detergents, these components being present in an amount of up to 95% by weight of the composition. 
     These include nonionic and zwitterionic surfactants, builder salts, bleaching agents and organic precursors therefor, suds suppression agents, soil suspending and anti-redeposition agents, enzymes, optical brighteners colouring agents and perfumes. 
     A wide range of anionic surfactants can be used in the compositions of the present invention. 
     Suitable anionic non-soap surfactants are water soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alphaolefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acdylozy-alkane-1-sulfonates, and beta-alkoxy alkane sulfonates. Soaps are also suitable anionic surfactants. 
     Especially preferred alkyl benzene sulfonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, more especially 11 to 13 carbon atoms. Suitable alkyl sulfates have 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms. Suitable alkyl polyethoxy ether sulfates have 10 to 18 carbon atoms in the alkyl chain and have an average of 1 to 12 --CH 2  CH 2  O-- groups per molecule, especially 10 to 16 carbon atoms in the alkyl chain and an average of 1 to 6 --CH 2  CH 2  O-- groups per molecule. 
     Suitable paraffin sulfonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carbon atoms. Suitable alphaolefin sulfonates have 10 to 24 carbon atoms, more especially 14 to 16 carbon atoms; alphaolefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulfonates. Suitable alphasulfocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alphasulfonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms. 
     Suitable alkyl glyceryl ether sulfates are ethers of alcohols having 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow. 
     Suitable alkyl phenol polyethoxy ether sulfates have 8 to 12 carbon atoms in the alkyl chain and an average of 1 to 6 --CH2CH20-- groups per molecule. Suitable 2-acyloxy-alkane-1-sulfonates contain from 2 to 9 carbon atoms in the acyl group and 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyloxy alkane sulfonates contain 1 to 3 carbon atoms in the alkyl group and 8 to 20 carbon atoms in the alkane moiety. 
     The alkyl chains of the foregoing non-soap anionic surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred. Mixtures of anionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulfonate having 11 to 13 carbon atoms in the alkyl group and alkyl sulfate having 12 to 18 carbon atoms in the alkyl group. 
     Suitable soaps contain 8 to 18 carbon atoms, more especially 12 to 18 carbon atoms. Soaps can be made by direct saponification of natural fats and oils such as coconut oil, tallow and palm oil, or by the neutralization of free fatty acids obtained from either natural or synthetic sources. The soap cation can be alkali metal, ammonium or alkanol-ammonium, sodium is preferred. 
     The compositions contain from 3 to 40% of anionic detergent, preferably from 4 to 15% of anionic detergent, more preferably, 5-10% of anionic surfactant. 
     As stated previously, the compositions of the present invention combine good softening and cleaning performance and in order to maintain the latter it is essential that the overall surfactant character be anionic. The molar ratio of the water-soluble quaternary ammonium compound to the anionic surfactant component should therefore be less than 1:1 and desirably should be less than 1:1.5. In preferred embodiments of the invention such as heavy duty laundry detergent formulations, the molar ratio should be less than 1:2. 
     Subject to these constraints the cationic compound will normally be present in an amount of from 0.5% to 15% by weight of the composition, preferably from 1% to 5% and most preferably from 1.5% to 3% by weight. 
     Nonionic and zwitterionic surfactants may be incorporated in amounts of up to 50% by weight of the total surfactant but normally are present in amounts of less than 30% of the total surfactant. By &#34;total surfactant&#34; is meant the sum of the anionic surfactant (a) cationic component (b) and any added nonionic and/or zwitterionic surfactant. The incorporation of 15-25% nonionic surfactant based on the total surfactant weight (corresponding to 1-2% on a total composition basis) has been found to provide advantages in the removal of oily soils. Suitable nonionics are water soluble ethoxylated materials of HLB 11.5-177.0 and include (but are not limited to) C 10  -C 20  primary and secondary alcohol ethoxy ethoxylates and C 6  -C 10  alkylphenol ethoxylates. C 14  -C 18  linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C 14  -C 15  (EO)7, C 16  -C 18  (EO) 25 and especially C 16  -C 18  (EO) 11. 
     Suitable zwitterionic surfactants include the C 12  -C 16  alkyl betaines and sultaines. These and other zwitterionic and nonionic surfactants are disclosed in Laughlin &amp; Heuring U.S. Pat. No. 3,929,678. 
     Detergent builder can be inorganic or organic in character. Non limiting examples of suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates, and silicates. Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, penta-polyphosphates and hexametaphosphates. Sulphates are usually also present. 
     Preferred water soluble builders are sodium tripolyphosphate and sodium silicate, and usually both are present. In particular, it is preferred that a substantial proportion, for instance for 3% to 15% by weight of the composition of sodium silicate (solids) or ratio (weights ratio SiO 2  :Na 2  O from 1:1 to 3.5:1 be employed. 
     A further class of detergency builder materials useful in the present invention are insoluble sodium alumino silicates of the formula: 
     
         Na.sub.z (AlO.sub.2).sub.z (SiO.sub.2).sub.y xH.sub.2 O 
    
     wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to 0.5:1 and x is an integer from 15 to 264. A preferred material is Na 12  (SiO 2  AlO 2 ) 12  27H 2  O. If present, incorporation of 5% to 25% by weight of aluminosilicate is suitable, partially replacing water-soluble builder salts, provided that sufficient water-soluble alkaline salts remain to provide the specified pH of the composition in aqueous solution. 
     Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight. 
     Bleaching agents, suds controlling agents, soil suspending agents, proteolytic, amylolytic or lipolytic enzymes, especially proteolytic, and optical brighteners, may be present. 
     Colours, non-substantive, and perfumes, as required to improve the aesthetic acceptability of the product, are usually incorporated. 
     The detergent compositions according to the invention can be in liquid, paste or granular forms. Granular compositions according to the present invention can also be in &#34;compact form&#34;, i.e. they may have a relatively higher density than conventional granular detergent compositions according to the present invention will contain a lower amount of &#34;inorganic filler salt&#34;, compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; &#34;compact&#34; detergents typically comprise not more than 10% filler salt. 
     PREPARATION OF THE COMPOSITIONS 
     The detergent compositions may be prepared in any way, as appropriate to their physical form, as by mixing the components, co-agglomerating them or dispersing them in a liquid carrier. In granular form a detergent salt builder can be incorporated and the granular is prepared by spray drying an aqueous slurry of the non-heat-sensitive components, and the builder salt to form spray dried granules into which may be admixed the heat sensitive components such as persalts, enzymes, perfumes. The water-soluble quaternary compound may be included in the slurry for spray drying or it may be incorporated by dissolving or dispersing the cationic component in water or another suitable volatile liquid and then spraying this solution of disperion onto the spray dried granules before or after other heat sensitive solids have been dry mixed with them. Alternatively the water-soluble quaternary compound can be dry mixed together with the other heat sensitive solids. Clay components may be added to the slurry for spray drying or may be dry mixed, as preferred for reasons unrelated to its softening effect, such as for optimum colour of the product. 
    
    
     The invention is illustrated by the following non-limiting examples. 
     The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow. 
     EXAMPLE I 
     Criticality of the Cellulase Performance Parameter of Claim 1 
     The following test was conducted: 
     Test conditions 
     Washing temperature: 60° C. (heat up cycle) 
     Washing time: 40 min. 
     pH=7.5 
     Water hardness: 4 mmol/L 
     Detergent concentration: 1% 
     Detergent composition: crf. EPA 350 098 ex. 1 
     Cellulases: 
     1) Celluzyme R  supplied by Novo Nordisk=reference 
     2) 43 kD endoglucanase=cellulase according to the invention 
     Test Results 
     
         ______________________________________          % C14-CMC Removal by Cellulase______________________________________Detergent without cellulase            0(= reference)Detergent + Celluzyme.sup.R1.5 mg protein/L (150 × 10.sup.-6 %)            12.73.0 mg protein/L (300 × 10.sup.-6 %)            17.74.5 mg protein/L (450 × 10.sup.-6 %)            21.5Detergent + 43kD endoglucanase0.3 mg protein/L (30 × 10.sup.-6 %)            20.3______________________________________ 
    
     Discussion of the Results 
     The above data clearly demonstrate the criticality of the claimed parameter for the cellulases of the invention over the commercially available Celluzyme. 
     EXAMPLE II 
     Two sets of different detergent compositions are prepared, all based on a compact granular detergent composition. 
     Such a compact granular detergent composition typically contains the following ingredients: 
     
         ______________________________________Linear alkyl benzene sulphonate (LAS)                 9.5%Alkyl suphate         3%Nonionic              4%Trisodium citrate     21%Zeolite               33%Citric acid           6%Polymer               4%Chelant               0.2%Sodium sulphate       6%Sodium silicate       2%Perborate             0.5%Phenol sulphonate     0.1%______________________________________ 
    
     The above detergent composition was supplemented as indicated below: 
     
         ______________________________________SET 1: With 43kD endoglucanase                    2.4 mg Cellulase/(*)Quaternary ammonium          No Cellulase                    L wash liquorcompounds level mg/l          (PSU)     (240 × 10.sup.-6 %) (PSU)______________________________________ 0             -2.5      0100            -2.5      1.5200            -2.5      3.5______________________________________SET 2: With Celluzyme.sup.R                    92 mg Cellulase/(*)Quaternary ammonium          No Cellulase                    L wash liquorcompounds level mg/l          (PSU)     (9200 × 10.sup.-6 %) (PSU)______________________________________ 0             -0.3      0100            -0.3      0200            -0.3      0______________________________________ (*)C.sub.12 -C.sub.14 dimethyl (hydroxyethyl) ammonium chloride 
    
     Test procedure 
     Cellulase has the property to de-pill worn cotton fabrics. In a model test the measurement of de-pilling is used to assess cellulase performance. Swatches of worn blue pyjama fabric were treated with different wash solutions in a Laundrometer (temperature 30° C.). The water hardness was 2.5 mM Calcium. After tumble drying, the fabrics were graded for de-pilling by direct comparison of the different detergent matrices. Visual grading was performed by expert judges using a 0 to 4 scale (PSU). In this scale 0 is fiven for no difference and 4 is given for maximum difference. The PSU grading are statistical recount, an average of 4 replicates is made, LSD (least significant difference) is 0.5 PSU at 95% confidence level. 
     The above results demonstrate the synergy between the quaternary ammonium compound and the 43 kD cellulase in that the performance of the 43 kD cellulase is significantly improved by the quaternary ammonium compound. 
     EXAMPLE III-VI 
     Test procedure 
     3.5 kg of clean fabric laundry loads were washed in an automatic drum washing machine Miele 423 at 60° C. The hardness of the water was 2.5 mM Calcium and the composition concentration was 0.7% in the wash liquor. For softness evaluation swatches of terry towel were line dried prior for assessment of softness. Comparative softness assessment was done by expert judges using a scale of 0 to 4 panel-score-units (PSU). In this scale 0 is given for no difference and 4 is given for maximum difference. Softness was assessed after one and after one, four and eight wash cycles. LSD is 0.5 psu at the 95% confidence level. The following compositions are made: 
     
         ______________________________________          Percentage by weightIngredients      III    IV       V    VI______________________________________SurfactantLinear alkylbenzene sulfonate            8      8        8    8Tallow alkyl sulphate            2      2        2    2C.sub.12 -C.sub.14 dimeth. hydroxyeth            5      --       5    --ammonium chloFatty alcohol (C.sub.12 -C.sub.15)            1.5    1.5      1.5  1.5ethoxylateBuilder/chelantsZeolite A        18.5   18.5     18.5 18.5Copolymer of maleic and            5      5        5    5acrylic acid, sodium saltBleachSodium perborate 11     11       11   11N.N.N,T-Tetraacetyl ethylene            4      4        4    4diaminePerfume          0.5    0.5      0.5  0.5Enzymes          --     --       --   --Protease         1.6    1.6      1.6  1.6Cellulase 43 kD  0.5    0.5      --   --Softness systemSmectite/montmorillonite clays            12.5   12.5     12.5 12.5Polyethylene oxide            0.3    0.3      0.3  0.3BufferCarbonate        10.6   10.6     10.6 10.6Silicate (2.0)   4      4        4    4CMC, chelantsAdmix and spray-on            balance to 100(suds suppression,miscellaneous, . . . )______________________________________ 
    
     Results 
     Detergent composition III 0.5% (=40×10 -6  % mg proteine wash liquor) 43 kD cellulase+5% quaternary ammonium component versus detergent composition IV 0.5% (=40×10 -6  % mg proteine wash liquor) 43 kD cellulase no quaternary ammonium component 
     
         ______________________________________Cycles    1             4      8______________________________________PSU       0             0.8s   1.8s______________________________________ 
    
     Detergent composition V+5% quaternary ammonium composition versus detergent composition VI no quaternary ammonium component 
     
         ______________________________________Cycles    1             4     8______________________________________PSU       --            --    0.1______________________________________ significant difference at 95% confidence 
    
     Conclusion 
     The above results demonstate that the quaternary ammonium compound/43 kD cellulase combination gives a statistical significant better performance than the sum of the individual actions of both ingredients. 
     Formulation Examples 
     The following compositions are made: 
     
         ______________________________________              Composition (% by weight)              Regular productsIngredients          I      II     III  IV______________________________________C.sub.11-12 alkyl benzene sulfonate                7      5      4    --Tallow alcohol sulfate (Na)                --     2      --   --C.sub.14-15 alkyl sulfate (Na)                --     --     3    4A-Olefin (C.sub.12-18) sulfonate (Na)                --     --     --   0.5Tallow alcohol ethoxylate (EO.sub.11)                0.5    --     --   --Fatty alcohol (C.sub.12-15) ethoxylate (EO.sub.7)                --     --     --   0.5Hydrogenated tallow fatty acid                --     0.5    --   --C.sub.12-14 Dimethyl (hydroethyl) ammonium                --     --     5    5chlorideSodium tripolyphosphate                24     --     --   25Zeolite A            --     20     20   --Sodium citrate       --     5      5    --Oleic fatty acid     --     --     --   --Citric acid          --     --     --   --C.sub.14-16 alkyl succinate                --     --     --   --1,2-Propanediol      --     --     --   --Ethanol              --     --     --   --Na Metaborate Octahydrate                --     --     --   --Polyethylene oxide 5 MM molecular weight                0.05   --     --   0.05Polyethylene oxide 0.3 MM molecular                --     0.3    --   --weightSodium sulfate       12     10     15   5Sodium carbonate     5      7      --   15Sodium silicate      4      4      4    4Sodium perborate (1 aq.)                15     15     18   15N,N,N,N-Tetraacetylethylene diamine                3      3      --   3CMC                  0.3    0.3    0.3  0.3Polyacrylate (MW 1000-20 000)                --     1.5    --   --Polyacrylate (MW 4000-5000)                --     --     3    --Maleic-acrylic copolymer                2      --     --   3Cellulase            0.5    0.5    0.5  1Smectite/montmorillonite clay                10.5   10.5   10.5 10.5Phosphate            --     --     --   0.3Admix and spray-on (perfumes, protease,                balance to 100amylase, lipolase, buffer, sud suppression,miscelaneous, moisture and minors)______________________________________              Composition (% by weight)              Compact  Liquid              product  productIngredients          I       II     I______________________________________C.sub.11-12 alkyl benzene sulfonate                8       --     10Tallow alcohol sulfate (Na)                2       2      --C.sub.14-15 alkyl sulfate (Na)                --      6      1A-Olefin (C.sub.12-18) sulfonate (Na)                --      --     --Tallow alcohol ethoxylate (EO.sub.11)                --      --     --Fatty alcohol (C.sub.12-15) ethoxylate (EO.sub.7)                --      --     --Hydrogenated tallow fatty acid                --      --     --C.sub.12-14 Dimethyl (hydroethyl) ammonium                5       5      --chlorideSodium tripolyphosphate                --      --     --Zeolite A            15      19     --Sodium citrate       --      6      --Oleic fatty acid     --      --     1Citric acid          --      --     2C.sub.14-16 alkyl succinate                --      --     101,2-Propanediol      --      --     3Ethanol              --      --     7Na Metaborate Octahydrate                --      --     1Polyethylene oxide 5 MM molecular weight                --      --     --Polyethylene oxide 0.3 MM molecular                0.3     0.3    --weightsulfonate            --      2      --Sodium carbonate     11      11     --Sodium silicate      4       3      --Sodium perborate (1 aq.)                11      12     --N,N,N,N-Tetraacetylethylene diamine                4       3      --CMC                  0.4     0.3    --Polyacrylate (MW 1000-20 000)                --      --     --Polyacrylate (MW 4000-5000)                --      --     --Maleic-acrylic copolymer                5       4      --Cellulase            1       0.5    1Smectite/montmorillonite clay                12      12     10.5Layered silicate     7       --     --Admix and spray-on (perfumes, protease,                balance to 100amylase, lipolase, buffer, sud suppression,miscelaneous, moisture and minors)______________________________________ ##STR1##