CA2233045A1 - Detergent composition - Google Patents

Abstract

A detergent composition is provided which contains a zeolite builder having a particle size, d50, of from 1.1 to 10.0 micrometres; and a proteolytic enzyme having an isoelectric point of less than 10.0. Alcalase is exemplified. The composition contains less than 7 % by weight of the composition of carbonate builder. Preferably the composition is free of proteolytic enzyme having an isoelectric point above 10.0.

Description

WO 97/12023 PCT/US96/lS450 DETERGENT COMPOSITION

The present invention relates to a ~elerye,)~ composition cGr"~JIisi"9 both zeolite as a se~ueslering agent for water hardness and an enzyme.

Deteryenl compositions for fabric ~4asl)il lg con\,e, llionally co. ,lai"
detergency builders which lower the coi ,cenll aliGn of calcium and ~agl~esium water hardness ions in the wash liquor and thereby provide good delergei ,cy effect in both hard and soft water.

Conventionally il,organic phosphales such as sodium tripoly~l.osphale have been used as builders for laundry delerge,-ls. More race..lly, alkali metal aluminosi!i~te ion~cl1al Igers particularly crystalline sodium aluminos~ te zeolite A have been pro~osed as repl~c~menls for the i"orga, .ic phosphates.

For example EP 21 491A (P,ol ter & Gamble) discloses detergelll cGIl~posilions col)laining a building system which incl!~des zeolite A X or P
(B) or a mixture thereof. EP 384070A (Unilever) ~ ~;scloses specific zeolite P
n,ate,ials having an espe~i 'ly low silicon to aluminium ratio not greater than 1.33 (her~i..dfler referred to as zeolite MAP) and desc..ibes its use as a deleryel ,cy builder optionally with cob~ ders-Dateryenl corl~l-osiliol,s co.,laining pr~te~ses are well-known in the art. By use of a ~,otease in a deler~e"l it is possible to hydrolyze the proteins ,ur~Se nt in stains and soil on the cl-~tl ,es, to such a degree that they L,ecome readily soluble in water.

The A~plicauts have now su~,risi, l~ly found that a pr~ . ., may Ot'rJ ~r when a water insoluble zeolite having a small pa, licla size is used as a deler~"el ,~ builder in a fabric launderi. l~ cleler~el ll composiliGi l conlai- .ing certain p.o~ease enzymes and relatively high levels of calbGI~al~ col7~ der.
The problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.

The choice of a small ,~allicle size for a zeolite MAP col"ponent that is to say particles having a pa,L~e size measured as a dso value of up to 1.0 "~icroi"etres has previously been taught to be prerer,ed in the art, asrepresented, for example, by EP 384070 A.

The problem relates to the arore",enliG"ed d~3lergenl co,nposilions having a marked incoll~p-lihility with prinledi cotton fabrics. In particular, it has been found that the use of det~rgent co"~positio"s cGnlaining small particle size zeolite tends to lead to the removal of printed pigment from a printed cotton fabric surface. The presence of certain proleolytic enzymes, in particular those having a high isoelectric point, and of relatively high levels of ca, L Ol Idle cobuilder has been found to e~arcebale this effect.

The Applicant has surprisingly found that this problel" can be ameliorated by using, as the detergenc~ builder, a zeolite having a particle size dso somewhat larger than the ~rt:rel, dd pal licle size ranges previously proposed, by limiting the level of any ca, L Gnale cobuilder and by incor~,orali"~ in the detergenl con~posil;on a proteolytic enzyme having an isoel~ctric point below 10Ø

The l,rese." invention is thus based on the une~~led finding that the pri"l~J cotton fabric care profile of a dietergent co"-position cc")~,isi.,g zeolito of higher particlc size, low levels of ca, L,onate builder and containing a ~,-otease having an isoelecl.ic point below 10.0 is superior to that of cGr"pa,able cc"~posilio,.s containing other pr~lc~scs having an isoelectric point of higher than 10Ø

ExamplQs of suitable p,.~ten~cs according to this invention having an iso~lecl, ic point below 10.0 include Alc~ s~ (Trade Marl<), M~ se (Trade Mark), O,c li,--ase (Trade Marl<) and Pl i"~ase (Trade Mark).
E,~amples of p.vlo~sos which have an isoelectric point of highsr than 10.0 and which have been found not to afford such a superior ~rinled cotton fabric care profile are Savinase (Trade Mark), which is ~iisclose~l in EP
384070A (Unilever) Opticlean (Trade Marlc), M~Y~r~l (Trade Mark), Purafect (Trade Mark), and Esperase (Trade Mark).

This finding allows the formulation of dQt~r~3~nt co,-~posilions providing both sxcellsnt cleaning and ,c,ri, ~led fabric care prope, lies on cotton fabrics.

Whilst the prior art as represented for example by European Patent ~ Aplicalions, EP 384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP
544492 A, EP ~0~53 A and EP 5520~4 A has envisaged the use of enzymes in combination with zeolite in laundry deterge"l co,r",osili~"s, none of these prior art documents specirically ~I;sclQse the use of a pruteolytic enzyme having an iso~l~cl,ic point ~realer than 10.0 with a larger particle size zeolite ~",pG"enl. FL.,lhe.",ore, none of these prior art documents provides any teaching relating to ths printed cotton fabric care problem addressed by the current invention nor of any scl ~tion U,ereto involving the selection of a particular zeolite particle size or pruleolytic enzyme.

Thus the present invention provides a dete,genl co",l-osilion containing (a) a zeolite builder having a particle size dso of from 1.1 to 10.0 mi~o",etres; and (b) a pn.leolytic enzyme having an isoele~tric point of less than 10.0 wherein said co,nposi~i4n contains less than 7% by weight of the composilion of carL,G"ale builder.

In a ~,r~fe",~d embodiment of the invention the zeolite builder co""~rises zeolite P having a silcon to aluminium ratio of not g,eat~r than 1.33 (zeolite MAP).

In anotl.er p-efell~d 6"lbodin,ent of the invention the delery~"t co,.~posit;on is free of any prl~teolytic enzyme which has an iso~lectric point yl~dterthan 10Ø

In a further pr~rt,r,~d embodiment the detery~nl c~ posiliG" according to the invention is formulated to be esp~c;-'ly useful in the launJe,iny of coloured fabrics and ~.referably is free of bleach. According to a"~ll,er aspect of the invention, the cbmpositibn is s~ lA-,lially free of an optical L rigl Itener.

Zeolite builder The first essenlial ccr.l,uo,.ent of the present invention is an aluminosilicatezeolite builder, oplionally in conjunction with one or more cobuilders.

The zeolite builder is typically prese, .t at a level of from 1% to 80%, more ,~rererably from 15% to 40% by weight of the co"",osilions.

~SIlit~le alulllinosilicate zeolites have the unit cell formula Nazl(AlO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more ,l.r~rerably from 10 to 264. The aluminosilicate material are in hydrated form and are prererdbly crystalline, containing from 10% to 28%, more prereraLly from 18% to 22% water in bound form.

The al~l...i"osilic~te ~eolites can be naturally occurring ",alerials, but are p~ereral~ly sy,-ll.etically derived. Sy--U,t:lic crystalline aluminosilicate ionexcl.a..ge ...aterials are available under the desiy"alions Zeolite A, Zeolite B, 7Polite P, 7eolito X, Zeolite MAP, 7F~olite HS and mixtures l5)ereor.

Zeolite A has the formula Na 12 [Al~2) 12 (SiO2)12l~ xH20 wherein x is from 20 to 30, es~JeciA"y 27. 7~oli~ X has the formula Na86 [(A102)g6(siO2)1o6]- 276 H20-7~olit~ MAP is cles~i~d in EP 384070A (Unilever). It is ~er.,.e~ as analkali metal alumino silic~ of the zeolite P type having a silicon to aluminium ratio not y,ealer than 1.33, pr~fe,dL.ly within the range from 0.9 to 1.33 and mor~ fera~ly within the range of from 0.9 to 1.2.

Of particular inler~sl is zeolite MAP having a silicon to aluminium ratio not ~a~aler than 1.15 and, more particularly, not ylealer than 1.07.

Zeolite P having a Si:AI ratio of 1.33 or less may be p.epar~d by the following steps:

(i) mixing together a sodium aluminate having a mole ratio Na20:AI203 within the range of from 1.4 to 2.0 and a sodium silicate having a mols ratio SiO2:Na2O within ths range of from 0.8 to 3.4 with vigorous stirring at a te"~peralure within the range of from 25~C to boiling point usually 95~C to give a gel having the following composition;
Al2O3: (1-75-3-5) SiO2 :(2.3-7.5) Na20 :P (80450)H20;

(ii) ageing the gel co",posilio" for 0.5 to 10 hours, fer~bly 2 to 5 hours at a ten,perature within the range of from 70~C to boiling point usually to 95~C with sufficient stirring to maintain any solids present in susp~i ,si~";

(iii) sepa, dlil ,9 the crystallins sodium aluminosilicats thus formed WdSI-ling to a pH within the range of from 10 to 12.5, and drying prerer~bly at a le",~eralure not P~cee~ lg 150~C to a moisture co.,lent of not less than 5 wt.%.

P~efel-~d drying .--etl-ods ars spray~rying and flash-drying. It apped.:~ that oven drying at too high a tei.,perdl.Jrs may adversely affect the calcium binding c~pA~ of the product under certain circu---~t~nces.

Co..".~er~ial sodium l"etAcilic~le pe"lahydrats dissolved in water and com...er~ial sodium cilic~te sc'ution (wite.glass) ars both slJt-~le silica sources for ths production of zeolite P in ac~,cJa.-ce with the invention.
The rea-~nt~ may be added togeUIer in any order either rapidly or slowly.
Rapid A~ ion at ambient temperalure and slow acldilio- . at elsvated ten.peralure (90-95~C) both give the clesi.e~ product.

Vigorous stirring of the gel during the acl~liliol) of the reac;iaols1 and at least ...o~erale stirring during ths sllhse~lent ageing step however appear to be essenlial for the ror...dtion of pure zeolite P. In ths abse"ce of sli,.iny various mixtures of crystalline and a.nG" hous ,nalerials may be obtained.

Zeolite MAP generally has a calcium binding capaciLy of at least 150 mgCaO per g of anhydrous aluminosilc~te as measured by the slancJard method des-;,iL ed in GB 1473201 (I l~nl el). The caicium binding car~city is normally 160 mg CaO/g and may be as high 170 mg CaO/g.

Although zeolite MAP liks other eoliles contains water of hydration for the purposes of the present invention amounts and per~i ,lages of zeolite are expressed in terms of the "olio,~al anhydrous ",ale, ial.

The amount of water prese"t in hydrated zeolite MAP at ambient te",,~,eralure and humidity is yel ,erally about 20 wt.%.

The zeolite builder used in the present invention has a particle size dso of from 1.1 to 10.0 ",icro",el-es preferably from 2.0 to 7.5 mic,ullletlesl most prefera~ly from 2.75 to 5 mi~".,elres. The dso value i"-l;c~les that 50%
by weight of the particles have a diameter smaller than that figure. The particle size may be determined by conventio,)al analytical techniques such as for example microscopic deter",i.,atiG" utilizing a scanning electron microscope or by means of a laser granulometer.

Zeolite builder having the required ~al~;~ e size according to the prese"l invention can for sxample, be ple~a~cl by the conveutional techniques as des~iLed above while ad~ y one or more of the following steps:-a) i"~easi,~acr~s'~ s l;o"time;
b) i~ easiny the size of the seed crystals used to producs the ~eolite;

c) feeding the aluminosili~te gels into the cry~ s~ ;on stage illlllle 1:- Iy after they forrn (i.e. eliminate ageing of gels);
d) sa-eei ,i. ,9 ths zeolite product to remove fine llldLel ial.

An article by D. Vucelic, puL,lished in Progr Colloid Polymsr Science 1994 Volume 95 pages 14 - 38 des~ibes ll-elllods for the s~ tl-esis of zeolite pa, liclas and in particular how to influence the pa. L: e size c;i .ar~:teristics of ths ~eolil*s by l-lodifl~tioll of the sy"tl,esis p~ucess steps.

WO 97/12023 PCT/US96/1~;450 r, otease enzvme The deteryent co",posilion acco.ding to the present invention essentially co" "c rises a pr~teolytic enzyme of isoelectric point below 10.0, more ~,rerel a~ly below 9.0, most prererably below 7Ø

Suitable proleases include ~ruloasas re,or~se, ~led by the genus of Subtilisin Carlsberg, produci~le by RA'~ IUS li~,e,)iro""is. Other suitable prol~ases include the pr4leA-ses r~prese,)led by the genus Subtilisin BPN' produ~
by R~cilllls amyloliquef2~ ons. Other s~iPhlc p,ule~ses are pr~leases which show a positive immuno!cs ~l uoss-reaction with the anlibody of the p,olo~scs as des~ibed hereinabûve. Highly preferred ~.role~ses are the proleAces that are com---e,~ially sold under the l.aJei)a",es ~.lc~ase (Trade Mark), M~ e (Trade Mark) Opli",ass (Trade Mark) r,i",ase (Trade Mark) or mixtures tl ,er~of.

The p.ote~sss according to the present invention are pr~fer~bly presenl in an amount from 0.001% to 2% more pr~ferably from 0.001% to 1%, more pr~rer~3bly from 0.002% to 0.5% of active enzyme by weight of the dete. ~enl cor"rosilio, ..

Cob~ dsr In A~ lioll to ~solit~ the deter~enl cûlllposiliGl)s may contain an organic or i~or~a,)ic cobu;'dsr.

Suitable or~a"-~ cob~ilders can bs mono",a.ic or polymeric carboxylatessuch as cillat~s or polymers of acrylic""~tl,acrylic and/or maleic acids in neut,alised form. Suitable i.,o.ganic cohni~ders include ca,bol,ates and a.~,orphous and crystalline layered ~ilic~t~s Suitable crystalline layered si~c~l~s have the comrosiliol):

NaMSix02x+1 ~ yH20 WO 97/12023 PCT~S96/15450 where M is sodium or hy~oyen, preferdbiy sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Sucn ,.,alerials are desc,iL,ed in US
Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG).
Fs,l~eci-'ly prefer.ed are co""~ounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as ~ -Na2 Si2O5 (SKS6) and is described in US Patent No. 4664830.

The total amount of cleterg~l ,~ builder in the granular cGmr~osilion typically ranges from 10 to 80 wt.%, more prefcrably from 15 to 60 wt% and most rJrererably from 10 to 45 wt.%.

In an essenlial aspect the level of calL,GIldle builder, that is of i.,orga,.ic cor"pound car~le of releasing carbonate ions into a wash sol~tion, is less than 7% by weight, preferably less than 4% by weight of the detery6l.l cc,lllposilion. Most ~.-ererably the detefgenl composilion is free from ~, L.o. ,ale builder.

Ad~ iGI Idl detef~ent CG~ Gll~ S

The datergenl colllpositiG,. according to the invention may conlain other deter~nl co, . .~,o. .ents such as slJ. ra~;tdnls, bleaches, fluoresc~ s, a..li,~.Jeposilion agants, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.

S~ raotd, .l The deler~e.,l ccn)lpOsiliO" a~ord;,)g to the invention ~rer~rdbly incl~les a sl"racla"l s~le~1e~1 from anionics, nonionics, zwilleriGni:s, a,.,~l-olytics and ~li~. ,. ~ s.

The s~lrdc~allt is pr~fe-ably prese,lt in the deter~ t col,~posilions at a levelof from 1% to 50%, pr~rerably from 3% to 30%, most ~refer~l~ly from 5% to 20% by weight of the Co.,~poSi'iol~s. ~, WO 97/12023 PCTfUS96/15450 Many suit~hle cJet~rgei ,l-active cc " "~ounds are available and fully described in the literature (for example "Surface Active Agents and Deter!Je"l, Volumes I and 11 by Schwartz, Perry and Berch).

Examples of suitable additional anionic su. ractanl~ include anionic sulfates, olefin sul,~ho,ldtes, alkyl xylene sul,c~h~"ales, dialkylsulphosu rx indles and fatty acid ester sul~ ho"dles. Sodium salts are generally prerer, ed.

Anionic sul~ate su, rdcla"l Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates fatty oleoyl glycerol sulfates alkyl phenol ethylene oxide ether sulfates the Cs-C17 acyl-N-(C1-C4 alkyl) and -N-(C1-C2 hydroxyalkyl) glucamine sulfates and sulfates of alkylpolysac~ ~ les such as the sulfates of alkylpolygll Ir~side (the nooio. .ic nonsulfated co."~ounds being desa ibed herein).

Alkyl ethoxysulfate su. rduta. Ils are pr~re, ably selecte~l from the group consisli.,g of the C6-C1g alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per ms~lec~ . More ~rererably the alkyl ethoxysulfate su~rd~;t~nl is a C6-C1g alkyl sulfate which has been ethoxylated with from 0.5 to 20 pre~rably from 0.5 to 5 moles of ethylene oxide per n.~l~c~'e Anionic sulFol .ale s-" ra~ 1ant Anionic s~lfio,)ale su, ra~;tdnls s~ liPhl~ for use herein include the salts of Cs-C20 linear alkylbe. ,~e-)e sulfio"ales alkyl ester sulro,)ates C6-C22 primary or secondar~ alkane sulrunates C6-C24 olefin sulrondles, sul~onaled polyca, Loxylic acids, alkyl glycerol sulfonales fatty acyl glycerol sulfonates fatty oleyl glycerol sulrondles and any mixtures ll,ereof.

Nonionic su, ractant ., The nonionic su,ractaot is p,-~fer;,bly a hyd~upl)obic nonionic su.ra~;ldnl particularly an alkoxylated nonionic su, ractant having a h~dropl lilic lipGphiliC balance (hlb) value of ~ 9.5 more prefer~bly < 10.5.

CA 02233045 l998-03-25 Examples of suitable hydrophobic alkoxylated nonionic su,rac1a"ls include alkoxylated ~dduc~-c of fatty alcohols containing an average of less than 5 alkylene oxide groups per mol~c~ "Q.

The alkylene oxide resi~ ~es may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide resid~ ~es.

rrere,-ed alkylene oxide Add~cts of fatty alcol,ols useful in the present invention can suitably be chosen from those of the general formula:

R-O-(CnH2nO)yH

wherein R is an alkyl or alkenyl group having at least 10 calL,o,l atoms, most prererably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or3.

rlefel--2d nonionic sL"rdclanl~ include primary C11-C1s aliphatic alcohols co"densed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide cG"tenl of less than 50% by weight, p,ererdbly from 25% to less than 50% by weight.

A particularly prere"ed aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain conclt:nsed with an average of three sthoxy groups per mole of alcohol.

Specific examples of suitable alkoxylated ~ddu~ts of fatty alcohols are Sy. "~eronic A3 (ex ICI), which is a C1 3-C15 alcohol with about three ethylene oxide ~roups per l"Dle~'e and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.

Another class of nonionic sl~racldnts cc, . .pri-ces alkyl polygl~ ~coside ~,.,pounds Of ~Je~ ,eral formula RO(CnH2nO)tzx wherein Z is a moiety derived from gl!Jcose; R is a saturated hydrophobic alkyl group that co, llai- ,s from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4 the compounds including less than 10%
unreacted fatty alcohol and less than 50% short chain alkyl polyglvc~sides.
Compounds of this type and their use in del~ry~r,l compositions are disclosed in EP-B 0070074 0070077 0075996 and 0094118.

Bleach Detergent co",positions acc~rd,;ng to the invention may also contain a bleach system. Where preser,l this prefe,ably comprises one or more peroxy bleach cG""~ounds for example i"orgd,lic persalts or oryallic peroxyacids which may be employed in conjunction with bleach precursors to improve bleaching action at low te",perdl-lres.

The bleach system ,urer~rdbly c~" ,p, ises a peroxy bleach con~pc)und p,~ferably an i"organic persalt opliGnally in conjunction with a peroxyacid bleach precursor. Suitable persalts include sodium ~ erborale monohydrate and tetrahydrate and sodium per~arl,onale with sodium per~, bonate being most pr~fer,ed.

r, ~fer,t: i bleach precursors are pe,acetic acid precursors such as telraacelylethylene dia",i,)e (TAED); peroxybel) ~ ~ acid precursors.

In one prere"~d ~spec~ the ciet6,ge,)l co~,posi(iGns are free of bleach and of particuiar utility in the w~sl,iny of loads co"lai..;"y brightly coloured fabrics.
Low DH/alkalinitv deler~er,l ~,nr~osilions r, ef~i, ed deterg~, ll compositions according to the invention are ~;hardcte, ised by having a pH measured as a 1% solution of the deleryenl co",posili~n in ~istilleri water at 25~C of ~ IQ.5 pr~rerably c 10.4 most pr~rerably ~ 10.3.

WO 97/12023 PCT/US96/154~0 It has been found that compositions having a low level of reserve alkaiinity are advar,l~geous in that they have a further reduced te"dency to cause the removal of printed pi~",e,1t from ~ ,i"ted cotton fabrics. Reserve alkalinity is e~uressed as g of NaOH per 100 9 of ool"posilion as determined by acid lil.~lion of a sample, as 1% sclution in distilled water to a pH of 9.S. r,efe"ed values of reserve alkalinity are < 8.0 9 pre~erdbly <
5.0 9 most ~( t re, dbly ~ 3.0 9 NaOH per 1009 of composition.

Phvsical form The dete, gent COI - .posilion accordi,)g to the invention may be of any physical type for example powders liquids and gels. However granular and liquid con,~osilions are prerer,ed.

Makinq ~,, ucess The delerge,~t co,.~positio"s of the invention may be prepared by any suitable ,--etl-od. The partia-~~'a detergenl co""~osiliol,s are suitably pl eS~al ~d by any towsr (spray-drying) or non-tower process.

In pro~sses based around a spray-drying tower a base powder is first prepared by spray-drying a slurry and then other ~""~or,enls unsuitable for processing via the slurry can be sprayed on or adl~ixed (IJosklose~

The zeolite builder is suitable for inclusion in the slurry although it may be adva.,ta~)eo~s for f,rocesci--~ reasGns for part of the zeolite builder to be inco, ~oraled post-tower. The crysblline layered silicate where this is employed is also illcGI~Gr&led via a non-tower process and is ,~rel~rdbly p~sl~los~l Aller.,alively, partiu~ deleryenl co-,~posilions in accorddnce with theinvention may be prepared by wholly non-tower prucesses such as granulation.

The granular det~rg6nt co-"posilions of the invention may be prepared to any suit~hl~ bulk density. The COIl~OsitiG"s ~,rt:rerably have a bulk density WO 97/12023 PCT~US96/15450 of at least 400 9/l preferably at least 550 9/l most preferdbly at least 700 g/land with particular ~, efere"ce at least 800 g/l.

The benefits of the present invention are particularly evident in powders of high bulk density, for example of 700 g/l or above. Such powders may be ple~ar~d either by post-tower densi~catiG,. of spray-dried powder or by wholly non-tower ",ell,ods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advan~ageo~ ~sly be used.
ProGesses using high-speed mixer/granulators are ~lisclose~l for exa,n~le in EP340 013A EP 367 339A EP 390 251A and EP 420 317A (Unilever).

The deter~enl ~n"~osilion of the invention may be formulated as a liquid detersae"t composition which may be ~lueo~s or anhydrous. The terrn "liquid' used herein includes pasty viscous formulations such as gels. The liquid ~ele,yent composition generally has a pH of from 6.5 to 10.5.

The total amount of deter~en.;y builder in the liquid composition is p, erel-~bly from S to 70% of the total liquid cornposilion.

Illustrative cc l~ osiliG,)s accordi. ,g to the present invention are prese"led in the following Examples. In the del~r5~e,)l co,..~osilions the abbreviated CCilllpOI ,e, It idellliric~lio--s have the following meanings:

24AS : Sodium alkyl sulfate s~" r~tanl containing predo~;,)antly C12 and C14 alkyl chains TAS : Sodium alkyl sulfate su. ractanl conlai. ,in~
predo,ninantly C16 - C18 alkyl chains derived from tallow oil.

24AE3S : C12-C14 alkyl ethoxysulfate cor,taining an average of three ethoxy groups per mole 35E3 : A C13 15 primary alcol,ol co"Jensecl with an average of 3 moles of ethylene oxide 25E3 : A C12-C1s primary alcohol co"cle"sed with an average of 3 moles of ethylene oxide Ca,L,Gnale : Anhydrous sodium carL,G"ale rerbor~ Sodium perL,o(ale tetrahydrate TAED : Tetra acetyl ethylene diar"i"e Silicate : Amorphous Sodium Silicate (SiO2: Na2O ratio normally follows) SKS6 : Crystalline layered silicate available from Hoechst AG as SKS6 (lrade"an)e) Zeolite MAP : Hydrated sodium aluminosilicate zeolite MAP
having a silicon to aluminiurn ratio of 1.07 having a ,v~ size expressed as a dso value of 3.0 ",icrcr"etres Zeolite A : Hydrated sodium aluminosilic~te zeolite A
having a yal licle size expressed as a dso value of 3.0 ~"icromel,es MA/AA : Copolymer of 1:4 maleiclacrylic acid, average molecular weight about 80,000.

Al~ '~,e : r~o~eolytic enzyme sold under the l,adena"~e Alc~ ' .e by Novo Industries AIS (approx 1%
enzyme activity by weight) BSA : Amylolytic enzyme sold under the l,ade"d",e LE17 by Novo Industries A/S (approx 1%
enzyme activity) ExamPle 1 The following granular laundry deter~e. Il compositions were prepared (parts by weight) in accorda- ,ce with the invention.

A B C D E

24AS 7.6 6.5 4.8 6.8 TAS - - - - 8.6 24AE3S 2.4 - 1.2 1.7 25E3 3.26 - - - 6.3 35E3 - 5.0 5.0 5.0 Zeolite MAP 20.0 25.0 25.0 - 16.0 Zeolite A - - - 25.0 15.0 SKS6 7.0 5.0 10.0 Carboi ,ale 5.0 3.0 MA/AA 4.25 4.25 4.25 4.25 2.0 rerL,or~le 16.0 16.0 16.0 16.0 20.0 TAED 5.0 5.0 5.0 5.0 6.7 Al~~'~se 0.2 0.5 0.3 0.2 0.1 BSA - - 0.1 Protease 0.04 0.08 - 0.05 0.05 Silicate (2.0 4.0 - - 4.0 3.0 ratio) Water and miscql'-neous (Including suds suppressor sodium sulphate perfume) to bala"ce The dete,gent coll~posiliGI~s according to the invention which cc."prise zeolite builder of larger pdlL~.lQ size and Al~'~.e show good results in stain removal and lower ~,,i-,led cotton fabric cla",age as cor"part,d with a co"",osition cG"",risi"g small particle size zeolite and Savinase.

Claims (11)

What is claimed is:

1. A detergent composition containing (a) a zeolite builder having a particle size d50, of from 1.1 to 10.0 micrometres; and (b) a proteolytic enzyme having an isoelectric point of less than 10.0 wherein said composition contains less than 7% by weight of the composition of carbonate builder.

2. A detergent composition according to claim 1 wherein the zeolite builder has a particle size d50 of from 2.0 to 7.5 micrometres.

3. A detergent composition according to either of claims 1 or 2 wherein the zeolite builder comprises zeolite P having a silcon to aluminium ratio of not greater than 1.33 (zeolite MAP).

4. A detergent composition according to claim 3 wherein the zeolite MAP has a silicon to aluminium ratio not greater than 1.15.

5. A detergent composition according to any one of claims 1 to 4, which comprises from 1 to 80% by weight of the zeolite builder.

6. A detergent composition according to any of claims 1 to 5, which comprises the proteolytic enzyme in an amount to provide from 0.001% to 2% active enzyme by weight of the detergent composition.

7. A detergent composition according to any of claims 1 to 6, which contains no proteolytic enzyme of isoelectric point greater than 10Ø

8. A detergent composition according to any of claims 1 to 7, wherein the proteolytic enzyme is represented by subtilisin BPN1 protease.

9. A detergent composition according to any of Claims 1 to 7 wherein the proteolytic enzyme is represented by subtilisin Carlsberg protease.

10. A detergent composition according to any of claims 1 to 9, wherein the composition has a reserve alkalinity (expressed as g of NaOH per 100 g of composition as determined by acid titration of a sample as 1%
solution in distilled water to a pH of 9.5) of less than 8.0 g.

11. A detergent composition according to any of claims 1 to 10, which is free of bleach or optical brightener.