CA2263435A1 - Detergent compositions comprising antibody controlled lipolytic activity - Google Patents

Abstract

The present invention relates to detergent compositions including laundry, dishwashing and hard surface cleaning compositions comprising a lipolytic enzyme and a lipolytic enzyme-directed antibody in order to prevent potential malodour formation related to the hydrolytic activity of lipolytic enzyme while maintaining excellent wash performance.

Description

CA 0226343~ 1999-02-11 WO 98106810 1 PCTrUS97114287 DETERGENT COMPOSITIONS COMPRISING ANTIBODY
CONTROLLED LIPOLYTIC ACTIVITY

FIELD of the INVENTION

The present invention relates to detergent co",posilions including laundry dishwashing and hard surface cleaning compositions comprising a lipolytic enzyme and a lipolytic enzyme-directed anlil,ody in order to prevent potential malodour fon~,ation related to the hydrolytic activity of lipolytic enzyme whilemaintaining excellent wash perfor",ance.

BACKGROUND of the INVENTION

An important part of the system which protects vertebrates against infe~;tions by bacteria and viruses is the humoral immune system. Specialised cells present in bone marrow Iymphoid tissues and blood produce immunoglobulins (antibody) which appear in response to the introduction of micro- or ",aclo",ol~cule foreign to that body and bind the body-foreign structure initiating its destruction. Such a body-foreign molecule is called an antigen. The a,ltiboJy is di,~cted against the antigenic determinant or hapten of the antigene.g. an amino acid sequence parts of oligosaccharides polysaccharides lipopolysaccharides glycoproteins lipoproteins lipoteichoinic acids.
The speciric alllil-odies generated in this manner can combine with the antigen which elicited their formation to form an antigen-antibody complex.
- Antibody mol ~ ~u'es have binding sites that are very specific for and coi"plementary to the structural features of the antigen that induced their ~UI 11 IdliOI I .

, . , _ , _ CA 0226343~ 1999-02-11 W O98/06810 2 PCT~US97/14287 This highly specific antigen-antibody recognition and binding has found several applications such as recognition agent binding agent or carrier agent invarious domains such as analytical che~ y therapeutictreatment health and beauty care.

EP 479 600 EP 453 097 and EP 450 800 relate to the use of antibodies or fragments thereof for the delivery of active ingredients to a target site. EP 481 701 discloses treatment compositions for topical application containing microcapsules which enclose a belleficial agent at a target location the "~iclocapsules having an antibody or antibody fragment specific to the target location or a lectin.

W092/04380 describes reshaped human antibody or reshaped human antibody frag")enl~ having speci~city for human polymorphic epithelial mucin to be used in the l,adt"~ent or diagnosis of cancer. The use of Epstein-Barr virus specific polypeptides for the production of antihodies and the diagnostic and treatment of said disease is disclosed in W094/06470.

Oral compositions comprising antibodies as anti-caries or periodontal dise~ses treatment have been extensively clesc,iLed in WO95/01155 167 299 DE 4324859 US 5 401 723 and EP 280 576.

EP 673 683 and EP 542 309 disclose hair cosr"elic compositions containing an anlil.ody to hair or hair extract obtained from egg yolk or poultry immunised with the hair or hair extract and a polymer emulsion to provide reduced hair dar"a~e softness moistened feel and sr"ooll,ness said composition being adsorbed only onto a specified part of the hair.

Cor"posilions co,)lailling antagollists (tyrpl,osli"s or anti~odies) against epidermal and transforming growth factors suitable for use in treatment of acne are described in W095/24896.

The use of al lliL,odies in the overall detergency context has been suggested in Unilever Researchprijs Molecule zoekt partner 1992 wherein CA 0226343~ 1999-02-11 WO 98/06810 3 PCTrUS97/14287 modified antibodies directed to specific stains are proposed to be used in bleaching process.

The production of antibodies by hyperimmunisation of mammals such as a cow with a vaccine derived from E. coli bacteria is described in EP 102 831. EP
400 569 discloses a method for preparing vaccine composition for dental caries in nasal drops comprising an a"li~en produced by integrating a protein antigen-expressing gene into the chnj",osomal gene of a s~ ptococcl)s mutants GS-5 strain. WO94/25591 disclQses the production of antibodies or functionalised fragments thereof derived from heavy chain immunoglobulins of camelidae.

Deteryent co"~positions include nowadays a complex combination of active ingredients which fulfill certain specific needs: a sur~actant system, enzymes providing cleaning and fabric care benefits, bleaching agents, a buildersystem, suds Supple:ssors~ soil-suspending agents, soil-release agents, optical b-iyhteners, softening agents, dispersants, dye transfer inhibition compounds, abrasives, bactericides, perfumes, and their overall pe,fi.l",auce has indeed improved over the years.
In particular, current laundry detergent formulations generally include detergent enzymes and more specifically lipolytic enzymes.

However, overe~l~osure of the substrate to the lipolytic activity and/or transfer of the lipolytic activity to the post mainwash part of the washing cycle such as rinse, spinning and/or drying steps can lead to unwanted effects e.g.
malodour for,ndtion. It is well known that detergent lipolytic enzymes can undercertain circ--",:,ta,lces lead to unattractive odor. It is bel.~ved that lipolytic enzymes which are adsorbed in the wash cycle onto re~idu~l lipid stains / soils,continues to function thereafter, especia!~y in the rinse and drying cycles. Wlthout meaning to be bound by theory, it is believed that this malodor is stei"",i"g from the post mainwash hydrolysis of residual lipid soils/ stains.

It has now been surprisingly found that the applicalion of antil,Gdies raised aga.nsl lipolytic enzyme prevents the occurrence of undesirable residual lipolytic activity. The lipolytic activity can be fully controlled during the cleaning process so that the potential negative effects, i.e. malodor fon"ation due to the overexposure of the sul~sl,ale to the active lipolytic enzyme can now be avoided.

CA 0226343~ 1999-02-11 It is therefore an object of the present invention to provide a lipase-containing detergent composition delivering excellent cleaning performance such as stain and/or soil removal, dingy cieaning and which has improved odor characteristics.

The above need has been met by specific detergent compositions including laundry, dishwashing and hard surface cleaning, Co"",,i~il,y a lipolytic enzyme and an antibody directed to the lipolytic enzyme.

SUMMARY of the INVENTION

The present invention relates to detergent cGI~positions including laundry, dishwashing and hard surface cleaning compositions colnp,ising a lipolytic enzyme and a lipolytic enzyme-dir~cted antibody in order to prevent potential malodor fo.",aliol) related to the hydrolytic activity of lipolytic enzyme whilemainl~ ing exce"ent wash performance.

DETAILED DESCRIPTION of the INVENTION

ANTIBODY

An essenlial element of the deler~ent compositions of the present invention is an antiboJy.

The immunoglol~ ins are classified into 5 cl -sses, respectively: IgM, IgG, IgA, IgD and IgE. rl~f~ndd types of immunoglobulins are IgG and IgA. Secretory slgA which are found into human excreted body fluids such as milk, saliva, respiratory and i"teslinal fluids are especially designed to survive in said secretio"s, they have enhanced binding characteristics and are resistant to proteolytic hydrolysis.

The anlibG.Jy which may be monoclonal or polyclonal or an antibody ~,a!Jr"enl, may be generated by techniques conventional in the art, for example by using recombinant DNA techniques allowing to produce ar,liL.od;es variants CA 0226343~ 1999-02-11 W O 98tO6810 5 PCTAUS97/14287 with new properties: reduced immunogenecity, enhanced affinity, altered size, ...
Specific binding may also be used. Preferred for the purpose of the present invention is a monoclonal antibody, more preferred is a fragment thereof. These fragments may be si~ nilcirly generated by conventional techniques such as enzymatic digestion by papain or pepsin, or using recombinant DNA techniques.
Antibody fldgn,ents may also be generated by conventional recombinant DNA
techniques. Antibodies and antibodies' f~dyl"e~ may be humanised, such as described in Meded. - Fac. Landbouwkd. Toegepast Biol. Wet. (Univ. Gent) (1995), 60(4a, Forum forApplied Biotechnology, 1995, Part 1), 2057-63.

Heavy and light chains are indeed co"~posed of consla,)l and variable domains. In the organisms producing immunoglobulins in their natural state the constant domains are very important for a number of ful)~tiGns, but for many applications in industrial proGesses and products their variable domains are sufficient. Consequently many methods have been described to produce antibody f,dgme"t~.

Antibody f,dy-"ents which are used may be a Fab, a Fv, a scFv or any other fragment having similar binding plope,lies. Preferred routes to antibodiesfrasiments are through ~co"lbinant DNA technology, so that the fragment is expressed by a genatically l,~nsformed organism.

Antibodies and antibody fragments produced by l~:con,binant DNA
techn~logy do not need to be identical to fragment of antibodies produced in vertebrates, having neve,lî,eless the same binding properties eval~ tecl by their Km, Ki and Kcat. For insta. ~ce they may include sequences of amino acids and/orglycosyl.llions which differ from those found in antibodies produced in other ways, especially sequences at the end of fidgl"ent~. Somewhat analogously, antibody r,ay,nel1ts produced through recol"bi.)al)l DNA technology may include extra amino acid sequences at their termini which have no counterpart in antibodies produced in other ways.

A related possibility is that a binding agent for use in this invention is a natural or sy,ltl,~lic polymer which mimics the specific b.nding activity of a natural antibody's complel"eillairy region(s). Such a polymer is for exa.nple a .. , , .. , . , . . ~ ..

CA 0226343~ 1999-02-11 W O98/06810 6 rCTnUS97/14287 polypeptide or a polymer imprinting (Angew. Chem. Int. Ed. Engl. 1995, 34, 1812-1832).

The usual method for the production of antibodies may be adopted in immunising mam~llals or poultry with the cGr~esponding antigens. As mammals to be immunised, mice, rabbits, goats, sheep, horses, cows, etc. may be used. The antibody (immunoglobulin fraction) may be separated from the antiserum, the milk or the eggs according to the ordinary antibody pu,ificalion ~elhod including salting-out n~elhod, Polson extraction, gel-fillldtiGn chro",alography, ion-exchange chro",a~ography, afffinity chromalography and the like, the salting-outmethod using ammo~ m sulfate to produce the prec;~.itdtes, followed by dialysing the pr~c;~vilates against physiological saline to obtain the purified precipitates as the antibody.

Plants are also capable of synthesising and assernbling every kind o antibody molecule and allow a large scale of production of antibodies as described in Tibtech. Dec 1995, Vol 13, pp 522-527; Plant Mol. Biol., 26, pp 1701-1710, 1994 and Biotechnol. proj. 1991, 7, pp 455461 and in US patent 5, 202,422. Antibodies can also ~e produced into microorganisms such as E. coli or S. cerevisiae via b.orelll)entation process as illusl,aled in the EP patent 667 394.

Techniques for the production of antibody rldy",e"ts are well known in the literature: Saiki et al. Science 230 1350-54 (1985); Orlandi et al. PNAS USA 86 3833-7 (1989); W089/09825; EP 368 684; WO 91/08482 and WO94/25591.

The drawbacks due to plolonged activity of the enzyme can be avoided by an effective control of the enzymatic activity trough the introduction of the specifically wr,~:spo"Jing antibody. Such antibodies can be either polyclonal -directed to the whole enzyme structure - or mol1oclonal - directed to specific epitopes of the enzyme activity controlling regions of the enzyme structure.
Antibodies raised against specific enzyme can effectively deactivate the enzyme by the antibody-antigen binding in or very near the active site. The fo""dlion of such compl_x leads to the enzyme deactivation and could be explained by the distortion of the 3-di,-~e"sional structure and/or steric hindrance at the substrate - cleft. The deactivation of the enzyme can also be achieved by the precipitation of CA 0226343~ 1999-02-ll W O 98/06810 7 PCTrUS97/14287 the complex antibody-antigen from the washing solution. Due to very high specificity and efficiency of the antibody-antigen interaction, no other detergent active is thereby affected.

The lipolytic enzyme-directed antibodies are pref~rdbly comprised in the detergent compositions of the ~resenl invention at a level of from 10E-6% to 10E+1% by weight of total cG"~rosition. In some instances, antibodies raised against a specific lipolytic enzyme have the capability of binding other lipolytic enzymes of high structural similarity, providing cross-reactivity. Typically, a mo'ecul~r ratio of lipolytic enzyme-directed antibody to lipolytic enzyme will be of 100:1 or lower, p,t:ferably of 50:1 or lower. For monoclonal antibodies or fragments thereof, the molecu~r ratio of lipolytic enzyme-directed antibody to lipolytic enzyme will be generally of 50:1 or lower, preferably of 20:1 or lower.

The antibodies raised against the lipolytic enzyme are rclw-.cd in the wash solution after a lag-period allowing to deliver exc~ nl benefits to be achieved by the end of the wash process.

Therefore, the antiL,ocl.~s are pr~:reral~ly incG,,uoraled into a release agent in order to control their release timing and rate in the wash solution. The physical form of the antibody-containing release agent is adapted to the. physical form of the corresponding detergent or additive.

For granular and powder detergent and cleaning products, the antibodies and release agents can be conlained in a granulate. Said a,ltil,oJy granulate can suitably contain various granulation aids, binders, fillers, plaslici~e,s, lubricants, cores and the like. Examples ll,ereof include cellulose (e.g. cellulosic fibers or in microcrystalline form), cel' ~ose derivatives (CMC, MC, HPC, HPMC), gelatin, starch, dextrins, sugars, polyvinylpyrrolidone, PVA, PEG, salts (e.g. sodium sulfate, calcium sulfate), titanium dioxide, talc, clays (kaolin or bentonite)and nonioni~ su~ rdclarils. Other materials of relevance for incorporation in the granulate are described in EP 304 331.

The lelease agent may be, for example, a cOdtillg. Said coali"g protects said granulates in the wash environment for a certain period of time. The codling will normally be app' ed to said granulates in an amount in the range of 1% to CA 0226343~ 1999-02-11 W O 98/06810 8 PCT~US97/14287 50% by weight (calcul~ted on the basis of the weight of the uncoated, dry granulate), preferably in the range of 5 % to 40 % by weight The amount of coating to be applied to said granulates will depend to a considerable extent onthe nature and composition of the desired coating, and to the kind of protectionsaid coating should offer to said granulates. For example, the thickness of saidcoating or a multi-layered coating applied onto any of the above granulates may determine the period in which the content of said granulates is released. A
possible multi-layered coating may be a coati~g in which, for example, a fast release coating is applied over a slow release coating.
Also co-granulates can be constructed containing in the outer layer the detergent enzyme and a fast releasing agent and in the inner core, the antibody and a slow releasing agent.

Suitable release coalings are coali"~s which give rise to release of the contents of antibody-containing granulates under the cor,.litions prevailing during the use thereof. Thus, for example, when a prepardliGn of the invention is to beintroduced into a washing liquor containing a washing detergent (normally comprising, e.g. one or more types of surfactants), the coating should be one which ensures the release of the contents of said granulates from the release agent when it is introduced into the washing medium.
Fr~ft:r,ed rel2asc coating are codlings which are sul,sl~nt;a"y insoluble in water. Release coalinys which are appropriate in washing media may suitably co,nprise substances s~lected from the following: cellulose and cellulase derivatives, F~VA, PVP, tallow; hydrogenated tallow; partially hydrolyzed tallow;
fatty acids and fatty alcohols of natural and sy~ltl,elic origin; long-chain fatty acid mono-, di- and l,iest~r~ of glycerol (e.g. glycerol monostearate); ethoxylated fatty alcohols; I~P~eS; hydrocarbons of melting point in the range of 50-80~C; and waxes. Melt-co~li"g agents are a preferred class of fast or slow l~lease coatingagents which can be used without dilution with water. Reference may be made to Controlled Release Systems: Fabricalion Technology, Vol. I, CRC Press, 1988, for further info""dlion on slow release coating.

Codli"gs may suitably further comprise substdnces such as clays (e.g. kaolin), titanium ~ioxide, pigments, salts (such as calcium carbonate) and the like. The person skilled in the art will be aware of further codling constituents of relevance in the present invention.

CA 0226343~ 1999-02-11 WO 98/06810 9 PCT~US97/14287 In liquid detergent compositions, the antibody can be incorporated as a dispersion of particles containing in addition to the antibody, a release agent. The antibody can be present in a liquid or solid form. Suitable particles consist of a porous hydrophobic material (e.g., silica with an average pore diameter of 500 Angstrom or higher) containing into the pores a solution of antibodies and a surfactant as described in EP 583 512 of Surukidis A. et al.
The release agent might be a coali"g which protects said particles in the wash cycle for a certain period of time. The coating is pr~ferably a hydrophobic coating ,naterial such as a hydrophibic liquid polymer. Said polymer can be an organo polysi'3xal1e oil, alternatively a high olecula weight hydrocarbon or water illsolu~lc but water permeable polymeric material such as carboxymethylcellulose, PVA, PVP. The polymer properties are selected to achieve a suitable release profile of the antibody in the wash solution.

THE LIPOLYTIC ENZYME

Suitable specific lipolytic enzymes for use herein include those of bacterial and fungal origin.Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.).
Purified or non-purified forms of these enzymes may be used. Also included by def",ilio", are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modir,~dliGns of native enzymes. Co""nGn practice as well is the expression of the enzyme via host o~ani_."s in which the genetic malerial responsible for the pro~uction of the enzyme has been cloned.

In the presel)t contexl, the term "lipolytic enzyme" is inlended to i"clicale an enzyme exhibiting a lipid deg~acling capability, such as a c~p~hility of degrading a triglyceride, a phospholipid, a wax-ester or cutin. The lipolytic enzyme may, e.g., be a lipase, a phospholipase, an esterase or a cutinase.

An essential ele."eilt of the present invention is carboxylic ester hydrolase EC 3.1.1 and especi~ly a lipase EC 1.1.1.3. Said lipolytic enzyme is incorporated at a level of from 0.0001 to 2%, preferably from 0.0002% to 1%, CA 0226343~ 1999-02-11 more preferably from 0.0005% to 0.1 % pure enzyme by weight of total composition.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stukeri ATCC 19.154, as dis-~losed in British Patent 1,372,034. Suitable lipases includethose which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057.
This lipase is available from Amano Phar")aceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter r~fer~J to as "Amano-P".
Other s~lit~le co""ner~,ial lipases include Amano-CES, lipases ex Chromobacter viscosvm, e.g. Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chrcmobacter viscosvm lipases from ~J.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Especially suitable lipases are lipases such as M1 LipaseR and LipomaxR (Gist-Br(,cades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in cGillbi.ldlion with the compositions of the present invention. Also suitables are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as a spsci-' kind of lipase, nan,ely lipases which do not require interfacial activation.
Suitable cutinases are described in WO 94/14963 and WO 94/14964. Addition of culinases to deter~enl compositions have been described in e.g. WO-A-88/09367 (Gel)encor) and WO 90/09446 (Plant Genetic System).
The cutinases are normally incol~ordted in the deleryenl composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.

Deter~ent ~."~,onents The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical forrn of the co,,,,uosilion, and the nature of the cleaning operation for which it is to be used.

CA 0226343~ 1999-02-11 The detergent compositions according to the invention can be liquid paste gels bars. tablets powder or granular forms. Granular compositions can also be in "compact " form the liquid compositions can also be in a "concentrated" form.

The co",positions of the invention may for example be formulated as hard surface cleaner hand and machine dishwashing c~i "positi~ns hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the soalcing and/or pr~t,eat",eilt of sldi"ed fabrics rinse added fabric softener CGIllpositions.

When formulated as compositions for use in manual dishwashing methods the compositions of the invention p~eferably contain a surfactant and preferablyother detergent compounds seJected from organic polymeric cG~Ipounds suds enhancing agents group 11 metal ions solvents hydrotropes and additional enzymes.

When formulated as cGr"positions suitable for use in a laundry machine washing method the cGIlll~ositiGl)s of the invention p~rerdbly contain both a surfactant and a buiider compound and additiG"ally one or more detergent components preferably s~lected from organic polymeric compounds bleaching agents additional enzymes suds suppressor~ disper~.anls lime-soap disper~ants soil suspension and anti-~edeposition agents and corrosion inhibitors. Laundry c~",,~ositions can also conlain sorlenL)g agents as additional detergent components.

The cG"~positions of the invention can also be used as deteryent additive products CGIIIp~iSillg a lipolytic enzyme-directed allliLody and will be added to conventional deteryent lipolytic enzyme-containing compositiGns. The detergent additives can also cGmprise a lipolytic enzyme and a lipolytic enzyme-directed antibody. Such additive products are intended to supplement or boost the perfor",ance of convenliGnal detergent co~positions prererably comprise up to 50% antibodies by weight of total c~l"position.

. .

CA 0226343~ 1999-02-11 W O 98/06810 12 PCT~US97/14287 If needed the density of the granular laundry detergent compositions herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at 20~C.

The "compact" form of the granular laundry detergent compositions herein is best reflected by density and, in terms of composition, by the amount of inorga"ic filler salt; inorganic filler salts are conventional ingredients of detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in subst~rltial amounts, typically 17-35% by weight of the total composition.
In the compact compositions, the filler salt is present in amounts not exceecling 15% of the total composition, preferably not exceeding 10%, most preferably not exceeding 5% by weight of the cG"".osition.
The inGrgan.c hller salts, such as meant in the present compositions are selected from the alkali and alkaline-earth-metal salts of sul~hales and chlorides.
A prefer,ed filler salt is sodium sulphate.

Liquid detergent compositions according to the present invention can also be in a "col1ce"t~dted form", in such case, the liquid detergenl cGmpositions according the present invention will contain a lower amount of water, compared to conventional liquid detergents.
Typically the water contenl of the conce, ILlaled liquid detergent is p~eferdbly less than 50%, more preferably less than 40%, most preferably less than 30% by weight of the detergent composition.

Surfactant s~t~.,.

The detergent co"~positions according to the present invention comprise a surfactant system wherein the surfactant can be selected from nonionic and/or anionic and/or cdlioni~ and/or a",pholytic and/or zwitlerionic and/or semi-polarsurfactants.

The surfactant is typically present at a level of from 0.1% to 60% by weight.
More preferred levels of incorporation are 1% to 35% by weight, most preferably from 1% to 30% by weight of detergent compositions in accord with the invention.

CA 0226343~ 1999-02-11 WO 98/06810 13 ~CTrUS97/14287 The surfactant is preferably formulated to be compatible with enzyme components present in the composition. In liquid or gel compositions the surfactant is most preferably formulated such that it promotes, or at least doesnot degrade, the stability of any enzyme in these compositions.

Preferred surfactant systems to be used according to the present invention comprise as a surfactant one or more of the nonionic and/or anionic surfactants described herein.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group co"tai"ing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment,the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Com",ercially available nonionic surfactants of this type include IgepalTM C0-630. marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed bythe Rohm & Haas Cornpany. These surfactants ar c~-lllllonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylat~).

The condensdlion products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nGni~ni~ surfactant of the nonionic surractant systems of the present invention.The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or seco"~ary, and generally contains from about 8 to about 22 carbon atoms.
P,efer,~:d are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in said condensation products. Examples of co"""ercially available nonionic surfactants of this type include TergitolTM 1 5-S-9 (the condensation product of ., CA 0226343~ 1999-02-11 W O 98/06810 14 PCTnUS97/14287 C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW
(the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molec~ r weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM
45-7 (the condensation product of C14-C1~ linear alcohol with 7 moles of ethylene oxide), NeodolTM 4~-5 (the condensation product of C14-C1s iinear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company, KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA
030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products is from 8-11 and most preferred from 8-10.

Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group conlaini"~ from about 6 to about 30 carbon atoms, preferdbly from about 10 to about 16 carbon atoms and a polysaccl,aride, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most prererably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing5 or 6 carbon atoms can be used, e.g., glucose, galactose and g~l~Gtosyl moieties can be substituted for the glucosyl moieties (o,uliGnally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or g~l~ctosiç!e). The intersaccharide bonds can be, e.g., between the one position of the additiona! saccharide units and the 2-, 3-, 4-, and/or 6- posilio"s on the preceding saccharide units.
The pre~r,e~ alkylpolyglycosicles have the formula R20(CnH2nO)t(91Yc~syl)x wl ,erei., R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groupscontain from about 10 to about 18, preferably from about 12 to about t4, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, pr~rerably 0; and x is from CA 0226343~ 1999-02-ll about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (allacl~")ent at the 1-position). The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

The condensation products of ethylene oxide with a hydrophobic base formed by the cGnde,lsdlion of propylene oxide with propylene glycol are also suitable for use as the additional nonionic su,ractant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. ExanlFles of compounds of this type include certain of the commercially-available PlurafacTM
LF404 and PluronicTM surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the "oni3"ic surfactant system of the present invention, are the conde"saliGn products of ethylene oxidewith the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of th reaction product of ethyle.)ediai,line and excess propylene oxide, and generallyhas a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a nl~lBCUI~r weight of from about 5,000 to about 11,000. Examples of this type of nonionic SUI ractant include certain of the cGrr,r"er~,ially available TetronicTM col"pounds, marketed by BASF.

r~t:rer,ed for use as the nonionic su,racldl~t of the su,r~ctant systems of the present invention are polyethylene oxide condensates of alkyl phenols, condensation products of primary and seconddly aliphatic alcohols with from .

CA 0226343~ 1999-02-11 WO 98/06810 16 PCT~US97/14287 about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures thereof. Most preferred are Cg-C14 alkyl phenol ethoxylates having from 3 to 15 ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C10 avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

Highly preferred nonionic su~ ractdnls are polyhydroxy fatty acid amide surfactants of the formula.
R2 C-N-Z, Il I
o R1 wherein R1 is H, or R1 is C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl ora mixture thereof, R2 is Cs 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. Pleferably, R1 is methyl, R2 is a straight C11 15 alkyl or C16 18 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, l~ctose, in a reductive an~ lion ,eactiGn.

Suitable anionic surfactants to be used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with ~seolJs SO3 according to "The Joumal of the American Oil Cl~e~ t~ Society", 52 (1975), pp. 323-329. Suitable starting ~,aterials would include natural fatty substances as derived from tallow, palm oil, etc.
The prefer,ed alkyl ester sulrur~ate surfactant, especi~ly for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula:
o Il R3 - CH - C - oR4 I

wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof,R4 is a C1-C6 hydloca~byl, preferably an alkyl, or combination thereof, and M isa cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, poPssium, and lithium, and CA 0226343~ 1999-02-11 W O 98106810 17 PCTrUS97/14287 substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R3 is C10-c16 alkyl, and R4 is methyl, ethyl or isopropyl. Especially pr~re:r,ecl are the methyl ester sulfonates wherein R3 is C10-C16 alkyl.

Other suitable anioniC surfactants include the alkyl sulfate surfactants which are water soluble salts or acids of the formula ROS03M wherein R pr~f~::,ably isa C10-C24 hydrocarbyl, p~efer~bly an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, pot~ssium, lithium), or ammonium or s~bstituted amn,ol,ium (e.g. methyl-, di~ thyl-, and l,i.netl,yl ammonium cations and quaternary ammonium cations such as tel,arnetl,yl-a"""onium and di",etl,yl piperdinium catio"s and quaternary ammonium calions derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Typically, alkyl chains of C12-C16 are preferred for lower wash te""~erdlures (e.g. below about 50~C) and C16 18 alkyl chains are preferred for higher wash temperatures (e.g. above about 50~C).

Other anionic surfactants useful for detersive purposes can also be included in the detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22 primary of secondary alkanesulrunales, Cg-C24 olefinsulrùnates, sulru"d~ed polycarboxylic acids pfepared by sulfonation of the pyrolyzed product of alkaline earth metal citlat~s, e.g., as desc~ibed in British patent specificalion No.
1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, pararrin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succi"a",ates and sulfosuccinales, monoesters of sulfosucc;nales (especially saturated and unsaturated C12-C18 monoesLer~) and diesters of sulfosucci"ates (especially saturated and unsaturated C6-C12 diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as thoseof the formula RO(CH2CH20)k-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is .. ..

CA 0226343~ 1999-02-ll W O98/06810 18 PCTrUS97/14287 an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil.

Further e~ ples are described in "Surface Active A~ents and Detergents"
(Vol. I and ll by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the laundry detergent co~positions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of such anionic su, ra~;tdnts.

Highly preferred anionic SIJ~ ractar,l~ include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M
wherein R is an unsubstitl~ted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically ~et.veEn about 0.5 and about 6, more p~ferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or suhstitl~ted-a,l,monium cation. Alkyl ethoxylated sulfates aswell as alkyl propoxylated sulfates are col)te,l.,~lated herein. Specific examples of substituted ammonium caliol)s include methyl-, dilllelllyl, Iril"ell~yl-am"~ollium cations and quaternary an)mG~Iium cations such as tetldmetl,yl-ammonium and diln~tl.yl piperdi~ lm cdtions and those derived from alkylamines such as ethylall,i,)e, diethylamine, triethylamine, mixtures thereof, and the like. Exer"pla,y surfactants are C12-C1g alkyl polyethoxylate (1.0) sulfate (C12-C1gE(1.0)M), C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-C1gE(2.25)M), C12-C1g alkyl polyethoxylate (3.0) sulfate (C12-C1gE(3.0)M), and C12-C1g alkyl polyethoxylate (4.0) sulfate (C12-C1gE(4.0)M), wherein M is conveniently selected from sodium and potassium.
The detergent compositions of the present invention may also conlai" cationic, ampholytic, z~itle,iol-ic, and semi-polar surfactants, as well as the nonionic and/or anionic surr~Ctanls other than those already described herein.

CA 0226343~ 1999-02-11 W O 98tO6810 PCTnUS97/14287 Cationic detersive surfactants suitable for use in the detergent compositions ofthe present invention are those having one long-chain hydrocarbyl group.
Exar"plss of such cationic surfactants include the ammonium surfactants such as alkyltrimethylarrlillolliUm halogenides, and those surfactants having the formula:

[R2(oR3)y][R4(0R3)y]2R5N+X-wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is select~d from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures ron"ed by joining the two R4 groups, -CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose polymer having a "~o'e~.ul~r weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 1~; and X is any compatible anion.

Quaternary ammonium surfactant suitable for the present invention has the formula (I):

Rl~o~ ~R, Formula I

whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the formula (Il):

N~

Formula ll y is 2-4, preferably 3.

CA 0226343~ 1999-02-11 W O98/06810 20 PCTrUS97/14287 whereby R2 is H or a C1-C3 alkyl, whereby x is 0-4, preferably 0-2, most preferably 0, whereby R3, R4 and RS are either the same or different and can be either a shortchain alkyl (C1-C3) or alkoxylated alkyl of the formula lll, whereby X- is a counterion, preferably a halide, e.g. chloride or methylsulfate.

H
Formula lll R6 is C1-C4 and z is 1 or2.

Pr~fer~ed quat ammonium surfactants are those as defined in formula I
whereby R1 is Cg, C10 or mixtures thereof, x=o, R3, R4 = CH3 and R~ = CH2CH2~H

Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula:
R1 R2R3R4N+X- (i) wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40)XH where x has a value from 2 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C1s particularly where the alkyl group is a mixture of chain le"!Jths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Prefer~t:d groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and phosphate ions.
Exanlples of suitable quaternary ammonium compounds of formulae (i) for use herein are:
coconut l,i,neU,yl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12 15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;

CA 02263435 1999-02-ll WO 98/06810 21 PCTnUS97/14287 myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is CH2-CH2-O-C-C12 14 alkyl and R2R3R4 are methyl).
Il o di-alkyl imidazolines [compounds of formula (i)].

Other cationic surfactants useful herein are also descril,ed in U.S. Patent 4,228,044, Cambre, issued October 14, 1980 and in European Patent Application EP 000,224.

When included therein, the deteryent compositions of the present invention typically co",prise from 0.2% to about 25%, plef~r~bly from about 1% to about 8% by weight of such cationic surfactants.

Ampholytic surfactants are also suitable for use in the detergent con,positions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertialy amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be strai~ht- orbranched-chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 to Laughlin et al., issued Dece",ber 30, 1975 at column 19, lines 18-35, for examples of ampholytic sulractdnts.

When inchlded therein, the deteryent co",rositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such ampholytic surfactants.

Zwitterionic surfactants are also suitable for use in detergent compositions.
These sul~ddd~ can be broadly described as derivatives of seconda~y and tertiary amines, derivatives of heterocyclic secondaly and tertialy amines, or derivatives of quate"~aly ammonium, quaternary phosphonium or tertialy sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued CA 0226343~ 1999-02-ll W O98/06810 22 PCTrUS97/14287 December 30, 1975 at column 19, line 38 through column 22, line 48, for examples of zwitterionic surfactants.

When included therein, the detergent compositions of the present invention typically cGn,l rise from 0.2% to about 15%, pref~r~bly from about 1% to about 10% by weight of such zwitterionic surfactants.

Semi-polar nonionic surFactants are a special calegory of nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 ~oielies selected from the group consisting of alkyl groups and hydroxyalkyl groups conlain;"g from about 1 to about 3 carbon atoms; water-soluble phosphine oxides cGntaini"g one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisli"g of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide su,rdctanla having the formula o R3(oR4)xN(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof containing from about 8 to about 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures ll,ereof, x is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to forma ring structure.

These amine oxide surfactants in particular include C10-c18 alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.

CA 0226343~ 1999-02-11 W O 98/06810 23 rcTrusg7/14287 When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of such semi-polar nonionic surfactants.

The deteryent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.
Suitable primary ai"ines for use herein include amines according to the formula R1NH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X
is -O-,-C(O)NH- or-NH-, R4 is a C6-C12 alkyl chain n is between 1 to 5, preferably 3. R1 alkyl chains may be straight or branched and may be interrupted with up to 12, preferably less than 5 ethylene oxide ",oieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein may be seiected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amido propylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines having the formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or - (CH2- CH - O ~H

R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-,R4 is a C4-C12, n is between 1 to 5, prererably 2-3. Rs is H or C1-C2 alkyl and x is between 1 to 6 .
R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted with up to 12, p~3f~rably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or - (CH2- CH - O ~H

where R5 is H or CH3 and x = 1-2.

~,. ... . . .. .

CA 0226343~ 1999-02-11 WO 98/06810 PCT~US97/14287 Also preferred are the amidoamines of the formula:
ll Rl--C--NH--~ CH2 )--N--( R2 ) wherein R1 is C6-C12 alkyl; n is 24, preferably n is 3; R2 and R3 is C1-C4 Most pr~rerre:d amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1 -dodecylamine,C8-1 Ooxypropylamine, N coco 1-3dia",i"o~,ropane, coconutalkyldimetllylamine, lauryldimethylamine, lauryl bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles propoxylated, octyl amine 2 moles propoxylated, lau~yl amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10 amidopropyldi",etl ,ylamine.
The most plef~ned amines for use in the compositions herein are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-dodecylJ;,netl"~lamine and bishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated, lauryl amido propylamine and cocoamido propylamine.

C~ .,tional detergent ~ ".es The detergent co"l~ositions can further co~,prise one or more enzymes which provide deterye"t pe, ror",ance and/or fabric care benefits.

Said enzymes include enzymes selected from hemicellulnses, peroxidases, proteases, gluco-amylases, amylases, xylanases, pectinases, keratanases, reducPses, oxid~ses, phencl~xid~ses, lipoxygenases, lig"i,lases, pullulanases, tannases, pentosanases, malanases, r~-glucanases, arabinosid~ses, hyaluronidase, chondroitinase, l~cc~se or mixtures thereof.

A preferred combination is a detergent composition having cocktail of conventional app'i~~~le enzymes like protease, amylase, lipase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.

CA 0226343~ 1999-02-ll WO 98/06810 25 PCT~US97/14287 The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, which discloses fungal cellulase produced from Humicola insolens. Suitable cellul~-ses are also disclosed in GB-A-2.07~.028; GB-A-2.095.275 and DE-OS-2.247.832.

Exa,nples of such cellu~ases are cellulases produced by a strain of Humicola illsolel)s (Humicola grisea var. ther,llcidea), particularly the Humicola strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens havina molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids and a -43kD endoglucanase derived from Humicola insolens, DSM
1800, exhibiting cellulase activity; a preferred endoglucanase component has theamino acid sequence cliscl~sed in PCT Patent Application No. WO 91/17243.
Also suitable cellulases are the EGIII cell~ llases from Trichoderma longibracl,iatum described in WO94/21801, Genencor, published September 29, 1994. Fspecially suitahle cellulases are the cellul~ses having color care benefits.
Examples of such cellulases are cellulases described in European patent applicalion No. 91202879.2, filed November 6, 1991 (Novo).

Peroxid~se enzymes are used in combination with oxygen sources, e.g.
percar6Onate, perborate, persù1fate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from su~sl,~te3 during wash operations to other su~sl~ates in the wash solution.
PerOxid~sç enzymes are known in the art, and include, for exa",ple, horseradish peroxld~se, ligninase, and haloperoxid~se such as chloro- and bromo-peroxldase.
Peroxidase-containing detergent cG",positions are dicclosed, for example, in PCT Intel-,atiol)al Application WO 89/099813 and in European Patent applic~lioll EP No. 91202882.6, filed on November 6, 1991.
Other suitable oxkl~ses is the laccase enzyme, using oxugen, hydrogen peroxide as primary sul/slldtes.

CA 0226343~ 1999-02-11 Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. Iicheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, dcvelo,~ed and sold as ESPERASE~) by Novo Industries AIS of Denri,arh, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~), DURAZYM~) and SAVINASE~) from Novo and MAXATASE~), MA)(ACAL~, PROPERASE~g) and MA~(APEM~ (protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also enco",pass modified bacterial serine proteAses, such as those cJescribed in European PatentApplication Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "P~otease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modi~ied bacterial serine protealytic enzyme which is calied "P~o~ease A" herein.
More preferred is what is called herein "P~otease C", which is a variant of an alkaline serine protease from Ri9c~ s in which Iysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274. P,otease C is described in EP 90915958:4, cor,esl onding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Plotease C, are also included herein. See also a high pH p,otease from R~ci'lus sp. NCIMB 40338 descri6ed in WO 93/18140 A to Novo. Enzymatic detergcnts comprisi"g protease, one or more other enzymes, and a reversible protease inhibitor are described in WO
92/03529 A to Novo. When desired, a protease having decreased adsor~tiGn and increased hydrolysis is available as described in WO 95/07791 to P~o-;ter &
Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
In more detail, plotease referred to as "Protease D" is a carbonyi hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substitllting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of+99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the nu-,lberi,)g of Bacillus amyloliq~Jefaciens subtilisin, as described in W095/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994. Also suitable for the present invention are proteAses desc~iLed in patent ap~licdtiGns EP 251 446 and WO91/06637 and pr~tease BLAP~) desc.i~ed in W091/02792. The proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001% to 2%, pr~rer~bly from 0.001% to 0.2%, more pl~:r~r~bly from 0.005% to 0.1% pure enzyme by weight of the cG,.,position.

Amylases (a and/or ~) can be included for removal of carbohydrate-based stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes deterge,)t compositions which incG~,uorale mutant amylases. See also WO94/18314, Genencor, published August 18, 1994 and WO95/10603, Novo Nordisk A/S, published April 20, 1995 . Other amylases known for use in detergent cornrositions include both a- and ~-amylases. a-Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666;
WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British Patent specificdtion no. 1,296,839 (Novo). Other suit~hlc amylase are stability-enhanced amylases including Purafact Ox AmR dascribed in WO 94/18314, pulished August 18, 1994; W096/05295, Genencor, published February 22, 1996 and amylase variants having ad~ilional mo-lificdlion in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Exam~les of comloercial a-amylases products are Te,man~yl~,Ban(~) Fungamyl~) and Duramyl~l9, all available from Novo Nordisk A~S Denmark.
W095/26397 descril es other s!~it~ble amylases: a-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl(~ at a te"".erdl.lre range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095l35382.

_ . , .

CA 0226343~ l999-02-ll W O 98/06810 28 PCT~US97/14287 The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or ex~ lophilic (psychrophilic, psyc~,rol~ophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of nativeenzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modificaliG"s of native enzymes. Common practice as well is the expression of the enzyme via host organism in which the genetic Il,aterial responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the detergent composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent co",position. The enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc., containing one enzyme) or as mixtures of two or more enzymes (e.g., cogranulates).

Other suitable detergent ingredients that can be added are enzyme oxidation scavengers which are described in Co-pending European Patent application 92870018.6 filed on January 31, 1992. Examples of such enzyme oxidaliG~I scavengers are ethoxylated tetraethylene polya,l,ines.

A range of enzyme n~aterials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO
9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.
3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,21g, Hughes, March 26, 1985. Enzyme materials useful for liquid detergen~ formulations, and their incor~,oration into such forrnulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 19.81. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful R~c~ us~ sp. AC13 giving proteases, xylanases and cell~'a,es. is described in WO 9401532 A to Novo.

Color care benefts CA 0226343~ 1999-02-11 Technologies which provide a type of color care benefit can also be included.- Examples of these technologies are metallo catalysts for color maintenance. Such ",ete"o catalysts are described in co-pending European PatentApplication No. 92870181.2.

The Bleaching agent The detergent composiliGns of the present invention can further include bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate with a pa-licle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending upon the bleaching agent chosen~ one or more bleach activators. When present oxygen bleaching compounds will typically be present at levels of from about 1 % to about 25%..

The bleaching agent co, nponent for use herein can be any of the bleaching agents useful for detergent cGmpositions including oxygen bleaches as well as others known in the art. The bleachi~,g agent suitable for the present invention can be an activated or non-activated bleaching agent.

One category of oxygen bleaching agent that can be used encon,p~sses percarboxylic acid bleaching agents and salts thereof. Suitable examples of thisclass of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino~-oxopero~ybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446, European Patent Arp'~~tion 0,133,354 and U.S. Patent 4,412,934. Highly pr~f-e,led bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as desc,il.ed in U.S. Patent 4,634,551.
Another category of bleachi"g agents that can be used enco,npasses the halogen bleaching agents. Exampl_s of hypohalite bleaching agents, for exal"pl~, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphona",ides. Such materials are normally added at 0.5-10% by weight of the finished product, prêferably 1-5% by weight.

.

CA 0226343~ 1999-02-11 WO 98/06810 30 PCTrUS97/14287 The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO94/28106), which are perhydrolyzed to form a peracid as the active bleaching species, leading to improved bleaching effect. Also suitable activators are acylated citrate esters such as discloserl in Co-pending European Patent Application No. 91870207.7.

Useful bleaching agents, including peroxyacids and bleaching systems col"prising bleach activators and peroxygen bleaching compounds for use in detergent compositions according to the invention are described in our co-pendi"g applicaliol Is USSN 08/136,626, PCT/US95/07823, W095/27772, W095/27773, W095/27774 and W095/27775.

The hydrogen peroxide may also be present by adding an enzymatic system (i.e., an enzyme and a subsll ate therefore) which is capable of ge~,eraling hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.

Metal-containing catalysts for use in bleach composiliGns, include cobalt-containing catalysts such as Pentaamine ~cet~te cobalt(lll) salts and ",angallese-containing catalysts such as those described in EPA 549 271; EPA
549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US

5,114,611. Bleaching composition co",prising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in the patent application No 94870206.3.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. These r"aleridls can be deposited upon the substldte during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging cloll,es out to dry in the CA 0226343~ l999-02-ll W O98/06810 31 PCTrUS97/14287 daylight, the sulfonated zinc phthalocyanine is activated and, consequently, thesubstrate is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718. Typically, detergent compositions will contain about 0.025% to about 1.25%, by weightl of sulfonated zinc phthalocyanine.

Bu~lder system The composilions accGrdiny to the present invention may further cG")p,ise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarl,oxylates, alkyl- or alkenyl-succinic acid and fatty acids, materials such as ethylenediamine tetraacetate, diethylene triamine penlamethyleneacetate, metal ion sequesl,anls such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethyle-,ephosphonic acid.
Phosphate builders can also be used herein.

Suitable builders can be an inor~an c ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated sy"ll,elic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6 (I loechst). SKS-6 is a crystalline layered silicate consislillg of sodium silicate (Na2Si2~5) Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid and ether derivatives thereof as disclQsed in Belgian PatentNos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) di~etic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Orrer,!s3enschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carl,oxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxy groups include, in particular, water-soluble citlales, aconitrates and citraconates as well as succ,i"ate derivativessuch as the carboxymethyloxysucc,i"ates described in British Patent No.
1,379,241, lactoxysuccil~ates described in Netheriands ApplicaliGn 7205873, and CA 0226343~ 1999-02-11 WO 98/06810 32 PCTrUS97tl4287 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 oxydisucci"ales 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. 1,3~8,421 and 1,398,422 and in U.S.Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in BritishPatent No. 1,082,179, while polycarl,oxylates containing phosphone substituents are disclosed in British Patent No.1,439,000.

Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclo,l~enladienide pentacarboxylates, 2,3,4,5-tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis -dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -hex~c~r-boxylates and and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. A-o",atic poly-carboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the p,erer-ad polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly cit,ates.

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. pr~fer.ed builder systems for use in liquid dekr~ent co".positions of the present invention are soaps and polycarboxylates.

A suitable chelant for inclusion in the deteryent compositions in accGr~Jance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) orthe alkali metal, alkaiine earth metal, ammonium, or substituted a,."-,onium salts thereof, or mixtures ~hereof. P,~rened EDDS compounds are the free acid forrn and the sodium or ma~nesium salt thereof. Exa",pl-s of such prerer,ed sodium salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium CA 0226343~ 1999-02-11 salts are the most preferred for inclusion in compositions in accordance with the invention.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, and a watersoluble carboxylate chelating agent such as citric acid.

Other builder materials that can form part of the builder system for use in granular compositions include inorganic n~aterials such as alkali metal carbonates, bicarbonates, silicates, and organic nldterials such as the organic phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.

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-1,596,7~6. 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.
Detergency builder salts are normally inctuded in amounts of from 5% to 80% by weight of the composition preferably from 10% to 70% and most usually from 30% to 60% by weight.

Suds suppressor Another G~JtiGnal ingredient is a suds suppressor, exemplified by silicones, and silic~ si'icone mixtures. Silicones can be generally represented by alkylated polysiloxane materials while siiica is nGm~ally used in finely divided forms exemplified by silica aer(,gels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particul~tes in which the suds suppressor is advantageously rele~s~hly incorporated in a water-soluble or water-dispersible, subst~utially non-surface-active detergent imperrneable 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.
A p,efer,~7d silicone suds controlling agent is disclosed in Bartollota et al.
U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-,,, , " , . ~

CA 0226343~ l999-02-ll 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, com-nercially available from Dow Corning, which is a siloxane-glycol copolymer. Especially preferred suds controlling agent are the suds suppressor system comprising a mixture of silicone oiis and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-butyl-octanol which are c~ mercially available under the trade name Isofol 12 R.
Such suds suppressor system is described in Co-pending European Patent application N 92870174.7 filed 10 November, 1992.
Especially preferled silicone suds controlling agents are described in Co-pending European Patent arp'.c~tion N~92201649.8. Said compositions can con,prise a silicone/silica mixture in combination with fumed nonporous silica such as AerosilR.

The suds suppr~ssGr~ described above are normally employed at levels of from 0.001 % to 2% by weight of the coi,-position, preferably from 0.01 % to 1 % by weight.

Others Other components used in detergent compositions may be employed, such as soil-suspe,-Ji--g agents, soil-release agents, optical brighteners, abrasives, ba~:teric;des, tarnish inhibitors, coloring agents, and/or encapsulated or non-encapsulated perfumes.

rS~eci~lly suitable el,cal~s~ ting ~,-aleri.ls are water soluble capsules which co"si:,l of a matrix of polysaccha, ide and polyhydroxy compounds such as desc,il,ed in GB 1,464,616.

Other suitable water soluble encapsulating materials cor"~.rise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as described in US 3,45~,838. These acid-ester dextrins are, preferably, prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable exar.,ples of said encapsulating materials include N-Lok manufactured by National Starch. The N-Lok encapsulating material consists of a CA 0226343~ 1999-02-11 W O98/06810 PCTAUS97/14287_ modified maize starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenyl succinic acid anhydride.

Antiredeposition and soil suspension agents s~ ~itahl_ herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their sa,ts. 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 m~::ll,a~;rylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These n,dlerials 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 c~" lpositioi ~.

Preferred optical brighteners are anionic in character, examples of which are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino4-anilino-s-triazin-6-ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri-azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyî-N-2-hydroxyethylarr,;,~o)-s-triazin-6-ylamino)stilbene-2,2' - disulphonate, di-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-anilino4-(1-methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl 4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are the sp~ific brightel)er~ of copending European Patent applica~ion No.
95201943.8.

Other useful polymeric materials are the polyethylene glycols, particularly those of ,,,olec~ weight 1000-10000, more particularly 2000 to 8000 and most pr~rably 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.

.. . . . . ..

CA 0226343~ 1999-02-11 WO 98/06810 36 PCT~US97/14287 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 lJS Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0 272 033. A patticular preferred polymer in accordance with EP-A-0 272 033 has the formula (CH3(PEG)43)0.75(PoH)o.25[T-po)2.8(T-pEG)o-4]T( H)o.25((pEG)43cH3~o.75 where PEG is -(OC2H4)0-,PO is (OC3tl60) and T is (pcOC6H4CO).

Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, 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 isto obtain a polymer capped at both end by sulphobenzoate groups, ",~rimarilyl', 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 s~lected polyesters herein contain about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weightethylene glycol about 13% by weight of dimethyl sulruberl oic acid and about 15% by weight of sulfoisophthalic acid, and have a molecu~~ weight of about 3.000. The polyesters and their method of preparation are desclibed in detail inEPA 311 342.

It is well known in the art that free chlorine in tap water rapidly deactivates the enzymes comprised in detergent compositions. Therefore, using chlorine scavenger such as perborate, a, l ,monium sulfate, sodium sulphite or polyethyleneimine at a level above 0.1% by weight of total composition, in the formulas will provide improved through the wash stability of the detergent W 098/06810 PCT~US97/14287 enzymes. Compositions comprising chlorine scavenger are described in the European patent application 92870018.6 filed January 31, 1992.

Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additiQnal grease removal peiro,-.,ar,ce. Such n,aterials are described in WO 91/08281 and PCT gO/01815 at p. 4 et seq.7 incorporated herein by referel)ce. Chemically, these materials com~,rise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are o~ the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The mo'ec llar weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.

Softening agents Fabric softening agents can also be incorporated into laundry detergent compositions in accor~a,~ce with the present invention. These agents may be inorganic or organic in type. InGrya,)ic softening agents are exemplified by thesmeclil~ clays disclosed in GB-A-1 400 898 and in USP 5,019,292 Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their cGmbi,)alion 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 ami.l~s as disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as ~isclose~ in EP-A-0 299 575 and 0 313146.

Levels of smectite clay are normally in the range from 2% to 20%, more preferably from 5% 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 dilong chain amide n,dler;als are incorporated at le\~els 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 l"aterials are ~ .

CA 0226343~ 1999-02-ll W O 98/06810 38 PCTrUS97/14287 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 molten liquid on to other solid components of the composition.

Dispersants The detergent composition of the present invention can also contain dispersants: 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 r~cals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Exalllples of such salts are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 1,000 to 100,000.

Especially, copolymer of acrylate and methylacrylate such as the 480N
having a molecular weight of 4000, at a level from 0.5-20% by weight of composition can be added in the detergent compositions of the present invention.

The colll~,osiliG"s of the invention may contain a lime soap peptiser compound, which has a lime soap dispersing power (LSDP), as defined hereinafter of no more than 8, pr~ferably no more than 7, most preferably no more than 6. The lime soap peptiser compound is preferably present at a level from 0% to 20% by weight.

A nu"~erical measure of the effectiveness of a lime soap peptiser is given by the lime soap dispersant power (LSDP) which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and C.A.
Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime soap dispersion test Ill~thod is widely used by practitioners in this art field being referred to, for exa"~p'e, in the following review articles; W.N. Linfield, Surfactant science Series, Volume 7, page 3; W.N. Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of dispersing agent to sodium oleate required to disperse the lime soap deposits CA 0226343~ 1999-02-11 W O 98tO6810 39 PCTAUS97/14287 formed by 0.0259 of sodium oleate in 30ml of water of 333ppm CaCo3 (Ca:Mg=3:2) equivalent hardness.

Surfactants having good lime soap peptiser capability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accord with the present invention include C16-C1g dimethyl amine oxide, C12-C1g alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly C12-C1s alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3(LSDP=4), and the C14-C1s ethoxylated alcohols with an average degree of ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol A012 and Lutensol A030 respectively, by BASF GmbH.

Polymeric lime soap pepliser~ suitable for use herein are described in the article by M.K. Nagar~jan, W.F. Masler, to be found in Cosmetics and To.!et,ies,volume 104, pages 71-73, (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyllbenzene sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-aminohexanoyl]~e, I,ene sulfonate and mixtures thereof; and nonanoyloxy benzene sulfonate to~~ll,er with hydrophilic / hyd,ophobic bleach formulations can also be used as lime soap peptisers compounds.

Dye transfer inhibiffon The detergent cornpositions of the present invention can also include compounds for inhibiting dye t,ansfer from one fabric to another of solubilized and suspended dyes encountered during fabric laundering operations involving colored fabrics.

Polymeric dye transfer inhibiting agents The detergent compositions according to the present invention also co.nprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably , . . . . . . .

CA 0226343~ 1999-02-11 WO 98/06810 4 o PCT/US97114287 from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said polymeric dye transfer inhibiting agents are normally incorporated into detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to complex or adsorb the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity to become attached to other articles in the wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyllolidolne polymers, polyvinylox?~oliclones and polyvinylimid~7oles or mixtures thereof.
Addition of such polymers also enhances the performance of the enzymes according the invention.
a) Polyamine N-oxide polymers The polyamine N-oxide polymers suitable for use contain units having the following structure formula:
p I

(I) Ax R

wherein P is a poly",erisable unit, whereto the R-N-O group can be attached to or wherein the R-N-O group forms part of the polymerisable unit or a co",l~ dtion of both.

O O O
Il 11 11 AisNC, CO,C,-O-,-S-,-N-;xisOor1;
R are aliphatic, ethoxylated aliphatics, alu",alic, heterocyclic or alicyclic groups or any co",bindlion thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.
The N-O group can be represented by the following general structures:

CA 0226343~ 1999-02-11 W O98/06810 41 PCT~US97/14287 ~ O

(R1)x -N- (R2)y =N- (R1)x I

(R3)z wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations lhereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups.

The N-O group can be part of the poly~erisable unit (P) or can be attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selectecl from aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides co"~prises the group of polyamine N-oxides wherein the nitrogen of the N-O group is attached to the R-group.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attacl,ed to the poly",erisable unit.
P,efer,ed class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the llilloye" of the N-0 functional group is part of said R group.
Examples of these cl-~sses are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another prerer,ed class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groupswherein the nit,ogen of the N-0 functional group is dllached to said R groups.
Examples of these c~-sses are polyamine oxides wherein R groups can be ar~." ,dlic such as phenyl.

. .

CA 0226343~ 1999-02-11 Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of amine oxide groups pr~senl in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxkl~tion. Pleferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably from 1:4 to 1:1000000, most preferdbly from 1:7 to 1:1000000. The polymers of the present invention actually encompass random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is either an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more preferred PKa ~ 6.
The polyamine oxides can be oLldi"ed in almost any degree of polyme,i~aliG,).
The degree of poly-"eris~liol- is not critical provided the material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to 1000,000;
preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most preferably from 3,000 to 20,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimid~-21e The N-vinylimidazole N-vinylpyrrolidone polymers used in the present invention have an average ",c'ecul~r weight range from 5,000-1,000,000, p,t:fera~ly from 5,000-200,000.
Highly prefer,ed polymers for use in detergent com~ositions according to the pr~:sent invention co"~rise a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers wherein said polymer has an average molecular weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most p~feldbly from 10,000 to 20,000.
The average molecular weight range was determined by light scalleri"g as descriled in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern Methods of Polymer Characte,i~aliGn".

CA 0226343~ 1999-02-11 W O 98/06810 PCTrUS97/14287 Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an average molec~llar weight range from 5,000 to 50,000; more preferably from 8,000 to 30,000; most preferably from 10,000 to 20,000.

The N-vinylimid~le N-vinylpyrrolidone copolymers characterized by having said average ",c'erl~'qr weight range provide excellent dye transfer inhibiting properties while not adversely drrecti"g the cleaning pe,rur-"ance ofdetergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has amolar ratio of N-vinyli-~ z~ to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone The deter5Jent composilions of the present invention may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, p,eferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most p,~ferdbly from about 5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average mlo'ecul-r weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinylpyrrolidones which are cG")n,ercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
d) Polyvinylox~ol done:

The detergent compositions of the present invention may also utilize polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinylox~-~l dones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 1 5,000.

CA 0226343~ 1999-02-11 W O 98/06810 PCT~US97/14287 e) Polyvinylimidazole:

The detergent compositions of the present invention may also utilize polyvinylimida~clc as poiymeric dye transfer inhibiting agent. Said polyvinylimi ~7c'es have an average about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferdbly from about 5,000 to about 50,000, and most ~ r~rably from about 5,000 to about 15,000.

f) Cross-linked polymers:

Cross-linked polymers are polymers whose backbone are interconnected to a certain degree; these links can be of chemical or physical nature, possibly withactive groups n the backbone or on branches; cross-linked polymers have been desc,ibed in the Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way that they form a three-di."ellsional rigid structure, which can entrap dyes in the pores formed by the three-dimensional structure. In another embocli,~ent, the cross-linked polymers entrap the dyes by swelling.

Such cross-linked polymers are described in the co-pending patent application 948702 1 3.9 Method of washin~

The co""~ositio,-s of the invention may be used in essentially any washing or cleaning Ill~thods, including soaking methods, pretreatment methods and Illelllods with rinsing steps for which a separate rinse aid cGr"position may beadded.

The process described herein comprises contacting fabrics with a laundering sohltion in the usual manner and exel"p!;fied hereunder.

The process of the invention is conveniently carried out in the course of the cleaning process. The method of cleaning is preferably carried out at ~ ~C to CA 0226343~ 1999-02-11 W O98/06810 PCT~US97/14287 95 ~C, especially between 10~C and 60~C. The pH of the treatment solution is preferably from 7 to 11.

A preferred machine dishwashing method comprises treating soiled articles with an aqueous solution of the machine dishwashing or rinsing composition. A conventional effective amount of the machine dishwashing composition means from 8-60 9 of product dissolved or dispersed in a wash volume from 3-10 litres.

According to a manual dishwashing method, soiled dishes are contacted with an effective amount of the diswashing cG,-",osition, typically from 0.5-209 (per 25dishes being treated). Preferred manual dishwashing methods include the application of a concenlraled solution to the surfaces of the dishes or the soaking in large volume of dilute solution of the detergent composition.

The compositions of the invention may also be formulated as hard surface cleaner compositions.

The f~ g examples are meant to exemplify compositions of the present invention, but are not necess~rily meant to limit or otherwise define the scope of the invention.

In the delt:rgent cG,n~ositions, the level of the enzymes are expressed in pure enzyme by weight of total composition and the abbreviated component ide,~tiricdtions have the fc'lo~u;.,g meanings:

LAS : Sodium linear C12 alkyl ben~ene sulphonate TAS : Sodium tallow alkyl sulphate CXYAS : Sodium C1x - C1y alkyl sulfate 25EY : A C12 C1s predominantly linear primary alcohol condensed with an average of Y moles of ethylene oxide . .

CA 0226343~ 1999-02-ll W O98/06810 46 rcTrusg7/14287 CXYEZ : A C1x - C1y predominantly linear primary alcohol condensed with an average of Z moles of ethylene oxide XYEZS : C1X - C1y sodium alkyl sulfate condensed with an average of Z moles of ethylene oxide per mole QAS : R2 N+(cH3)2(c2H4oH) with R2 = C12-C14 Soap : Sodium linear alkyl carboxylate derived from a 80/20 mixture of tallow and coconut oils.

Nonionic : C13-C1smixedethoxylated/propoxylated fattyalcohol with an average degree of ethoxylation of 3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by BASF Gmbh.

CFAA : C12-C14 alkyl N-methyl glucamide TFAA : C16-C1g alkyl N-methyl glucamide.

TPKFA : C12-C14 topped whole cut fatty acids.
DEQA : Di-(tallow-oxy-ethyl)dimethyl ammonium chloride.

SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed stearic acid.

Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by Shell Cher"ical CO.

Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0) NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si2Os Carbonate : Anhydrous sodium carbonate with a particle size between 200 ~lm and 900~1m.

WO98/06810 47 PCTrUS97/14287 Bicarbonate : Anhydrous sodium bicarbonate with a particle size behNeen 400 llm and 1200~m.

STPP : Anhydrous sodium tripolyphosphate MA/M : Copolymer of 1:4 maleic/acrylic acid, average mc'Qcl~lar weight about 80,000 PA30 : Polyacrylic acid of average molecular weight of approxi")ately 8,000.

Terpolymer : Terpolymer of average "~ole~ 4r weight approx.
7,000, coln~rising acrylic:maleic:ethylacrylic acid ",onor"er units at a weight ratio of 60:20:20 480N : Random copolymer of 3:7 acrylic/methacrylic acid, average mol~cul~r weight about 3,500.

Polyacrylate : Polyacrylate homopolymerwith an average ",c'ecul-~
weight of 8,000 sold under the tradename PA30 by BASF GmbH

Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A1~2Si~2)12 27H2o having a primary particle size in the range from 0.1 to 10 ",icru",eter~

Citrate : Tri-sodium citrate dihydrate of activity 86,4% with a particle size distribution uetvlecn 425 ~m and 850 ~m.

Citric : Anhydrous citric acid PB1 : Anhydrous sodium perborate monohydrate bleach, empirical formula NaBo2.H2o2 PB4 : Anhydrous sodium perborate tetrahydrate . .

CA 0226343~ 1999-02-11 W O98/06810 48 PCTrUS97/14287 Percarbonate : Anhydrous sodium percarbonate bleach of empirical formula 2Na2co3.3H2o2 TAED : Tetraacetyl ethylene diamine.

NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.

Photoactivated : Sulfonated zinc phtlocyanine encarsu~ted in dextrin Bleach soluble polymer.

PMC : Penldaloine acetate cobalt(lll) salt.
Pararfi" : Paraffin oil sold under the tradename Winog 70 by Wintershall.

BzP : Benzoyl Peroxide.
Antibody : Anti-Lipolase antibody LAJR 009-012, available from Novo Nordisk A/S.

Lipolytic enzyme : Lipolytic enzymes sold under the tradename Lipolase, Lipolase Ultra by Novo Nordisk A/S.

Protease : Proteolytic enzyme sold under the tradename Savinase, Alc~l~se, Durazym by Novo Nordisk A/S, M~Y~C~I, Maxapem sold by Gist-Brocades and p~oteases described in pdlenls WO91/06637 and/or WO95/10591 and/or EP 251 446.

Amylase : Amylolytic enzyme sold under the tradename Purafact Ox AmR described in WO 94/18314,WO96/05295 sold by Genencor; Termamyl~, Fungamyl(~) and Duramyl~g), all availabl~ from Novo Nordisk A/S and those desc,iL.ed in W095/26397.

CA 0226343~ 1999-02-11 WO 98/06810 PCT/US97tl4287 Cellulase : Cellulytic enzyme sold under the tradename Carezyme, Celluzyme and/or Endolase by Novo Nordisk A/S.

CMC : Sodium carboxymethylcellulose.

I IEDP ~ hydroxyethane diphosphonic acid.

DETPMP Diethylene triamine penta (methylene phosphonic acid), marketed by Monsa,)to under the Trade name Dequest 2060.

PVNO : Poly(4-vinylpyridine)-N-Oxide.
PVPVI : Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl-imidazole and vinyl-pyrrolidone.

B~iyhtener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
B,ightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl) stilbene-2:2'-disulfonate.

Silicone antiroail, : Polydi~nelhylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

Granular Suds : 12% Silicone/silica, 18% stearyl alcohol,70% starch in Suppressor granular form SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone.

SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short block polymer.

Sulphate : Anhydroussodium sulphate.

CA 0226343~ 1999-02-11 W O 98/06810 o rCTrUS97/14287 HMWPEO : High molecular weight polyethylene oxide PEG : Polyethylene glycol.

BTA : Ben~ol, ~_ole Bismuth nitrate : Bismuth nitratesalt NaDCC : Sodium dichloroisocyanurate Encapsulated : Insoluble fragrance delivery technology utilising zeolite perfume particles 13x, perfume and a dextrose/glycerin agglomerating binder.

KOH : 100% Active solution of Potassium Hydroxide pH : Measured as a 1% solution in distilled water at 20~C.

Exa,nple 1:

Antibodies' production:
Chickens were injected in the breast muscle with 1 ml of a 1 mg/ml Lipolase~
emulsion. The lipolytic emulsion was prepared with a Freunds completed adjuvants (Freund and McDermott, 1942; Freund 1956) by intensively mixing an equal amount of the Lipolase~) solution (2 mg/ml)and Freunds co,l,pletc adjuvant.
The immunisation scheme was completed with injections using a Freunds uncomplete adjuvant and after a 4 weeks period, the eggs were collected during one week. The e~l,action of the antibodies from the eggs yolks was done accorJi.~g to the Polson extraction method as described in Immunological Inve:~tiy~iGn 19, 1990, pp 253-258.

Lipase enzymatic inactivation:
A I ipol~se~l9 stock solution was prepar~d in a Tris Buffer (5x10-2M Tris, 25 mMNaCI, pH= 7 and 10) at a concentration of 0.3% active enzyme. A Phosphate Buffer (0.05M KH2PO4, pH 6.8) contained the antibody (0.18 mglml). The interaction lipolytic enzyme (Final conce~ llralion of 0.08%) / antibody was achieved Tris buffers and co",-,lercially available detergent solutions comprising Ariel liquid (0.8% in city water, pH 8.5) and Ariel Color Futur (0.8% in city water, pH 9.5) during 5 minutes at 40~C.

CA 0226343~ l999-02-ll W O98/06810 PCTAUS97tl4287 51 _ The lipolytic residual activity was measured according the method based on the butyric acid 4 nitrophenol ester hydrolysis. Within 5 minutes the enzymatic activity of the lipase was successfully blocked as shown in the table below.

Residual lipolytic activity (in % after 5 minutes) Tris PH=7Tris DH=10 Ariel liquid Ariel Color Futur ExamPle 2 The following laundry detergent compositions were prepared in accord with the invention:

11 111 lV V Vl LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 QAS - 0.8 0.8 - 0.8 0.8 Zeolite A 18.118.1 18.1 18.1 18.1 18.1 Carbonate 13.013.0 13.0 27.0 27.0 27.0 Sj'jG~te 1.4 1.4 1.4 3.0 3.0 3.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5. 1.5 1.5 1.5 1.5 DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 t~EDP 0.3 0.3 0.3 0.3 0.3 0.3 Protease 0.00260.0026 0.0026 0.0026 0.0026 0.0026 Amylase 0.00150.0015 0.0015 0.0015 0.0015 0.0015 Antibody 10E-1 10E-3 10E-3 10E+1 10E-2 10E-1 Lipolytic enzyme 0.04 0.002 0.001 0.2 0.005 0.01 MA/M 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated 15 15 15 15 15 15 bleach (ppm) .
.

CA 0226343~ 1999-02-11 W O98/06810 52 PCT~US97/14287 Brightener 1 0.09 0.09 0.09 0.09 0.090.09 Perfume 0.3 0.3 0.3 0.3 03 03 Silicone antifoam 0.5 0.5 0.5 0 5 0 5 0 5 Misc/minors to 100%
Densityin g/litre 850 850 850 850 850 850 ExamPle 3 The following granular laundry detergent compositions of bulk density 750 g/litre were prepared in accord with the invention:

ll lll LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 QAS 0.8 2.0 2.0 STPP 19.7 Zeolite A - 19.5 19.5 NaSKS-6/citric acid (79:21) - 10.6 10.6 Carbonate 6.1 21.4 21.4 Bicarbonate - 2.0 2.0 Silicate 6.8 Sodium sulfate 39.8 -. 14.3 PB4 5.0 12.7 TAED 0.5 3.1 DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 Antibody 1 OE-1 1 OE-2 1 OE-3 Lipolytic enzyme 0.03 0.003 0.001 Protease 0.0026 0.0085 0.045 CA 0226343~ 1999-02-11 WO 98/06810 PCT~US97/14287 Cellulase 0.0006 0.0006 0.0006 Amylase 0.0009 0 0009 0 0009 MA/M 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated bleach15 ppm 27 ppm 27 ppm (ppm) Brightener 1 0.08 0.19 0.19 Brightener 2 - 0.04 0.04 Encapsulated perfume 0.3 0.3 0.8 particles Silicone a~ltiroa"~ 0.5 2.4 2.4 Minors/miscto 100%

ExamDle 4 The following detergent formulations, according to the presenl invention were prepared, where I is a phosphorus-containing detergent composition, ll is a zeolite-containing deteryent composition and lll is a compacl deteryent composition:

Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 9.0 6.0 13.0 MA/M 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 ~ilic~t~ 7.0 3.0 3 ~
CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.4 0.4 0.2 Spray On , .. . ..... .

C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone a"liroam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 ~
TAED 3.0 3.0 1.0 Photoa.:ti~/ated bleach 0.02 0.02 0.02 Protease 0.01 0.01 0.01 Amylase 0.002 0.003 0.001 Lipolytic enzyme 0.04 0.002 0.001 Antibody 1 OE-1 0.002 1 OE-3 Dry mixed sodium sulfate 3.0 3.0 5.0 Balance (Moisture & 100.0 100.0 100.0 Miscel~aneous) Density~g/litre) 630 670 670 W O98106810 55 PCTrUS97/14287 Example 5 The following nil bleach-containing detergent formulations of particular use in the washing of colored clothin~, accordi~8 to the present invention were prepared:
. 1 Blown Powder Zeolite A 15.0 15.0 Sodiumsulfate 0.0 5.0 LAS 3.0 3 0 DETPMP 0.4 0.5 CMC 0.4 0.4 MA/M 4.0 4.0 Agglo,ner..tes C45AS - - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA/M - - 2.0 Ca, Lol .ate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives MA/M - - 3.0 NaSKS-6 - - 12.0 Cltrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0.5 0.5 Protease 0.026 0.016 0.047 Amylase 0.005 0 005 0.005 Cellulase 0.006 0.006 0.006 . ~

CA 0226343~ 1999-02-11 W O 98106810 56 PCTnUS97/14287 Lipolytic enzyme 0.02 0.001 0.005 Antibody 1 OE-1 1 OE-3 1 OE-2 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodiumsulfate 0.0 9.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 700 700 700 ExamPle 6 The following detergent formulations, according to the present invention were prepared:

11 111 lV

LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFM - 1.0 - -C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0 Bicar~onale - 7.5 DETPMP 0.7 1.0 SRP 1 0.3 0.2 - 0.1 MA/M 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 Protease 0.008 0.01 0.025 0.025 Amylase 0.007 0.004 - 0.002 Cellulase 0.0015 0.0005 Lipolytic enzyme 0.04 0.01 0.004 0.002 Antibody 10E-1 10E-1 10E-2 10E-2 Photoactivated 70ppm 45ppm - 1 Oppm bleach (ppm) W O 98/06810 PCT~US97/14287 Brightener 1 0.2 0.2 0.08 0.2 P B1 6.0 2.0 NOBS 2.0 1.0 Balance (Moisture100 100 100 100 and Miscellaneous) Example 7 The f~llDw;ng deter~ent formulations, according to the present invention were prepared:

11 111 lV

Blown Powder Zeolite A 30.0 22.0 6.0 6.7 Na SkS-6 - - - 3.3 Polycarboxylate - - - 7.1 Sodium sulfate 19 0 5.0 7.0 MA/~4~ 3.0 3.0 6.0 LAS 14.0 12.0 22.0 21.5 C45AS 8.0 7.0 7.0 5.5 Cationic - - - 1.0 Silicate - 1.0 5.0 11.4 Soap - - 2.0 Bri~l)tener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 10.0 DETPMP - 0.4 o 4 Spray On C45E7 1.0 1.0 . 1.0 3.2 Dry additives PVPVI/PVNO 0.5 0.5 0.5 Antibody 1 OE-1 1 OE-1 1 O E-3 Lipolytic enzyme 0.009 0.002 0.0005 0 009 Protease 0.053 0.001 0.001 0.001 Amylase 0.0008 0.0008 0.0008 0.0008 Cellulase 0.0002 0.0002 0.0002 0.0002 .. . ... ....

CA 0226343~ 1999-02-11 WO 98/06810 5 8 ~CT/US97/14287 NOBS - 6.1 4.5 3.2 PB1 1.0 5.0 6.0 3.9 Sodium sulfate - 6.0 -to balance Balance (Moisture and 100 100 100 Misc~ neous) Example 8 The following high density and bleach-contai"ing detergent formulations, according to the present invention were prepared:

1. Il 111 Blown Powder Zeolite A 15.0 15.0 15.0 Sodiumsulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DETPMP 0.4 0.4 0.4 CMC 0.4 04 0.4 MA/M 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 CA 0226343~ 1999-02-ll W O98/06810 59 PCTrUS97/14287 PB1 14.0 7.0 10.0 Polyethylene oxide of MW - - 0.2 5,000,000 Bentonite clay - - 10.0 Antibody 1 OE-3 1 1 OE-2 Lipolytic enzyme 0.001 0.05 0.006 Protease 0.01 0.01 0.01 Amylase 0.005 0.005 0.005 Cellulase 0.0014 0.00140.0014 Silicone a"liroar" 5.0 5.0 5.0 Dry additives Sodiumsulfate 0.0 3.0 0.0 Balance (Moisture and 100.0 100.0 100.0 Miscellaneous) Density (g/litre) 850 850 850 Example 9 The following high density detergent formulations, accordh~g to the present invention were prepared:

AgglG",er~e C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/M 4.0 2.0 CMC 0.5 0.5 DETPMP 0.4 0 4 Spray On C25E5 5.0 5.0 Perfume 0.5 0.5 Dry Adds HEDP 0.5 03 SKS 6 13.0 10.0 Citrate 3.0 1.0 CA 0226343~ 1999-02-11 W O 98/06810 PCTnUS97/14287 TAED 5.0 70 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Antibody 0.09 0.006 Lipolytic enzyme 0.02 0.001 P,oteasa 0.014 0.014 Cellulase 0.0014 0.0014 Amylase 0.005 0.005 Silicone a"liroar, 5.0 5.0 Brightener 1 0.2 0.2 B,i~htener 2 0.2 Balance (Moisture and 100 100 Miscellaneous) Density(g/litre) 850 850 Example 10 The follaw;ng granular detergent formulations, accordi"g to the present invention were prepared:

11 111 lV V

LAS 21.0 25.0 18.0 18.0 Coco C12-14 AS - - - - 21.9 AE3S - - 1.5 1.5 2.3 Decyl dimethyl hydroxyethyl - 0.4 0.7 0.7 0.8 NH4+CI
Nonionic 1.2 - 0.9 0.5 Coco C12-14 Fatty Alcohol - - - - 1.0 STPP 44.0 25.0 22.5 22.5 22.5 Zeolite A 7.0 10.0 - - 8.0 MAIM ~ ~ 09 09 SRP1 0.3 0.15 0.2 0.1 0.2 CMC 0.3 2.0 0.75 0.4 1.0 Carbonate 17.5 29.3 5.0 13.0 15.0 Silicate 2.0 - 7.6 7.9 CA 0226343~ 1999-02-ll W 098/068106l PCT~US97/14287 Antibody 0.01 0.001 0.1 0.01 1.0 Lipolytic enzyme 0.003 0.001 0.01 0.003 0.04 r, otease .007 .007 .007 .007 .007 Amylase - 0.004 0.004 - .004 Cellulase - 0.001 0.001 .001 .001 NOBS - - - 1.2 1.0 PB1 - - - 2.4 1.2 Diethylene triamine penta - - - 0.7 1.0 acetic acid Diethylene triamine penta - - 0.6 methyl phosphonic acid Mg Sulfate - - 0.8 - -Pl,otoacti~ated bleach 45 50 ppm 15 45 ppm 42 ppm ppm ppm Brightener 1 0.05 - 0.04 0.04 0.04 Brightener 2 0.1 0.3 0.05 0.13 0.13 Water and Minors up to 100%

Example 11 The following liquid detergent formulations, according to the present invention were prepared:

11 111 lV V Vl Vll Vlll LAS 10.0 13.0 9.0 - 25.0 - - -C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFM - - - 4.5 - 6.0 8.0 8.0 QAS - - - - 3.0 1.0 TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0 Rapeseed fatty - - - 5.0 - - 4.0 4.0 aclds Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 CA 0226343~ 1999-02-11 Dodecenyl/ 12.0 10.0 - - 15.0 tetradecenyl succinic acid Oleic acid 4.0 2.0 1.0 - 1.0 - - -Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-Mono Ethanol - - - 5 0 - - g 0 9 0Amine Tri Ethanol - - 8 Amine NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3 tetraethylene pentamine DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 S R P 2 0.3 - 0.3 0.1 - - 0.2 0.1 PVNO - - - - - - - 0.10 Antibody 1 OE- 1 OE+ 1 OE- 1 OE-2 1 OE-2 1 OE-2 1 OE-3 1 OE-1 Lipolytic enzyme 0.02 0.15 .001 0.01 .005 .003 .001 .003 P,otease .016 .016 .013 .008 .048 .016 0.01 .019 Amylase - .002 - .004 .005 .005 Cellulase - - - .001 - - .002 .001Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5 Na foi",dte - - 1.0 Ca chloride - 0.015 - 0.01 Bentonite clay - - - - 4.0 4.0 Suspending clay - - - - 0.6 0.3 Balance moisture and miscellaneous: Up to 100%

W O 98/06810 63 _ Example 12 Granular fabric cleaning compositions which provide "softening through the wash" capability were prepared in accord with the present invention:

45AS - 10.0 LAS 7.6 68AS 1.3 45E7 4.0 25E3 - 5.0 Coco-alkyl-dimethyl hydroxy- 1.4 1.0 ethyl ammonium chloride Citrate 5.0 3 0 Na-SKS-6 - 11.0 Zeolite A 15.0 15.0 MA/AA 4.0 4.0 DETPMP 0.4 0.4 PB1 1 5.0 Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO - 0.1 Antibody 0.9 1 OE-4 Lipolytic enzyme 0.02 0.002 P,otease 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001 Silicate 3.0 5.0 Carbonate 10.0 10.0 Granular suds suppressor 1.0 4.0 CMC 0.2 0.1 Water/minors Up to 100%

.. ... ... ... .. . ..

CA 0226343~ 1999-02-11 W O 98106810 64 PCTrUS97114287 Example 13 The following rinse added fabric softener composition was prepared in accord with the present invention:

Softener active 20.0 Antibody 1 OE-2 lipolytic enzyme 0.003 Cellul~se 0.001 HCL 0.03 Antifoam agent 0.01 Blue dye 25ppm CaC12 0.20 Perfume 0.90 Water / minors Up to 100%

Exam~le 14 The fo'l~.i,)g fabric softener composition was prepared in accord with the present invention:

ll lll D~QA 2.60 19.00 SDASA - - 70.00 Stearic acid of IV=O 0.30 Neodol 45-13 - - 13.00 Hydrochloride acid 0.02 0.02 Ethanol - - 1.00 PEG - 0.60 Antibody 0.09 0.009 0.01 Lipolytic enzyme 0.01 0.001 0.005 Perfume 1.00 1.00 0.75 Digeranyl Succi,idte - - 0.38 Silicone ar,lifioa", 0.01 0.01 Electrolyte - 600ppm Dye 1 OOppm 50ppm 0.01 Water and minors 100% 100%

Example 15 Syndet bar fabric cleaning con)positions were prepared in accord with the present invention:

11 111 lV

C26 AS 20.00 20.00 20.00 20.00 CFM 5.0 50 50 50 LAS (C11-13) 10.0 10.0 10.0 10.0 Sodium carbonate 25.0 25.0 25.0 25.0 Sodium pyrophosphate 7.0 7.0 7.0 7.0 Zeolite A 5.0 5.0 5.0 5.0 CMC 0.2 0.2 0.2 0.2 Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2 Coconut monethanolamide 5.0 5.0 5.0 5.0 Antibody 0.01 0.1 0.1 0.01 Lipolytic enzyme 0.003 0.05 0.1 0.005 Amylase 0.01 0.02 - -r~tease 0.3 - 0.5 0.05 Brightel)er, perfume 0.2 0.2 0.2 0.2 CaS04 1.0 1.0 1.0 1.0 MgSO4 1.0 1.0 1.0 1.0 Water 40 40 40 40 Filler*: balal)ce to 100%

*Can be s~l~cte~ from convenient ~aterials such as CaC03, talc, clay (Kaolinite,S",e~;tite), silicates, and the like.

~, . .. . ... ..

CA 0226343~ 1999-02-11 W O 98tO6810 PCTrUS97/14287 Example 16 The following compact high density (0.96Kg/l) dishwashing detergent compositions I to Vl were prepared in accord with the present invention:

11 111 lV V Vl STPP - - 49.0 38.0 Citrate 33.0 17.5 - - 54.0 25.4 Carbonate - 17.5 - 20.0 14.0 25.4 Silicate 33.0 14.8 20.4 14.8 14.8 Metasilicate - 2.5 2.5 PB1 1.9 9.7 7.8 14.3 7.8 PB4 8.6 Percarbonate - - - - - 6.7 Nonionic 1.5 2.0 1.5 1.5 1.5 2.6 TAED 4.8 2.4 2.4 - 2.4 4.0 HEDP 0.8 1.0 0.5 - - -DETPMP 0.6 0.6 - - - -PMC - - - 0.2 BzP - - - 4.4 Pararfi" 0.5 0.5 0.5 0.5 0.5 0.2 Antibody 1 OE-1 1 OE-2 1 OE-3 1 OE-1 1 OE-6 1 OE-3 Lipolytic enzyme 0.02 0.01 0.001 0.06 0.002 0.001 P,otease 0.075 0.05 0.1 0.1 0.08 0.01 Amylase 0.01 0.005 0.015 0.015 0.01 0.0025 BTA 0.3 0.3 0.3 0.3 03 Bismuth Nitrate - 0.3 PA30 4.0 Terpolymer - - - 4.0 480N - 6.0 2.8 Sulphate 7.1 20.8 8.4 - 0.5 1.0 pH (1% solution) 10.8 11.0 10.9 10.8 10.9 9.6 CA 0226343~ 1999-02-11 W O 98/06~10 67 PCT~US97/14287 Example 17 The following granular dishwashing detergent compositions examples I to IV of bulk density 1.02Kg/L were prepared in accord with the present invention:

11 111 lV V Vl STPP 30.0 30.0 30.0 27.9 34.5 26.7 Carbonate 30.5 30.5 30.5 23.0 30.5 2.80 Silicate 7.4 7.4 7.4 12.0 8.0 20.3 PB 1 4.4 4.4 4.4 4.4 NaDCC - - - 2.0 - 1.5 Nonionic 0.75 0.75 0.75 1.9 1.2 0.5 TAED 1.0 1.0 - - 1.0 PMC - ~ 0-004 BzP - 1.4 Paraffin 0.25 0.25 0.25 Antibody 0.4 0.1 0.005 0.08 0.007 0.2 Lipolytic enzyme0.06 0.02 0.001 0.008 0.002 0.005 Protease 0.05 0.05 0.05 - 0.1 Amylase - - 0.01 0.02 0.01 BTA 0.15 - 0.15 Sulphate 23.9 23.9 23.9 31.4 17.4 pH (1% solution)10.8 10.8 10.8 10.7 10.7 12.3 Example 18 The following detergent composition tablets of 25g weight were prepared in accord with the present invention by compression of a granular dishwashing detergent co",position at a pressure of 13KN/cm2 using a standard 12 head rotary press:
ll lll STPP - 48.8 47.5 Citrate 26.4 Carbonate - 5.0 .. , . , . _ . .

CA 0226343~ 1999-02-ll Silicate 26.4 14.8 25.0 Antibody 0.06 0.015 0.009 Lipolytic enzyme0.01 0.005 0.002 Protease 0.03 0.075 0 01 Amylase 0.01 - 0.001 PB1 1.6 7.8 PB4 6.9 - 11.4 Nonionic 1.2 2.0 1.1 TAED 4.3 2.4 0.8 HEDP 0.7 - -DETPMP 0.65 Paraffn 0 4 0 5 BTA 0.2 0.3 PA30 3.2 Sulphate 25.0 14.7 3.2 pH (1% sc'~ltion)10.6 10.6 11.0 EXd~ ~ IPIe 19 The following liquid dishwashing detergent compositions were prepared in accord with the present invention I to ll, of density 1.40Kg/L:

ll STPP 33.3 20.0 Carbonate 2.7 2.0 .Sil~c:lt~
NaDCC 1.1 1.15 Nonionic 2.5 1.0 Paraffin 2.2 Antibody 0.1 0.006 Lipolytic enzyme 0.04 0.001 Plotease 0.03 0.02 Amylase 0.005 480N 0 50 4.00 KOH - 6.00 CA 0226343~ 1999-02-11 Sulphate 1.6 pH (1% solution) 9.1 10.0 Exam~le 20 The following liquid dish~,vashing compositions were prepared according to the present invention:

11 111 lV V
C17ES 28.5 27.4 19.2 34.1 34.1 Amineoxide 2.6 5.0 2.0 3.0 3.0 C12 glucose amide - - 6.0 - -Betaine 0.9 - - 2.0 2.0 Xylene sulfonate 2.0 4.0 - 2.0 Neodol C11E9 - - 5.0 Polyhydroxy fatty acid amide - - - 6.5 6.5 Sodium diethylene penta acetdte - - 0.03 (40%) TAED - - - 0.06 0.06 Sucrose - - - 1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyl diphenyl oxide disulronal~ - - - - 2.
Ca fo""dte - - - 0.5 1.1 Ammonium citrate 0.06 0.1 Na chloride - 1.0 - - -Mg chloride 3.3 - 0.7 Ca chloride - - 0.4 Na sulfate - - 0.06 Mg sulfate 0.08 Mg hydroxide - - - 2.2 2.2 Na hydroxide - - - 1.1 1.1 Hydrogen peroxide 200ppm 0.16 0.006 Lipolytic enzyme 0.004 0.01 0.008 0.02 0.002 Antibody 1 OE-3 1 OE-2 1 OE-1 1 OE-2 1 OE4 Perfume 0.18 0.09 0.09 0.2 0.2 Water and minors Up to 100%

CA 0226343~ 1999-02-11 W O98/06810 70 PCT~U~97/14287 Example 21 The following liquid hard surface cleaning compositions were prepared in accord with the present invention:

11 111 lV V Vl Antibody 0.007 0.05 0.1 0.3 0.6 0.5 Lipolytic enzyme 0.001 0.005 0.005 0.01 0.01 0.07 Amylase - - 0.005 0.02 - 0.005 Protease 0.05 0.01 0.02 0.03 0.005 0.005 EDTA* - - 2.90 2.90 Citrate - - - - 2.90 2.90 LAS 1.95 - 1.95 - 1.95 C12 AS - 2.20 - 2.20 - 2.20 NaC12(ethoxy) - 2.20 - 2.20 - 2.20 **sulfate C12 Dimethylamine - 0.50 - 0.50 - 0.50 oxide SCS 1.30 - 1.30 - 1.30 Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30 Water Balance to 100%

*Na4 ethylenediarnine cl~cetic acid **Diethylene glycol ".G"ohexyl ether ***AII formulas adjusted to pH 7 ExamPle 22 The following spray composition for cleaning of hard surfaces and removing household mildew was prepared in accord with the present invention:

Antibody 0.05 Lipolytic enzyme 0.005 Protease 0.01 Sodium octyl sulfate 2.00 Sodium dodecyl sulfate 4.00 Sodium hydroxide 0.80 Silicate (Na) 0.04 Perfume 0.35 Water/minors up to 100%

Ex~",~le 23 Deteryenl additives were prepared in accord with the present invention:

LAS

Zeolite A 35 r, otease - 0.3 Lipolytic enzyme 0.5 - 0.2 Antibody 10 10 2

Claims (15)

WHAT IS CLAIMED IS:

1. A detergent composition comprising a lipolytic enzyme and a lipolytic enzyme-directed antibody.

2. A detergent composition according to claim 1 wherein said lipolytic enzyme-directed antibody is comprised at a level of from 10E-6% to 10E+1% by weight of total composition.

3. A detergent composition according to claims 1-2 wherein said lipolytic enzyme is selected from lipase, phospholipase and/or cutinase.

4. A detergent composition according to claims 1-3 wherein said lipolytic enzyme is comprised at a level of from 0.0001 to 2%, preferably from 0.0002% to 1%, more preferably from 0.0005% to 0.1% pure enzyme by weight of total composition.

5. A detergent composition according to claims 14 wherein the molecular ratio of lipolytic enzyme-directed antibody to lipolytic enzyme is equal or less than 100:1, preferably equal or less than 50:1.

6. A detergent composition according to claims 1-5 wherein said lipolytic enzyme-directed antibody is a monoclonal antibody, preferably a fragment thereof.

7. A detergent composition according to claim 6 wherein the molecular ratio of said lipolytic enzyme-directed antibody to lipolytic enzyme is equal or less than 50:1, preferably equal or less than 20:1.

8. A detergent composition according to any of the preceding claims wherein said lipolytic enzyme-directed antibody is incorporated into a release agent.

9. A detergent composition according to any of the preceding claims further comprising one or more components selected from anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, builder, bleach system, suds suppressors, soil release polymer, lime soap dispersant, soil suspension and anti-redeposition agents, smectite clays and/or mixtures thereof.

10. A detergent composition according to any of the preceding claims which is in the form of a liquid, granular, powder, gel, paste or bar.

11. A detergent additive comprising a lipolytic enzyme-directed antibody.

12. A detergent additive according to claim 11 further comprising a lipolytic enzyme.

13. A detergent additive according to claim 12 wherein said lipolytic enzyme is selected from lipase, phospholipase and/or cutinase.

14. Use of a lipolytic enzyme-directed antibody in a detergent composition for controlling the lipolytic enzymatic activity.

15. Use of a lipolytic enzyme-directed antibody according to claim 14 in a detergent composition for improved odour characteristics.