AU634705B2 - Detergent compositions containing cellulase granulates - Google Patents

Abstract

Detergent compositions for the cleaning and softening of fabrics are claimed, in which cellulase granulates containing a water-insoluble calcium salt, preferably calcium carbonate, are incorporated. Softness and fabric-appearance benefits are excellent. The cellulase granulates per-se are also claimed.

Description

OPI DATE 14/06/89 WORI AOJP DATE 20/07/89 APPLN. ID 26117 88 PCT NUMBER PCT/DK88/00189

PCT

INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International Publication Number: WO 89/ 04862 C11D 3/386, 3/12 Al (43) International Publication Date: 1 June 1989 (01.06.89) (21) International Application Number: PCT/DK88/00189 (81) Designated States: AT, AT (European patent), AU, BB, BE (European patent), BG, BJ (OAPI patent), BR, (22) International Filing Date: 18 November 1988 (18.11.88) CF (OAPI patent), CG (OAPI patent), CH, CH (European patent), CM (OAPI patent), DE, DE (Euro-: pean patent), DK, FI, FR (European patent), GA (31) Priority Application Number: 8727081 (OAPI patent), GB, GB (European patent), HU, IT (European patent), JP, KP, KR, LK, LU, LU (Euro- (32) Priority Date: 19 November 1987 (19.11.87) pean patent), MC, MG, ML (OAPI patent), MR (OA- PI patent), MW, NL, NL (European patent), NO, (33) Priority Country: GB RO, SD, SE, SE (European patent), SN (OAPI patent), SU, TD (OAPI patent), TG (OAPI patent), US.

(71) Applicants (for all designated States except US): NOVt !NDUBSTR+ A/f [DK/DK]: Novo All, DK-2880 Published Bagsvaerd THE PROCTER GAMBLE With international search report.

COMPANY [US/US]: I Procter Gamble Plaza, Before the expiration of the time limit for amending the Cincinatti, OH 45202 claims and to be republished in the event of the receipt of amendments.

(72) Inentors; and of am Inventors/Applicants (for US only) JENSEN, Poul, Erik [DK/DK]; Lathyrusvej 3, DK-3450 Alleroed. 3 DE MARTELAERE, Dirk [BE/BE]; Tervu- t 1 ursevest 120, B-3000 Leuven 1 (54) Title: DETERGENT COMPOSITIONS CONTAINING CELLULASE GRANULATES (57) Abstract, Detergent compositions for the cleaning and softening of fabrics are claimed, in which cellulase granulates containing a water-insoluble calcium salt, preferably calcium carbonate, are incorporated. Softness and fabric-appearance benefits are excellent. The cellulase granulates per-se are also claimed.

WO 89/04862 PCT/DK88/00189 -1- DETERGENT COMPOSITIONS CONTAINING CELLUIASE GRANULATES Technical field The present invention is related to granular detergent compositions which are useful for cleaning and softening of fabrics, and for giving other fabric-care benefits such as appearance improvements and rejuvenation.

The compositions herein contain a fabric-softening clay material, and a cellulase enzyme, which is in the form of granulates containing calcium carbonate.

WO 89/04862 PCT/DK88/00189 2 Background of the Invention It has been the objective of many detergent manufactures to formulate laundry detergent compositions which provide the good cleaning performance expected of them, and which also exhibit fabric-care properties, inclusive of softness.

Representative of such detergent compositions are the ones which have been disclosed in British patent 1,514,275 1,400,898, or EPA 0 026 528.

Cellulase enzymes have already been used in detergent compositions for their cleaning abilities, as disclosed in British Patent Application GB-A 2,095,275, GB-2,094,826, or Japanese patent 57108-199.

Cellulases have also been found to give softness benefits to fabrics as in U.S. 4,435,307; EP-A 0 120 528 teaches alkaline softening detergent compositions comprising a synergistic mixture of a water-insoluble C 10

-C

26 tertiary amine and cellulase.

EP-A 0 177 165 discloses alkaline softening detergent compositions containing a mixture of smectite clay and cellulase.

EP-A 0 220 016 discloses the fabric color-clarification effect derivable from the use of cellulase in a detergent context.

WO 89/04862 PCT'/DK88/00189 3 When such detergent and/or softening compositions are in granular forms, the cellulase enzymes are usually incorporated in the composition in the form of granulates, also identified as marumes, or prills, which are supplied by the enzyme manufacturer.

U.S. 4,435,307, which relates to a hardness reducing agent for detergent compositions, discloses the use of cellulase granulates, and mentions certain ingredients which need to be incorporated to the granulates during their making, for e.g. non-dusting and color purposes.

It has been discovered, however, that certain of these ingredients are detrimental to the softness/fabric care properties of the composition, when cellulase granulates containing these ingredients are incorporated into a detergent composition.

When looking for a replacement to these undesirable ingredients, it has now been discovered that waterinsoluble salts of calcium, surprisingly substantially enhance the softness/fabric care performance of the detergent compositions containing the enzyme granulates.

It is therefore the object of the present invention to provide detergent compositions which possess excellent softness/fabric care properties, due to the use of cellulase granulates containing a water-insoluble salt of calcium.

Summary of the Invention The present invention relates to granular detergent compositions containing a fabric-softening clay material, and cellulase granulates containing from 1% to 50%, by weight, preferably 5% to 15% of the granulates, of calcium carbonate.

WO 89/04862 PCT/DK88/00189 4 Calcium carbonate is preferably coated onto the cellulase granulates.

The invention also relates to the above-described cellulase granulates per-sd.

Detailed Description of the Invention The compositions herein are capable of cleaning and softening the treated fabrics, as well as giving benefits in terms of fabric appearance improvements and rejuvenation.

SThis is achieved by the presence, in the granular compositions herein, of surface active agents, of fabric-softening clay materials, and of cellulase granulates containing calcium carbonate.

In the following, these compulsory, as well as optional ingredients are described in detail The Cellulase The cellulase usable in the present invention may be any bacterial or fungal cellulase having a pH optimum of between 5 and Suitable cellulases are disclosed in U.S. 4,435,307, GB-A-2.095.275, DE-OS-2.247.832, and EP-A 0 220 016.

WO 89/04862 PCT/DK88/00189 5 Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var.

thermoidea), particularly by the Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).

Activity determination for the cellulase herein is based on the hydrolysis of carboxymethyl cellulose.

Generated low molecular reducing carbohydrates are colorimetrically determined by the ferrocyanide reaction as described by W.S. Hoffman Biol. Chem." 120,51 (1973). Key conditions of incubation are pH temperature of 40* C and incubation time of 20 minutes.

One CMCase unit is defined as the amount of enzyme which forms per minute an amount of reducing carbohydrate equivalent to 10 6 mole of glucose, in the abovedescribed conditions.

A useful range of cellulase activity in the present context is from 5 to 1360, preferably from 60 to 140 CMCase activity units/gram of detergent composition.

The Cellulase Granulates Cellulase enzymes for use in granular detergent compositions are typically supplied in the form of granulates, e.g. marumes or prills.

Such granulates contain a majority of crude cellulase enzyme, together with additional ingredients, such as polyethylene glycol, at typical levels of from 5 to 7 WO 89/04862 PCT/DK88/00189 6 and cellulose at typical levels of about 10%. the polyethylene glycol for use herein can have a molecular weight in the range from 500 to 8000.

The amount of cellulase in the granules is determined by the total cellulase activity of the composition, which has to be in the limits set up hereinabove.

It has been discovered that certain materials which have been used by enzyme manufacturers as dustness-preventing and whitening agents, which are Titanium dioxide and Magnesium silicate, interact negatively with the softness performance of the compositions herein.

The compositions of the invention should, therefore, preferably by free of Titanium dioxide and Magnesium silicate.

It has now been found that calcium carbonate possesses the dustness-preventing function when added to the cellulase granulates, and also givesunexpected softness/fabric care benefits as shown hereinafter.

The calcium carbonate should be present in the cellulase granulates, at levels of from 1% to-1 0 4, preferably 5% to 15% by weight, of the granulates.

Calcium carbonates of a particle size range from 1 to microns have been found to be particularly suitable for the purpose of the present invention.

WO 89/04862 PCT/DK88/00189 7 The calcium carbonate used herein may be used as is or in coated form, typically coated with stearic acid. In a preferred execution of the present invention, calcium carbonate, either as is or already coated with e.g. stearic acid, is coated onto the cellulase granulates.

Cellulase granulates can be prepared in a number of different ways, for example by means of a "Marumerizer" as described in British Pat.Nos. 1,362,365 and 1,361,387 or by means of a granulating machine, as described in Aufbereitungs-Technik No. 3/1970, pp. 147-153 and No. 5/1970, pp. 262-278, or can be prilled granulates as described in Belgian Patent Specification No. 760.135. In all cases, the granulates must have low dusting properties.

The calcium carbonate herein is either mixed with the other ingredients during the making of the granulates, or mixed with cellulase before granulation, or, preferably, coated onto the granulates which have been prepared as described hereinabove, by conventional coating methods.

The cellulase granulates according to the present invention are present at levels of from 1 to 50 by weight of the detergent composition herein, preferably to 10 by weight.

The surface-active agent The surface active agent useful herein may be selected from anionic, nonionic, zwitterionic surfactants and is present at levels of from 1 to 50 by weight of the composition, preferably from 10 to 30 WO 89/04862 PCT/DK88/00189 8 Suitable anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alphaolefin sulphonates, alpha-sulphocarboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy either sulphates, 2-acyloxt-alkane-lsulphonates, and beta-alkyloxy alkane sulphonates.

Especially preferred alkyl benzene sulphonates have 9 to 15 carbon atoms in a linear or branched alkyl chain, especially from 11 to 13 carbon atoms. Suitable alkyl sulphates have from 10 to 22 carbon atoms in the alkyl chain, more especially from 12 to 18 carbon atoms.

Suitable alkyl polyethoxy ether sulphates have from 10 to 18 carbon atoms in the alkyl chain and have an average of from 1 to 12 CH2CH20- groups per molecule, especially from 10 to 16 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH20-groups per molecule.

Suitable paraffin sulphonates are essentially linear and contain from 8 to 24 carbon atoms, more especially from 14 to 18 carton atoms. Suitable alpha-olefin sulphonates have from 10 to 24 carbon atoms, more especially from 14 to 16 carbon atoms; alpha-olefin sulphonates can be made by reaction with sulphur trioxide, followed by neutralization under conditions such that any sultones present are hydrolyzed to the corresponding hydroxy alkane sulphonates. Suitable alpha-sulphocarboxylates contain from 6 to 20 carbon atoms; included herein are not only the salts of alpha-sulphonated fatty acids but also their esters made from alcohols containing 1 to 14 carbon atoms.

WO 89/04862 PCT/DK88/00189 9 Suitable alkyl glyceryl ether sulphates are ethers of alcohols having from 10 to 18 carbon atoms, more especially those derived from coconut oil and tallow. Suitable alkyl phenol polyethoxy ether sulphates have from 8 to 12 carbon atoms in the alkyl chain and an average of from 1 to 6 -CH2CH20-groups per molecule. Suitable 2-acyloxyalkane -1-sulphonates contain from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety. Suitable beta-alkyloxy alkane sulphonates contain from 1 to 3 carbon atoms in the alkyl group and from 8 to carbon atoms in the alkane moiety.

The alkyl chains of the foregoing anionic surfactants can be derived from natural sources such as coconut oil to tallow, or can be made synthetically as for example by using the Ziegler or Oxo processes. Water-solubility can be achieved by using alkali metal, ammonium, or alkanolammonium cations; sodium is preferred. Mixtures of anionic .surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11-13 carbon atoms in the alkyl group and alkyl sulphate having 12 to 18 carbon atoms in the alkyl group.

Suitable nonionic surfactants to be incorporated in the ccepositions herein, are water-soluble ethoxylated materials of HLB 11.5-17.0 and include (but are not limited to) C 10

-C

20 primary and secondary alcohol ethoxylates and C6-C10 alkylphenol ethoxylates.

C14-C18 linear primary alcohols condensed with from seven to thirty moles of ethylene oxide per mole of alcohol are preferred, examples being C14-C1 (E0)7, C16-C18 (E0) 25 and especially C16-C18 EO) 11 Cationic co-surfactants which can be used herein, include water-soluble quaternary ammonium compounds of the WO 89/04862 PCT/DK88/00189 10 form R4R R667N wherein R4 is alky1 having from 10 to 20, preferably from 12-18 carbon atoms, and

R

5

R

6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X- is an anion, e.g. chloride. Examples of such trimethyl ammonium compounds include C 1 2

-C

14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.

The compositions of the invention are essentially free of water-insoluble long-chain alkyl amine softening agents, and derivatives thereof, since it has been discovered that they interact negatively with cellulase, in the pH conditions of the present invention. Derivatives of the amine softening agents include the corresponding amine compounds. Such amine softening agents are disclosed in e.g. EP.A 0.026.528 and EP.1 0.120.528. and include in particular amines of the formula RR 2R3N where R 1 and R 2 are C 6 to C20 alkyl chains, and R 3 is C 1 to C10 alkyl chain or hydrogen.

The compositions herein are formulated at a pH in the range of from 6.5 to 9.5, measured as a 1 X solution of the composition in distilled water.

At this pH-range, the cellulases for use herein have their optimum performance.

The fabric-softening clay material The compositions herein must contain a clay softening agent.

WO 89/04862 PCT/DK88/00189 11 Such clay softening agents are well-known in the detergency patent literature and are in bload conmercial use, both in Europe and in the United States. Included among such clay softeners are various heat-treated kaolins and various multi-layer smectites. Preferred clay softeners are amectite softener clays that are described in German patent document 23 34 899 and in U.K. patent 1,400,898, which can be referred to for details.

The most preferred clay fabric softening materials include those materials of bentonitic origin, bentonites being primarily montmorillonite type clays together with various impurities, the level and nature of which depends vn the source of the clay material. Softener clays are used in the p-pcfnre compositions at levels of at least generally 1-20 preferably 2-10 Optional ingredients The compositions herein may contain, in addition to the essential ingredients, certain optional ingredients.

S For instance, it is preferred that through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant. Compounds classifiable and well-known in the art as detergent builders include the nitrilotriacetates, polycarboxuylates, citrates, water-soluble phosphates such as tri-polyphosphate and sodium ortho- aid pyro-phosphates, and mixtures thereof.

Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-polyphosphonates and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3.579.454 for typical examples of the use of such materials in various cleaning compositions. Preferred polyfunctional organic acids species for use herein are citric acid, ethylene diamine tetramethylenephosphonic acid, anA dietheylene triaminepentamethylenephosphonic acid.

WO 89/04862 PCT/DK88/00189 12 A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates. The 1-10 micron size zeolite zeolite A) builders disclosed in German patent 24.22.655 are especially preferred for use in low-phosphate or non-phosphate compositions. In general, the builder/sequestrant will comprise from 0.5 to 45 X of the composition.

The compositions herein can also contain fatty acids, saturated or unsaturated, and the corresponding soaps.

Suitably fatty acids, saturated or unsaturated, have from to 18 carbon atoms in the alkyl chain. Preferred are unsaturated species having from 14 to 18 carbon atoms in the alkyl chain, most preferably oleic acid. The corresponding soaps can also be used. The optional fatty acid/soaps are used in levels up to 20 X.

The compositions herein can also contain compounds of the general formula R-CH(COOH)CH 2 (COOH) i.e. derivatives of succinic acid, wherein R is C 0-C2 alkyl or alkenyl, preferably C 12

-C

16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents.

The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potasslum, ammonium and alkanolammonium salts. Specific examples of succinate builders include lauryl succinate, ryristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like.

Also useful as builders in the present context are the compounds described in U.S. patent 4.663.071, i.e. mixtures WO 89/04862 PCT/DK88/00189 13 of tartrate monosuccinic acid and tartrate disuccinic acid in a weight ration of monosuccinic to disuccinic of from 97:3 to 20:80, preferably 95:5 to 40:60.

Another optional ingredient is a bleaching agent.

Preferred are peroxygen bleaching agents such as sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.

Bleach activators may be used in combination with the above peroxygen bleaching agents. Classes of bleach activators include esters, imides, imidazoles, oximes, and carbonates. In those classes, preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-octanoyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4decanoyloxybenzenesulfonate biophenol diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.

Other highly preferred peroxygen bleach activators which are disclosed in U.S. Patents 4,483,778 and 4,539,130, are alpho-substituted alkyl or alkenyl esters, such as sodium-4(2-chlorooctanoyloxy)benzene sulfonate, sodium 5, 5-trimethyl hexanoyloxy)benzene sulfonate.

Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application 0 166 571, compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a heteroatom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.

Enzymes other than cellulases, such as proteolytic, amylolytic, or lipolytic enzymes can be used in addition to WO 89/04862 PCT/DK88/00189 14 the cellulase herein.

Soil-release/soil-suspending agents can be present in the composition herein at levels typically from 0.1 Z to X by weight. In particular alkoxylated polyamines suitable as clay-soil removal/anti-redeposition agents can be used. These components, as well as their preparation, are disclosed in EP-PA 0 112 593, the disclosures of which are incorporated herein by reference.

It is to be understood that the term "polyamines" as used herein represents generically the alkoxylated polyamines, both in their amine form and in their quaternarized form. Such materials can conventiently be represented as molecules of the empirical structures with repeating units: N R Amine form and (Alkoxy)y

R

1 N x Quaternized I form (Alkoxy)y wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R 1 may be a CIC 2 0 hydrocarbon; the alkoxy groups are ethoxy, propoxy, and the like, and y is 2-30, most preferably 10-20; n is an integer of at least 2, preferably 2-20, most preferably 3-5; and X is an anion such as halide or methylsulfate, resulting from the quaternization reaction.

WO 89/04862 PCT/DK88/00189 15 The most highly preferred polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with ethyline-imine, having the general formula CR CH- N- -(EtO) I I E t O)y (EtO)y w: !rein n is an integer of 3 to 5 and y is an integer of to Soil suspending agents can also be selected from polyethylene glycols, of molecular weight 400 to 1000, polyacrylates, or copolymers of acrylic acid and maleic anhydride/acid.

SThe detergent compositions herein are preferably free of carboxymethylcellulose.

Moreover, the compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additonal product performance benefits. Typical ingredients include pH regulants, perfumes, dyes, optical brighteners, hydrotropes and gelcontrol agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach stabilizing agents.

WO 89/04862 PCT/DK88/00189 16 EXPERIMENTAL PART A granular detergent composition was prepared, according to the following table Ingredients Sodium Linear C12 alkyl benzene sulfonate Sodium Tallow alkyl sulfate Tallow alcohol ethoxylate (EOl) Sodium tripolyphosphate Bentonite clay Soil suspending agent* Proteolytiz enzyme Sodium sulfate, water, minors by weight 11.0 0.3 24.0 0.9 up to balance copolymer of acrylic and maleic acid, MW 60.000 (sodium salt).

From the basic composition hereinabove,, two compositions were prepared Composition A, to be used as reference, where cellulase granulates (1.79 X by weight of total composition) containing crude cellulase enzymes and cellulose, were dry-mixed with the rest of the composition.

Composition B, a composition according to the present invention, where cellulase granulates (1.79 by weight of total composition) containing crude cellulase enzyme, cellulose, and a coating of polyethylene glycol (5 weight level of granulates, MW 1500) and of calcium carbonate (10 weight level of granulates).

WO 89/04862 PCT/DK88/00189 17 In both compositions A and B, the cellu3ase was of the type described in U.S. 4,435,,07 and its amc2_ts were such as to give an activity of 68 CMCase activity units/g of composition.

Compositions I and B were compared for softness and fabric-care performance.

The design of the test was such as to compare softness of textile pieces laundered 4, 8 and 12 times (multi-cycle) each time with invention and reference composition.

The testing conditions were as follows Product usage 92 grams 0.75 cone.

Wash temperature 40* C.

18 grains/gallon (0.31 g/l) water hardness (3:1 Ca/Mg ratio).

The washed and line dried swatches were compared by a panel of two expert judges, working independently, by a paired comparison technique using a 9-point Scheffe scale.

Differences were recorded in panel score units (psu), positive being performancewise better. indicate significant results, with least significant difference (LSD) calculated at 95 confidence.

The testing results were as follows a) Softness number of cycles comp.B vs. comp.A (bath towels) 4 0.38 psu 8 1.00* psu 12 0.75* psu WO 89/04862 PCT/DK88/00189 18 b) Fabric appearance (improved color and anti-pilling performance) (average on main cottom items) number of cycles comp.B vs. comp. A 4 0.69* psu 8 0.75* psu 12 0.75* psu The effect of polyethyleneglycol coating alone was measured as well, and results indicated negative performance effect, thus showing that the positive effect on both softness and fabric appearance are due to the presence of the calcium carbonate.

Claims (15)

1. A particulate composition for the cleaning and softening of fabrics comprising: from 1% to 50%, by weight of detergent surfactants; from 1% to 20%, by weight of a fabric-softening clay material; from 1% to 50%, by weight of cellulase granulates, said granulates comprising; from 1% to 50%, by weight of the granulate of calcium carbonate; (ii) cellulase to provide activity from 5 to 1350 CMCase units per gram of the total detergent composition; (iii) essentially no amount of titanium dioxide and magnesium silicate; (iv) a pH optimum from 5 to said composition being essentially free of water-insoluble long-chain alkyl amine fabric softening agents.

2. A composition in accordance with claim 1, wherein the calcium carbonate is present at levels of from 5% to 15% by weight of the cellulase granulates.

3. A composition in accordance with claim 1 or claim 2, wherein the calcium carbonate has a particle size of from 1 micron to 10 microns.

4. A composition in accordance with any one of claims 1 to 3, wherein the calcium carbonate is coated onto the cellulase granulates.

5. A composition in accordance with any one of claims 1 to 3 4, wherein the cellulase is bacterial or fungal cellulase having a pH optimum of between 5 and

6. A composition in accordance with any one of claims 1 to S 5, wherein the cellulase is a cellulase having an optimum pH from 6.5 to 9

7. A composition in accordance with claim 1 wherein the cellulase granulates are present at a level of from 1.5% to by weight, and the fabric-softening clay material is present at a level from 2% to 10% by weight.

8. A composition in accordance with any one of claims 1 to 19 7 wherein the fabric-softening clay material is a bentonite clay.

9. Cellulase granulates when used in the composition of claim 1, characterized in that they contain from 1% to 50%, by weight, of calcium carbonate. Cellulase granulates according to claim 9, wherein the calcium carbonate is present at levels of from 5% to 15% by weight.

11. Cellulase granulates according to claim 9 or claim wherein the calcium carbonate has a particle size of from 1 micron to 10 microns.

12. Cellulase granulates according to any one of claims 9 to 11 which have the calcium carbonate coated onto them.

13. Cellulase granulates according to any one of claims 9 to 12, wherein the cellulase is bacterial or fungal cellulase having a pH optimum of between 5 and

14. Cellulase granulates according to any one of claims 9 to 13, wherein the cellulase is a cellulase having an optimum pH from 6.5 to

15. A composition in accordance with claim 1 substantially as hereinbefore described with rtference to any one of the examples. 5 DATED: 29 December 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: S THE PROCTER GAMBLE COMPANY and NOVO-NORDISK A/S 20 INTERNATIONAL SEARCH REPORT International Application No pCI'/Dp( pg~n 2, Ol 4 1. CLASSIFICATION OF SUBJECT MATTER (it seve~al classific3lion symbols apply. nalicate all) According to International Patent Classification (IPC) or to both National Classification and IPC TrPC 4 C 11 D 3/386; C 11 D 3/12 tt. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System IClassification Symbols 4 iPC C 11D; C12 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are included In the Fields Searched

111. DOCUMENTS CONSIDERED TO BE RELEVANT' Category Citation of Document, 11 with Indication, where appropriate, of the relevant passages 1t 1 Relevant to Claim No,.i Y EP, A, 0177165 (UNILEVER) 11 9 April 1986 see the whole document cited in the application Y GB, A, 2167758 (SHOWA DENKO 1-16 4 June 1986 see claims 1,3,6,7; page 2, lines 39-43,78-93 Y Chemical Abstracts, volume 105, no. 26, 11-15 December 1986, (Columbus, Ohio, US), see page 119, abstract 228963p, JP, A, 61107935 (SH-OWA DENKO K.K.) I26 May 1986 Y EP, A, 0170360 (NOVO INDUSTRI) 11-15 February 1986 see claims Special categories of cited documents: 10 T" later document published after the international filinj date ocuentdefiingthegenral tat oftheart hic Isnot or Frrority dale and riot in conflict with theo applica ion but A"dcnde n te gerart lr releaeteatwihsnt cited to' underistand the principle or theory underlying the consdere tobe o paticuar elevnceinvention earilier document but published on or &ftar the International document of particular relevance; the claimed invention filing data cannot be considered novel or cannot be considered to LV doctument which may throw doiubti on priority claim(%) or Involve an inventive slop w hichn is cited to establisIh the publication dale of another document ot particular relevance;* the claimed invention Citation or other special reaiton las specilied) cannot be considered to Involve en inventive step when the document referring to an oral disclosure, use, exhibition or document it combined with one or more other such docu- other means mants, such combination being obvious to a parson %killed document published prior to the International filing date but in the art. laier than the priority date claimaid document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search Date of Mailing of this International Starch Report 6oth March 1989 1 fi. K4 B9 Internationat Searching Authority fie EUROPEAN PATENT OFFICE NDRPTE Form PCTIISA/210 (second shoot) (January 1985) ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. OK 8800189 SA 25649 This annex lists the patent family members relating to the patent documents cited in the abo'.e-mcelioned international search report. The members are as contained in the European Patent Office EDP File on 30/03/89 Thc European Patent Office is in no -Aa liable for these particulars iihich are merel) gi'.en for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date EP-A- 0177165 09-04-86 AU-A- 4664585 06-03-86 AU-B- 561138 30-04-87 GB-A- 2167758 04-06-86 JP-A- 61092570 10-05-86 US-A- 4740469 26-04-88 CA-A- 1242663 04-10-88 EP-A- 0170360 05-02-86 JP-A- 60262900 26-12-85 AU-A- 4304285 05-12-85 US-A- 4661452 28-04-87 AU-B- 574468 07-07-88 ZFor more details about this annex :see Offirial Journal of the European Patent Office, No. 12/82