CA2257987A1 - Process for producing a particulate laundry additive for perfume delivery having improved physical properties - Google Patents

Abstract

A process for producing a particulate laundry additive composition for perfume delivery primarily in laundry detergent and fabric softening products is disclosed. The process essentially includes the steps of drying an aqueous mixture of a pigment and an encapsulating material to form a fluid that preferably is devoid of water or at least has a portion of the water evaporated by this drying step, and thereafter, extruding an encapsulating material, preferably a glassy carbohydrate material, with porous carrier particles, preferably loaded with a perfume, so as to form a hot extrudate. Subsequently, the steps of cooling and grinding the extrudate into particles is completed.

Description

PROCESS FOR PRODUCING A PARTICULATE LAUNDRY ADDlTlVE FOR PERI;UME DELTVERY
HAVING IMPROVED P~YSTCAL PROPkK ~ S
s FIELD OF THE INVENTION
The present invention generally relates to a process for p.uducing a particulatelaundry additive colllposilion, and more particularly, to an extrusion process which produces a particulate laundry additive for p~, r,.".c delivery in laundry d~,t~ t co",pos;~ if s~ especially those in the forrn of gTanules, ~lo~ utes, laundry bars or p~ctilles This process improves upon existing l"ucesses in that it provides a c~ o~;l;ol-having ~ e~t~ ~ly better physical p,up~,lies such as appearance ("~ "), moistureprotection and p~,ru~.c plvt,~,tioll as evidenced by its s.~ba~ ly reduced odor product form. The process of the inv~ tio.l may also be employed to produce particulate additive co~ oC;l;onc which may be used in fabric softening and disl,- ~sl.ing as well as laundry d~.t."~,~"t C~ o~ n~
BACKGROUND OF THE INVENTION
Most COU~ -,-a have come to expect scented laundry pluducl~ and to expect that fabrics which have been hu,.d. ,~,d also to have a pleasing fragrance. re.~,..c additives make laundry COmpOsi~iQnc more ~ t~ ly ~ lg to the CQn~ , and in some cases the perfume imparts a pk- ~-t L. gldilce to fabrics tTeated therewith. However, the amount of p~" rull-c carryover from an aqueous laundry bath onto fabrics is often 25 marginal. The d~ t~ nl manufacturing industry, lh~r~e~ has long sed.-,hed for an effective pc ru---c delivery system for use in laundry ~J~OduC;la which provides long-lasting, aL~,...~5e-stable r...~ce to the product, as well as fTagTance to the laulldeled fabrics.
Laundry and other fabric care CO...i~O~ u ~ which contain perfume mixed with or 30 sprayed onto the cc-...po~;~;ons are well known in the art and ~iull~ltly collu~ rcialized.
Because perfumes are made of a combination of volatile compounds, p~,. ru...c can be cQ..~ oucly emitted from simple solutions and dry mixes to which the pe.ru.,lc has been added. Various techniques have been developed to hinder or delay the release of p~,,ru~lc from composi~ionC so that they will remain a-~-he~ q~ly pleasing for a longer 35 length of time. To date, however, few of the methods deliver significant fabric odor benefits after prolonged storage of the product.

W O 97/47720 PCTrUS97/09972 Moreover, there has been a contimJin~ search for methods and compositionc which will effectively and cfr.~ielltly deliver pclru",c from laundering solutions onto fabric surfaces. As can be seen from the following disclosures in the prior art, various methQ(Ic of ~,. rulllc delivery have been d~ eloped involving protection of the perfume through 5 the wash cycle, with release of the perfume onto fabrics. For example, one method entails delivering fabric con~itionin~ agents, inc!ndin~ p.,.ru..lc, through the wash and dry cycle via a fatty quaternary ammonium salt. Another method involves a mic.oF ~-~a,- ,UI~tion technique which involves the forrn~ tic-n of a shell material which will allow for di~u ,;on of perfume out of the capsule only at certain t~,..lp~ lu.cs. Yet 10 another method involves incu,~orating p.,lrull,c into waxy particles to protect the p~.lrulllc through storage in dry co",posilions and through the laundry process. The p~l Çull.c allegedly diffuses through the wax on the fabric in the dryer. Further prior art disclosures involve perfume disp~.~ed with a water-insoluble nonpolymeric carrier material and F ncqrslllated in a protective shell by coating with a water-inco! I Ie friable 15 coating material, and a perfume/cyclod~ ,i" complex plut,.,ted by clay which provides p.~l rL..~.c benefits to at least partially wetted fabrics.
Still another method for delivery of pelrulllc in the wash cycle involves combining the p~lrullle with an emulsifier and water- soluble polymer, forming the mixture into particles, and adding them to a laundry co. .l,os:'ion The p~,.ru~c can also be adso.l.ed 20 onto a porous carrier material, such as a polymeric material. ~e. r ...les have also been adsorbed onto a clay or zeolite material which is then ~lmiY~d into particulate d.,t~ enl co .I-os;L;ons Generally, the p.ef~ ,d zeolites have been Type A or 4A Zeolites with a nomin~l pore size of appro~im~tply 4 Angstrom units. It is now beli~,~red that with Zeolite A or 4A, the p~.ru..-c is adsorbed onto the zeolite surface with relatively little of 25 the p~,. ÇIJ..,C actually abso- l.;ng into the zeolite pores.
While the adsorption of p~.ru--.c onto zeolite or polymeric carriers may perhaps provide some i...pn)J~,Il.el~t over the addition of neat p~,l ru...c ~ ed with d~,te.~,enl cou~;~os ~;nnc, industry is still searching for improvements in the length of storage time of the laundry cG...posilions without loss of p.,l runlc cha~a~,t~ lics, in the intensity or 30 amount of r~ ce delivered to fabrics, and in the du-_ ~r of the pCIÇu..lC scent on the treated fabric surfaces. Fu~lhe.more, even with the ~ul,~ l work done by prior skilled artisans in this area, a need still exists for a simple, more ~rr ci~,.n and effective p~,. rulllc delivery system, p.~f~,l bly in particulate form, which can be mixed with laundry co.--l-o~il ;onc to provide initial and lasting pe. ru-llc benefits to fabrics which have been 35 treated with the laundry product.
Another p~obl~,... associated with perfume delivery systems, eepeciqlly those inparticulate form, is conc.,...ed with the method by which such particulate perfume CA 022~7987 1998-12-11 delivery systems are made. It has been difficult to produce perfume delivery systems particularly those involving zeolite or polymeric carriers in an economic and efficient manner. on~ 5, a significant amount of the pe. ru...c will evaporate from the carrier material during ~J~ocF,ss: ~g as well as during storage prior to use. A~ tion~q-lly~ many 5 materials which are included in the p~lru...c delivery system to prevent the vol~ili7qti~n of p~,.ru..lc prior to deposition on fabrics can degrade during n~ r '- e, thereby losing their effectiveness.
Yet another p~ob~ ~m encountered with such p~.. ru.~.c delivery systems is conr- ..cd with discoloration oc-,u..i..g during the ~f~ e of such systems. In 10 particular, the pe.ru.--c delivery systems have a l~ den~y to "yellow" or become less "white" in ~t~c~ce. This discoloration problem has a negative impact on the p.odù., into which the ~.ru--.c delivery system is h~co.~ ted in that this discoloration affects the overall color of the final product. Con~ s of laundry, dish and other c! e - - ing products typically prefer a uniform color such as white with the occ~:o~ql brightly 15 colored specL-les rather than a "yellowish" product. Thus, there has been a need for not only an effective perfume delivery system or additive for laundry d~h~ ta~ but for a process which can produce such a laundry p~.ru--lc delivery additive which is efficient, economi~ql~ and minimi7~c or elimin~es product discoloration, evaporation of ~.~UlllC
and dc,5l ' of materials used to minimi7r p~,.ru...c evaporation during ~.~.cec~ g Accordingly, despite the ar~ on~d discloaulei~ in the art, there remains a need for a process for proJucing a particulate laundry additive cr.---poai~;on for p~,.rl e delivery in laundry d~t~rg~ and other cl~-qning or fabric sort~..ing ~ ,.lu-;b.
itit~nqlly, there is a need for such a process which is not only more eC(!nomic~l and efficient, but also minimi7~s discoloration, evaporation of p~.Çul~lc and the de~ n 25 of materials used in this regard during producti- n.
BACKGROUND ART
U.S. Patent 4,539,135, Ran.c~ an et al, issued September 3, 1985, discloses particulate laundry cc.--.pou~ s co...l>. iah~g a clay or zeolite material carrying perfi~me.
U.S. Patent 4,713,193, Tai, issued l:!ece"-b~- 15, 1987, diccloses a free-flowing 30 particulate dete.~ t additive co---p ;si--g a liquid or oily adjunct with a zeolite material.
Ja~ -se Patent ~IEI 4[1992]-218583, Nishishiro, published August 10, 1992, discloses controlled-release materials including p.,.ru...es plus zeolites. U.S. Patent 4,304,675, Corey et al, issued December 8, 1981, teaches a method and co,..poailion co...p. ;ah~g zeolites for deodorizing articles. East German Patent Publication No. 248,508, published August 12, 1987; East German Patent Publication No. 137,599, published September 12, 1979; European Patent Publication No. 535,942, published April 7, 1993, and Publication No. 536,942, published April 14, 1993, by Unilever PLC; U.S. Patent 5,336,665, issued August 9, 1994 to Garner-Gray et al.; and WO 94/28107, published Dec~ .f. 8, 1994.

~5 SUMMARY OF THE INVENTION
The aro,~ c................... l ;sned needs in the art are met by the present invention which provides a process for producing a particulate laundry additive composition for perfume delivery primarily in laundry det~.~nl and fabric softening products. The process eCc~ont~ yco~lpl ;ses the steps of drying an ~queQuC mixture of a pigment and an çnrars~ tine material to form a fluid that pl ef~ .- bly is devoid of water or at least has a portion of the water e i 1~ aled by this drying step, and th~ a~ e.~lrudh~g an enc~rslJlating material, ~tef~ bly a glassy carbohydrate material, with a porous carrier particles, preferably loaded with a perfume, so as to form hot extrudate. Sul.~,e~ Iy, 10 the steps of cooling and grinding the ex~u' ~f into particles is completed. In essence, the inchJq~ol of a pigment in the drying step produces a laundry additive which,ect,.~lly, cont~inc p~lÇU-~.C that has not e~apvldted or other vise leached out ofthe carrier material have been de-natured during p,ucessi,~g In fact, as a result of this process, the pe. rul..c is sealed into the carrier material s~ffiri~ntly to not permit e.~o~ui e 15 until ~ubject~,d to the laund~ . ing or softening process.
As used herein, the term "~.~t" J t~ ~ refers to a continuous phase material formed from an e.~t, udel which can have virtually any desired shape. As used herein, the term "enrobed" means that the carbohydrate material substantially covers the carrier p&. licles regardless of the overall shape of the materials together, e.g. agglo,..- ...tes, extrudate or 20 particles. As used herein, the phrase "glass phase" or "glassy" materials refers to mi.~,oscupi~lly amorphous solid materials having a glass transition t~.."p~ , Tg As used herein, the phrase "co.~ ,OI.c phase" refers to a single fused mass of individual or discrete particles. As used herein, the phrase "median particle size" means the "mean"
particle size in that about 50% of the particles are larger and about 50% are smaller than 25 this particle size as ".ea~J,.d by ~ '~ ~d sieve analysis. All perc~ .t~ePs and ratios used herein are e..~,e..s~d as p~ t ~ by weight (anhydrous basis) unless otherwise n~ I All ~ ; are inco",o-aled herein by ,~f.,.~..ce.
In acco,J~nce with one aspect of the invention, a process for producing a particulate laundry additive cc,...l~osilion is provided. This process co...pflses the steps of:
30 (a) drying an aqueous mixture of a pigment and an enrars~ tine material to forrn an enr~ps~ ting fluid;
(b) inpunin~ the ~nrarS~ tin~ fluid and porous carrier particles into an extruder, the porous carrier particles having a perfume adsorbed therein; (c) extruding the porous carrier particles and the çnc~ps~l g fluid so as tû form an extrudate co..tz~in; -g the porous 35 carrier particles enrobed with the çnc~rs~ tine fluid; (d) cooling the extrudate; and (e) g.;"din& the extrudate to form particles having a predetermined particle size for addition into a d~,te.~ent composition, thereby forming the particulate laundry additive composition W 097/~7720 rCT~US97/09972 ~O
In accord~lce with another aspect of the invention, another process for producing a particulate laundry additive CO~..pO~;IiO.l is provided. This process co",l" ises the steps of:
(a) h"~ullii~g an encarsul~tine material, a pi~""_..l and porous carrier particles into a mixer, the porous carrier particles having a perfume adsG. l,ed therein; (b) e.stl udi"g the porous 5 carrier particles, the pigrnent and the encapsulating material so as to form an extrudate contQinir~g the porous carrier particles enrobed with the ençAps~lating material and the pi~,.e.,l, (c) cooling the extrudate; and (d) grinding the extrudate to form particles having a p,-,d~t~...,ined particle size for addition into a dct~.E,ent cu"")osilion, thereby forming the particulate laundry additive co,..rss~
The present invention also provides the particulate laundry additive co .po~;l;on made acco,dil,g to any one of the p.ocesses de~c- ;l,ed herein.
Acco-.l;ngly, it is an object of the present invention to provide a process for producing a particulate laundry additive composition for pe.rull~e delivery in laundry d~ te.~ t and other cl~~ -ing or fabric softening products. It is also an object of the 15 invention to provide such a process which is more econ~mirAI elTi~ t and one which minimi7~S product discoloration and the evaporation of p~,~ ru...c and deE;, ~ ~ - :- of the materials used during ~J~U~ l;On- These and other objects, features and a~ A~
advantages of the present invention will become app. ci.n to those skilled in the art from a reading of the following detailed des." ;~tion of the p- ef~ d embodi~nPnt) drawings and the AMPndpd claims.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. I is a schPmAtiC flow diagram of one embodiment of the process in which theunde.~i~e~ particle recycling step is co,.,plet~,d by feeding the ~,nde.~iLed particles back to just before the cooling step; and Fig. 2 is a schematic flow diagram of another embodiment of the process in whichthe recycling of ~ ,d particles is completed by recycling the undersized particles back through a particle c.. ~,~ h~
DETAILED DESCRIPTION O~ THE PREFERRED EMBODIMENT
Process The process ofthe invention ~ peci~ y provides a means by which a pe.rulllc-co.~ particulate laundry additive composition can be prepared without having excessive discoloration and perfume evaporation or de~adalion during p,ucessi"g and which forms a particulate cû~pû ~ilion m~intAining such perfume prior to its use during the l. .md~,. ;..g of fabrics. By m9~ ing the perfume prior to use, it is meant that the pc. rull~c 35 is not emitted while stored in the product co~tAiner, but is only allowed to be emitted during and after deposition on the laundered fabrics as int~n~ Further, the process W 097/47720 PCTrUSg7tO9972 ~n~ xpec~ ly prev~ a the disp!- - ment of p~ . ruu~c from the porous carrier particles into the Rnrars~lsting material.
Ad~litionqlly, the process ~ ç~tçdly plG~ Ila the çnrsrs~ ing material used to enrobe the pclru..-c-loaded carrier material from deg~ n during procçccing by 5 ll~qintsining a low process residçnre time. While not intending to be bound by theory, it is believed that typically the inrh~si<!n of a pigment in the process raises the viscosity of an Rnrqrs~lating fluid such as one colltq~ ;n8 a carbohydrate material. ~ itionqlly, additives that de~ .&se the viscosity of an ~nrap~ulqting fluid typically lowers the glass ~ ion lp~. ' G (Tg). However, aultJI ~ zly, the in~ si ~ ~~ of a P;u ~~ in the present process 10 lowered the viscosity and m~ tqinPd the glass transition temperature. This positively affects the ultimate laundry additive composition produced in that the ...~ t ;nGd high glass transition temperature of the encars~l- g material (e.g. carbohydrate) retains its low hy~ ity, thereby p..,.~e.,tillg moisture from cQntqcting the perfume-loaded carrier material. Also, the lower viscosity of the erlraps~lsting fluid which contains the 15 en~arsulqting material and p-~l-- -lt renders it easier to process into the G~ in .~,b,e~ nl process steps.
Turning now to Fig. 1 which provides a srll~m - flow diagram of one embodiment of the process 10, the first step of the process 10 involves ~ ;nB anRnrarslllstin~ material 6 in ~I-leou~ form and a pi~ t 8 into a mixer 5 to form an 20 aqueous mixture 7. The mixer 5 can be any con~r~ nlional tank or vessel having stirring or agitating apparatus inrh~ded therein. The aqueous mixture 7 of the pigment 8 andPting material 6 is fed to a binder forming/drying aFF dtus 12 to form an encarsulsting fluid 14. Typically, the pigment 8 is added in an amount of from about 0.1%
to about 10%, and most preferably from about 0.5% to about 5% by weight of the final 25 product. In the binder formingldrying ap~ alus 12, at least a portion of the water hltlu-luccd via the aqueous . -, ~l ing material 6 is evaporated via the drying step in this apparatus 12 By a portion, it is meant that the resulting e -~ ting fluid 14 contains from about 50% to about 95% of the water originally cc.--~ ed in the encapsulating material 6. Most ~,lef~.~bly, ho..~,~e~, the ~n~psul -ing fluid 14 is substantially free of 30 water.
The p.~ll~nt 8 is p.~f~,. bly selected from the group COIlC;~ g of titanium dioxide, silica, sodium alumina silicate, ultramarines, optical bl ;ghl~ a and mixtures thereof, although other materials can be used, some of which are listed hereinafter. The most p,~,f.,..~,d pigment 8 is titanium dioxide. As alluded to earlier, while the pigment 8 is 35 inclllded to prevent discoloration of the ultimate product formed, it aul~JIiaillgly has the benefit of rn~int~ining the glass transition temperature of the er; 1~ .ul~ting fluid 14, lowering its viscosity, and providing unPxpectçdly superior sealing properties in that the W O 97147720 PCT~US97109972 enrarsulsting fluid is able to prevent emissions of the p. . ru..,c prior to deposition of the additive on laundered fabrics. The binder/drying app_.dlus 12 can be a Wiped Film E~a~Jvl d~l (WFE), or heated extruder, in the sillldlion where the en~ ars~ ting material 6 is in the molten phase or a cG"~/e.ltional spray-drying tower or similar a~J~dtb~ when the 5 enrqrs~ tine material 6 is in the solid phase. Preferably, the ~ sul~ting material 6 is a carbohydrate material, which even more preferably, is in the glass phase.
In the next step of the process, the ~nc~rs~lating fluid 14 is inputted to an e.~l~ uder 16. It should be u..de.~l~,od that while e.~lrudc~ 16 can be mixing apparatus, it plef~ 'Gly is an cAlllJdel. Porous carrier partic1es or material 18 as described in detail he.~ alt~,. is also added to the eAl.ud~r 16, p.efe.~ly near the end ofthe cAl,.. J~,r 16. The extruder 16 can be any known mixing, extrusion, co-,,puul-di.,g or other q~ pr ~tus, inclu~ing but not limited to, extruders commercially available from APV Baker (CP Series), Werner &
Pfleiderer (Continua and ZSK Series), Wenger (TF Series); Leistritz (ZSE Series), Buss (LR Series), Reiten Lausar (BT Series); Weber (DS Series), and Columbo (RC Series).
In an alternative embo~ .1 of the process in~e.ltion, a p.~,.~.,l 17 is added to the extruder 16 to aid in the discoloration problem and to modify the viscosity of the mixture beingcAl,~d~' Itshouldbel",d~,.aloodthatthebenefitsoftheinstantprocessinvention can be achi~,~ed by adding the pi~,.cnt 17 as shown in Fig. I and de3_- ilxd herein alone, or in ~-lriition to the addition of pi~j...L.lt 6 as described previously. The p,~"ent 6 and 17 can 20 be the same, di~. ~,..t or various mixtures of the p;~.l._.lt materials des_, ibed previously.
Also, the amount of the p.~"e..l 17 added is typically from about 0.1% to about 5%, most prcf~,~ably from about 1% to about 2% by weight ofthe final product.
Pl ~,f~ . _bly, the cAl, udel 16 is n~ ; . ed at a temperature of from about 50 ~C to about 200 ~C, more l,,ef,.l~ly from about 110 ~C to about 170 ~C, and most preferably from about 120 ~C to about 160 ~C. In this way, ~ mixing of the porous carrier p~licles 18 and the encapsulating fluid 14 is ensured. The ,~,;d~ ~e time ofthe porous carrier particles 18 and the e ~ 1~ lating fluid 14 in the eALl ude~ 16 is p,ef~;ably from about 0.1 minutes to about 10 minutes, more plcfi . bly from about 0.1 minutes to about 5 m s, and most pncf~,...bly from about 0.1 minutes to about 2 min-ltPs Optionally, the ~AI-uder 16 can be d~plc;~a~ d to a level of about 100 mm Hg to about 750 mm Hg, more p,ef~,.ably from about 450 mm Hg to about 735 mm Hg, and most p,~if~. bly from about 710 mm Hg to about 550 mm Hg.
A hot extrudate 20 corlt~ining the porous carrier particles 18 enrobed with the enc~rslllating fluid 14 is formed in the extruder 16 and ~uI,je d to a cooling step in p,~f~,.ably a chilled roll/flaker 22 or similar a~ r _;US. The cooling step preferably cools the extrudate 20 to a temp.,. ;u.c in a range from about 20 ~C to about 100 ~C, more preferably from about 20 ~C to about 80 ~C, and most preferably from about 20 ~C to about W O 97/47720 . ~CT~US97/09972 q 60 ~C. Preferably, the cooling step is completed within about 1 second to about 120 seCon~c~ more ~,.ef~,~ably from about I second to about 60 secon~, and most preferably from about I second to about 30 secc~n~
The c,~ll.JdalG 20 are then su~ie: d to a grinding step 24 which can be cc..l"~let~d 5 in any know grinding 1~ r dtUS such as a hammermill. The resulting p~ licles 26 are sc-c~lled to provide particles 34 having a median particle size in a range from about 150 microns to about 1100 microns, more p~cfe.ably from about 200 microns to about 800 microns, and more p~er~_bly from about 400 microns to about 600 microns.
Optionally, the process further co---~ - ;ses the step of screening or separating the 10 particles 26 into ~ d~,.a;~.d or "fines" and Ov-,~ai~d or "overs" particles, wherein the und~,.aiLcd particles 32 have a median particle size of iess than about 150 microns and the ove.~i~ed particles 30 have a median particle size of at least 1100 microns. In this regard, the afor~ ic ~ d I ~ d particles are recycled back to just before the cooling step or chilled rolVflaker 22, while the oversized particles are sent back to the grinding step 24.
15 Past conventional wisdom by the skilled artisan would have recycled the o e.aized particles 30 and l.nd~,.ai~,d particles 32 back to the cAIlud~, 16. However, the recycle steps de;,_. ibed herein do not follow this scheme, but rather, recycle back to the cooling and/or grinding step as a~".,o~";a1e. These process steps u .- ~l-e~tedly result in minimi7~d carbohydrate material and p~.rulllc de~.dution as the recycled p.uliclcs are only subject to 20 high l~ .p~ es for an c.~llc.l~cly short period of time.
Rcfe~ ,e is now made to Fig. 2 which illustrates another ~rnbo~ of the process invention in which the process I Oa has identi~l steps/apparatus 6a through 34a as process 10. I".~,o-l~.lly, h~ er, rather than recycling the u..d-,.ai~,d particles 32a back to just before the cooling step 22a, the process I Oa subjects u..d~ . ai ~cd particles 32a to a CO~pl~ ;On step 36. The co,. pact;on step 36 produces particles 38 having a median particle size in a range from about 100 microns to about 100,000 microns, more p,ef~,rably from about 200 microns to about 10,000 microns, and more ~"ef~ bly from about 250 microns to about 1,500 microns. These particles 38 are then fed to the grinding step 24a.
It should also be noted that ~ liti~n~l surface co- ing~ (e.g. dyes and pi~ ut~) in the form of finely divided particles andtor liquids may be applied at any point in the plocesaes desc, ibed herein. By way of example, dyes and/or p ~ may be added during or after grinding steps 24 and 24a in Figs. I and 2, ~ ",e~ /ely.
Particulate LaundrY Additive Co"")osilion The process i"~t.~tion produces a particulate laundry additive co .poc;l;ol) useful in the delivery of pe.ru"~es for laundering processes The composition inciudes an enc~ps~ in~ material which p,ef~,. bly is a carbohydrate material derived from one or more at least partially water-soluble hydroxylic compounds, wherein at least one of said hydroxylic compounds has an anhydrous, nonplsctici7Pr~ glass transition l.,..-p~ lu.e, Tg , of about 0~C or higher, most preferably from about 40 ~C to about ioo oc. Further, the carbohydrate material has a hy~loscop:cily value of less than about 80%. These p~..rl....c delivery co-,l?osiliolls are çspeciqlly useful in granular d~t~ e~llcGllll~o-t; S, 5 particularly to deliver laundry and cl~ ~ng agents useful at low levels in the C~J---rO~ C
The ~nrqp~lating materials useful herein are pf~f~ bly selected from the following.
1. Carbohydrates, which can be any or mixture of: i) Simple sugars (or 10 monos~~ides); ii) Oli~ c~harides (defined as carbohydrate chains con~ of 2-10 m"~os ~ cl~--ide molecules); iii) Poly;.acchal;des (defined as carbohydrate chains CQ~ g of at least 35 mo n ~ ' ide molecules); and iv) Starches.
Both linear and branched carbohydrate chains may be used. In addition t~hf-mirslly ,nc~lified starches and poly-/oligo-sacch~ides may be used. Typicalmodill- - include the a ~ of hydn,phobic moieties of the form of alkyl, aryl, etc.
identicql to those found in ~ ntc tO impart some surface activity to these compounds.
In nd~litiQn, the following classes of materials may be used as an adjunct with the carbohydrate or as a _Jb:'-' t~.

2. All natural or synthetic gums such as alginate esters, . ~Aee~ agar-agar, pectic acid, and natural gums such as gum Arabic, gum tragacanth and gum karaya. 3. Chitin and çl~iloS;~.~
4. Cellulose and cellulose derivatives. Examples include: i) Cellulose acehte and Cellulose acetate phth9lqte (CAP); ii) Hydroxypropyl Methyl Cellulose (HPMC);
iii) Carboxymethylcellulose (CMC); iv) all enteric/aquateric co~tin~s and mixtures thereof.
5. Silicates, Pi ~;p~ s and Borates.
6. Polyvinyl alcohol (PVA).
7. Polyethylene glycol (PEG).
8. Nonil , ~u.f.~ l t~ including but not limited to polyhydroxy fatty acid amides.
Materials within these classes which are not at least partially water soluble and which have glass transition l~ p~alu~s~ Tg, below the lower limit herein of about 0~C
are useful herein only when mixed in such amounts with the hydroxylic col..pounds 35 useful herein having the .~,~Jui.~d higher Tg such that the particles produced has the ui.~d h~,~oscop.cily value of less than about 80%.

W O 97/4M20 PCT~US97/Og972 Il Glass transition temperature, commonly abbreviated "Tg", is a well known and readily determined property for glassy materials. This ~ ion is described as being equivalent to the li4uirl upon heating through the Tg region, of a material in the glassy state to one in the liquid state. It is not a phase transition such as melting, S ~,~ _ ' 'nn, or sublim~tion See William P. Brennan, "'What is a Tg?' A review of the s ,~ in~ calc.- hll.,tly of the glass transition", Thermal Analysis Application Study #7, Perkin-Elmer Col~ulalion, March 1973 for further details. M-- - re - of Tg is readily obt~ rd by using a Di~le.,1ial Scsnnin~ Calo,;...~,t~,..
For purposes of the present invention, the Tg of the hydroxylic cu.. p o~ c is 10 ob~,ned for the anhydrous co...poul.d not cont~ ,, any pl~St;";~ (which will impact the measured Tg value of the hydroxylic CQ po ~d). Glass transition t~ e is also described in detail in P. Peyser, "Glass Transition Tc...pe. es of Polymers", Polvmer Handbook. Third Edition, J. I~a~dlup and E. H. I-l-l"~ 1 (Wiley-Il,t~ ,;ence; 1989), pp. VI/209 - V~/277.
At least one of the hydroxylic co",poll"ds useful in the present invention particulate co...~.osil ;onC must have an anhydrous, nonpl&itic;-ed Tg of at least 0 ~C, and for particles not having a moisture barrier coating, at least about 20 ~C, I,,~f~,...bly at least about 40 ~C, more plefe~lhly at least 60 ~C, and most p,efe~bly at least about 100 ~C. It is also plefe.,cd that these compounds be low t~ p~.ulu~e p,oc ~ 5r~le', p,cf~,.ubly within the range of from about 40 ~C to about 200 ~C, and more preferably within the range of from about 60 ~C to about 160 ~C. P~cfe..ed such hydroxylic co,npo. nds include sucrose, glucose, lactose, and m~ d~ ~n;"
The "hy~oscopici~y value", as used herein, means the level of moisture uptake bythe particulate co,npos;lionc~ as ...ea~ d by the percent i..~,lcase in weight ofthe 25 particles under the following test method. The hy~oscopicity value required for the present i~ ~ particulate c~. .pO~;~ ;O~c is determined by placing 2 grams of particles (app,. t ~'y 500 micron size particles; not having any moisture barrier coating) in an open cQ"~ r petri dish under con~liti~.nc of 90 ~F and 80% relative humidity for a period of 4 weeks. The percent increase in weight of the particles at the end of this time 30 is the particles hy~y~ascopicily value as used herein. Plef~,.lcd particles have hy~scoFi::~ value of less than about S0%, more p~eferably less than about 10%.
The particulate co .r~os;l;om ofthe present invention typically comprise from about 10% to about 95% ofthe carbohydrate material, p~cfe~a' ly from about 20% to about 90%, and more ~ ,ef,.ably from about 20% to about 75%. The particulate 35 co...po~l ;onC of the present invention also typically comprise from about 0% to about 90% of agents useful for laundry or cle~ning comrositions, p.ef~,&bly from about 10% to about 80%, and more plefe.~.bly from about 25% to about 80%.

1~
Porous Carrier Particles As used herein, "porous carrier particles" means any material capable of auppG~ lg (e.g., by absorption onto the surface or adsorption into pores) a p.,.rulllc agent for incol~,ordtion into the particulate compos~ n~ Such materials include porous solids S selected from the group co~ of amorphous cilic2tes~ crystalline nonlayer si layer silicates, calcium calb-~~ s, c~lci-~m/sodium c~lo double salts, sodium carbonates, clays, ~o' s, so~lqli~c~ alkali metal ph~s~ k~ 7 macr~?ù.. - zeolites, chitin mic.obc~~s~ carboxyalkylcell~lose~ carboxyalkylstarches, cyclod~ s, porous starches and mixtures thereof.
Plef~ ,d ~.r~.-lc carrier materials are zeolite X, zeolite Y and mixtures thereof.
The term "zeolite" used herein refers to a crystalline aluminosili~qte material. The alluclul~l formula of a zeolite is based on the crystal unit cell, the ~llest unit of alluul~llc represented by Mm/n[(A102)m(SiO2)y~-xH20 15 where n is the valencé of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is I to 100. Most preferably, y/m is 1 to 5. The cation M can be Group IA and Group IIA el,. -..- .1~, such as sodium, pulA~c; ~ f s;- .., and c~lri~lm The zeolite useful herein is a r Jr ~r-1ype zeolite, inrlu~ing Type X Zeolite or20 Type Y Zeolite, both with a rolnir~l pore size of about 8 Angstrom units, typically in the range of from about 7.4 to about 10 Angstrom units.
The ~IIl~ino~ zeolite materials useful in the practice ofthis invention are coll.n.c.cially available. Methods for producing X and Y-type zeolites are well- known and available in sl~ d&~ texts. P~fe.-~,d synthetic crystalline aluminosilicate materials 25 useful herein are available under the d~cign ~ion Type X or Type Y.
For ~,u.~jes of illustration and not by way of lim' "on, in a plere... d ~ .-~1;-..~ --' the crystalline al~ s licate material is Type X and is seiected from the following:

(1) Na86~A102]86-(sio2)lo6] XH2~' (II) K86[A1o2]86-(sio2)106] XH2~, (III) Ca40Na6[Alo2]g6 (Si~2)l06] XH2~ ' (IV) Sr2lBa22~Alo2]g6-(sio2)lo6] xH20, CA 022~7987 1998-12-11 WO 97/47720 PCT~US97/09972 1~
and mixtures thereof, wherein x is from about 0 to about 276. Zeolites of Formula (I) and (Il) have a nominal pore size or opening of 8.4 Angstroms units. Zeolites of Formula (III) and (IV) have a nominql pore size or opening of 8.0 Ang~l.u...s units.
In another p.ere.-~,d embodiment, the crystalline aluminos~ material is Type S Y and is selected from the following:
(V) Na56[Al02]s6-(sio2)l36] XH2~' (Vl) K56[A102]s6-(sio2)l36] XH2~
and mixture thereof, wherein x is from about 0 to about 276. Zeolites of Formula (V) 10 and (VI) have a nominal pore size or opening of 8.0 An ~ U~IIS units.
Zeolites used in the present invention are in particle form having an average particle size from about 0.5 microns to about 120 microns, p--,f, .~bly from about 0.5 microns to about 30 microns, as measured by standard particle size analysis te~ hnique.
The size of the zeolite particles allows them to be e .,~ai..ed in the fabrics with 15 which they come in contact. Once e ~ l,ed on the fabric surface (with their coating matrix having been washed away during the laundry process), the zeolites can begin to release their inco-~ù,dt~d laundry agents, especislly when ~ub;e~.ted to heat or humid c<~n~itil~n~
Inco",û. on of Perfume in Zeolite - The Type X or Type Y Zeolites to be used 20 herein p~ef~ 'sly contain less than about 15% de~J,; ~ water, more plefe.ably less than about 8% desu.L ~'le water, and most p~efe. bly less than about 5% desu.t7b'e water. Such materials may be obP~ ed by first activating/dehydrating by heating to about 150 to 350 C, optionally with reduced p.ei.;,u.e (from about 0.001 to about 20 Torr). After ~ . . the agent is slowly and Ihu~uughly mixed with the activated 25 zeolite and, opti~ qlly, heated to about 60~C for up to about 2 hours to accelet -~ equilibrium within the zeolite particles. The p~. ru.-.c/zeolite mixture is then cooled to room t~,...p~..dtul~ and is in the forrn of a free-flowing powder.
The amount of laundry agent incullJol ' ~ into the zeolite carrier is less than about 20%, typically less than about 18.5%, by weight of the loaded particle, given the limits~0 on the pore volume of the zeolite. It is to be ~ec(iE~ i7.~d, however, that the present tiOIl particles may exceed this level of laundry agent by weight of the particle, but ,ecog,.i~; ~g that excess levels of laundry agents will not be inco,pu.a~d into the zeolite, even if only deliverable agents are used. Therefore, the present invention particles may cc..,.p.i3e more than 20% by weight of laundry agents. Since any excess laundry agents 35 (as well as any non-deliverable agents present) are not hlcOI~ulal d into the zeolite pores, these materials are likely to be immediqtely released to the wash solution upon contact with the aqueous wash medh~rn W 097/47720 PCTnUS97/09972 1~
In ~dditiQn to its function of cont~inin~ ote~iting the p.,.rulllc in the zeolite particles, the carbohydrate material also conveniently serves to agglomerate multiple p~,rull.ed zeolite pa licles into agglc,---elal- s having an overall particles size in the range of 200 to 1000 microns, pl~fe...bly 400 to 600 microns. This reduces d~ctinPss 5 Moreover, it lessens the tend~,n~;y of the smaller, individual p~,. ru...ed zeolites to sift t the bottom of contsinPrs filled with granular d~,t~ t~, which, themselves, typically have particle sizes in the range of 200 to 1000 microns.

CA 022~7987 1998-12-11 W 097147720 PCTrUS97/09972 Perfume As used herein the term "pc.rL e" is used to indicate any od~,lir.,.uus materialwhich is subseq.J~ ~tly released into the aqueous bath and/or onto fabrics co..1 cted th~ h. The p.,.rull.c will most often be liquid at ambient l~,...p~,.dul~,s. A wide 5 variety of chemicals are known for p~.rl..lc uses, including materials such as aldehydes, ketones and esters. More commonly, naturally occurring plant and animal oils andn ' ~ ~ cO...~.I ish~g comrl mixtures of various çh~mirql col~ru ,~1~ are known for use as p~.ru~es. The pe.rull.es herein can be relatively simple in their con-posilirll-c or can colll~,l;se highly sophicticated co..lpl~ mixtures of natural and synthetic chPmirsl 10 COIIIpOI}~.,ta, all chosen to provide any desired odor. Typical p~.r....es can cc,-llpl;ae, for example, woody/earthy bases contq-ining exotic materials such as sandalwood, civet and patchouli oil. Tbe p~,.rulllcs can be of a light floral rra~ance, e.g., rose extract, violet extract, and lilac. The pc. ru~..es can also be formulated to provide desirable fruity odors, e.g., lime, lemon, and orange. Any rh~rniçqlly compatible material which exudes a 15 pl-- or otherwise de;~ le odor can be used in the p~ cO---rc,~ nC herein.Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-rl,.~ ~ ester pro-rl..~ances (e.g., digeranyl s~ ), hydrolyzable inOI~a liC-organic pro-La~ances, and mixtures thereof. These pro-rl,.~ances may release thep~,. Çulllc material as a result of simple hydrolysis, or may be pE~-change-triggered pro-20 rr..~ances (e.g., pH drop) or may be enzymatically 1~ ble pro-r,..~a ues.
P~ef~.l~ perfume agents useful herein are defined as follows.
For ~ .oses of the present invention compositions exposed to the aqueous medium of the laundry wash process, several ch&l .._1~. ;alic parameters of perfume molecules are illl~x)ll~t to identify and define: their longest and widest ~..easu-- ~, cross sectional area; molecular volume; and molecular surface area T!hese values are calculated for individual p~. rull.c molecules using the CHEMX program (from Chemical Design, Ltd.) for molecules in a minim~m energy conr~l as determined by the standard geometry optimi7~d in CHEMX and using -' rd atomic van der Waal radii.
Definit - r . of the parameters are as follows:
"Longest": the greatest ~ t~n~e (in Angstroms) between atoms in the molecule aug,..- -,n d by their van der Waal radii.
"Widest": the greatest distance (in Angstroms) between atoms in the molecule au~l~c~lled by their van der Waal radii in the projection of the molecule on a plane perpçn-licn~r to the "longest" axis of the molecule.
"Cross Sectional Area": area (in square Angstrom units) filled by the projection of the molecule in the plane perpendicular to the longest axis.

~(9 "Molecular Volume": the volume (in cubic Angstrom units) filled by the molecule in its minimum energy u!l.r~g. ~ n "Molecular Surface Area": arbitrary units that scale as square Angstroms (for calibration pu.~-oses, the molecules methyl beta naphthyl ketone, benzyl salicylate, and c mrhor gum have surface areas r.. easu,ing 128 + 3, 163.5 + 3, and 122.5 + 3 units ~e;>lJccli~ely).
The shape of the molecule is also i---pG~ Iallt for ;..co. ~,o.~tion. For c~ ,pl ~, a symmetric pe.f~,~.lly ~hc.ical molecule that is small enough to be included into the zeolite channels has no p.ef,.-~,d orientation and is il.co,~lated from any a~
lO direction. However, for molecules that have a length that exceeds the pore d;...enci~
there is a l)~eÇ~ ,d "a~ '~ or;Pnt~~ion" for inclusion. Cqlc~lq-tion of a molecule's volume/surface area ratio is used herein to express the "shape index" for a molecule. The higher the value, the more ~,he.ical the molec--hP
For p~ ,oses of the present invention, p~.r..."e agents . re c~ ;ri~d accord- g to 15 their ability to be i,.co.~ into zeolite pores, and hence their utility as COmr~QnPnt~
for delivery from the zeolite carrier through an aqueous en~in~.."lcnt. Plotting these agents in a volume/surface area ratio vs. cross sectil~nql area plane permits convenient cla .~ificalion of the agents in groups P -c Ji..g to their h,co, ~n~ ,ility into zeolite. In particular, for the zeolite X and Y carriers acco..li..g to the present invention, agents are 20 h~cG-~ -at~d if they fall below the line (herein referred to as the "i"co.~ .lion line") defined by the e, I
y = -0.0 1 068x + I .497 where x is cross sectionql area and y is volu...e/su.r~ce area ratio. Agents that fall below the ~ uldtion line are referred to herein as "deliverable agents"; those agents 25 that fall above the line are referred to herein as "non-deliverable agents".
For containment through the wash, deliverable agents are retained in the zeolitecarrier as a fi~nCtion of their affinity for the carrier relative to co...~ ;ng deliverable agents. Affinity is ~ d by the molecule's size, h~ ,p~ ~ ~ ity, fi~nrti~nqlhy, volatility, etc., and can be effected via interaction between deliverable agents within the 30 zeolite carrier. ~hese inte.a t on~ permit improved through the wash CO~ ....- ~.1 for the deliverable agents mixture i"co",u._ ~ Specifically, for the present invention, the use of deliverable agents having at least one dim~nc jon that is closely r~qtc~ed to the zeolite carrier pore di .~ nC-o~l slows the loss of other deliverable agents in the aqueous wash envi-~""..ent. Deliverable agents that function in this manner are referred to herein as 35 "blocker agents", and are defined herein in the volume/surface area ratio vs. cross se~Lio~~l area plane as those deliverable agent molecules falling below the "incorporation CA 022~7987 1998-12-11 W 097/47720 PCTrUS97/09972 line" (as defined h~ .~;..bcfore) but above the line (herein referred to as the "blocker line") defined by the equ~ion:
y = -0.01325x + 1 .46 where x is cross section~l area and y is volume/surface area ratio.
For the present invention composil;ol-~ which utilize zeolite X and Y as the carriers, all deliverable agents below the "h~cu~l,o.~lion line" can be delivered and released from the present invention compositionc, with the plef~ d materials being those falling below the "blocker line". Also p,cfe.,ed are mixtures of blocker agents and other deliverable agents. Laundry p~.rulllc agent mixtures useful for the present invention laundry particles p~f~ .~bly co",p,;se from about 5% to about 100%
(prefe.ably from about 25% to about 100%; more ~ f~ ~ably from about 50% to about 100%) deliverable agents; and p~ fe.ably co",~ ;..g from about 0.1% to about 100%
(preferably from about 0.1% to about 50%) blocker agents, by weight of the laundry agents mixture.
Obviously for the present invention cornpositionc wh~.et"r p~.ru~.~c agents are being delivered by the co...ros ~ n~ sensory pe~ ~t;OI) is n~lui,~ d for a benefit to be seen by the co~ . For the present invention pc. r ...,c cQmrosition~, the most p.cr. .,ed p~ .rumc agents useful herein have a threshold of noticability (-"e&su,l d as odor detection Ih,~ sholds ("ODT") under carefully controlled GC cQnrlitio~ as dcs., ;bed in detail he~hlart~ ~) less than or equal to 10 parts per billion ("ppb") Agents with ODTs between 10 ppb and I part per million ("ppm") are less l,-ef~ .,cd. Agents with ODTs above 1 ppm are preferably avoided. Laundry agent p~. Çulllc mixtures useful for the present invention laundry particles p,efe.dbly CG""~ ;se from about 0% to about 80% of deliverable agents with ODTs between 10 ppb and I ppm, and from about 20% to about 1 00% (p. cr~ . lkly from about 30% to about 100%; more preferably from about 50% to about 100%) of del;~ 'e agents with ODTs less than or equal to 10 ppb Also l,.efe..ed are perfumes carried through the laundry process and ll.e.eall- .
released into the air around the dried fabrics (e.g., such as the space around the fabric during storage). This requires movement of the p~ . rull.c out of the zeolite pores with 30 s.~l,se~lu~- l par~iti~nin~ into the air around the fabric Plef~ d p~ .rulllc agents are lL~.Gro-e further id~ntified on the basis of their volatility. Boiling point is used herein as a U.C~~ of volatility and plefe.- cd materials have a boiling point less than 300 C. Laundry agent perfume mixtures useful for the present invention laundry particles p.~ir~. bly cu---~ -;se at least about S0% of deliverable agents with boiling point less than 300 C
35 (p.ef~.ubly at least about 60%; more preferably at least about 70%).

In addition, I,.c f,.,~,d laundry particles herein comprise co...posilions wherein at least about 80%, and more preferably at least about 90%, of the deliverable agents have a "ClogP value" greater than about 1Ø ClogP values are obtained as follows.

W O 97/47720 PCT~US97/09972 Iq Calculation of ClogP:
These p~ . rulllc ingredients are chal~ ed by their octanoUwater partition coGlrcienl P. The octanol/water partition coefficient of a pe. rulllc ingredient is the ratio between its equilibrium co~c~ alion in octanol and in water. Since the partition5 co.,rf,ci~ t~ of most p~. rulllc h~.edi.,.lt~ are large, they are more conveniently given in the form of their logarithm to the base 10, logP.
The logP of many perfume ingredients has been ~~"o-t~,d; for eA~..plo, the Pomona92 database, available from Daylight Chemical Information Systems, Inc.
(Daylight CIS), contains many, along with citq-tionc to the original literature.However, the logP values are most conveniently cqlc~lst~d by the "CLOGP"
program, also available from Daylight CIS. This pro~;l~" also lists ciA~.;.lle.lti l logP
values when they are available in the Pomona92 flqtqh-~cç The "cqlc-~ logP" (ClogP) is determined by the r,~.~..c..l app,uach of Hansch and Leo (cf., A. Leo, in CG...~,lehensive ~e~lici ~l Chemistry, Vol. 4, C. Hansch, P.G. Sq~nmPnc, J. B. Taylor and C. A. ~qmcden, Eds., p. 295, Pergamon Press, 1990). The rr.. ~l.,.~t approach is basèd on the ~1~ ~micql ~b ~ ..e of each p~ . rulllc ingredient and takes into account the numbers and types of atoms, the atom co~ e~ dty, and chP ni~sl bor~lin~ The ClogP
values, which are the most reliable and widely used ~ ~ ~ s for this phy~;coch~,nlical property, can be used instead of the ~;Ape. i,n~ l logP values in the sele~ I ;on of p~,. ru~lc 20 i~ t ..
Determination of Odor D~,t~l;on Thresholds:
The gas chrom~lu~aph is cha~ ,d to determine the exact volume of material injected by the syringe, the precise split ratio, and the hyJloc~ul,ùl) ,~ onsc using a hydrocarbon standard of known con~ . aLion and chain-length distribution. The air 25 flow rate is ac~ u, ly lc~wu.~d and, qCCIImin~ the duration of a human inhql~~ion to last 0.2 m- s, the sampled volume is cqlc~lqted Since the precise cv ~c~--t.dtion at the detector at any point in time is known, the mass per volume inhaled is kno~,vn and hence the c, --ntration of material. To determine whether a material has a threshold below 10 ppb, solutions are delivered to the sniff port at the back-cqlc~lsted COl c~ alion. A
panelist sniffs the GC effluent and identifies the retention time when odor is noticed.
The average over all F ~' s~c determines the threshold of nvti~ --bility.
The necessary arnount of analyte is injected onto the column to achieve a 10 ppbconc~ ~ 1- dtion at the detector. Typical gas chromatograph pal. ~ for determining odor detection thresholds are listed below.
GC: 5890 Series 11 with FID detector 7673 ~lltoqsnlpler Column: J&W Scientific DB-I

CA 022=,7987 1998-12-11 W O 97/47720 PCTrUS97/09972 Length 30 meters ID 0.25 mm film thirkn~occ 1 micron Method:
Split Tnject;on 17/1 split ratio Autl~s pler: 1.13 microliters per injection Column Flow: 1.10 mL/minute Air Flow: 345 mL/minute Inlet Temp. 245~C
Detector Temp. 285~C
Temperature In~, Initial Temp~.atu,c; S0~C
Rate: SC/minute Final Tc.n~)~,dt-..e: 280~C
Final Time: 6 minutes 1 e~ ~- g S ~ tiorlc: 0.02 minutes per sniff GC air adds to sample dilution . ru,..c Fixative:
Optionally, the perfume can be combined with a p.,.rulllc fixative. The perfume fixative materials employed herein are chal~ct~ ~izcid by several criteria which make them especiqlly suitable in the practice of this invention. Dispersible, toxicologically-accept-able, non-skin i" il~ting, inert to the p~.rull~c, de~ hle and/or available froml . nc ~. able I csources, and ~ ely odorless additives are used. Perfume fixatives are believed to slow the c., ~ ~sn of more volatile co.,.pon~ llt~ of the p.,. rulnc.
Examples of suitable fixatives include members selected from the group concicting of diethyl pht'r~l~te musks, and mixtures thereof. If used, the pc.run.e fixative COIll~n;:~eS from about 10% to abut 50%"v,~Ç~,. bly from about 20% to about 40%, by weight, of the p~.rul~lc.
Pi~nents A pi&J"~-~t is used in the instant process and may include any particulate matter that is insoluble in, and ~cc~nti~lly physically and ch~omic~lly un~ffPcted by, the e ~ tin~
media (e.g. carbohydrate) into which it is di~p~ . ~ed. The following lists examples of pi~m~ntc by their commonly used names, suitable for use in this process. More extensive lists are published in the liL~ e (e.g. in the Pigment Handbook vol. 1., edited by Temple C. Patton, published by John Wiley & Sons, Inc., 1973, ISBN 0-471-67123~
Useful pigments include titanium dioxide, zinc oxide, leaded zinc oxide, zinc sulfide, lithopone, basic lead carbonate, basic lead sulfate, basic lead silicate, basic lead silica sulfate, dibasic lead phoshite, antimony oxide, zirconium oxide, zircon, potassium titanate, calcium cal'L,orlaLe, amorphous silica, crystalline silica, ~i~tom~ceous silica, W O 97/47720 PCTrUS97/09972 microcrystalline silica, ~,le~ tcl silica, pyrogenic silica, synthetic silica, ~ nn jn silicate, calcium silicate, sodium alumino silicate, m. g~r,$;~ silicate, olllmininnl pot~ssi-..-, silicate, nepheline syenite, hydrated l..sL..e,i~ lminhlm silicate, barium sulfate, calcium sulfate, hydrated i lllmini~ n oxide, diotomaceQus calcite, pumice, calcium 5 s~llrh~lolu~ninate, perlite, light alumina hydrate, iron oxide, zinc ferrite, I ~ e7;~.... ferrite, chromium oxide green, hydrated chromium oxide green, lead chromate, lead silica chromate, molybate orange, chrome green pigments, cadmium sulfide, mercury sulfide, rc.lif~.lù~anide pi~-~P- l~ ultramarine P;v~ llc~ulic sulfide, nitroso pigment, nitro pig,lllent~ n~on~ o P ~~ , diazo P~v n~, disazo ~ , triphenyln~-t~ PiV..- .~t~
10 diphenyl~ lh~ pi~ trimethylm-,thsnçpigments,phloYine ~~Ih r~r, quinacridones, quinoline pi~ , diazine violet, al h~c Iake PiV..- ~~l~ vat pig...~nlc, thioindigo p,g"-P -1~i, rht~ok~cycnine blue piEmPntc~ phtholocycnine green pigments, carmine p.~"- P -1~ tetrachloroisoindolinones, carbon black P;v~ , graphite, iron oxide, copper chromite, aniline black, trilead tetraoxide, basic lead silico ch~ ~ zinc cl~ s,15 strontium chromates, calcium molybdate P~v -~ - ~c, calcium pl rnt~ ,ous pi~ .~ m ~, lUl--;n ~c~--l pi~m~ntC, optical blig' a, cuprous oxide, InC.~ l;C oxide, bariummetaborate.
Adiunct LaundrY or Cleanin~ Ing~d;e.,l~
Adjunct ingredients useful for in or with the laundry or cleaning particulate 20 co..lpoail;ons according to the present invention are selected from the group CQfi';'l ;-~g of :~JI r ~ntc, ~.rUlllcs~ b!~ P ~ - s, bleach promoters, bleach activators, bleach catalysts, chelants, antiscalants, threshold inhibitors, dye transfer inhibitors, photobleaches, enzymes,catalytico~tibo~liec brighteners,fabric-s.,b~ edyes,z.ltiru,lgdls, antimicrobials, insect repell~ntc soil release polymers, fabric softening agents, dye 25 fixatives, pH jump systems, and mixtures thereof. As can be app- cc - t~ ~ for the present hl~ iu.l, these agents useful for laundry or cl~ g compositionc which are i,.co. ~,u- ated into the particulate CGIl~pO5 il ;~nC of the present invention may be the same as or di~..,.ll from those agents which are used to formulate the remoin~-~ of the laundry and cl- g coml~o~;l;ol-s cQr~t--ining the particulate compositions pludùced by 30 the instant process. For example, the particulate conlro,:~ ;onc may COIIIIJI ;se a perfume agent and the same or dirr~ agent may also be blended into the final con.ros;~
along with the p~,.ru...c cQnt--ining particulate cr...rosil;on These agents are selected as desired for the type of culllpGailion being forrnll~ A such as granular laundry d~,t~,.g~
colllpGailions, granular autc-~ - dishwashing composili~",s, or hard surface cleaners.
The various types of agents useful in laundry and cl-- ing co",posilions are des- lil,cd hereinafter. The cQ.-.ros:~;ons CGu~ g particulate co...l~Qs;l;onc can optionally include one or more other d.,t-rg~ adjunct materials or other materials for W O 97/47720 PCT~US97/09972 accictine or enhr ~ ., cl~~nin~ p~,.ro----~ce, treatment of the substrate to be cleaned, or to modify the ~esthetirs of the d~,t~ comrosition Detersive Surfactant The granules and/or the aEgiG P'~ ~tes include surfachnts at the levels stated 5 previously. The detersive surfactant can be selected from the group co.~ g of anionic surfactants, n~ni- niC surfactants, cationic surfactants, zwitterionic surfactants and mixtures.
~Jonlimiting examples of surfactants useful herein include the co--~enlional C l l -C 1 8 alkyl e sulfonates ("LAS") and primary, b-~.~ched-chain and random Clo-C20 alkyl sulfates ("AS"), the C1o-C18 seconda. y (2,3) alkyl sulfates ofthe formula CH3(CH2)X(CHOSO3 M ) CH3 and CH3 (CH2)y(CHOSO3 M ) CH2CH3 where x and (y + I ) are integers of at least about 7, prcf~ ly at least about 9, and M is awater-solubilizing cation, ecpec~qlly sodium, IJ..satl-.dt~,d sulfates such as oleyl sulfate, the Clo-Clg alkyl alkoxy sulfates ("AEXS"; ecrecislly EO 1-7 ethoxy sulfates), Clo-CIg alkyl alkoxy carboxylates (especislly the EO 1-5 ethoxycarboxylates), the C!0-l8 glycerol 15 ethers, the Clo-C1 8 alkyl polyglycosides and their COIl~Sr_ ~ n~ sulfated polyglycosides, and C 12-C 18 alpha-sulr- ~~ t d fatty acid esters. If desired, the c ~ ional nonior ic and , ' cte~ic ~u- r ' ~C such as the C12-C1g alkyl ethoxylates ("AE") int~lllAing the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/~,ropo~-y), C12-C1g betaines and sul~,b~ es ("snltsinçs"), 20 C1o-CIg amine oxides, and the like, can also be incl~ded in the overall co...pos;~ c The Clo-C1g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examplesinclude the C12-C1g N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1o-C1g N-(3-,LI.(,Aypropyl) glucamide. The N-propyl through N-hexyl C12-CIg ~lucornides can be 25 used for low sudsing. Clo-C20 co..~ tional soaps may also be used. If high sudsing is desired, the branched-chain Clo-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are ~speci~ 'ly useful. Other conventional useful surfactants are listed in standard texts.
The Clo-CIg alkyl alkoxy sulfates ("AEXS"; ecreciolly EO 1-7 ethoxy sulfates) 30 and C 1 2-C 1 8 alkyl ethoxylates ("AE") are the most p-~ f~ ,d for the celllllqce-co..~ g d~ t-,.~nts d~sc. ibed herein.
Detersive Builder The granules and ~gglor..."~tes plc-fc. ~ly include a builder at the previously stated levels. To that end, inorganic as well as organic builders can be used. Also, crystalline as 35 well as a.--~ hous builder materials can be used Builders are typically used in fabric la.u~d.,.ing co~..roC;l;~-nc to assist in the removal of particulate soils.

Inorganic or P-con~sining dctc~ builders include, but are not limited to, the alkali metal, ammonium and al' -la..,.,lonium salts of pol~,ho,~h -t- s (exemplified by the tripolyphosphates, pyrcphcsr'- s, and glassy polyrneric meta-pl-- s~.h .t~ q), phosphor -c phyticacid,sil~ ~ cdlbu - c(i-~ch~lingbicarbonatesand 5 sesquic~-l,onat-,s),s ~p~- s,andsll~m ~~slirates. However,non-pho.~' buildersare ui,cd in some locales. Il..po.l~.tly, the compos;~ -c herein function ~u"" gly well even in the plcsence ofthe so-called "weak" builders (as cc r cd with phc "'~ ~) such as citrate, or in the so-called "under built" situation that may occur with zeolite or layered silicate builders.
F , les of silicate builders are the alkali metal silicstes~ particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered cili- te s, such as the layered sodium silicates dci- ,.bcd in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
NaSKS-6 is the l. ~-mqrk for a crystalline layered silicate marketed by Hoechst (c~,.. only abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate 15 builder does not contain ~ min--m NaSKS-6 has the delta-Na2SiOs morphology form of layered silicate. It can be prepared by methr~c such as those des_l;bed in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly p,ef.,.,~ layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSixO2x+l yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, pf.,f~. bly 2, and y is a number from 0 to 20, p,cl;.. ,bly 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS- I I, as the alpha, beta and gamma forms. As noted above, the delta-Na2SiOs (NaSKS-6 form) is most p~fe.,~d for use herein. Other silicates may also be useful such as for e.~h,nple...~.r~i--..
silicate, which can serve as a criepenin~ agent in g, --l form~ ionc as a stabilizing agent for oxygen bl ~ ;, and as a CO~pûC~ t of suds control systems.
E~u,.~l r ~ of carbonate builders are the alkaline earth and alkali metal calb~ -- s as A;c~loSed in German Patent Application No. 2,321,001 p~bliahed on November 15, 1973.
As m~ntior~d previously, aluminosilicate builders are useful builders in the present hl~ hl~ninreilirste builders are of great importance in most cu~c~lly marketed heavy duty granular d~,te.~- nt co",posiLions, and can also be a si~-ir~c~nt builder inb,~,J;e.
in liquid d~,tc.ge.lt form--lstionc ~lllminosilicate builders include those having the empirical formula:
MZ(zA102)y] xH2o wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful ~lllmino5ilicate ion eY~' g~ materials . re cc~ "~rcially available. These aluminosilicates can be crystalline or amorphous in ~I~uClu~c and can be naturally-CA 022~7987 1998-12-11 ~y occll-l;ng al~minosili~~~s or synthPtic~lly derived. A method for producing al~inosilir~te ion eYc~- ~e materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline ~ minosilir~t~ ion eY~ ~e materials useful herein are available under the decigrstionc Zeolite A, Zeolite P (B), 5 Zeolite MAP and Zeolite X. In an ~Cpeciqlly p-cir~ d embo~im~nt the crystalline m jnosil - ion eY~ - ng~ material has the formula:
Na 12[(AIO2) 12(si~2) 12] ~XH2O
wherein x is from about 20 to about 30, eCpeciqlly about 27. This material is Icnown as Zeolite A. Dehydrated zeolites (x = O - 10) may also be used herein. Plef~. ',ly, the 10 ~luminosili - has a particle size of about 0.1- 10 microns in diameter.
Organic det~ nl builders suitable for the p~ .osc s of the present ;..~el.lion include, but are not l~;.b iclc~d to, a wide variety of polycarboxylate co...poul.ds. As used herein, "polycarboxylate" refers to co-.-pou--ds having a plurality of carboxylate groups, ~.ef~,, bly at least 3 carboxylates. Polycarboxylate builder can generally be added to the 15 c~ po .ilion in acid forrn, but can also be added in the form of a neutralized salt. When utilized in salt forrn, alkali metals, such as sodium, pol; ssi ~ .. and lithium, or alkanolan....o ~ - - salts are p-tl~ .d.
Included among the polycarboxylate builders are a variety of CategOI;ei of useful materials. One i-..po, la.ll category of polycarboxylate builders ~ c ~ "r ~ the ether polycarboxylates, inc~ lin~ oxyd;c.,cc ;--~t~, as tlicclos~od in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972.
See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic cG...r~u-.Ac, particularly alicyclic co--.pu~ , such as those desc,ibed in U.S. Patents 3,923,679; 3,835,163; 4,158,635;

4,120,874 and 4,102,903.
Other useful d~,ter~ncy builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy ~.~z.,nc-2, 4, 6-l-.~-~lp~ e acid, and carboxymethyloxysuccinic acid, the various alkali metal, ~ ; .. and s--b~ d ammonium salts of polyacetic acids such as 30 ethyl~ ,~f ~1 i - -in~ tehaac~ lic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid d~ t~ . eul 35 formnl~ti~nc due to their availability from renewable resources and their biode~adâbility Citrates can also be used in ~ranular compositions, especi~lly in combination with zeolite W O 97/47720 PCT~US97/09972 ~5 andlor layered silicate builders. Oxydisucch,at. s are also especiolly useful in such Co!..ro~;~;nl,c and combinations.
Also suitable in the d~ t-,. E,_nl co.,lposilions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hf ~ ~' ~ ~I s and the related co...pou--ds ~isclosed in U.S. Patent 4,566,g84, Bush, issued January 28, 1986. Useful succinic acid builders include the Cs-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly p,.,fe.,Gd comr_ of this type is dodece"ylsuccinic acid. Specific examples of s-lcc builders include:
laurylsuccinate, myristy6~ c~ -, palmitylcuccinqte~ 2-dodcc~ lsuccinate (pnGfe..~d), 2-p 'e. ylsuccinate,andthelike. Laurylcu~ arethe~"ef~,.,Gdbuildersofthis group, and are desc,ibed in European Patent Application 86200690.510,?0Q ?63, published NovemberS, 1986.
Other suitable polycarboxylates are ~licclosed in U.S. Patent 4,144,226, C.- ~- l-fi~d et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.
See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., C 12-C 18 monocarboxylic acids, can also be i"co, t~~~ 1 ~ into the cu~uros ~ c alone, or in combination with the aforesaid builders, çspecislly citrate and/or the su~ ci- builders, to provide r ' ~ ' ~ ~ I builder activity. Such use of fatty acids will generally result in a ~iminlltion of sudsing, which should be taken into account by the formulator.
In - where phos~ o~us-based builders can be used, and especiqlly in the formulation of bars used for hand-l..~ "d~,. ing ope. ~ - - s, the various alkali metal phosphl s such as the well-known sodium tripolyphQsp~ s, sodium py,uphos~ and sodium ortho~ ,k-~e can be used. Phos~i on ~t~, builders such as ethane-l-hydroxy-1,1-~iphosFhnnate and other known pho~phon~ s (see, for example, U.S. Patents 3,159,581;
3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
EnzYmes One such adjunct i..~lGdi.~ are enzymes which can be ineluded form~ tinnc herein for a wide variety of fabric l. u"d~,. i"g pu"Joses, including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and for the prevention of 30 refugee dye transfer, and for fabric ~1 ;,t~_ on. The ~ iti~nql enzymes to be i.-co.~,o,~t~,d include cellulases, l"vl~ases, amylases, lipases, and peroYi-l~sec, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as v~O I ' le, animal, bacterial, fungal and yeast origin. However, their choice is govemed by several factors such as pH-activity and/or stability optima, themmostability, 35 stability versus active d~ t.,.~ , builders as well as their potential to cause malodors during use. In this respect bacterial or fungal enzymes are p~efe.,.,d, such as bacterial arnylases and pr-~lGases.
-W 097/47720 PCTrUS97109972 a~
Enzyrnes are normally incorporated at levels sufficient to provide up to about S mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the col.lpo~;l io~
Stated otherwise, the cornrositions herein will typically cG.ul,.;se from about 0.001% to about 5%, p~er~.ably 0.01%-1% by weight of a cGllllll~.cidl enyme preparation. P~ ~ enzymes are S usually present in such coll.ll.~.cial u~pr dlions 8t levels ~ l to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of compositinn The ce~ ce suitable for the present invention include both bacterial or fungal ce~ lqc~
P~ef~,. bly, they will have a pH optimum of between 5 and 9.5. Suitable cell--lqc~c are ~icclosed in U.S. Patent 4,435,307, Bal L esg~ ~1 et al, issued March 6, 1984, which dicrl~ses fungal ce~ lsce 10 pludu-,ed from I' . s ~1~7 insolens and I'- - . cal~r strain DSM 1800 or a celllllqce 21 2-~luduCil~g fungus belo~ to the genus At ,, ~..~, and cell'-lqce eAIla~,led from the ~ep~t~p - ~ ~s of a marine mollusk (DoJabella Auricula So~ er), suitable cellul. ses are also fli~closed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. In addition, cellula e ~Cpeciqlly suitable for use herein are disclosed in WO 92-13057 (Procter & Gamble). Most p,er,.dbly, the cellulases used 15 in the instant d.,te.~ 1 c~ o~;l;o~c are ~u..,hased cu...l,le..,;ally from NOVO Indus~ s A/S
under the product names CAREZYME~ and CELLUZYME~.
Suitable exarnples of plot~,~es are the suhtilicinc which are obtained from particular strains of B. subtilis and B. Iich_,.ifo, ..~. Another suitable p10t~ ase is oblai..ed from a strain of B~rl~u~ having maximum activity Ihrùu~l-out the pH range of 8- 12, deiclûp~d and sold by Novo Ir.ul.lall;.s A/S under the l. g - e~ trade name ESPERASE.
The preparation ofthis enzyme and '9n91ogovC enzymes is des_.;bed in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASL by Novo Industries A/S (Denmark) and MAXATASE by International Bio-synth~tirc~ Inc. (The N et, lal~ds). Other ,~l- ~~ include Pl~tease A
~see European Patent Application 130,756, published January 9, 198S) and P~ut~ ~se B (see European Patent ~rpl ~ ~ ~ Serial No. 87303761.8, filed April 28, 1987, and European Patent Al-p' on 130,756, Bott et al, publislled January 9, 1985).
Amylases include, for exarnple, a-arnylases des~l ;bcd in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synth~ ti~e, Inc. and TERMAMYL, Novo Ir..lual.;cs.
Suitable lipase enzyrnes for det.,.gc.ll usage include those ~.uduced by microo. ~,&~i~---S of the Pseu(lo~on~ group, such as Pseudc ~JI~ stutzeri ATCC 1 g. l 54, as ~iicclosçd in British Patent 1,372,034. See also lipases in Jap~ ~~se Patent Apl l;cdtiun 53,20487, laid open to public inepection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd.~ Nagoya, Japan, under the trade name Lipase P"Amano," he.~i;..ar~r referred to as "Arnano-P." Other c~ nc..;.al lipases include Amano-a~
CES, lipases ex Chl'u~oba viccos~m, e.g. Chromobacter ~ Cos. . var. Iipolyticum NRRLB 3673, cc...l..e..,;ally available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter visco~unl lipases from U.S. Biocllernicql Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex P~ ~ ~.. gln~ioli The LIPOLASE enzyme derived from II- ~ln Id,.J~ sa and co.l,l,.e.~iially available from Novo (see also EPO 341,947) is a ~)~f~ d lipase for use herein.
P~.u-~ida3e enzymes are used in combination with oxygen sources, e.g., per~,~ I" p~,.l,o~at~" persulfate, hydrogen peroxide, etc. They are used for "solution bl ~ ~ '~ ing," i.e. to prevent transfer of dyes or pigments removed from ~ L,dt~i, during 10 wash ope-tions to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for e~..ple, horseradish peroxidase, li~inqcç, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-contqining d~,t~ co---po~ - aredisclosed, for example, in PCT I ~ - onal Application WO 89/099813, published October 19, 1989, by O. Kirk, ~ec;~-~d to Novo InJ.~ ,s A/S.
A wide range of enzyrne materials and means for their i.,cc.-~,u- c:- into synthetic d-,t~ l comros;tionc are also ~Iic~losed in U.S. Patent 3,553,139, issued January 5, 197 to McCarty et al. Enzymes are further dicclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both.
Enzyme materials useful for liquid d~,t~,r~nl formulqtionc and their i..co.~,o.~lion into such form--lqtinnc are ~I; ~c loseJ in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981.
Enzymes for use in d~.t~ t~ can be stabilized by various tecllniques. Typical granular or pu~.d.,.- d dete.gc.~b can be stabilized effectively by using enzyrne granulates. Enzyrne stabilization terhni~ln~c are dicclosed and exemplified in U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also desc.il~d, for example, in U.S. Patent 3,519,570. Pol~nneric Soil Release A~ent Any polymeric soil release agent known to those skilled in the art can opti~nqlly be e.ll~l .y~,d in the con~l~or:' ;n ~c and p.ocess~,s of this invention. Polymeric soil release agents are ch~ d by having both hydrophilic se~ to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hyd,uphob.c se~ c, to deposit upon hyd-uphobic fibers and remain adhered thereto through co.,.pl(: r 1 of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic sc~..~..ts. This can enable stains oc-,u..i-.g ~ u-n~ to lreal...~ with the soil release agent to be more easily 35 cleaned in later washing p,ocedu.~ s.
The polymeric soil release agents useful herein especi-qlly include those soil release agents having: (a) one or more nonionic hydrophile components consisling escenti~lly of (i) W O 97t47720 PCT~US97/09972 polyoxyethylene seg,..~ . with a degree of pol~ll.c. ;~,lion of at least 2, or (ii) oxypropylene or polyoxypropylene se~ with a degree of polymerization of from 2 to 10, wherein said hydrophile se~;,.- 1l does not c-~co...pA5s any oxypropylene unit unless it is bonded to a~jacc.lt moieties at each end by ether 1 I--ag~, or (iii) a mixture of oxyalkylene 5 units co...~ h~g oxyethylene and from I to about 30 oxypropylene units wherein said mixture contsinC a s~ffici~nt amount of oxyethylene units such that the hydrophile cO-..i)Q ~ 1 has hydroFhilir;ty great enough to increase the hydrophilicity of conventional polyester synthetic fiber ~u. ~ ~ ~ upon deposit of the soil release agent on such surface, said hydrophile se~ p.ef~,lably COIlllJl ;Shlg at least about 25% oxyethylene units and 10 more ~"ef~.~bly, çspecisl~y for such u....~o ~ having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more h~dlophobc co~-po~
COlllpl ;sin~ (i) C3 oxyalkylene t~,.epkl~sl se~.~-c-~1~ wherein, if said hyd~ophobe cGIllponc .1l~ also comprise oxyethylene t~l~,ph~ t~, the ratio of oxyethylene tc.epkll.sl-ste C3 oxyalkylene ~ units is about 2:1 or lower, (ii) C4-C6 alkylene 15 or oxy C4-C6 alkylene se~ , or Illi~lUl~S therein, (iii) poly (vinyl ester) S~ r ~
preferably polyvinyl acetate), having a degree of pOIylllCl ;~tion of at least 2, or (iv) C l-C4 alkyl ether or C4 hydroxyalkyl ether s~,h,~ t~, or mixtures therein, wherein said substituent~ are present in the form of C I -C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures therein, and such cellulose derivatives are Amphirhilic, whéreby 20 they have a ~ ici~ -~ level of Cl-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon cu~ nlional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such con~clllional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).
Typically, the polyoxyethylene segrn~ntC of (a)(i) will have a degree of 25 polymerization of from about 200, sltho~gh higher levels can be used, ple(~ldbly from 3 to about 150, more ~r~f.._~ly from 6 to about 100. Suitable oxy C4-C6 alkylene hydluphobe s~ t~ include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH2O-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
Polymeric soil release agents useful in the present hl~rel-tion also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene lcl~pk~ 9te or propylene l~,lcph l~91A~A with polyethylene oxide or polypropyléne oxide tcro,l ths-lste and the like. Such agents are collll..clcially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for 35 use herein also include those selected from the group consi~lillg of C I -C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.

CA 022~7987 1998-12-11 W O 97/47720 PCTrUS97/09972 as Soil release agents Chal~tC~;Led by poly(vinyl ester) h~d-ophobe segm- ~ includegraft copolymers of poly(vinyl ester), e.g., C l -C6 vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide b~c~honloc, such as polyethylene oxide bacl~horlPs See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al.
S Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
One type of p~er~ ,d soil release agent is a copolymer having random blocks of ethylene t~ h~lDtç and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 2S,000 to about 55,000.
See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
Another l,lef,.,~d polymeric soil release agent is a polyester with repeat units of ethylene te.~klh~l~9-te units cont-s-in~ 10-15% by weight of ethylene l~ lst~ units luge~ with 90-80% by weight of polyoxyethylene t~ hCla~ units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the cul~ ;ally available material ZELCON 5126 (from DuPont) and MILEASE
T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to GOSJ~
Another ~,.ef~.-ed polymeric soil release agent is a sulfonated product of a s~lb - -lly linear ester oligomer co...,~ ed of an oligomeric ester ba-'-b~ - ofte.~,~Jhtl-aloyl and oxyalkyleneoxy repeat units and terminal moieties covalently ~ to the bacl~bûne. These soil release agents are des~,l;bed fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosseiink Other suitable polymeric soil release agents include the te.epllll.alate polyesters of U.S. Patent 4,71 1,730, issued ~c.,---bel 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S.
Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric co...~unAc of U.S. Patent 4,702,857, issued October 27, 1987 to Go~celin~
F~,f~ d poly ic soil release agents also include the soil release agents of U.S.Patent 4,877,896, issued October 31, 1989 to ~s~ -r ~d- et al, which discloses anionic, esl~ecislly sulfoarolyl, end-capped t.,.~.h~ esters.
If utilized, soil release sgents will generally COIIIPI ;se from about 0.01% to about 10.0%, by weight, of the d~,te.~ t compositions herein, typically from about 0.1% to about . 5%, preferably from about 0.2% to about 3.0%.
Still another plef~ d soil release agent is an oligomer with repeat units of tereFhthsloyl units, sulÇoisol~ Jllll,aloyl units, oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form the b~bone of the oligomer and are p~f~.ably terminated with morlified i~.o,thionste end-caps. A particularly ~I - f~ d soil release agent of this type colll~...ses about one sulfoisophthaloyl unit, S t, .~phll.aloyl units, oxyethyleneoxy and oxy-W 097/47720 PCT~US97/09972 1,2-propyleneoxy units in a ratio of from about 1.7 to about 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy) ~ s~lfonate. Said soil release agent also CO.,.~,l ises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group con~ieting of xylene sulfonate, cumene sulfonate, 5 toluene sulfonate, and mixtures thereof.
Alkoxylated polycarboxylates such as those p.epal~;d from polyacrylates are useful herein to provide a~ l grease removal performance. Such materials are desc..bed in WO 91/08281 and PCT 90/01815 at p. 4 et seq., hlcol ~IOl dted herein by ~~f~ ,nce.
Chemir~lly, these materials co."l - ;se polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type sllu~,lul~;. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can co".~,. ;se from about 0.05% to about 10%, by weight, of the co..,po~ ;~ ;onc herein.
SudsS~ so.s Co...pou.lds for ,~,.luc.~g or su~ ssing the forrnation of suds can be i..cu.~,o. ~ ' into the co~r~s~ nc of the present invention. Suds ~up~"ci;,sion can be of particular impull~.rlce in the so-called "high col-ce- '~alion cle~ning process" and in front-loading Euro~ ~ style washing ~ ' -A wide variety of materials may be used as suds ~u~ . esso. ~, and suds ~u~ 5G
are well known to those skilled in the art. See, for eY rle Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds ~u~,pressor of particular interest ellCC ---r - ~ ~ monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monoca.l~Aylic fatty acids and salts thereof used as sudsSUP~ SOI typically have hyd,ocLl,yl chains of 10 to about 24 carbon atoms""~f,. ~Iy 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potai. .iu--., and lithium salts, and ~mmoni~m. and alkanolammonium salts.
The d~,t~,.ge.~t c.. ~s;tior~ herein may also contain non-surfactant suds 30 ~U~ 5Ul~. Theseinclude,forexample: highmolecularweighthy~,ocal,onssuchas paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, alipl c Clg-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino l,;~ines such as tri- to hexa-alkylmel~min~s or di- to tetra-alkyl~ nine chlo- ll ia i..cs formed as products of cyanuric chloride with two or three moles of a primary 35 or secondary amine cont~ining 1 to 24 carbon atoms, propylene oxide, and monost. a.yl rho5~h t 5 such as l..~no~learyl alcohol rhosph~te ester and mono~t~,a.;l di-alkali metal (e.g., K, Na, and Li) phos~ c and phosph~te esters. The hydrocarbons such as paraffin 3~
and halo paraffin can be utilized in liquid forrn. The liquid hy~ ~ bOIIS will be liquid at room t.,..lp~ UlG and atmo~l c.;c plG.~:~UlG, and will have a pour point in the range of about -40~C and about 50~C, and a minim boiling point not less than about 110~C(atmospheric plG~:~U~G). It is also known to utilize waxy hyd.ocg~l,ons, preferably having a 5 melting point below about 100~C. The hydrocarbons co,.slil~"~ a pl~,f~,..Gd ~ ~c, y of suds supplessor for d~,t~,r~e.ll colllposilions. H~J..~c~l,ull suds su~/ylG~svl~ are de3c.;bed, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. Thehydlw&lons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term"paraffin," as used in this suds aUt)lJ~G~SOl d;QCUCr;' , ;S ' ' '~ i to include mixtures of true paraffln and cyclic hydrocarbons.
Another l,.efe.-~d category of non-~- - r ,~gnt suds aupplessol~ co.,.~ es silicone suds ~UplJlG~ This category inrlu-les the use of pol~ s loYgnç oils, such as polydimethylcil - di~ ions or emulsions of POI~U~L 4 ~1~ - oils or resins, and comb;nalions of pol~,o.g,~ o~ Y - with silica particles wherein the POI~OIL ~ -iS
~h~micorbcd or fused onto the silica. Silicone suds , r 'eS301a are well known in the art and are, for example, dicclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9,1,ublial.ed February 7, 1990, by Starch, M. S.
Other silicone suds suyple33~n~ are d;ccl~ed in U.S. Patent 3,455,839 which relates to cû-..pG~il;ol s and plUC6SS~s for defoaming a, e~ ~ solutions by inco.~,u. g therein small amounts of polydimethylsiloxane fluids.
Mixtures of silicone and ~ J silica are described, for inctsnce, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular d~.t~ t cu.. ~ on~ are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, RagincL-i et al, issued March 24, 1987.
An exemplary silicone based suds ~upp~ O~ for use herein is a suds ~ul")~ss;ng amount of a suds controlling agent CQn~ ;n~ es~ntigîly of:
(i) polydimethyl~ - - fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per l 00 parts by weight of (i) of siloxane resin coll.po3ed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from about 0.6: I to about 1.2: 1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the plefe.l~,d silicone suds s..pl)le~ol used herein, the solvent for a continnQus phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol W O 97t47720 PCT~US97/09972 3~
copolymers or mixtures thereof (I,lef~ d), or polypropylene glycol. The primary silicone suds ~up~-essor is branched/cros~lin1~ed and plef,.ably not linear.
To illustrate this point further, typical liquid laundry d~tc.~ t compositisne with controlled suds will c,~ ly comprise from about 0.001 to about 1, ~.~Ç.,._bly from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5, weight % of said silicone suds su~ sor, which co...~,.13es ( I ) a non~ ous cl..ulsion of a primary antifoam agent which is a mixture of (a) a polyorga ~oeilo e, (b) a lesL~ous cil- ~ or a silicone resin-producing silicone cc,...pou.~d, (c) a finely divided filler material, and (d) a catalyst to ~lUlllOt~ the reaction of mixture c~n..l one.lts (a), (b) und (c), to form sil ~!~tes 10 (2) at least one r D ic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room h.~p~.alule of more than about 2 weight %; and without polypropylene glycol. Similu ~mol-nte can be used in granulu co. ~ros;~ ione, gels, etc. See also U.S. Patents 4,978,471, Starch, issued Dece~bç~ 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., issued Februuy 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column I, line 46 through column 4, line 35.
The silicone suds su~p.essor herein l~lef~.a~ly cu---~,J-ses polyethylene glycol and a copolymer of polyethylene glycoUpolypropylene glycol, all having un average ~le~ ' -weight of less than about 1,000, ~,.ef. .ubly between about 100 and 800 The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, ~, ~,f~ ~ak ly more than about 5 weight %.
The ~.ef~ ;d solvent herein is polyethylene glycol having an average moleculu weight of less thun about 1,000, more ~.cf~.ably between about 100 and 800, most~.ef~,.ably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. ~-,f~ . l ed is a weight ratio of between about 1: 1 and 1: 10, most p~efc ' Iy t~h _~,.. I :3 und I :6, of polyethylene glycol:copolyrner of pol~-lhyl~e pol~,.o~lene glycol.
The ~,.cfe.-~;d silicone suds su~ "o-~ used herein do not contain polypropylene glycol, particululy of 4,000 l.-ole; I weight. They also preferably do not contain block 30 copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
Other suds ~u~ ssu. ~ useful herein c~,...~,. ;;,e the se c ~r ~ - ry alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secon~l~ry alcohols include the C6-C16 alkyl alcohols having a C I -C 16 chain. A ,~)l ef~. . ed alcohol is 2-butyl octanol, which is 35 available from Condea under the trademark ISOFOL 12 Mixtures of secondary alcohols are available under the Irad~,.llal k ISALCHEM 123 from F.ni~ n. Mixed suds ~u~l,-e;.su-typically comprise mixtures of alcohol + silicone at a weight ratio of I :5 to 5: 1 3~
For any d~,t~,, g_.,t compositions to be used in ~ut< m~tic laundry washing m~rhinPs, suds should not form to the extent that they overflow the washing m~rhine Suds sul/p~ ola, when utilized, are preferably present in a "suds su~ c;.ahlg amount. By "suds au~ ;,sing amount" is meant that the forrnulator of the composition can select an amount 5 of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry d~,te.~,_nt for use in ~ m~ir laundry washing .- ~ h j~5.
The CQ ~1~~S ~ ;onc herein will generally CGlllpl ise from 0% to about 5% of suds au~",.c~sor. When utilized as suds aup~,,ci,aola, mnnoc ~boxylic fatty acids, and salts therein, will be present typically in - ~o~ up to about 5%, by weight, of the d~,t~ n~
o cO...l~Oi;1;~ Q- ~,cr~. bly, from about 0.5% to about 3% of fatty monocarboxylate suds auy~lci~sot is utilized. Silicone suds au~"ulci,sorj are typically utilized in ~ tQ Up to about 2.0%, by weight, ofthe det,.~.lt comrosition, although higher ~ t~ may be used. This upper limit is practical in nature, due primarily to concern with keeping costs minimi7rd and effectiveness of lower amounts for effectively controlling sudsing.
~ef,.ubly from about 0.01% to about 1% of silicone suds s~ cssor is used, more p.ef.,, ~ly from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorg~ as well as any adjunct materials that may be utilized. 1~ arYl FhD p' -~ suds aOIa are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the c~ ~C ~;on Hydrocarbon suds aUt~JICS50l~a are typically utilized in amounts ranging from about 0.01% to about 5.0%, ~Ithough higher levels can be used. The alcohol suds auppresaola are typically used at 0.2%-3% by weight of the finishedcc".... ..rosil ;r,r~c DYe Transfer Inhibil~
The co. ~po5~ of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the Clf~ ~ing process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylim '- ~1~ manganese rhthslocyanine, pe~ s and mixtures thereo~ If used, 30 these agents typically co,l,. iae from about O.Ol % to about l 0% by weight of the culllpo~;~;orl~ p,ef.,...bly from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More specifirslly, the polyamine N-oxide polymers plef~ ,d for use herein contain units having the following alru~,lul~l formula: R-AX-P; wherein P is a poly...- .i~tlc unit to 35 which an N-0 group can be ~ d or the N-0 group can form part of the potymerizable unit or the N-0 group can be stt~rh~d to both units; A is one of the following all U~IUI~.S
NC(0)-, -C(0)0-, -S-, -0-, -N=; x is 0 or l; and R is ~lip~ c, ethoxylated ~ ' ,s, W 097/47720 rCT~US97/09972 a~/
aromq-ticc, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be d~ ed or the N-O group is part of these groups. P~ ~f~ ,d polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be rep,.. ~ ~ by the following general structures:
~x 7 (R2)y; N (Rl)x (R3)z wherein Rl, R2, R3 are qliphqtic, aromatic, heterocyclic or alicyclic groups or comb;~-~tionc thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or fonn part of any of the afol ~ ;o-~d groups. The amine oxide unit of the polyamine N-oxides 10 has a pKa <10, preferably pKa <7, more plef~ d pKa <6.
Any polymer b--~hone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting p~opc. Iies. Examples of suitable polymeric b~ hQn~C are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polyrners include random or block copolymers 15 where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. I IO.. ~ ier, the number of amine oxide groups present in the polyamine oxide polymer can be varied by applU~ .le copoly.ll~ alion or by an ~ r 'U~l iate degree of N-rYil' ~ on The polyamine oxides can be obtained in almost any degree of 20 polyll~ alion. Typically, the average moiecular weight is within the range of 500 to 1,000,000; more plef~ ;d 1,000 to 500,000; most plef~ d 5,000 to 100,000. This E,l~;fe.l.id class of materials can be referred to as "PVNO".
The most plef~ d polyamine N-oxide useful in the d~,t~ at co.~ os:~ ;ons herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of about 50,000 25 and an a nine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimi~l~7nle polymers (referred to as a class as "PVPVI") are also ~lel~llc;d for use herein. Pl~,f~._bly the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is 30 determined by light scattering as described in Barth, et al., Chemical Analysis~ Vol 113.
"Modern Methods of Polymer Cha~ ;tc~ on", the disclosures of which are h~col~.ol : d herein by refe.encc.) The PVPVI copolymers typically have a molar ratio of N-vinylimi~ ole to N-vinylpyrrolidone from 1:1 to 0.2:1, more preferably from 0.8:1 to W 097/47720 rcTrusg7/og972 ~5 0.3:1,mostp-Gfe. blyfromO.6:1 to04 1 Thesecopolymerscanbeeitherlinearor b,~ched.
The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000,p.~,f~" lbly from about 5,000 to about 200,000, and more p~cr~ ly from about 5,000 to about 50,000. PVP's are known to persons skilled in the det~ t field; see, for I - r~-EP-A-262,897 and EP-A-256,696, h~cu.~,û,ut~,d herein by ref~l~,nce. CG...PUS ~ nC
CQ~ B PVP can also contain polyethylene glycol ("PEG") having an average l-.ole _ weight from about 500 to about 100,000, yrGf~l bly from about 1,000 to about 10,000.
10 P~Gfe.~bly, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
The d~t,.~_nt colnpositions herein may also opL~ --lly contain from about 0.005%to 5% by weight of certain types of hydrophilic optical b, ~ which also provide a dye transfer inhibition action. If used, the Cu...yosilions herein will ,c.efe. ~Iy co...ylise from 15 about 0.01% to 1% by weight of such optical b. ~t~ ~.
The hydrophilic optical brig' - ~ useful in the present i..iel~lioa are those having the ~llucL-.-dl formula:

N>_ ~C=C~ I--<~
R2 SO3M SO3M Rl wherein R1 is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is 20 selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and arnino; and M is a salt-forming cation such as sodium or p~,!A~
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the b. ;ghl~ ,. is 4~4',-bis[(~ ino-6-(N-2-bis-hydroxyethyl~s-ll;~;ne-2-yl)amino]-2~2~-stilb~f A;~ ~lfonic acid and di~o~inm salt. This particular 25 brightener species is Cu...~ .cially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the prefe..~d hydrophilic optical bl;gllt~,n., useful in the d~.t~ l.t co...posilions herein.
When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-30 hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbene~ llfonic acid disodium salt. This particular b. i~ht~,l.c. species is commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation W 097/47720 PCTrUS97/09972 3~
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as sodium, the b. ig' is 4,4'-bis[(~ ilino-6-morphilino-s-1~ iazh~c-2-yl)amino]2,2'-stilt~ rdi~.~lfonic acid, sodium salt. This particular brightener species is commercially marketed under the trade name Tinopal AMS-GX by Giba Geigy Corporation.
5The specific optical l,.ivht~ner species selected for use in the present invention provide especially effective dye transfer inhibition p~ .Çu -e benefits when used in combination with the selected polymeric dye transfer inhibiting agents he.e- ' fo.e de~,. il~d. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX
10 and/or Tinopal 30 AMS-GX) provides c~ Iy better dye transfer h~hit~ on in aqueol~e wash solutions than does either of these two d~ter~l co- .rOc;l ;on cGIl.~onc,.lt~ when used alone. Without being bound by theory, it is believed that such bligl.t.,n~.a work this way because they have high affinity for fabrics in the wash solution and l~ erort deposit relatively quick on these 15 fabrics. The extent to which bri~' - a deposit on fabrics in the wash solution can be defined by a parameter called the "PY~ ~tion coerr.~ .lt". The e~h - ,l ;nl- cocrr..,;- - ~ is in general as the ratio of a) the brightener material dcpoçit, d on fabric to b) the initial b. i~ht,.~e. c~ n~ alion in the wash liquor. Bright~,..c, a with relatively high ~YI~nction coerr.ci~,nls are the most suihble for inhibiting dye transfer in the context of the present invention.
Of course, it will be p~ r~cial.,d that other, conventional optical ~.-g~ types of compounds can optionally be used in the present comrocitions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to dct~.ge.-l formul~~ionc Other Adiunct InL~ d;~.lta The d-,t~ t co",po~ition may also include enzyme shbilizers, blight~.lc.a, polymeric dis~ah~g agents (i.e. polyacrylates), carriers, h~drol.o~,.,s, suds boosters, and p.oce~ g aids.
In order to make the present invention more readily ~..d~,. alood~ ~f,.~.~ce is made to the following ~ ~' which are ;~.t~ rd to be illustrative only and not i.~n d~d to be limiting in scope.
EXAMPLES
The "whit~,ness" ofthe p~licles can be ~--e&sJ-~d in terrns ofthe Hunter Whiteness Values (W), which is c~lcul~ted acco~ding to the following e~u~1;ol-W=(7L2-40Lb)/700 wherein L, a, b are deter nined from a tristimulus meter reading and ~,p,esenl a three axis o~)pone..l color scale system based on the theory that color is p~ ed by black-white (L), i~, red-green (a), and yellow-blue (b) s~~nC~tiQnc The higher the value for W, the "whiter" the particles. See R. S. Hunter and R. W. Harold, The Me&i,ule..lc..l of A~oc& -e Second Ed., lohn Wiley & Sons, New York, 1987 and ASTM S~ dalds on Color and Appea.anceMessulci.lle,ll. Third Ed., ASTM, Philadelphia, PA, l99l.
S Example I
A solution of 82% solid ca-l,oh~drate material (having â d~,AI~ose equivalence 62) and the balance water is premixed in an agitated mixing vessel with 1.5% by weight TiO2 powder (co--....e.-,ially sold under the trade name Tronox by the Kerr McGee Ch~miçql Corporation) to form a carbohydrate encapsulation fluid solution. The carbohydrate fluid is 10 dried to form a solid glassy material in a LuwaTM Wiped Film Ev l~ ~ ("WFE"). The resulting carbohydrate fluid has a moisture level of 2.0%. Th~.,~",ll~,., the carbohydrate fluid and zeolite X loaded with 16% p~.rulllc by weight ("PLZ") are inputted at a weight ratio of 1: l into a 12 barrel, Werner & PfleidererTM ZSK 30 twin screw ~iAIrude~ (nTSE") without a con~ll ;.,li..g die plate to form agglo~ Barrels I through 4 of the TSE are 15 m~int~in-~d at a temperature of 80 ~C while barrels 5 and 6 are ~ d at a t~ .lure of 90 ~C, barrels 7 and 8 at a temp~,.dlu.~i of 130 ~C, barrels 9 and 10 at a temperature of 135 ~Ct and barrels 11 and 12 at a t~ p~ tUl~i of 130 ~C. The carbohydrate fluid is fed at a temperature of 160 ~C to the TSE in barrel 7, while the PLZ is added in barrel l l and - Iy mixed with the carbohydrate fluid prior to leaving the TSE as an t;AIl ~ ' t~
having a di~ch~ ~,c t~.. p~ of 145 ~C and a rate of 500 g/min. The product is cooled at room temperature to form free flowing particles which are ground in a Fitz MillTM
(co...--.c..,;dlly available from the F: r ~ icl~ Company) and sized via sclee.~ g to result in particles in the size range of 150 microns to 1180 microns which are ~;~lr~ cly suitable for use as a laundry additive co...~ ,;I;on The particles formed ~ t~ Aly have HunterTM Whiteness value of W = -34.5, as measured using a Hunter Association Laboldt~,ly Inc. Optical Sensor : ' ~d,~ed to a white C2-2790 standard tile. ~.dditi~ ~lly, the particles ~ re~l ~Iy have a superior "Neat Product Odor" ('l~PO") value of 8.5 when added to a co~e~lional laundry d, t.,.~
product. The NPO value ranges from 0 to 10 wherein 0 is the worst and 10 is the best in that it does not emit any ~ ete l ~le odor over the base product odor as observed by a st~ti~ti~ y significant number of panelist graders. The viscosity of the carbohydrate encapsulation fluid solution is ~ ecl~dly low.
ExamPle II
This Example is outside the scope of the process invention, but provides a co.l.pa~.son in that this Example is carried forth exactly as set forth in Example 1, except iu.n dioxide (TiO2) is omitted from the process. The particles formed have HunterTM
Whiteness values of W = -60.3, as llle&sul~.d using a Hunter ~soci~tiQn Labo.al~ Inr.

W O 97/47720 PCT~US97/09972 Optical Sensor ~laildaldi~d to a white C2-2790 standard tile. ~d~lition~lly, the particles have a "Neat Product Odor" ("NPO") value of 7.0 when added to a conventional laundry d~,t~ t product. The NPO value ranges from 0 to 10 wherein 0 is the worst and 10 is the best in that it does not emit any detect~b'e odor over the base product as observed by a S St~tictir~lly significant number of panelist graders. The Hunter Whiten~ss and NPO values are significantly worse than the those rc~,~nl~d in Example I, thereby ~ul,po. g the e~t~AIy superior benefits achieved by the process invention. Also, the ~ ,Oa;ly of the ing fluid is rotices~ly higher than ~he fluid in F-~ 1 e I.
Having thus deJ~ . il,cd the invention in detail, it will be clear to those skilled in the 10 art that various changes may be made without departing from the scope of the invention and the invention is not to be co~ del ed limited to what is described in the specifir-~ion

Claims (10)

WHAT IS CLAIMED IS:

1. A process for producing a particulate laundry additive composition characterized by the steps of:
(a) drying an aqueous mixture of a pigment and an encapsulating material to form an encapsulating fluid;
(b) inputting said encapsulating fluid and porous carrier particles into an extruder, said porous carrier particles having a perfume adsorbed therein;
(c) extruding said porous carrier particles and said encapsulating fluid so as to form an extrudate containing said porous carrier particles enrobed with said encapsulating fluid;
(d) cooling said extrudate; and (e) grinding said extrudate to form particles having a predetermined particle size for addition into a detergent composition, thereby forming said particulate laundry additive composition.

2. A process according to claim 1 wherein said pigment is selected from the group consisting of titanium dioxide, silica, sodium alumina silicate, ultramarines, optical brighteners and mixtures thereof.

3. A process according to claims 1-2 wherein said pigment is titanium dioxide.

4. A process according to claims 1-3 wherein said encapsulating fluid is substantially free of water.

5. A process according to claims 1-4 wherein said cooling step includes cooling said extrudate to be within a temperature range of from 20°C to 100°C.

6. A process according to claims 1-5 wherein said cooling step is completed within 1 second to 120 seconds.

7. A process according to claims 1-6 wherein said porous carrier material is selected from the group consisting of amorphous silicates, crystalline nonlayered silicates, layered silicates, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, clays, zeolites, sodalites, alkali metal phosphates, macroporous zeolites, chitin microbeads, carboxyalkylcelluloses, carboxyalkylstarches, cyclodextrins, porous starches and mixtures thereof; and said porous solid has a surface area of at least 50 m2/g.

8. A process according to claims 1-7 wherein said encapsulating material is in the glass phase and has a glass transition temperature in the range of from 30°C to 200°C.

9. A process according to claims 1-8 wherein said encapsulating material is selected from starches, polysaccharides, oligosaccharides, disaccharides, monosaccharidesalginate esters, carrageenin, agar-agar, pectic acid, chitosan, chitin, cellulose acetate cellulose acetate phthalate, carboxymethylcellulase, silicates, phosphates, borates, polyethylene glycols, polyvinyl alcohol, nonionic surfactants and mixtures thereof.

10. A process for producing a particulate laundry additive composition characterized by the steps of:
(a) inputting an encapsulating material, a pigment and porous carrier particles into an extruder, said porous carrier particles having a perfume absorbed therein;
(b) extruding said porous carrier particles, said pigment and said encapsulating material so as to form an extrudate containing said porous carrier particles enrobed with said encapsulating material and said pigment;
(c) cooling said extrudate; and (d) grinding said extrudate to form particles having a predetermined particle size for addition into a detergent composition, thereby forming said particulate laundry additive composition.