CA2088275A1 - Detergent compositions - Google Patents

Abstract

Particulate laundry detergent compositions are disclosed incorporating 5 % to 50 % of a surfactant, from 10 % to 95 % of a three-component non-phosphorus builder system comprising a mixture of a sodium aluminosilicate zeolite, a water-soluble monomeric or oligomeric carboxylate chelating agent and a crystalline layered sodium silicate, and from 0 % to 40 % of non-surfactant, non-builder detergent ingredients. The crystalline layered silicate is of composition NaMSixO2x+1.yH2O where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
Preferably M is sodium, x is 2 and y is O.

Description

W092/0352:` 2a~327~j PCr/US91/05533 - ! -DE.ERGENT C0!:?3S'-- 0~5This invention relates to laundry detergent _ompositionsand more especially to laundry detergent compositions hat incorporate little or no phosphorus containing materials.
~aundry detergen. compositions of this type have become widely available as a result of public concern over, and~or iegislative action to cont ol, the environmentai impac~ ~ a~ueous effluent from untreated or partially ~r2àt~d dvi~es~ic s2wa52 contain~ng d~ssolvQA ?hospha'es~

~he co-l~nercial introduction of zero-phospha~e detergen.
products, whilst meeting the primary objective of reducing the phosphate load on the environment arising from detergent products, has added to formulation complexity and has also increased the load on the environment of organic materials. Zero phosphate compositions employ a combination of materials to replace the phosphate builder, the principal component usually being a water insoluble sodium aluminosilicate zeolite supplemented by a mixture of water soluble inorganic and polymeric organic salts.

Much effort has been e2pended by those working in the field in developing such multi-component builder systems, the need for which arises from the difficulty of finding a single material that will carry out all of the functions previously performed by the phosphate builder. Although not completely characterised, these functions include chelation of both Ca++ and Mg++ ion hardness together with peptisation and suspension of the soils removed from fabrics during the washing process.

It has now been found that the use of crystalline or so-called layered silicates (known ~ se) in particular combinations of detergent builder components provides enhanced performance and permits certain other materials 2 ~3 ~ ,'3 .~ 7 j 2 to be reduced in le~el or omitted altogether from the resultant particulato det~rgent pr~d~cts. Tn preferred embodiments of the invention, cleaning perfor~ance equivalent to ~ha. o 2~ J ?~ ts _~n _~ ob~ained at a significantly ;o~,ve 1~ 1 o_ uias~ o~ e detergent builder compo~se;~ s~ e~ .;e ;~ s.. ~-12 environment. Other advantages i~clude e:~;qanced dispensing characteristics, .e. ~ i s `~7 ' n~ J ~ ' O n ~ .e particulate product at the s~ar~ of the wash _ycle i~ an automatic domos~ic w~hlnc ~ a~ a ia insolubl~ pr~c~ ? ~ C ~ P~t~
in fabric v~
~ccording ~o '~2 `~ 2~a~ d particula;a ~e~rg~na ~ SL~''v~p'_S~
a) from 5~ to 50~ by weig`nt of one or ~ore a~ionic, nonionic, ampholytic, z~i~tsrionic o- cationic surfactants or a misture of any thereof;
(b) from 10~ to g5~ of a detergent builder system comprising a misture of i) from 20% to 60% by weight of the misture of a sodium aluminosilicate zeolite;
ii) from 10% to 30S by weight of the misture of a water soluble monomeric or oligomeric organic carbosyla~e chela~ing agen~; and iii) from 10% to 65% by weight of the mi~ture of a crystalline layered sodium silicate having the composition ~aMSi~O2s+l.yH2O, wherein M is sodium or .hydroqen, ~ is ~ number from 1.9 to 4 and y is a number from 0 to 20; and (c) from 0 to 40~ of non-surfactant, non-builder deterqent ingredients.

Preferably component (b)(iii) of the buildsr systsm is ~, , ~, or ~-Na2Si2o5 and component (b)(i) is a W092/03s2~ PCr/US91/0~33 - 3 - 2 ~ ~ 3 2, ~

synthetic hydrated zeolite of unit cell formula Naz[(AlO~)_(SiO2)v]. x~O

wherein ~ and ~- a~e ~ s_ ~" .he ~a~io ^- z to y is from 1.0 '3 ' . ~ ` a ~ ly ---om to 276.

Preferably also the monomeric or oiigomeric organic carbo~ylat~ s ~ yl logarith~ic ~ .?. ~ c '~ ?- S ~ 9, preferab~y o~ a The present ~nve-l~io-l COn_~ la a ~ iCU` a~e ~e.ergen~
composition incorporating one or more sur~ac~ants and a detergent builder system composed of th ee principal components viz. a sodium aluminosilicate zeolite, a water solùble monomeric or oligomeric organic carbo~ylate chelating agent and a crystalline layered sodium silicate. Preferred compositions in accordance with the invention, also contain other, non surfactant, non-builder detergent ingredients.

A wide range of surfactants can ~e us2d in the detergent compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in U.S.P. 3,66~,961 issued to Norris on May 23, 1972.

Mistures of anionic surfactants are particularly suitable herein, especially mi~tures of sulphonate and sulphate surfactants in a weight ratio of f om 5:1 to 1:2, preferably from 3:1 to 2:3, more ?-ef~orably from 3:1 to 1:1. Preferred sulphonates include alkyl benzene W092/03S2~ PCT/~S9l/0~533 2 7 ~
sulphonates having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid esters in which the fatty acid is derived from a C12-C18 fatty source, preferably ~rom a C16-C18 fatty source. In each instance the cation is an alkali metal, preferably sodium. Preferred sulpha~e surfactants are alkyl sulphates having from 12 to 22, preferably 14 to 18 carbon atoms in the alkyl radical, optionally in admi2ture with ethosy sulphates havinq ~om 10 to 20, preferably 10 to 16 carbon atoms i~ the alkyi radical and an average degree of etho~ylat~on of l .o 6.
~he cat on ~a ~ch. ~nstanco is ~gain an al`ia!~ ,~e~l cation, pr~forably sodium.

One class of nonionic suractants useful in the present invention are condensates of ethylene oside with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyosyethylene group which is condensed with any particular hydrophobic group can be eadily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Especially preferred nonionic surfactants of this type are the Cg-Cl5 primary alcohol ethosylates containi~g 3-8 moles of ethylene oside per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oside per mole of alcohol and the C12-C14 primary alcohols containing 3-5 moles of ethylene oside per mole of alcohol.

W092/03525 ~ PCT/US91/0~533 Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula ~o (CnH~nO)tzx wherein Z is a moiety derived from glucose; ~ is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; ~ is from 1.3 to 4, the compounds including less than 10~
uareacted atty alcohol and less than 50% sho-t chain alkyl polyglucosides. Compounds of this type and their ~ase in d~ on~ camQositions are disclosed in ~P-B
0070074, 007007 " 0075996 and 0094113.

A further class o~ surfactants are the semi-polar surfactants such as amine o~ides. Suitable amine o~ides are selected from mono C8-C20, preferably C10-Cl4 N-alkyl or alkenyl amine osides and propylene-1,3-diamine diosides wherein the remaining N positions are substituted by methyl, hydrosyethyl or hydrosypropyl groups.

Cationic surfactants can also be used in the detergent compositions herein and suitable ~uaternary ammonium surfactants are selected from mono C8-C16, preferably C10-Cl4 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydrosyethyl or hydrosypropyl groups.

The detergent compositions can comprise from 5~ to 50~ by weight of surfactant but usually comprises from 5% to 30%, more preferably from 5% to 15% by weight. Combinations of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic-cationic blends. Particularly preferred combinations are described W092/0352~ PCT/US91/0~33 ~l3~ a - 6 -in GB-A-2040987 and EP-A-0087914. Although the surfactants can be incorporated into the compositions as mixtures, it is preferable to control the point of addition of each sur~actan~ in order to opt.imise the physical characte.~isaics c:~ he _c~.pvsi '_i5n ~_,A avoi~
processing ?~a:2 e~;. ?~:a -~ ara ~_ S O_ surfactant addition are described hereinafter.

The second essen~ial compone.l~ of cGm?osi.ivas in accordance wi,h ~he i'a';ea`_.` _a ' S l ~e`i e .'~l'_ `aai!de-system comDrisin9 a :~i 3~n1r''? Cr so,d~m ~lnmisosil.~c.3te zeolite, ~ W2~ e ~ S ~ za _ i _ carbo~ylate che~ insJ a';~ n_ -~ __','_-a_`''~e ~-~yQ _~
sodium sil oa;e _.. ~_ _nae ~ s.

Whilst a range of aluminosilica~e ioa e~change materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula Naz t(AlO2)z (SiO2)y] sH20 wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and s is at least 5, preferably from 7.5 to 276, more preferably .rom 10 to 25~. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18~ to .2j water.

The above aluminosilicate ion e~change materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.~ to 4 micrometers~ The term ~particle size diameter~ herein represents the average particle si7e diameter of a given W092/0352~ 7 2 ~ 3 ~ ~ 7 ~ PCT/US91/0;533 -ion e~change material as determined by conventional analytical techniques such as, for e~ample, ~icroscopic determination utilizing a scanning elec.ron microscope.
The aluminosilicate ion e:;chan~e m~ ls are further characterised by their c lcin~. io~. e~c:~an.s~ oapacity, which is at 'eas ~0~ m^ ~ u ~ ! er hardness/g of aluminosilicate, calcula.-d on an anhydrous basis, and which gener~ is ~ ~ae ~ e of ~rom 300 mg eq./g to 352 mg eq./g. Th~e a`umi-.osi' _ate ion e~change materials hereia are -~ ised by t~eir calcium ion e_chanqe ra~e ~ic.~ is ~- le-~s :30 mg equivalQnt c~ c~c~ 'J-'?.;.'`~S
Ca~/gallon/~inute~;r3m~ s;licate (anhydrous ~as ), ~n~ .h_ h ,~ `ain ~h~
range of from !30 mg e~uivalent c-CaCO3/litrè/minute/~gram/litre) [ graias~gallon/minute/
(gram/gallon)~ to 390 mg equivalent ofCaCO3/litre/minute/ (gram/litre) [6 grains/gallon/minute/(gram/gallon)~, based on calcium ion hardness. Optimum aluminosilicates for builder purposes exhibit a calcium ion e~change rate of at least 260 mg e~uivalent of CaCO3/litre/minute/(gram/litre) ~4 grains/gallon/minute/(gram/gallon)].

Aluminosilicate ion e~change mate. als useful in the practice of this invention are commercially available and can be naturally occurring ma~erials, but are preferably synthetically derived. ~ method for producing aluminosilicate ion e~change materials is discussed in US
Patent No. 3,985,669. Preferred synthetic crystalline aluminosilicate ion e~change mater als useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mi~tures thereof. In an especially preferred embodiment, 'he crystalline 2 0 ~ X 2 7 ~
aluminosilicate ion e~change material is Zeolite A and has the formula Nal2[(~lO2)12 (Si2)12] 2 wherein ~ ;s -rom 20 to 30, especially 27. Zeolite X oL
ormula Na86 [(A12)86(Si2)106] 2 also suitable, as well as Zeolite HS of formula Na6 ~(AlO2)6(SiO2)6] 7-5 H2 ) The water-soluble monomeric or oligomeric organic carbo~,rla~e -be'a'inq agQr.~ can be selQctQd '-om a wid~
range or co~pounds but preferably has a fi st carbo~yl logarlthm~._ acidi~y~cons~ant (p~Cl) o. les~ ~an 9, preferably of between 2 and 8.5, more preferably of between 4 and 7.5.

The logarithmic acidity constant is defined by reference to the equilibrium H+ + A ~ H+A

where A is the fully ionized carbo~y;ate anion of the builder salt.
The ~quilibrium constant is therefore Kl = (H+ ~) (H+) (A) and pKl = loglOK.

For the purposes of this specification, acidity constants are defined at 25C and at zero ion c strength~ Literature W092/0352~ PCT/US91/05533 2~"27a - 9 -values are taken where possible (see Stability Constants of Metal-Ion Compleses, Special Publication No. 25, The Chemical Society, London): where doubt arises they are determined by potentiometric titration using a glass electrode.

Preferred carbosylates can also be defined in terms of their calcium ion stability constant (pKCa++) defined, analogously to pKl, by the equations pK_~ 910KC~

where ~a = ~Ca~ A) (Ca++~

Preferably, the polycarbosylate has a pKCa++ in the range from about 2 to about 7 especially from about 3 to about 6. Once again literature values of stability constants are taken where possible. The stability constant is defined at 25C and at zero ionic strength using a glass electrode method of measurement as described in Complesation in Analytical Chemistry by Anders Ringbom (1963).

The carbosylat2 or polycarbo~ylate builder can be momomeric or oligomeric in type although monomeric polycarbosylates are generally preferred for reasons of cost and performance.

Monomeric and oligomeric builders can be selected from acyclic, alicyclic, heterocyclic and aromatic carbosylates having the general formulae wo 92/0352j ~ t3 (~ ~3 2 7 .`:- lo PCT/US91/0~533 (a) Rl I X C j R~
_ Z I m t b ) .. ~
..
_ ~ ' or ( c ) y u wherein Rl re-.~sen~s ~,C; ~ù ~
optionally subs~i~u;ed ~i ..id;~ , _a.~o-~-v-, ~u o or phosphono groups or attached to a ?c ye~hylenc~y moiety containing up to 20 ethyleneo~y qrou~s; ~ -ep-esents H,Cl 4 alkyl, alkenyl or hydro~y alkyl, or alkaryl, sulfo, or phosphono groups;
X represents a single bond; O; S; SO; SO2; or NRl;
Y represents H; carbosy;hydro~y; carbosymethylosy; or Cl 30 alkyl or alkenyl optionally substituted by hydro~y or carbosy qroups;
Z represents ~; or carbosy;
m is an integer from 1 to 10;
n is an integer from 3 to 6;
p, q are integers from 0 to 6, p + q being from 1 to 6;
and wherein, X, Y, and Z each have the same or different representations when repeated in a siven molecular formula, and wherein at least one Y or Z in a molecule contain a carbosyl group.

Suitable carbosylates containing on_ carbo~y s-oup include lactic acid, glycollic acid and ethe- derivatives thereof W092/03525 ~J~ r~ 7 ~ PCT/US91/0~s3~

as disclosed in Belqian Patent Nos. 831,368, 821, 369 and 821,370. Polycarbo~ylates containing two carbo~y groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedio~y) aiacetic ac~d, maieic acid, diglycollic acid, .artaric ac::d. ta7:' aaic acid ~nd ~umaric acid, as .~e` lS "e ~ e ~ n~ e~ desc~i`~ed in German Offenlegenschrift 2,~4~,63~, and ~ a, 687 and U.S. Patent No. 3,935,257 and ~;,e sul~inyl carbo~ylates described in ael~ian ~ater.. .\1O. ~I0,~_. ?o~,carbo~ylates containing three carbo~y G ~^U^S in-. ~ U~ articular, water-soluble citra.as~ aconi;~ e-~ ano ci-:-3conates as well as st~cc~n~to ~a..~:~
carboxy~ethylo~ysuc-inat.~ ~_a-,~.:`a.aa ~a ~ a ?aten~ ~o~
1,379,2~ c ^~,s~ ?~
No. 1,389,73~, and 3minosuccina ^-s d^-sc ibed in Netherlands Application 7205873, and .he oxypolycarbo~ylate materials such as 2-o~a-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447. `

Polycarbosylates containing four carbosy groups include osydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarbosylates, 1,1,3,3-propane tetracarbosylates and 1,1,2,3-propane tetracarbosylates.
Polycarbosylates containing sulrQ substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No.
3,936,448, and the sulfonated ?yro'ysed cltrates described in British Patent No. 1,082,179, while polycarbo~ylates containin~ phosphone substituents are disclosed in British Patent No. 1,~39,000.

Alicyclic and heterocyclic polycarbo~ylates include cyclopentane-cis,cis,cis-tetracar~o~yiates, cyclopentadienide pentacarbo~ylates, 2 0 ~ ~2 7 ~ 12 -2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran -cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarbo~ylates, 1,2,3,4,5,6-he~ane -he~acarboxylates and carbo~ymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol a~.d ;;yl~.ol. ~.omatic polycarbo~yla~es include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of ~he a~ove, the preferred polycarbo~ylates are hydro~yca~o~ylates containing up to three carbosy groups per molecllle, more ~articularly citrates.

m~.e ~ar~n~ acids of ~he ~,onome~ic or ollgomeric poiycar~o~yl~ce cn21a~ing agen;s or mis.ures thereof with their salts, eg. citric acid or citrate/citric acid mi~tures are also contemplated as components of builder systems useful in the present invention.

The third element of the builder system is a crystalline layered sodium silicate having the general formula NaMSi~c2~+1' YH2 wherein M is sodium or hydrogen, s is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-~-3742043. For the purposes of the present invention ~, in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred e~amples of this formula comprise the ~ -,~ - and -forms of Na2Si205. These materials are available from Hoechst AG FRG as respectively NaSKS-5, NaSKS-7, W092/0352~ PCT/US91/05533 2 7~

NaS~S-ll and NaSKS-6. The most preferred material is ~ 2 2 5' o~ther detersent buiider materials can also form par~ o' the builder system but are not essential elements thereof. Such materials can be organic or inorganic in nature.

Inorganic builder materials that can form optional el~mon~s ~f ~he ~ui?der system for the purposes of the ~nvention include alkali metal car~onates, bicar~onates and sil c t~s. S~ bl~ organic materi~ls include ~he organic phosphonates and amino polyalkylene phosphonates although these materials are less preferred where the minimisation of phosphorus compounds in the compositions is desired Other suitable water soluble organic salts are the homo-or co-polymeric polycarbo~ylic acids or their salts in which the polycarbo~ylic acid comprises at least two carbo~yl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. E~amples of such salts are polyacrylates of MWt 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. These materials are normally used at levels of from 0.5~ to 10% by weight more preferably from 0.75~ to 8%, most preferably from 1% to 6% by weight of the composition.

The optional builder materials, if present, will total no more than 25~ by weight of the composition normally less than 20~ and most usually less ~han 15% by weight.

W O 92/03525 PC~r/US91/05~33 ~ o ~ ~ ~ rl '`

For the purposes of compositions in accordar.ce with the invention, 'he builder system wili c^-?rise ^rom lO~s to 95% by weight of the compos tior.~s, ~nv ~ ~re a-âblv ~-om 20% to 60~ ? -~sodium aluminosilicate zeoli~e iviii _or~ r àe '0.~ 20~ to 60~ by weight of the mi~ture. tra ~ n^;~~er:c ar ^ilgo~erlc carboxylate will comprise ~o~ s `` `~ el~n~ cf ~he mi~ture and the crystallie~ ap r~ ` a~ c~ ise from 10~ to 65~ by ~eigil~ c~ e ili;;ur~ .ç~e ~reerabl~,~
the zeolite is oresent ;n ln ~ 9 the monomeric or oligcineric car`as;~ ^m ~^is~x ~^o to 25~ ~tn~ t~t~ lav-~r~ r~
of the build2r sys~em. ~ a~_~r __s~a ~n~ uiit~ar s~;s~e~
incorporates a combination of au~ ry inorjanic and organic builders such as sodium carbonate ar.d maleic anhydride/acrylic acid copolymers in amounts of up to 25~.

Compositions in accordance with the invention can also contain up to 40~ of non-surfactant non detergent builder components as optional ingredients. Anti-redeposition and soil-suspension agents, optical brighteners, soil release agents, dyes and pigments are e~ampies of such optional ingredients and can be added in varying amounts as desired.

Anti-redeposition and soil-suspension agents suitable herein include cellulose deriva'ives such as methylcellulose, carbosymethylcellulose and hydro2yethylcellulose, and homo- or co-polymeric W092/0352~ - lS _ ? ~ 7 ~CT/US91/0;~33 polycarbosylic acids or their salts. Polymers of this type include copolymers of maleic anhydride with ethylene, methylvinyl ether, ~cr~ C ~r me~hacrylic acid, the maleic anhydriàa consei~lu~ , a~ s_ 20 ~ole percen. of the copolymer. Th~s~ ma~rials a ~ no ~tally used at lev81s of ~ .5 ~ ~ r ~ ~ ? ~ ~ , ~ , , _ ~ ~ _ _ _ _ _ _ ~ _ ~ i from 0.7S~ to 8~, ~os. P~ ~o~ ~ 50 5~ by ~ctight of the composition.

Other useul pol~ sric ma~ ;h~ poi~sthylan_ glycols, pa;ti~ular iy _.`OS~ h`.;
10 d o--10 o o o, ?~ tO ~ ;~ p ;i ~ C _ .. ~:1 .~ .. ,- .. ~. `, b~ _ _ _ ~.1 ~ O i ~
preferably abou~ ~000. Th~3~ -' " 3?`' `~ als or t rom 0~20~ to 5~ ~,n~ ?~ ? ~t ~ n ~ 5~ ~,t ~ h~.

co-polymeric polycar~o~ylai~ ~di~S ar~ valua~l~ ror improving whitana~3 maintananc3, ~abrio as~ dsposition, and cleaning performancs on clay, prot~inac~ous and o~idiza~le soils in the pre~ence of tran~ition metal impurities.

However one advantage of compositions in accordance with the present invention i~ their ability to maintain the suspension o~ insolu~ld particulat~ solids (a~h) wi~h rQdUCed 18VQ1~ of polym~ric polycarboxylate builder/anti redeposition agents or eYen, in preferred compoaitions of the invention, with no polym~ric polycarboxylats pre3~nt.
Thus a level of polymeric polycar~oxylate o~ 5% in conventlonal products can ba h~lvad, i.a. to 2.5S with no increase in fabric ash level in compositions according to the present invention. If t~e polymeric polycarboxylate is removed entirely only a alight increase in ra~ric ash take~ placs in contrast to a vi-tual dou~ling Or the ash level if the polymer i8 removed fro~ a conventional formulation.

W092/0352~ PcT/~S91/o~533 Compositions in accordance with the invention also show robustness in hardness control in under built situatior.s.
i.e. where insufficient detergent builder is available to control all of the ~ineral hardness present. ~his benefit is believed to arise because of the ability of shQ tern~ uildQr syst2m co~pon~nt~ to r~dis~ributP ,~.P
calcium and ~agnesium hardness ions amongst themselves in underbuil~ sltuations, ta~in~ advanta~e of t~e enhancQd affinity of t~e crystalline layarad silicate component 'or ~g~iu~ ion.

.~ ~ f~d~d ~ c~ si~ior.................. ~ ~C~ 2 ith ~ho ~~~3ant inventisn is ~ r~duction in da~ag2 t~
f~ric3 a~ q ~a~ 33. ~3 lo~
beLiov~d tO aris~ from the interaction o~ heavy metal ions depositad on ~abrics during the washing proce~s with oxygen bleache~. Fabrlcs waehed in composition~ of the presQnt lnvention show a level o~ dQposition o~ heavy metal ions and a reduced tQnsilQ strength 108~, rolatlvQ
to compositions in whlch tho crystalline layerQd sllicate component i~ replaced by a conventional amorp~ou~
silicate Preferred op~ical brightener~ are anionlc in character, esamplea of whlch aro di~odiu~
4,4l-bi3-~2-diethanolamino-~-anilino -~- triazin-6-ylamino)~tilbene-2:21 di~ulphonate, di~odium 4, 41-bia-(2-morpholino-~-anilino-~-triazin-6 -ylamino~tilbene-2:21 - di8ulphonato, di~odium 4, 41 _ bi~-(2,4-dianilino-a-triasin-6-ylamino)atilbeno-2:21 -disulphonata, mono~odium 41,411 -bi~-(2,4-dianilino-~-triazin-6-ylamino)~tilbeno-2-~ulphonato, di30dium 4,41 -bis-(2-anilino-~ -mathyl-~-2-hydrosyothylamino)-s-triazin -6-ylamino~tilbsns-2,21 - di~ul~honat~, disodium 4,41 -bi~-(4-~nonyl-2,1,3-triazol-2-yl)-~tilbeno-2,2 di~ulpho~at 3, disodium 4,41bis(2-anilino-4-(1-methyl-Wog2/o352s PCT/US91/0~533 2 ~ 7 ~
2-hydrosyethylamino)-s-triazin-6-ylamino)stilbene-2,21disulphonate and sodium 2(stilbyl-411-(naphtho-ll, 21:4,5)-1,2,3 - triazole-211-sulphonate.

Soil-release agsnts useful in compositions of the present ..ve~t _- ~r;~ ~o,~v3~tionally copolymers or t~rpclyme~s o~
tPrephthalic acid wi~h ethylene ~lycol and/or p~opylene glycol units in various arranqements. E~amples of such polyme~ are ~isclosed in the commonly assigned US Patent Nos. ~11S335 ~nd ~711730 and Europsan ~ublis~ed Patent ~pplica~ion ~o. 0272333. A particular preferred polymer in acro;danc3 wi~h ~P-~-0272083 has the ormula 3 ~3 0.~5 ~ o.a6~ )2.8~' ~EG)o,~(oo-~)3 25~tP~G)~3C~3)0 Y~r~ P~ _,pO i~ ~OC3~i60) ~d, ~ pcCCs ~
Cartain pol~fmeric materials suc~ as polyvinyl pyrrolidones typically of ~Wt 5000-20000, preferably 1000~-15000, also form usaful agents in pre~entinq the transfer of labile dye~tuffs between fabric~ during the wa~hing process.

Another optional but hlghly preferred ~ngredient is a particulate inorganic perhydrate bleach. Any particulate inorgan~c perhydrate bleach can b~ u~ed, in an amount of from 3t to 40t by wcisht, more preferably from 8~ to 25~
by weiqht and most preferably from 12~ to 20~ by weight of the compositlon~. Preferred esamples of such bleaches are sodium per~orate monohydrato and tetrahydrato and mi2~uras t~arao~.
Another preferred inqredient is a perosy carbo~ylic acid bleach precursor, commonly referred to as a bleach activator, which is preferably added in a prilled or agglomerated form. Esamples of suitable compounds of this type are di~clo~d in British Pat~nt ~os, 1586769 and 2143231 and a method for their formation into a prilled form is described in European Published Patent Application No. 0062523. ~referred e~amples of such compounds are tetracst~ hylana diamins and sodium 3, 5, 5 trimethyl hesanoylosybenzene sulphonate.

W092/03525 PCT/US91/0~533 ~ O ~ i 8 -Bleach activators are normally em~loved at levels of from 0.5% to 10% by weight! more frequently ~rom 1~ to 8~ and preferably from 2`'s to 6~ by waig~t c ~.a_ co~?osi~ion.

Another optionai i:~g~:edie~ ?~
e2emplified by silicones, and siiica-silicone mi~tures.
Silicones can be generall~ p~asa.n'-~ btr ~. I.';t~?l.?~tod polysilo ane mat~rials whila si_ios is -..o~ s2d ln ~inely di~id~ ~o~s, ~erogels and hydropnoolc si~.ic~i o` ?~: ~us ~s. ~rh materials can b~ r~
suds suppras~or is a;l~ `311~ '0~'`:.^. ` :`~?~X ~ en~r,?o~ d in a wa~r - ~ iub non-surface-active deterg~n--i.~ ar..i~ car~
Alternatively the suds suppr-ssor can `29 dissolv~d or dispersed in a liquid car.ier and a~pli2d ~y spraying on to one or more of the other components.

As mentioned above, useful silicone suds controlling agents can comprise a misture of an alkylated silosane, of the type referred to hereinbefore, and solid silica. Such mistures are prepared by affising the silicone to the surface of the solid silica. A oreferred silicone suds controlling asent is represented by a hydropho`oic silanated (most preferably trimethyl-~ilanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area aboYe 50 m2/g, intimately admi~ed with dimethyl si" cone fluid haYing a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about l:l to about 1:2.

A preferred silicone suds controlli..g agent is disclosed in 8artollota et al. U.S Patent 3,g33, 672. Other particularly useful suds supprsssor- a 3 ths self-emulsifying silicons sud~ sup~-essors, d~scri~ed in W092/03525 PCT/~S91/05;33 German Patent Application DTOS 2,646,126 published April 28, 1977. An example of such a compound is DC-544, commercially availably from Dow Corning, which is a silo~ane/glycol copol~mer.

The suds supp~esso s 'esc _a_ b_- :a ~ e~ o~_d at levels of from 0.001'~ to 0.5~ by weight of the composition, pr22rably ~rom C.31~j ~.o d.~'i by ~eic~t.

The preferred met:~ods of i~co;n~;a~ a _o~ e ~ her applicaticn cf ` ``3 ~`!dS ~`.n~ -^.0~ n ~ 9U~ Co~ m b~
spray-on ~o C~le 0- .ilO:.3 ~ `._ C Y ~ O~ ` `a_ composition or al~eL~ el~ ;aa ~o;~maz~ .e suias suppressors in~o ~e~ara~e g~ a;_a ~ an 'h~n ~a mi~ed with the other solid componan~3 o~ ~he composition.
The incorporation of the suds modifiar3 as separate particulate~ also permits the inclusion therein o~ other suds controlling material~ such as C20-C24 atty acids, microcrystalline wa~es and high MWt copolymers of ethylene oside and propylene oside which would otherwise adversely affect the dispersibility of the matri~. Technigues for forming such suds modifying particulates are disclosed in t~e previously mentioned Bartolotta et al U.S. Patent No.
3,933,672.
Another optional ingredient useful in the present invention is one or more enzymes.

Prefersed enzymatic materials include the commercially ava~lably amylases, neutral and alkaline proteases, lipases, esterases and cellulase~ conventionally incorporated into detergent composition~. Suitable enzymes are discussad in U.S. Patents 3,519,570 and 3,533,139.

Fabric softening agents can also be incorporated into detergent compositions in acco: a..o~ ~i.h the pr2sPnt invention. Thasa agents ~ay be lnc:~an~ organic in type. Inorganic softening agents a e e~emplified by the W092/03525 PCT/US9~/0~533 20~27~ ~ -smectite clays disclosed in GB-A-1,400,898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in ~B-A-lS14276 and Ep-a-ooll34o.
Their combination with mono C12-C14 guaternary ammonium salts is disclosed in EP-8-0026527 ~ 528. Other useful organic fabric softening agents are the dilong chain amides as disclosed in r?-~-0242919. Additional organic ingredients of fabric softening systems include high molecular weignt polyethylene oside materials as disclosed in E-~-0~9~75 and 031~146.

Levels o~ smec~ito clay are normally in the rangs from S%
~o 1~?~, m~ f3rably ~rom 9~ ~o 1?~ by weiqht, with the material being added a~ a dry mi~ed component to the remaind~ oe ~.~e eormulation. Org2n~ C fabric so~ni~.a ag~nts such a~ ~h2 water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5~ to S~ by weight, normally from 1~ to ~ by weight, whilst the high molecular weight polyethylene oside 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. Where a portion of the composition is spray dried, these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mised particulate, or spray them as a molten liquid on to other solid components of the composition.

The compositions of the invention can be made via a ~ariety of methods including dry misinq, spray dryiny, agglomeration and granula~ion and preferred methods involve combinations of these technigue~. A preferred method of making ths compositions involves a combination of spray drying, agqlomeration in a high speed mi~er and dry mi~ing.

~seforrQd dQtorgsnt compositions in accordance with the invention also comprise at least t~o particulate multi-ingredient components. The first component comprises at W092/03525 2 ~ g ~ 2 7 ~ PCT/US91/0~533 ~; _ least 20%, conventionally from 30~ to 70%, but more preferably no more than 40% by weight of the composition and the second component ,rom 1~ to 50~, more preferably 10~ to 40~ by weight of the composition.

The first component comprises a particulate incorporating an anion__ su~_~c~3nt in a~ ~mount of from 0.75~ to ~5~ by weight of the powder and one or more inorganic and/or organic sal~s in an amount of from 99.2S~ to 65~ by weight of the powder. The particulate can have any suitable form such as qrai1uta;. flak2s, prills, marumes or noodles but is pre~r~?~ aular~ The ~nule~ themselYes may be ~;g'~m~ J ~ - ?~ u~um ~g~ 'ion cr ~ ~n-iine mi~ars ~ut a.2 p;~oferably spray dried particles produced by atomis~ng an aqueous slurry of the ingredients in a hot air s~r~am which removes most of the water. In certain processes, the spray dried granules forming the first component may themselves be subjected to densification steps, eg. by high speed cutter mi~ers, to increase density before being reagglomerated. For illustrative purposes, the first component is described hereinafter as a spray dried powder as this constitutes a preferred embodiment of the invention.

.~n important cha~act_ristic of the principal anionic surfactant in the first component i~ that it should have a low rate of solubility in aqueous media at the water temperatures ~hat pravail during ths fill step of the wash cycle in an autcmatic washing machine. With respect to European wash habits the water temperature during the fill step is predominantly in the range from 5C to 20C, more usually from 7C to 12-C.

Suitabla anicni_ su factants for the purposes of the first component have been found to ba linear alkyl sulfate salts in which tha alkyl group has an average of from 16 to 22 carbon atoms, and linear alkyl carbo~ylate salts in which tha al~yl srouP ha~ an aYerage of from 16 to 24 carbon atoms.

5 PCr/US91/0:~;33 ~ O ~
The alkyl groups for both types o~ s~rfactant are preferably derived from natural fats such ~s ~llo~.
Shorter chain alkyl sulfates or carbosylates, in which th~
alkyl group is derived from so~ ^es ooi,.?risin. ~ mix~uz~ o~
alkyl moieties more than ~ o- lich coe~in l; or less carbon atoms, are !ss sui~s~ s -s-p ~ ee ~-~rs..
component to form a sel !ike ~ass du~ing dlssolutlon.

The level o. anionic su.acta..' .~ e s ra ~ ?o~de.
formin~ the first componen~ is ~ b, ~al~-.at, more usually 2.S~ ~o 5~s ~re~Ia ~b~ _m ~ aa_ ;-o~
pre'erably rom 5~s ~o lS~; b-r :i3ia;~ .s~a:-sa ~
surfactants such as linear a ~ t;l. b~ n~ ss -`s^s~ s c~. ba included or alt~r~ !Y ?~ o '?~ 5'`~.~?.9"~
the spray dri~d powd~: b~- Sr;~

The other major ingredient o~ the spray dri-d powder is one or more inorganic or organic salts that provide the crystalline structure for the granules. The inorganic and~or organic salts may be water-soluble or water-insoluble, the latter type being comprised by the, or the major pàrt of the, water-insoluble builders where these form part of the builder system. Suitable water soluble inorganic salts include the alkali metal ca~onatas, bicarbonates, sulphates and borate~ lkali m2tal silicates can also be pre~ent in the spray dried granulP provided that aluminosilicate does not form part of the spray dried component.

It is preferred that at least part or the alumino~ilicate builder be incorporated into the spray dried granule and, as indicated above, where this takes place, any silicate present should not ~orm part or the spray dried component.
In these circumstances incorporation o~ tha silicats can be achieved in several ways, e.g. by producing a separate W092/03525 2 ~ ~) 3 ~ 7 ~; PCT/~S91/0;~3~

silicate containing spray dri~d ~ar~i-ulata, by incorporating the silicate into an agglomerat~ of other ingredients, or more pr~rarahl~ y a~ g ~.a ~ ate as a dry mi~ed solid ingrodi~ont.

Any of the previously montlon~d ~?~oaal~ ~uil~e~ salts C?~n also be incorporated in the spray d~ed ?owc~ ~orming ;he first component. .he s?ray driad ~ - aa~^ ;'so iaclude some or even all of tll~ ~iai:ar '0'~ ~S-~:? .~ e ar oligomeric carbo~ylat2 chelaain~ ag2a~ ~U~. ~m~s iS l~ss preferred as i~ tends to i~`.s.o ~ aa ~e~l o ingredient. The osgani~ and~or inoxganic s~ s comprise from 60~6 to 90~ r ~ 9 ~ t ~ `~ '. '`~ ~? ~ ~ ~ ~ ?~ ~ n~ r c.
preferably from 70~ ~o 90~s an' .os~ -ref~rs~t ~r -sm ~5~S
85~ by weight.

The spray dried powder also normally contains up to 15% by weight of miscellaneous ingredients.

In preferred compositions where the first component is a spray dried powder, optional ingredients included in the first component should be heat stable to the estent necessary to withstand the temperatu~ encountsred .n the spray drying process. Where the first component is a spray dried powder it will normally be dried to a moisture content of from 7~ to 11~ by weight, mors preferably from 8~ to 10~ by weight of the spray driAd pow~ar. ~oistura content3 of powder~ produced by other processe~ such a3 agglomeration may ~e lower and can be in the range 1-10~ by weight.

~0~ 5 24 -The particle size of the first component is conventional and preferably not more than ;s by weight should be above i.Y mm, wh~ie nc~ more than 10% oy w~Qight should be less than 0.15 mm in maximum dimension. Preferably at least 60~
and most preferably at least 80% by weight of the powder lies between 0.~ mm and 0.25 mm in size. For spray dried powders, ~h~ `oul~ density of the particles should lie in the range from 350 g/litre to 650g~1itre but is ccn~entiona'l~ hQ rangQ f~cm ~40 to 6Q0 s~'it~e . ~ulk densities in the upper part of ~he range rom 600-650 s~litre _~a par~ la-ly use-~ul W~.Q~e produc~ion o~ so called concentrated products is desired. Bulk densities above this ranse may be produced if the spray dried powder is subjected to further processing steps such as size reduction in a high speed cutter/mi~er followed by compaction. Alternatively, processes other than spray drying may be used to form the powder.

A second component of a preferred composition in accordance with the invention is a particulate containing a water soluble surfactant.

This may be anionic, nonionic, cationic or semipolar in type or a mi~ture of any of these. Suitable surfactants are listed hereinbefore but preferred surfactants are linear Cll-C15 alkyl benzene sulfonates and fatty C14-Cl8 methyl ester sulponates.

The second component may have any suitable physical form i.e. it may take the form of fla~es, prills, marumes, noodles, ribbons, or granules which may be spray-dried or non spray-dried agglomerates. Although the second component could in theory comprise ;he water soluble surfactant on its own, in practlce at least one organic or inorganic salt is included to facil tate processing. This W O 92/03525 2 0 ~ 3 ~ 7 3 P ~ /~S91/05533 provides a degree of crystallinity, and hence acceptable flow characteristics, to the particulate and may be any one or more of the organic or inorganic salts present in the lirs t c0~ .2~.t.

The particle si~e range of the second component is not critical bu~ should be such as to obviate segregation ~rom the pa.~iolea of the spray dried firs. component when blended thQrowi~h. Thus not more than 5% by weight should a~ m ~hila no~ ~o~e than 10% should be less than 0.15 ~.~ ir. ma-imum dimQnsion.

The bulk densi.y of the second component will oe a function of its mode of preparation. Thus, in spray dried granular form the second component may have a density of from 3S0 g/litre to 650 g/litre but more preferably will be in the range from 500 g/litre to 630 g/litre. The preferred form of the second component however is a mechanically mised agglomerate which may be made by adding the ingredients dry or with an agglomerating agent to a pan agglomerator, Z
blade miser or more preferably an in-line miser such as those manufactured by Schuqi (Holland) BV, 29 Chroomstraat 8211 AS, L~lystad, Netherlands and Gebruder Lodige Maschinenban GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 20S0 F.R.G. By this means the second component can be given a bulk density in the range from 650 g/litre to 1190 g/litre more preferably from 750 g/litre to 850 g/litre. This is particularly useful in formulating the so called 'concentrated' products.

W 0 92/03525 P ~ /US91/Oaa33 2 G ~ 3 ~ ~ v Preferred compositions include a level of ~lkali metal carbonate in the seccnd COm?OnQ~. _vr es?on' a.~ .o an amount of from 3~ to 15~ by wei~ a-. ~`ae ca~ osi~ion, mo~e ?referably from 5"~ to 1~ h~
level of carbonate in the second component o ~rom 20% to 40% by weigh..

A highly preferred ing~edien~ a~ ;U:! ~ie~ aC; ~ aen~- i~-, also a hvdra~ed wat~r insolu'.l.~ s~ ^ e .
e~changs ma~e~ al af ~ s-.-n~ . n hereinbeor~Q, pres2nt a~ ~rom ~ o ~J`~ V'~ `e ~ 0 second component. ~he amoun~ o ~ia~ n to ~oi~
aluminosilicate material incorpora~-d in this way is ~ rom 1~ to 10~ by weight of the composition~ more pret2rably from 2~ to 8~ by weight. If the second component is spray dried, it is important that it does not contain both silicate and aluminosilicate ingredients for the reasons stated hereinbefore. In such circumstances, the silicate may be incorporated in the first component or, if that also contains aluminosilicate, may be added as a solid, together with other dry mi~ed materials, to the first and second components.

In one process for preparing the second component, the surfactant salt is formed in situ in an inline mi~er. The liquid acid form of the surfactant is addad to a mi~ture of particulate anhydrous sodium carbcnate and hydrated sodium aluminosilicate in a continuous hish speed blender such as a Lodige KM mi~er and neutralised to form the surfactant salt whilst maintaining the partic~late nature of the mi2ture. The resultant agglomera~ed mi~ture forms the second component which is then added to other components of the product. In a variant of this process, the surfactant salt is pre-neutralised and added as a viscous paste to the mi~ture of the other ingredients. In this variant, the mixer serves merely to agglomerate the ingredients to ~orm the second component.

W092/03525 PCT/US91/0~533 ~a~ '~2 ~lv In a particularly preferred process for making compositions in accordance with the invention, par~ o- ~he spray ~ried product comprising the firs. srar.ular c~m~onen~ s div~trted and subjected to â low level o_ ..oni~n~ s~
on before being reblended with the remainder. The second granular component is made using ~he -e st--oA process described above. The first and second components ~ogether with other dry mi~ ingredien~s such as ~ha _~ bo~f i tt_ chelating ~q~nt, inorganic pero.~ gat. ~'~--h activator, soil-r~leas~ ?oli,r~e~ si ~ ^a;
then fed to a conveyor belL, ~.o;~n _`~,ic'~ 2'; ~;2 transferred to a horizontaiiy ~OLàL.,IL ~ nic.-perfume and silicone suds suppressor are sprayed on to ~he product. In highly preferred composi'ions, a further drum mi~ing step is employed in which a low ~appro~. 2% by weight) level of finely divided crystalline aluminosilicate is introduced to increase density and improve granular flow characteristics.

Compositions in accordance with the invention can also benefit from delivery systems that provide transient localised high concentrations of product in the drum o' an automatic washing machine at the start of the wash cycle, thereby also avoiding problems associated with loss of product in the pipework or sump of the machine.

Delivery to the drum can most easily be achieved by incorporation of the composition in a bag or container from which it is rapidly releasable at the start of the wash cycle in response to agitation, a rlse in temperature or immersion in the wash water in the drum. Alternatively the washing machine itself may be aàapted to oermit direct addition of the compostion to the d~um e.g. by a dispensing arrangement in the access door.

W092/03525 PCT/US91/0~33 2~ 7~ 28 -Products comprising a detergent composition enclosed in a bag or contain~r ar~ usually designed in such a way that containe. i.._aS -.y is maintained in the dry state to ena eg aS ~ `'e _^r.~er.~s whQn dry, but are adapted for release o,~ the container contents on esposure to a washins env ~~nment, normally on im~ersion in an aqueous solutio~.

Usuallv ~e -~ in~- ~ilt be Cle~ible, such as a bag or c~ c 'i`~ v.~ ;uc~_on ~oa~ed wi~.
a wat~- imr~ .e~le F o~eC'iVQ ma~er_al so as 'o retain the _cn~en~s, suca aa ~a ~.sclos~d ~n ~uropean ?ublished ?atent Application ~lo. OOlA~78. ~lte;natively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edqe of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

In a variant of the bag or container product form, laminated sheet products can be employed in which a central fle~ible layer is impreqnated and/or coated with a composition and ~her. one or more outer layers are applied to produce a fabric-like aesthetic effect. The layers may be sealed together so as to remain attached during use or may separate on contact with water to facilitate the release of the coated or impregnated material.

An alternative laminate form comprises one layer embossed or deformed to orovide a series of ?ouch-like containers into each of which the detergent components are deposited WO 92/03525 PCl`/US91/0~533 ~S32~

in measur_d amounts, with a second layer overlying the first lay~r and sealed thereto in those areas between the pouch-lil;~ containers where the two layers are in -on~act. ~ a~-~on-n-a may be deposi~ed in particulate, paste or mol~en .orm and the laminaté layers should prevent egress o. ~he _~n~orA~s o~ ~he pouch-like containers prior to their addi~.ion to wate~. The layers may separate or .ay ~ain ^~ac:s~ g~thQr on contact with water, the only re~ ;_m~ `oe i~g ~A~a~ Ae st ' UC~U_ e should permit ~ap~ld ~ ~a_a a na ^an~enas o tn~ ~ouch-L~ke containers in~o solu~ia". i~e num~ c- ?ouch-like containers per unit area of su~s~~ate is a mat~er o~ choice but will normally varV be~ween 500 and ~5,000 per square metre.

Suitable materials which can be used for the fle~ible laminate layers in this aspect of the invention include, among others, sponges, paper and woven and non-woven fabrics.

However the preferred means of carrying out the process of the invention is to introduce the composition into the ~iquid su.rour,dins the fabrics that are in the drum via a reusable dispensing device having walls that are permeable to liquid but impermeable to the solid composition.

Devices of this ~ind are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a fle~ible sheath in the form of a bag eYtending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient p.oduct for one wash ng cycle in a washing cycle. A portion of the washing medium flows through the orifice in~o the bag, dissolves the product, and the solution then passes outwardly through the orifice into the W092/03525 rCT/US91/0~533 20~327~

washing medium. The support ring is provideà with a mas'~ing arrangement to prevent egress of we~~ed, u-.disso!ved, product, this arrangement typicall~ c3m~r' a' ng ra~_a e~tending walls e~tending rom c-nsr_` oo__ in ~ s~
wheel configuration, or a similar structure in s~hich tha walls have a helical ~orm.

WO 92/0352~ PCI/13S91/0~533 20~27 e~

The invention is illustrated in the following non limiting E~amples, in which all percentages are on a weight ~asis unless otherwise stated.

In the detergent compositions, the ab~reviated component identifications have the following ~eanin~s:.
C12 LAS : Sodium !inear Cl~ alkyl ~er.~ene sulphonate TAS : Sodium tallow alcohol s;lloaa~n~
C14/li AS : Scdium Cl~-Cls alXyi ~ulpha~o TAE~ : ~al'ow al_^hol ~t~.~- '.at~ `. z moles of ethylene o~ide per mole of alcohol 45E7 : A C4-Cls predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide CnAE~6.5 A C12-C13 primary alcohol condensed with 5.5 moles of ethylene oside.
PEG : Polyethylene glycol (MWt normally follows) TAED : Tetraacetyl ethylene Diamine Silicate : Amorphous Sodium silicate (SiO2:Na20 ratio normally follows) NaSKS-6 : Crystalline layered silicate of formula ~ -Na2si25 Carbonate : Anhydrous sodium carbonate CMC : Sodium ca_~o~ymethyl cellulose Zeolite A : Hydrated Sodium Aluminosilicate of formula Nal2(AlO~Sio2)l2 27H20 having a primary particle size -the ranse from 1 to 10 micrometers Polyacrylate : domopol~.. er of acrylic acid of MWt 4000 Citrate : Sodium citrate trihydrate W O 92/03525 P(~r/US91/0~533 ` 7-Photoactivated : Tetra sulphonated Zinc Bleach ?h~halocyanine ~L~ C~?c `~ `~'me- or 1: ~ m~ieic/acryi~c acid, average molecular weight about 80,000~

~5VEk5.~ ielc anhyd ide,'vinyl methyl èther copol~mer. believed to have an ~? ~e mo~.ecu!ae ~e:-ght o~ 2~10,000.
~`a~s ma~.erial was prehydrolvsed with .`'..`'_`.i `~^_~^e addl~iQ-..

Perborate : Sod~um perborate tetrahydra~e of nominal formula NaB02 3H20 ~ H22 Perborate : Anhydrous sodium perborate bleach monohydrate empirical formula NaBO2.H2O2 Enzyme : Mi~ed proteolytic and amylolytic en~yme sold by Novo Industrie AS.

Brightener : Disodium 4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2:2'-disulphonate.

DETPMP : Diethylene triamine penta (methylene phosphonic acid), marketed by Monsanto under the Trade name Dequest 2060 Mised Suds : 25% paraf in wa~ Mpt 50C, 17~
Suppressor hydropho~ c silica, 58~ paraffin oil.

WO 92/03525 2 ~ 2 7 ~f PCI/US91/05533 EXAMPLE I

The granula~ ~e~arja~. produc~s we~e prepared having composi~ lo~ :~ r ~ Y ~ 2 i g ~ ~ .

A B
C~ S ~.~ 4.4 TAS ;.0 4.0 t ~; 'B . 3, ? 3 . 7 ~ ~,,~ _, _ 1 . 1 1 ` ~ 8 . 0 L~i a - ,,.is- :~ - 11 . O
Citrate 9.25 6.0 MA/~A ~.9 4.9 TAED 5.0 5.0 Perborate 10.0 10.0 Perborate monohydrate 6.0 6.0 DETPMP 0.19 0.19 Enzyme ,1.40 1.40 Silicate (2.0 ratio)4.0 Carbonate lS.5 9.0 Suds suppressor 0.55 0.55 CMC 0.~ 0.8 PhotoactiYated bleach 20 ppm 20 ppm Perfume 0~43 0-43 Brishtenar 0.24 0.24 Moisture ~ Misc. 10.34 ~ 6.29 Both products were made by a combination of spray dryinq, agglomeration and dry mi~ing techniques. A spray dried powder was made incorporating all of the TAS, approsimately one quarter of the LAS, all of the Maleic anhydride/acrylic acid copolymer, DETPMP, CMC and W092/03525 ~CT/US91/05~33 2 ~ ~ ~ 2 7~ 34 brightener and part of the carbonate and zeolite builders. For Product A appro~ima~ely 82~ of th~ a and 65% of the carbonate were included in th.Q spra~,- d~
portion, while ~or Product B appro~ ~a~e!y t~
zeolite and 45~ of the carbonate were added in this way.
The spray dried product was passed hro~gh 2 LCdi9Q ~
high speed mi~er/cutter and the 45E, nonionic was sprayed on to the granules. The treated granules t~er_ ~h_.-transferred to a conveyor belt. The ~emai~A~e~ o~ ~a hAS, car~onate and ~eclitQ wQre pr~cess~ n a B~
high speed mi~er to ~orm agglomerated ~rtic'_s ~;`a_C~A;;e~e fed to the c~r.veyor bel_. Tha o~h~ so'_d ingredients viz. the citrate, silicate, per~rate and bleach activator were also added to the belt at the same time. Finally the mi~ed particulates were subjected to a low intensity blending step in a mis drum, during which step the perfume and suds suppressor were sprayed on to the particulates to form the finished product.

These products were then compared in a split bundle wash testing programme to enable the assessment of cleaning and stain removal performance. The test proqram~e was designed, and contained sufficient replicates, to permit statistical treatment of the results. Product A was used in an amount of 95g per load whereas Product 8 was used in an amount of 79g per load. The di~ference reflected the higher concentration of ingredients per 100 parts of Product B and thus the need to use less weight in order to provide the same levels of non builder ingredients. The test programme used AEG ~avamat 980 automatic washing machines set to the No. 2 cycle. The machines were charged with water of 25 German Hardness having a 8:1 Ca:Mg ratio. Testing was carried ~ut at three W092/03525 2 ~ 3 ~ 2 7 ~ PCT/USgl/0;533 temperatures, viz. 40C, 60C and 95C, for which respectively, fabric loads o~ 1.81 kg 2.25 kg, and 2.7~ kg were employed. Each load comprised a mi~ture of naturally soiled white cotton ~abric 2r~icles tos~-ha~
with swatches soiled with a variety of stains viz. greasy, clay soil, en~ymatic and bleachable, to permit the assessment of whiteness and stain removal performance.
Each swatch comprised half of a pair, the other hal` _ n~
washed in the same machine using the comoarison oroduct.
~f~er washins, th~ fabrics wer~ dr~ed at ambien.t temperature and were then subjec~ed to panelling ~, a~
judges using a ~-~ Schef.e scale ~ .arac-_ se differences in whiteness and stain removal performance between Products A and 3 at the selected temperatures.

The panelling showed significant advantages for Product B
over Product A on greasy and clay stains at 40C and on clay stains at 95C, the overall stain removal performance of the products being otherwise statistically indistinguishable. Useful performance advantages therefore exist for a composition incorporating a builder system in accordance with the present invention over a prior art composition. Moreover, such advantages can be obtained with a significant reduction (13.0 parts) in the level of builder ingredients.

WO 92/03525 PCT/US91/05~i33 2 J ~ b~ .~ 7 ~o E~l?Lr T I

A comparison ~_ na c!?~OUn~ O_ deJosi.ed inorsanic material on ,abr~ s .~,~d~ ~etween Product B in _-~mplQ and a non-phosphate laundry detergen~ ~Ui `~ U.`-~ .`.a`~ C u~ad ~r. u.; `~y Procter &
Gamble Limi~s;).

no~ra~ e 0~ 95C. Saca -J~ Ob'~iicl was use~ ~0 w`_ jh d '~oad comprisir.g .,2 `,~ d~ric 3nd tne respective wash2à loads were ~her. subjec~ed to a further 14 complete wash cycl~s.

A sample of the fabric from each load was then weighed, incinerated and the residue weighed to provide a value for the inorganic material deposited during the wash cycles.

Results were as follows:

Produc. ~osage/wash (g) Ash (wt%) Ariel Ultra '25g 0.698t Product 8 102g 0.483%

The results indi_ate that com?ositions in accordance with the invention produce lower levels of inorganic salt deposition than those obtained with commercially available non-phosphate detergent products.

W O 92/03525 PC~r/US91/05533 2 ~ 3 ~3 `~ 7 ''3 EX~MPLE III

T~2 follG.;~ .r~ itn the invention and is made i~ the same manner as product B of E~ample ~.

Cl~L.~S j, ~
T~S ~,~o ~201 NaS~S ~
Citrat~ 6.00 MA/~A i.2~
Carbonate 9.00 TAED 5.00 Perborate Monohydrate 12.50 DETPMP 0.19 Enzyme 1.20 CMC 0.48 Photac~iva~Pd Bleach 20 ppm Brightener 0.2~
Suds Suppressor 0.49 Perfume 0.~3 Moisture & Misc. 8.70 W O 92/03525 PC~r/US91/05~33 2 G ~ ~ 2 7 .j EXAMPLE IV
Three detergent products C,D & E were preparPd in the manner o.~ and having compositions identical to, Composition B of Example I other than the builder system differences shown below (values are in part.s ',~y weight in the composition)~

C D E
Zeolite A 13.0 13Q !3.~3 Citrate 6.0 6.0 6~0 NaSK36 11.0 11.0 Silica~e (~ .0 Ratio~* - - 13 ., _ M.~/AA ~.''5 ~.u .v ~supplied as (,0~o active, providing 11.0 parts on an annvdrous I~S!S

The products were used to conduct full scale washing machine tests in which terry towelling cotton swatches were included with 4 Kg of clean fabric ballast loads and subjected to multiple wash cycles to determine the levels of heavy metal ions (Fe & Mn) and total ash (inorganic salts) building up on the fabrics after repeated washing. A heavy metal ion 'spike' of 2.5 ppm Fe as FeCl3 and 0.2 ppm Mn as MnCl2 was added to the water fed to the machines.

The wash conditions were Machine Type Miele Hydromatic W698 Machine Cycle 95 C Cotton Wa~er Hardness Newcastle upon Tyne (UK) City Wate.
adjusted to give 25 German Hardness with Ca:Mg ratio of 3:1. (This water source typically contains 0-3ppm Cu).
Artificial Soil 20g/load of a mixture made up of Palmitic Acid 250g Stearic Acid 250g Garden Clay 2C0g Dirty Motor Oil 150g Glyceryl trioleate 150g Iron Oxide (Fe ~ O3) 5 .36g WO 92/03525 PCl/US9]/05533 2 ~ ~ g 2 ~ ~

The swatches are subjected to 25 wash cycles and then analysed for heavy metal ion content (ppm! and total inorganic salt content (ash).
The latter required the burning of a weighed terry towelling ~abric swatch in a flame for 3 minutes followed by calcination at 3C0C for 2 1/2 hours. The ash was then analysed for che el~m~n.s b~lo~.v reported as a fraction of the original sample wéight.

Results were as follows:
C D
Fe ppm 8.8 9.9 '7.
Mn ppm 1.9 3.5 ;~
Cuppm 1.4 2.3 ~.0 Ca+Mg% 0.42 0.16 1.05 Si & Al% 0.18 0.27 0.4~

It can be seen that cotton fàbrics washed in Products C + D, comprising compositions in accordance with the invention, display similar ash and heavy metal ion contents. However Composition D
contains a level of polymeric pol`ycarboxylate auxiliary builder which is ~50% of that used conventionally, showing that the use of the ternary builder system of the invention provides enhanced robustness to detergent compositions.

The results for Products C + D, when compared with those of Comparative Product E, also show the reduction in the level of deposited inorganic salts (ash) arising from the use of the ternasy builder system relative to prior art builder systems. More particularly, the comparision of Products C + D with Product E shows the significant reduction in heavy metal ion levels on fabrics resulting from use of the compositions of the invention. Fabric heavy metal ion content can be direcsly correlated with Tensile Strength Loss in fabrics which is believed to arise from catalytic decomposition of inorganic perhydrate bleaches on the surface of the fabrics.

Claims (22)

1. A particulate detergent composition comprising (a) from about 5% to about 50% by weight of an organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and cationic surfactants and mixtures of any thereof;

(b) from about 10% to about 95% of a detergent builder system comprising a mixture of (i) from about 20% to about 60% by weight of the mixture of a sodium aluminosilicate zeolite;
(ii) from about 10% to about 30% by weight of the mixture of a water soluble chelating agent selected from the group consisting of monomeric and oligomeric organic carboxylates and mixtures thereof; and (iii) from about 10% to about 65% by weight of the mixture of a crystalline layered sodium silicate having the composition NaMSixO2x+1.yH2O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and v is a number from 0 to 20; and (c) from 0 to about 40% of non-surfactant, non-builder detergent ingredients.

2. A particulate detergent composition according to claim 1 wherein, in component (b) (iii), x has a value of 2.

3. A detergent composition according to claim 2 wherein, in component (b) (iii), M is sodium.

4. A detergent composition according to claim 3 wherein the component (b) (iii) is .alpha., .beta., .delta. or -Na2Si2O5.

5. A detergent composition according to claim 1 wherein the sodium aluminosilicate zeolite is a hydrated synthetic zeolite having a Calcium ion exchange capacity of at least about 200 mg eq CaCO3 water hardness per g of zeolite calculated on an anhydrous basis.

6. A detergent composition according to claim 5 wherein the synthetic hydrated zeolite has a unit cell formula Naz[(AlO2)z(SiO2)y].xH2O

wherein z & y are at least 6, the ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276.

7. A detergent composition according to claim 6 wherein the sodium aluminosilicate zeolite is hydrated Zeolite Z, X, B or HS.

8. A detergent composition according to claim 1 wherein the organic carboxylate chelating agent has a first carboxyl logarithmic acidity constant (pk1) of less than about 9.

9. A detergent composition according to claim 8 wherein the organic carboxylate chelating agent has a pk1 of from about 2 to about 8.5.

10. A detergent composition according to claim 9 wherein the organic carboxylate chelating agent comprises a monomeric polycarboxylate having a pk1 of from about 4 to about 7.5.

11. A detergent composition according to claim 10 wherein the monomeric polycarboxylate comprises an aliphatic monomeric polycarboxylate containing from 2 to 4 carboxyl groups.

12. A particulate detergent composition comprising (a) from about 5% to about 50% by weight of an organic surfactant selected from the group consisting of anionic, nonionic, ampholytic and cationic surfactants and mixtures of any thereof;

(b) from about 10% to about 95% of a detergent builder system comprising a mixture of (i) from about 20% to about 60% by weight of the mixture of a synthetic sodium aluminosilicate zeolite having the unit cell formula Naz[(AlO2)z(SiO2)y].xH2O

wherein z & y are at least 6, the ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276.
(ii) from about 10% to about 30% by weight of the mixture of a water soluble aliphatic monomeric polycarboxylate chelating agent containing from 2 to 4 carboxyl groups and having a pk1 of from about 4 to about 7.5; and (iii) from about 10% to about 65% by weight of the mixture of a crystalline layered sodium silicate having the formula .delta. - Na2SisO5; and (c) from 0 to about 40% of non-surfactant, non-builder detergent ingredients.

13. A detergent composition according to claim 12 comprising from about 5% to about 30% of component a), from about 20% to about 60% of component b) and from about 20% to about 40% of other detergent ingredients.

14. A detergent composition according to claim 12 wherein the water soluble aliphatic monomeric polycarboxylate chelating agent is selected from citric acid, a water soluble citrate salt and mixtures thereof.

15. A detergent composition according to claim 14 wherein component (b) also includes an auxiliary builder.

16. A detergent composition according to claim 15 wherein the auxiliary builder is selected from the group consisting of water soluble amino poly alkylene phosphonates, alkali metal carbonates and bicarbonates, homo-/or copolymeric polycarboxylic acids and their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms, and mixtures of any thereof.

17. A detergent composition according to claim 16 wherein component (c) comprises an oxygen bleach.

18. A detergent composition according to claim 17 wherein the oxygen bleach is an inorganic perhydrate.

19. A detergent composition according to claim 18 wherein the oxygen bleach includes an organic peroxy acid precursor.

20. A detergent composition according to claim 12 wherein component (c) includes a detergent enzyme.

21. A method of preparing a particulate detergent composition comprising (a) from about 5% to about 50% by weight of an organic surfactant selected from the group consists of anionic, nonionic, ampholytic and cationic surfactants and mixtures of any thereof;
(b) from about 10% to about 95% of a detergent builder system comprising a mixture of (i) from about 20% to about 60% by weight of the mixture of a synthetic sodium aluminosilicate zeolite having the unit cell formula Naz[(AlO2)z(SiO2)y].xH2O

wherein 2 & y are at least 6, the ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276.
(ii) from about 10% to about 30% by weight of the mixture of a water soluble aliphatic monomeric poly carboxylate chelating agent containing from 2 to 4 carboxyl groups and having a pk1 of from about 4 to about 75; and (iii) from about 10% to about 65% by weight of the mixture of a crystalline layered sodium silicate having the formula .delta. -Na2Si2O5; and (c) from 0 to about 40% of non-surfactant, non-builder detergent ingredients wherein the crystalline layered sodium silicate (b) (iii) is added as a finely divided particulate solid to one or more granular solids comprising component (a), component (b) (i) & (ii) and, if present, component (c), at least one of said granular solids comprising a multicomponent mixture, present in an amount of at least about 20% by weight of the composition.

22. A method of preparing a particulate detergent composition according to claim 21 comprising the steps of (i) spray drying a first granular solid, comprising from about 30% to about 70% of the composition said component consisting essentially of from about 0.75% to about 35% by weight of an anionic surfactant and from about 65% to about 99.25% of a salt selected from the group consisting of the synthetic aluminosilicate zeolite and other inorganic and organic detergent builder salts;

(ii) preparing a second granular solid, comprising from about 1% to about 50% by weight of the composition and consisting essentially of an agglomerated mixture of anionic surfactant, synthetic aluminosilicate zeolite and other inorganic detergent builder salts;

(iii) forming an admixture of said first and second granular solids; and (iv) adding thereto said water soluble aliphatic monomeric carboxylate chelating agent and said crystalline layered sodium silicate as separate particulates.