CA2265804A1 - Process for making particulate laundry additive composition - 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 aforementioned 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 detergent and fabric softening products. The process essentially includes the steps of inputting an aqueous mixture a first encapsulating material and porous carrier particles (e.g., zeolite X) into an extruder, and thereafter, extruding the first encapsulating material, which is 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 granules is completed. In the final step, a second encapsulating material is coated onto the granules to enrobe further the perfume in the carrier particles.

Description

CA 02265804 l999-03- 16WO 98112298 PCT/US97/15630lDUAL COATING PROCESS FOR PRODUCING A PARTICULATE LAUNDRYADDITIVE COMPOSITION FOR PERFUME DELIVERY HAVING IIVIPROVEDPHYSICAL PROPERTIESFIELD OF THE INVENTIONThe present invention generally relates to a process for producing a particulatelaundry additive composition, and more particularly, to an extrusion process whichproduces a dual-coated particulate laundry additive for perfume delivery in laundrydetergent compositions, especially those in the form of granules, agglomerates, laundrybars or pastilles. This process improves upon existing processes in that it provides acomposition having unexpectedly better physical properties such as appearance("whiteness"), moisture protection and perfume protection as evidenced by its substantiallyreduced odor that is emitted by the particles. The process of the invention may also beemployed to produce particulate additive compositions which may be used in fabricsoftening and dishwashing as well as laundry detergent compositions.BACKGROUND OF THE INVENTIONMost consumers have come to expect scented laundry products and to expect thatfabrics which have been laundered also have a pleasing fragrance. Perfume additivesmake laundry compositions more aesthetically pleasing to the consumer, and in somecases the perfume imparts a pleasant fragrance to fabrics treated therewith. However, theamount of perfume carryover from an aqueous laundry bath onto fabrics is oftenmarginal. The detergent manufacturing industry, therefore, has long searched for aneffective perfume delivery system for use in laundry products which provides long-lasting, storage-stable fragrance to the product, as well as fragrance to the launderedfabrics.Laundry and other fabric care compositions which contain perfume mixed with orsprayed onto the compositions are well known in the art and currently commercialized.Because perfumes are made of a combination of volatile compounds, perfume can becontinuously emitted from simple solutions and dry mixes to which the perfume has beenadded. Various techniques have been developed to hinder or delay the release ofperfume from compositions so that they will remain aesthetically pleasing for a longerlength of time. To date, however, few of the methods deliver significant fabric odorbenefits after prolonged storage of the product.Moreover, there has been a continuing search for methods and compositions whichwill effectively and efficiently deliver perfume from laundering solutions onto fabricsurfaces. As can be seen from the following disclosures in the prior art, various methodsof perfume delivery have been developed involving protection of the perfume throughCA 02265804 l999-03- 16W0 98/ 12298 PCT/US97I156302the wash cycle, with release of the perfume onto fabrics. For example, one methodentails delivering fabric conditioning agents, including perfume, through the wash anddry cycle via a fatty quaternary ammonium salt. Another method involves amicroencapsulation technique which involves the formulation of a shell material whichwill allow for diffusion of perfume out of the capsule only at certain temperatures. Yetanother method involves incorporating perfume into waxy particles to protect theperfiime through storage in dry compositions and through the laundry process. Theperfume allegedly diffuses through the wax on the fabric in the dryer. Further prior artdisclosures involve perfume dispersed with a water-insoluble nonpolymeric carriermaterial and encapsulated in a protective shell by coating with a water-insoluble friablecoating material, and a perfume/cyclodextrin complex protected by clay which providesperfume benefits to at least partially wetted fabrics.Still another method for delivery of perfume in the wash cycle involves combiningthe perfume with an emulsifier and water- soluble polymer, forming the mixture intoparticles, and adding them to a laundry composition. The perfume can also be absorbedonto a porous carrier material, such as a polymeric material. Perfumes have also beenabsorbed onto a clay or zeolite material which is then admixed into particulate detergentcompositions. Generally, the preferred zeolites have been Type A or 4A Zeolites with anominal pore size of approximately 4 Angstrom units. It is now believed that withZeolite A or 4A, the perfume is absorbed onto the zeolite surface with relatively little ofthe perfume actually absorbing into the zeolite pores.While the adsorption of perfume onto zeolite or polymeric carriers may perhapsprovide some improvement over the addition of neat perfume admixed with detergentcompositions, industry is still searching for improvements in the length of storage time ofthe laundry compositions without loss of perfume characteristics, in the intensity oramount of fragrance delivered to fabrics, and in the duration of the perfume scent on thetreated fabric surfaces. Furthennore, even with the substantial work done by prior skilledartisans in this area, a need still exists for a simple, more efficient and effective perfumedelivery system, preferably in particulate fonn, which can be mixed with laundrycompositions to provide initial and lasting perfume benefits to fabrics which have beentreated with the laundry product.Another problem associated with perfume delivery systems, especially those inparticulate fonn, is concerned with the method by which such particulate perfumedelivery systems are made. It has been difficult to produce perfume delivery systemsparticularly those involving zeolite or polymeric carriers in an economic and efficientmanner. Oftentimes, a significant amount of the perfume will evaporate from the carriermaterial during processing as well as during storage prior to use. Additionally, manyCA 02265804 l999-03- 16WO 98/12298 PCTIUS97ll56303materials which are included in the perfume delivery system to prevent the volatilizationof perfume prior to deposition on fabrics can degrade during manufacture, thereby losingtheir effectiveness. As a consequence, the particulate perfume delivery systemsometimes has a tendency to emit its perfume component while stored in the finalproduct, thereby interfering with the desired odor of other perfumes contained in theproduct. Thus, there has been a need for not only an effective perfume delivery systemor additive for laundry detergents, but for a process which can produce such a laundryperfume delivery additive which is efficient, economical, and minimizes or eliminatesevaporation of perfume and degradation of materials used during processing.Accordingly, despite the aforementioned disclosures in the art, there remains aneed for a process for producing a particulate laundry additive composition for perfumedelivery in laundry detergent and other cleaning or fabric softening products.Additionally, there is a need for such a process which is not only more economical andefficient, but also minimizes evaporation of perfume and the degradation of materialsused in this regard during production.BACKGROUND ARTU.S. Patent 4,539,135, Ramachandran et al, issued September 3, 1985, disclosesparticulate laundry compounds comprising a clay or zeolite material carrying perfume.U.S. Patent 4,713,193, Tai, issued December 15, 1987, discloses a free-flowingparticulate detergent additive comprising a liquid or oily adjunct with a zeolite material.Japanese Patent HEI 4[l992]-218583, Nishishiro, published August 10, 1992, disclosescontrolled-release materials including perfumes plus zeolites. U.S. Patent 4,304,675,Corey et al, issued December 8, 1981, teaches a method and composition comprisingzeolites for deodorizing articles. East German Patent Publication No. 248,508, publishedAugust 12, 1987; East German Patent Publication No. 137,599, published September 12,1979; European Patent Publication No. 535,942, published April 7, 1993, and PublicationNo. 536,942, published April l4, 1993, by Unilever PLC; U.S. Patent 5,336,665, issuedAugust 9, 1994 to Gamer-Gray et al,; and WO 94/28107, published December 8, l994.SUMMARY OF THE INVENTIONThe aforementioned needs in the art are met by the present invention whichprovides a process for producing a particulate laundry additive composition for perfumedelivery primarily in laundry detergent and fabric softening products. The processessentially comprises the steps of inputting an aqueous mixture a first encapsulatingmaterial and porous carrier particles (e.g., zeolite X) into an extruder, and thereafter,extruding the first encapsulating material, which is preferably a glassy carbohydratematerial, with porous carrier particles, preferably loaded with a perfume, so as to form ahot extrudate. Subsequently, the steps of cooling and grinding the extrudate into granulesCA 02265804 l999-03- 16W0 98/12298 PCT/US97/156304is completed. In the final step, a second encapsulating material is coated onto thegranules to enrobe further the perfume in the carrier particles. Unexpectedly, as a resultof this process, the perfume is sealed significantly better into the carrier materialsufficiently so as not to permit exposure or leaching until subjected to the laundering orsoftening process.As used herein, the term "extrudate" refers to a continuous phase material formedfrom an extruder which can have virtually any desired shape. As used herein, the temis"enrobed" or "coated" mean that the carbohydrate material substantially covers thecarrier particles regardless of the overall shape of the particles or material to be enrobedor coated, e.g. agglomerates, extrudate or particles. As used herein, the phrase "glassphase" or "glassy" materials refers to microscopically amorphous solid materials havinga glass transition temperature, Tg. As used herein, the phrase "continuous phase" refersto a single fused mass of individual or discrete particles. As used herein, the phrase"median particle size" means the "average" particle size in that about 50% of the particlesby number (not mass) are larger and about 50% are smaller than this particle size asmeasured by standard sieve analysis. All percentages and ratios used herein areexpressed as percentages by weight (anhydrous basis) unless otherwise indicated. Alldocuments are incorporated herein by reference.In accordance with one aspect of the invention, a process for producing aparticulate laundry additive composition is provided. This process comprises the steps of:(a) inputting a first encapsulating material and porous carrier particles into an extruder, theporous carrier particles having a perfume absorbed therein; (b) extruding the porous carrierparticles and the first encapsulating material so as to form an extrudate containing theporous carrier particles enrobed with the first encapsulating material; (c) cooling theextrudate; (d) grinding the extrudate into granules; and (e) coating the granules with asecond encapsulating material, thereby forming the particulate laundry additivecomposition.In accordance with another aspect of the invention, another process for producing aparticulate laundry additive composition is provided. This process comprises the steps of:(a) inputting a first carbohydrate material and porous carrier particles into an extruder, theporous carrier particles having a perfume absorbed therein; (b) mixing the porous carrierparticles and the first encapsulating material so as to form a particulate mixture containingthe porous carrier particles enrobed with the first encapsulating material; (c) cooling theparticulate mixture; (d) grinding the particulate mixture into granules; and (e) coating thegranules with a mixture of a second carbohydrate material, thereby forming the particulatelaundry additive composition. The present invention also provides the particulate laundryadditive composition made according to any one of the processes described herein.CA 02265804 l999-03- 16W0 98/ 12298 PCT /US97/156305Accordingly, it is an object of the present invention to provide a process forproducing a particulate laundry additive composition for perfume delivery in laundrydetergent and other cleaning or fabric softening products. It is also an object of theinvention to provide such a process which is more economical, efficient, and one whichminimizes product discoloration and the evaporation of perfume and degradation of thematerials used during production. These and other objects, features and attendantadvantages of the present invention will become apparent to those skilled in the art froma reading of the following detailed description of the preferred embodiment, drawingsand the appended claims.BRIEF DESCRIPTION OF THE DRAWINGSFig. 1 is a schematic flow diagram of the process including a preferredembodiment in which the undersized particle recycling step is completed by feeding theundersized particles back to just before the cooling step.DETAILED DESCRIPTION OF TI-IE PREFERRED EMBODIMENTEmThe process of the invention unexpectedly provides a means by which a perfume-containing particulate laundry additive composition can be prepared without havingexcessive discoloration and perfume evaporation or degradation during processing andwhich forms a particulate composition maintaining such perfume prior to its use during thelaundering of fabrics. By maintaining the perfume prior to use, it is meant that the perfumeis not emitted while stored in the product container, but is only allowed to be emittedduring and after deposition on the laundered fabrics as intended. Further, the processunexpectedly prevents the displacement of perfume from the porous carrier particles intothe encapsulating material.While intending not to be bound by theory, it is believed that the processunexpectedly prevents perfume displacement by including a second coating of theencapsulating material onto the perfume-loaded carrier particles. The second coating ofencapsulating material is completed subsequent to the sizing operations and may becompleted via a variety of known processing techniques. By way of example, the secondcoating may be sprayed on or completed in a fluid bed coater or similar apparatus. Theencapsulating material is preferably a carbohydrate material having a high glass transitiontemperature (e.g. a Tg greater than 130°C), examples of which are provided hereinafter.Turning now to Fig. 1 which provides a schematic flow diagram of a preferredembodiment of the process 10, the first step of the process 10 involves inputting a firstencapsulating material 6 in aqueous fomi, and optionally a pigment 8, into a mixer 5 toform an aqueous mixture 7. The mixer 5 can be any conventional tank or vessel havingstirring or agitating apparatus included therein. The aqueous mixture 7 is fed to a binderCA 02265804 l999-03- 16W0 98/ 12298 PCT/US97/156306fonning/drying apparatus 12 to form an encapsulating fluid 14. In the binderfonning/drying apparatus 12, at least a portion of the water introduced via the aqueousencapsulating material 6 is evaporated via the drying step in this apparatus 12 By aportion, it is meant that the resulting encapsulating fluid l4 contains from about 5% toabout 50% of the water originally contained in the encapsulating material 6. Mostpreferably, however, the encapsulating fluid 14 is substantially free of water.If the optional pigment 8 is added, it is added in an amount of from about 0.1% toabout 10%, and most preferably from about 0.5% to about 5% by weight of the finalproduct. The pigment 8 is preferably selected from the group consisting of titaniumdioxide, silica, sodium alumina silicate, ultramarines, optical brighteners and mixturesthereof, although other materials can be used, some of which are listed hereinafter. Themost preferred pigment 8 is titanium dioxide. While the pigment 8 is included to preventdiscoloration of the ultimate product formed, it may also have the benefit of maintainingthe glass transition temperature of the encapsulating fluid 14, lowering its viscosity, andproviding superior sealing properties in that the encapsulating fluid is able to preventemissions of the perfume prior to deposition of the additive on laundered fabrics. Thebinder/drying apparatus 12 can be a Wiped Film Evaporator (WFE), or heated extruder, inthe situation where the encapsulating material 6 is in the molten phase or a conventionalspray-drying tower or similar apparatus when the encapsulating material 6 is in the solidphase. Preferably, the encapsulating material 6 is a carbohydrate material, which evenmore preferably, is in the glass phase after cooling.In the next step of the process, the encapsulating fluid 14 is inputted to an extruder16. It should be understood that while extruder 16 can be mixing apparatus, it preferably isan extruder. Porous carrier particles or material 18 as described in detail hereinafter is alsoadded to the extruder 16, preferably near the end of the extruder 16. The extruder 16 canbe any known mixing, extrusion, compounding or other apparatus, including but notlimited to, extruders commercially available from APV Baker (CP Series), Wemer &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 optional step of the process invention, a pigment 17 is added to the extruder16 to aid in the discoloration problem and to modify the viscosity of the mixture beingextruded. It should be understood that the benefits of the instant process invention can beachieved by adding the pigment 17 as shown in Fig. l and described herein alone, or inaddition to the addition of pigment 6 as described previously. The pigment 6 and 17 can bethe same, different or various mixtures of the pigment materials described previously.Also, the amount of the pigment 17 added is typically from about 0.1% to about 5%, mostpreferably from about 1% to about 2% by weight of the final product. Alternatively, dyesCA 02265804 l999-03- 16wo 98/12298 PCT/US97/156307may be used in place of pigments in a typical amount of from 0.01% to about 1%, mosttypically from about 0.02% to about 0.05%.Preferably, the extruder 16 is maintained at a temperature of from about 50°C toabout 200°C, more preferably from about 110°C to about 170°C, and most preferably fromabout 120°C to about 160°C. ln this way, adequate mixing of the porous carrier particles18 and the encapsulating fluid 14 is ensured. The residence time of the porous carrierparticles 18 and the encapsulating fluid 14 in the extruder 16 is preferably from about 0.1minutes to about 10 minutes, more preferably from about 0.1 minutes to about 5 minutes,and most preferably from about 0.1 minutes to about 2 minutes. Optionally, the extruder16 can be depressurized to a level of about 100 mm Hg to about 750 mm Hg, morepreferably from about 450 mm Hg to about 735 mm Hg, and most preferably from about710 mm Hg to about 550 mm Hg.A hot extrudate 20 containing the porous carrier particles 18 enrobed with theencapsulating fluid 14 is fonned in the extruder 16 and subjected to a cooling step inpreferably a chilled roll/flaker 22 or similar apparatus. The cooling step preferably coolsthe extrudate 20 to a temperature in a range from about 20°C to about 100°C, morepreferably from about 20°C to about 80°C, and most preferably from about 20°C to about60°C. Preferably, the cooling step is completed within about 1 second to about 120seconds, more preferably from about 1 second to about 60 seconds, and most preferablyfrom about 1 second to about 30 seconds. The extrudate 20 has a particulate physical formas it exits the chilled roll/flaker 22. In one particular embodiment, the extrudate 20 can bein the fomi of noodles which are subsequently processed as described hereinafter.The extrudate 20 are then subjected to a grinding step 24,which can be completedin any know grinding apparatus such as a hammennill. The resulting particles 26 arescreened in screening apparatus 28 to provide particles 34 having a median particle size ina range from about 150 microns to about 1100 microns, more preferably from about 200microns to about 800 microns, and more preferably from about 400 microns to about 600microns.Optionally, the process further comprises the step of screening or separating theparticles 26 into undersized or "fines" and oversized or "overs" particles, wherein theundersized particles 32 have a median particle size of less than about 150 microns and theoversized particles 30 have a median particle size of at least 1100 microns. In this regard,the aforementioned undersized particles are recycled back to just before the cooling step orchilled roll/flaker 22, while the oversized particles are sent back to the grinding step 24.Past conventional wisdom by the skilled artisan would have recycled the oversized particles30 and undersized particles 32 back to the extruder 16. However, the recycle stepsdescribed herein do not follow this scheme, but rather, recycle back to the cooling and/or. ..........-ti n£IlAsDvhAlA§I-CAIlA4«ll—9¢hk.lIAi .i..............,._....~.., ,CA 02265804 l999-03- 16W0 98/ 12298 PCT/U S97/ 156308grinding step as appropriate. The use of these process steps results in minimizedcarbohydrate material and perfume degradation as the recycled particles are only subject tohigh temperatures for an extremely short period of time.The particles 34 are subjected to a coating step 36 in which a second encapsulatingmaterial 38 is coated onto particles 34 to seal further the perfume into the particles. Theencapsulating material 38 can be the same as or different from the encapsulating material 6as described more fully hereinafter. As alluded to previously, the coating step 36 can becarried forth via conventional spraying techniques or in any standard fluid bed coatingapparatus. Additionally, optional plasticizers may be added with encapsulating material 38which include sorbitol, polyethylene glycol, propylene glycol, low molecular weightcarbohydrates and the like. A mixture of encapsulating material 38, sorbitol, andpolyethylene glycol is most preferred for this process.Optionally, mixtures of carbohydrates having various glass transition temperaturescan be used in the coating step 36, such carbohydrates are detailed hereinafier and includeCapsul ET” and Amiogum 23"‘ which are commercially available from National StarchChemical Co. and American Maze Co., respectively. Optionally, a small amount (e.g.0.01% to 1%) of a surfactant can be included to prevent clumping in the coating apparatus.Further, subsequent drying and cooling steps may be performed to insure that a uniformand smooth coating of the encapsulating material 38 and optional adjunct plasticizersresults on the finished particulate laundry additive composition 40.The laundry additive composition 40 typically comprises from about 10% to about95% of the encapsulating materials, preferably from about 20% to about 90%, and morepreferably from about 20% to about 75% with typical ratios of first encapsulating materialto second encapsulating material of about l:l to about 10:1, preferably about 5:1 to about2:1. The additive composition 40 of the present invention also typically comprise fromabout 0% to about 90% of agents useful for laundry or cleaning compositions, preferablyfrom about 10% to about 80%, and more preferably from about 25% to about 80%.The laundry additive composition 40 preferably has a hygroscopicity value of lessthan about 80%. The "hygroscopicity value", as used herein, means the level of moistureuptake by the glassy particles of the composition 40, as measured by the percent increasein weight of the particles under the following test method. The hygroscopicity valuerequired for the present invention glassy particles is determined by placing 2 grams ofparticles (approximately 500 micron size particles; not having any moisture barriercoating) in an open container petrie dish under conditions of 90°F and 80% relativehumidity for a period of 4 weeks. The percent increase in weight of the particles at theend of this time is the particles hygroscopicity value as used herein. Preferred particlesCA 02265804 1999-03-16wo 98l12298 PCT/US97l15630' 9of the composition have a hygroscopicity value of less than about 50%, more preferablyless than about 30%.CA 02265804 l999-03- 16WO 98/12298 PCT/US97/15630l 0Particulate Laundry Additive CompositionThe process invention produces a particulate laundry additive composition usefulin the delivery of perfumes for laundering processes. The composition includes first andsecond encapsulating materials, 6 and 38, respectively, both of which preferably are acarbohydrate material.First Encapsulating MaterialThe first encapsulating material 6 of the present invention is a glassy materialderived from one or more at least partially water-soluble hydroxylic compounds. The atleast partially water soluble hydroxylic compounds useful herein are preferably selectedfrom the following classes of materials.1. Carbohydrates, which can be any or a mixture of: i) Simple sugars (ormonosaccharides); ii) Oligosaccharides (defined as carbohydrate chains consisting of 2-10 monosaccharide molecules); iii) Polysaccharides (defined as carbohydrate chainsconsisting of at least 35 monosaccharide molecules); and iv) Starches including modifiedstarches.Both linear and branched carbohydrate chains may be used. In additionchemically modified starches and poly-/oligo-saccharides may be used. Typicalmodifications include the addition of hydrophobic moieties of the form of alkyl, aryl, etc.identical to those found in surfactants to impart some surface activity to thesecompounds.2. All natural or synthetic gums such as alginate esters, carrageenin, agar-agar,pectic acid, and natural gums such as gum arabic, gum tragacanth and gum karaya.3. Chitin and chitosan.4. Cellulose and cellulose derivatives. Examples include: i) Cellulose acetate andCellulose acetate phthalate (CAP); ii) Hydroxypropyl Methyl Cellulose (HPMC);iii)Carboxymethylcellulose (CMC); iv) all enteric/aquateric coatings and mixturesthereof.5. Silicates, Phosphates and Borates.6. Polyvinyl alcohol (PVA).7. Polyethylene glycol (PEG).8. Plasticizers.Materials within these classes which are not at least partially water soluble andwhich have glass transition temperatures, Tg, below the lower limit herein of about 0°Care useful herein only when mixed in such amounts with the hydroxylic compoundsuseful herein having the required higher Tg such that the glassy particle produced has therequired hygroscopicity value of less than about 80%.W0 98/ 12298CA 02265804 l999-03- 16PCT /U S97/ 15630I 1Glass transition temperature, commonly abbreviated "Tg", is a well known andreadily detennined property for glassy materials. This transition is described as beingequivalent to the liquification, upon heating through the Tg region, of a material in theglassy state to one in the liquid state. It is not a phase transition such as melting,vaporization, or sublimation. [See William P. Brennan, "'What is a Tg?' A review of thescanning calorimetry of the glass transition", Thermal Analysis Apglication Study #7,Perkin-Elmer Corporation, March 1973.] Measurement of Tg is readily obtained byusing a Differential Scanning Calorimeter.For purposes of the present invention, the Tg of the hydroxylic compounds isobtained for the anhydrous compound not containing any plasticizer (which will impactthe measured Tg value of the hydroxylic compound). Glass transition temperature is alsodescribed in detail in P. Peyser, "Glass Transition Temperatures of Polymers", Polymer"Handbook Third Edition, J. Brandrup and E. H. Immergut (Wiley~Interscience; 1989),pp. VI/209 - VI/277.At least one of the hydroxylic compounds useful in the present invention glassy particles must have an anhydrous, nonplasticized Tg of at least 0°C, and for particles not 'having a moisture barrier coating, at least about 20 °C, preferably at least about 40°C,more preferably at least 60°C, and most preferably at least about 100°C. It is alsopreferred that these compounds be low temperature processable, preferably within therange of from about 50°C to about 200°C, and more preferably within the range of fromabout 60 °C to about 160°C.Preferably, the hydroxylic compound is a carbohydrate material having a dextroseequivalence, DE, of about 75 or less, more preferably of about 65 or less, most preferablybetween about 25 and 65, and is a simple sugar. As used herein, the term "dextroseequivalence" and abbreviated "DE", refers to the total amount of reducing sugarsexpressed as dextrose that is present, calculated as a percentage of the total drysubstance. The amount is measured on a scale of 0 to 100 with 100 being the amountpresent in a pure sugar. The usual technique for determining dextrose equivalence is avolumetric alkaline copper method. Both dextrose equivalence and the methods formeasuring dextrose equivalence are well-known in the art particularly in the food andsyrup industries. Preferred carbohydrate materials of the first encapsulating material ofthe present invention include sucrose, glucose, lactose, and corn syrup solids.Second Encapsulating MaterialThe second encapsulating material 38 according to the present invention whichfomis the outer layer is a carbohydrate material having an anhydrous, nonplasticized, glasstransition temperature, Tg, of at least about 130°C, and more preferably at least about150 C, and most preferably about 175°C.CA 02265804 l999-03- 16wo 9s/1229s PCT/US97I15630' 12The carbohydrate of the second encapsulating material can be any or a mixture of:i) Simple sugars (or monosaccharides); ii) Oligosaccharides (defined as carbohydratechains consisting of 2-10 monosaccharide molecules); iii) Polysaccharides (defined ascarbohydrate chains consisting of at least 35 monosaccharide molecules); and iv)Starches including modified starches.Both linear and branched carbohydrate chains may be used. In addition chemicallymodified starches and poly-/oligo-saccharides may be used. Typical modifications includethe addition of hydrophobic moieties of the form of alkyl, aryl, etc. identical to those foundin surfactants to impart some surface activity to these compounds.The carbohydrate of the second encapsulating material preferably has a dextroseequivalence, DE, of about 20 or less, more preferably about 15 or less and most preferablyabout 10 or less. Preferably, the carbohydrate of the second encapsulating material is astarch or modified starch, or maltodextrin. Suitable maltodextrins include Maltrin M040”commercially available from Grains Products Processing, and suitable starches or modifiedstarches include Capsul ET“ and Amiogum 237” which are commercially available fromNational Starch Chemical Co. and American Maze Co., respectively.The second encapsulating material may include optional additive ingredients suchas plasticizers, anti-agglomeration agents, and mixtures thereof. The optional plasticizersinclude sorbitol, polyethylene glycol, propylene glycol, low molecular weightcarbohydrates and the like with a mixture of sorbitol and polyethylene glycol with smallmolecular weight polyols being the most preferred. The plasticizer is employed at levels offrom about 0.01% to about 5%. The anti-agglomeration agents according to the presentinvention are preferably a surfactant and are included at low levels of less than 1% of thesecond encapsulating material. Suitable surfactants for use in the present invention includeTWEEN 80"‘ commercially available from Imperial Chemicals, Inc..Porous Carrier ParticlesAs used herein, "porous carrier particles" means any material capable ofsupporting (e. g., by adsorption onto the surface or absorption into pores) a perfume agentfor incorporation into the particulate compositions. Such materials include porous solidsselected from the group consisting of amorphous silicates, crystalline nonlayer silicates,layer silicates, calcium carbonates, calcium/sodium carbonate double salts, sodiumcarbonates, clays, zeolites, sodalites, alkali metal phosphates, macroporous zeolites,chitin microbeads, carboxyalkylcelluloses, carboxyalkylstarches, cyclodextrins, porousstarches and mixtures thereof.Preferred perfilme carrier materials are zeolite X, zeolite Y and mixtures thereof.The term "zeolite" used herein refers to a crystalline aluminosilicate material. TheCA 02265804 l999-03- 16wo 93/12293 PCTIUS97/156301 3structural fonnula of a zeolite is based on the crystal unit cell, the smallest unit ofstructure represented byMm/n[(AlO2)m(SiO2)y]-xH20where n is the valence of the cation M, x is the number of water molecules per unit cell,in and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100. Mostpreferably, y/m is 1 to 5. The cation M can be Group IA and Group IIA elements, suchas sodium, potassium, magnesium, and calcium.The zeolite useful herein is a faujasite-type zeolite, including Type X Zeolite orType Y Zeolite, both with a nominal pore size of about 8 Angstrom units, typically in therange of from about 7.4 to about 10 Angstrom units.The aluminosilicate zeolite materials useful in the practice of this invention arecommercially available. Methods for producing X and Y-type zeolites are well- knownand available in standard texts. Preferred synthetic crystalline aluminosilicate materialsuseful herein are available under the designation Type X or Type Y.For purposes of illustration and not by way of limitation, in a preferredembodiment, the crystalline aluminosilicate material is Type X and is selected from thefollowing:(I) Na86[AlO2]86-(SiO2) I O6]-xH2O ,(II) K86[AlO2]86'(Sl02)106]'XH2O,(III) Ca 40Na6[AlO2]8 6-(S102) 1 0 6]-xH20 ,(IV) Srz I Ba22[AlO2]86-(SiO2)106]-xH2O,and mixtures thereof, wherein x is from about 0 to about 276. Zeolites of Formula (I)and (II) have a nominal pore size or opening of 8.4 Angstroms units. Zeolites of Formula(III) and (IV) have a nominal pore size or opening of 8.0 Angstroms units.In another preferred embodiment, the crystalline aluminosilicate material is TypeY and is selected from the following:(V) Na56[AlO2]56-(SiO2)136]-xH2O ,(W) K56[A'°2]56'(S‘02)136]"‘H2° ..and mixture thereof, wherein x is from about 0 to about 276. Zeolites of Formula (V)and (VI) have a nominal pore size or opening of 8.0 Angstroms units.Zeolites used in the present invention are in particle form having an averageparticle size from about 0.5 microns to about 120 microns, preferably from about 0.5microns to about 30 microns, as measured by standard particle size analysis technique.The size of the zeolite particles allows them to be entrained in the fabrics withwhich they come in contact. Once established on the fabric surface (with their coatingmatrix having been washed away during the laundry process), the zeolites can begin toCA 02265804 l999-03- 16WO 98/12298 PCT/US97Il56301 4release their incorporated laundry agents, especially when subjected to heat or humidconditions.lncogporation of Perfume in Zeolit - The Type X or Type Y Zeolites to be usedherein preferably contain less than about 15% desorbable water, more preferably lessthan about 8% desorbable water, and most preferably less than about 5% desorbablewater. Such materials may be obtained by first activating/dehydrating by heating toabout 150 to 350°C, optionally with reduced pressure (from about 0.00] to about 20Torr). After activation, the agent is slowly and thoroughly mixed with the activatedzeolite and, optionally, heated to about 60°C for up to about 2 hours to accelerateabsorption equilibrium within the zeolite particles. The perfume/zeolite mixture is thencooled to room temperature and is in the form of a free-flowing powder.The amount of laundry agent incorporated into the zeolite carrier is less than about20%, typically less than about 18.5%, by weight of the loaded particle, given the limitson the pore volume of the zeolite. It is to be recognized, however, that the presentinvention particles may exceed this level of laundry agent by weight of the particle, butrecognizing that excess levels of laundry agents will not be incorporated into the zeolite,even if only deliverable agents are used. Therefore, the present invention particles maycomprise more than 20% by weight of laundry agents. Since any excess laundry agents(as well as any non-deliverable agents present) are not incorporated into the zeolite pores,these materials are likely to be immediately released to the wash solution upon contactwith the aqueous wash medium.In addition to its function of containing/protecting the perfume in the zeoliteparticles, the carbohydrate material also conveniently serves to agglomerate multipleperfumed zeolite particles into agglomerates having an overall particles size in the rangeof 200 to 1000 microns, preferably 400 to 600 microns. This reduces dustiness.Moreover, it lessens the tendency of the smaller, individual perfumed zeolites to sift tothe bottom of containers filled with granular detergents, which, themselves, typicallyhave particle sizes in the range of 200 to 1000 microns.PerfumeAs used herein the term "perfume" is used to indicate any odoriferous materialwhich is subsequently released into the aqueous bath and/or onto fabrics contactedtherewith. The perfume will most often be liquid at ambient temperatures. A widevariety of chemicals are known for perfume uses, including materials such as aldehydes,ketones, alcohols and esters. More commonly, naturally occurring plant and animal oilsand exudates comprising complex mixtures of various chemical components are knownfor use as perfumes. The perfumes herein can be relatively simple in their compositionsor can comprise highly sophisticated complex mixtures of natural and synthetic chemicalCA 02265804 l999-03- 16W0 98/ 12298 PCT/US97/156301 5components, all chosen to provide any desired odor. Typical perfumes can comprise, forexample, woody/earthy bases containing exotic materials such as sandalwood, civet andpatchouli oil. The perfumes can be of a light floral fragrance, e.g., rose extract, violetextract, and lilac. The perfumes can also be formulated to provide desirable fruity odors,e.g., lime, lemon, and orange. Any chemically compatible material which exudes apleasant or otherwise desirable odor can be used in the perfumed compositions herein.Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances (e.g., digeranyl succinate), hydrolyzable inorganic-organic pro-fragrances, and mixtures thereof. These pro-fragrances may release theperfume material as a result of simple hydrolysis, or may be pH-change—triggered pro-fragrances (e.g., pH drop) or may be enzymatically releasable pro-fragrances.Preferred perfume agents useful herein are defined as follows.For purposes of the present invention compositions exposed to the aqueousmedium of the laundry wash process, several characteristic parameters of perfumemolecules are important to identify and define: their longest and widest measures; crosssectional area; molecular volume; and molecular surface area. These values arecalculated for individual perfume molecules using the CHEMX program (from ChemicalDesign, Ltd.) for molecules in a minimum energy conformation as determined by thestandard geometry optimized in CHEMX and using standard atomic van der Waal radii.Definitions of the parameters are as follows:"Longest": the greatest distance (in Angstroms) between atoms in the moleculeaugmented by their van der Waal radii."Widest": the greatest distance (in Angstroms) between atoms in the moleculeaugmented by their van der Waal radii in the projection of the molecule on a planeperpendicular to the "longest" axis of the molecule."Cross Sectional Area": area (in square Angstrom units) filled by the projection ofthe molecule in the plane perpendicular to the longest axis."Molecular Volume": the volume (in cubic Angstrom units) filled by themolecule in its minimum energy configuration."Molecular Surface Area": arbitrary units that scale as square Angstroms (forcalibration purposes, the molecules methyl beta naphthyl ketone, benzyl salicylate, andcamphor gum have surface areas measuring 128 1 3, l63.5 1 3, and 122.5 1 3 unitsrespectively).The shape of the molecule is also important for incorporation. For example, asymmetric perfectly spherical molecule that is small enough to be included into thezeolite channels has no preferred orientation and is incorporated from any approachdirection. However, for molecules that have a length that exceeds the pore dimension,CA 02265804 l999-03- 16WO 98/12298 PCT/U S97! 156301 6there is a preferred "approach orientation" for inclusion. Calculation of a molecule'svolume/surface area ratio is used herein to express the "shape index" for a molecule. Thehigher the value, the more spherical the molecule.For purposes of the present invention, perfume agents are classified according totheir ability to be incorporated into zeolite pores, and hence their utility as componentsfor delivery from the zeolite carrier through an aqueous environment. Plotting theseagents in a volume/surface area ratio vs. cross sectional area plane permits convenientclassification of the agents in groups according to their incorporability into zeolite. Inparticular, for the zeolite X and Y carriers according to the present invention, agents areincorporated if they fall below the line (herein referred to as the "incorporation line")defined by the equation:y = -0.0l068x + 1.497where x is cross sectional area and y is volume/surface area ratio. Agents that fallbelow the incorporation line are referred to herein as "deliverable agents"; those agentsthat 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 function of their affinity for the carrier relative to competing deliverableagents. Affinity is impacted by the molecule's size, hydrophibicity, functionality,volatility, etc., and can be effected via interaction between deliverable agents within thezeolite carrier. These interactions permit improved through the wash containment for thedeliverable agents mixture incorporated. Specifically, for the present invention, the useof deliverable agents having at least one dimension that is closely matched to the zeolitecarrier pore dimension slows the loss of other deliverable agents in the aqueous washenvironment. Deliverable agents that function in this manner are referred to herein as"blocker agents", and are defined herein in the volume/surface area ratio vs. crosssectional area plane as those deliverable agent molecules falling below the "incorporationline" (as defined herein before) but above the line (herein referred to as the "blockerline") defined by the equation:y = -0.0l325x +1.46where x is cross sectional area and y is volume/surface area ratio.For the present invention compositions which utilizezeolite X and Y as thecarriers, all deliverable agents below the "incorporation line" can be delivered andreleased from the present invention compositions, with the preferred materials beingthose falling below the "blocker line". Also preferred are mixtures of blocker agents andother deliverable agents. Laundry perfume agent mixtures useful for the presentinvention laundry particles preferably comprise from about 5% to about 100%(preferably from about 25% to about 100%; more preferably from about 50% to aboutCA 02265804 l999-03- 16WO 98/12298 PCTIUS97/156301 7100%) deliverable agents; and preferably comprising from about 0.1% to about 100%(preferably from about 0.1% to about 50%) blocker agents, by weight of the laundryagents mixture.Obviously for the present invention compositions whereby perfume agents arebeing delivered by the compositions, sensory perception is required for a benefit to beseen by the consumer. For the present invention perfume compositions, the mostpreferred perfume agents useful herein have a threshold of noticability (measured as odordetection thresholds ("ODT") under carefully controlled GC conditions as described indetail hereinafter) less than or equal to 10 parts per billion ("ppb"). Agents with ODTsbetween 10 ppb and 1 part per million ("ppm") are less preferred. Agents with ODTsabove 1 ppm are preferably avoided. Laundry agent perfume mixtures useful for thepresent invention laundry particles preferably comprise from about 0% to about 80% ofdeliverable agents with ODTs between 10 ppb and 1 ppm, and from about 20% to about100% (preferably from about 30% to about 100%; more preferably from about 50% toabout 100%) of deliverable agents with ODTs less than or equal to 10 ppb.Also preferred are perfumes carried through the laundry process and thereafterreleased into the air around the dried fabrics (e.g., such as the space around the fabricduring storage). This requires movement of the perfume out of the zeolite pores withsubsequent partitioning into the air around the fabric. Preferred perfume agents aretherefore further identified on the basis of their volatility. Boiling point is used herein as ameasure of volatility and preferred materials have a boiling point less than 300°C. Laundryagent perfume mixtures useful for the present invention laundry particles preferablycomprise at least about 50% of deliverable agents with boiling point less than 300°C(preferably at least about 60%; more preferably at least about 70%).In addition, preferred laundry particles herein comprise compositions wherein atleast 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.Calculation of C1ogP:These perfume ingredients are characterized by their octanol/water partitioncoefficient P. The octanol/water partition coefficient of a perfume ingredient is the ratiobetween its equilibrium concentration in octanol and in water. Since the partitioncoefficients of most perfume ingredients are large, they are more conveniently given inthe form of their logarithm to the base 10, logP.The logP of many perfume ingredients has been reported; for example, thePomona92 database, available from Daylight Chemical Infonnation Systems, lnc.(Daylight CIS), contains many, along with citations to the original literature.CA 02265804 l999-03- 16W0 98/12298 PCT/US97l15630l 8However, the logP values are most conveniently calculated by the "CLOGP"program, also available from Daylight CIS. This program also lists experimental logPvalues when they are available in the Pomona92 database. The "calculated logP" (ClogP)is determined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J. B. Taylorand C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990). The fragment approach isbased on the chemical structure of each perfume ingredient and takes into account thenumbers and types of atoms, the atom connectivity, and chemical bonding. The CIogPvalues, which are the most reliable and widely used estimates for this physicochemicalproperty, can be used instead of the experimental logP values in the selection of perfumeingredients.Determination of Odor Detection Thresholds: The gas chromatograph is characterized to determine the exact volume of materialinjected by the syringe, the precise split ratio, and the hydrocarbon response using ahydrocarbon standard of known concentration and chain-length distribution. The airflow rate is accurately measured and, assuming the duration of a human inhalation to last0.2 minutes, the sampled volume is calculated. Since the precise concentration at thedetector at any point in time is known, the mass per volume inhaled is known and hencethe concentration of material. To determine whether a material has a threshold below 10ppb, solutions are delivered to the sniff port at the back-calculated concentration. Apanelist sniffs the GC effluent and identifies the retention time when odor is noticed.The average over all panelists detennines the threshold of noticeability.The necessary amount of analyte is injected onto the column to achieve a 10 ppbconcentration at the detector. Typical gas chromatograph parameters for determiningodor detection thresholds are listed below.GC: 5890 Series II with FID detector7673 AutosamplerColumn: J&W Scientific DB-1Length 30 meters ID 0.25 mm film thickness 1 micronMethod:Split Injection: 17/1 split ratioAutosampler: l.l3 microliters per injectionColumn Flow: 1.10 mL/minuteAir Flow: 345 mL/minuteInlet Temp. 245°CDetector Temp. 285°CTemperature lnfomiationCA 02265804 l999-03- 16wo 93/12293 PCT/US97/15630I 9Initial Temperature: 50°CRate: SC/minuteFinal Temperature: 280°CFinal Time: 6 minutesLeading assumptions: 0.02 minutes per sniffGC air adds to sample dilutionPerfiime Fixative:Optionally, the perfume can be combined with a perfume fixative. The perfumefixative materials employed herein are characterized by several criteria which make themespecially suitable in the practice of this invention. Dispersible, toxicologically-accept-able, non-skin irritating, inert to the perfume, degradable and/or available fromrenewable resources, and relatively odorless additives are used. Perfume fixatives arebelieved to slow the evaporation of more volatile components of the perfume.Examples of suitable fixatives include members selected from the groupconsisting of diethyl phthalate, musks, and mixtures thereof. If used, the perfumefixative comprises from about 10% to abut 50%, preferably from about 20% to about40%, by weight, of the perfume.Adjunct Laundg or Cleaning IngredientsAdjunct ingredients useful for in or with the laundry or cleaning particulatecompositions according to the present invention are selected from the group consisting ofsurfactants, perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts,chelants, antiscalants, threshold inhibitors, dye transfer inhibitors, photobleaches,enzymes, catalytic antibodies, brighteners, fabric-substantive dyes, antifungals,antimicrobials, insect repellents, soil release polymers, fabric softening agents, dyefixatives, pH jump systems, and mixtures thereof. As can be appreciated for the presentinvention, these agents useful for laundry or cleaning compositions which areincorporated into the particulate compositions of the present invention may be the sameas or different from those agents which are used to formulate the remainder of thelaundry and cleaning compositions containing the particulate compositions produced bythe instant process. For example, the particulate compositions may comprise a perfumeagent and the same or different agent may also be blended into the final compositionalong with the perfume-containing particulate composition. These agents are selected asdesired for the type of composition being formulated, such as granular laundry detergentcompositions, granular automatic dishwashing compositions, or hard surface cleaners.The various types of agents useful in laundry and cleaning compositions aredescribed hereinafter. The compositions containing particulate compositions canoptionally include one or more other detergent adjunct materials or other materials forCA 02265804 l999-03- 16W0 98ll2298 PCT/US97/1563020assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or tomodify the aesthetics of the detergent composition.Detersive SurfactantThe granules and/or the agglomerates include surfactants at the levels statedpreviously. The detersive surfactant can be selected from the group consisting of anionicsurfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures.Nonlimiting examples of surfactants useful herein include the conventional C 1 1-C13 alkylbenzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkylsulfates ("AS"), the C10-C18 secondary (2,3) alkyl sulfates of the formulaCH3(CH2)x(CHOSO3'M+) CH3 and CH3 (CH2)y(CHOSO3'M+) CI-IZCH3 where x and(y + 1) are integers of at least about 7, preferably at least about 9, and M is awater—solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, theC10-C13 alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), C10—C13 alkylalkoxy carboxylates (especially the E0 1-5 ethoxycarboxylates), the C10_13 glycerolethers, the C10-C13 alkyl polyglycosides and their corresponding sulfated polyglycosides,and C12-C13 alpha-sulfonated fatty acid esters. If desired, the conventional nonionic andamphoteric surfactants such as the C12-C13 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), C 12-C13 betaines and sulfobetaines ("sultaines"),C10-C13 amine oxides, and the like, can also be included in the overall compositions. TheC10-C13 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examplesinclude the C12—C18 N-methylglucamides. See W0 9,206,154. Other sugar—derivedsurfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12~C13 glucamides can beused for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing isdesired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionicsurfactants are especially useful. Other conventional useful surfactants are listed instandard texts.The C10-C13 alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates)and C12-C18 alkyl-ethoxylates ("AE") are the most preferred for the cellulase-containingdetergents described herein.Detersive BuilderThe granules and agglomerates preferably include a builder at the previously statedlevels. To that end, inorganic as well as organic builders can be used. Also, crystalline aswell as amorphous builder materials can be used. Builders are typically used in fabriclaundering compositions to assist in the removal of particulate soils and to eliminate orminimize the effects of water hardness during eashing processes.CA 02265804 l999-03- 16wo 98/12298 PCT/US97/15630' 21Inorganic or P-containing detergent builders include, but are not limited to, thealkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified bythe tri.polyphosphates, pyrophosphates, and glassy polymeric meta-phosphates),phosphonates, phytic acid, silicates, carbonates (including bicarbonates andsesquicarbonates), sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. importantly, the compositions herein function surprisingly welleven in the presence of the so-called "weak" builders (as compared with phosphates) suchas citrate, or in the so-called "under built" situation that may occur with zeolite or layeredsilicate builders.Examples of silicate builders are the alkali metal silicates, particularly those havinga SiO2:Na2O ratio in the range 1.6:1 to 3.221 and layered silicates, such as the layeredsodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicatebuilder does not contain aluminum. NaSKS-6 has the delta-Na2SiO5 morphology form oflayered silicate. It can be prepared by methods such as those described in German DE-A-I3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein,but other such layered silicates, such as those having the general formulaNaMSixO2x+1-yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4,preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Variousother layered silicates from I-Ioechst include NaSKS-5, NaSKS-7 and NaSl(S-I 1, as thealpha, beta and gamma forms. As noted above, the delta-Na2SiO5 (NaSKS-6 form) is mostpreferred for use herein. Other silicates may also be useful such as for example magnesiumsilicate, which can serve as a crispening agent in granular formulations, as a stabilizingagent for oxygen bleaches, and as a component of suds control systems.Examples of carbonate builders are the alkaline earth and alkali metal carbonates asdisclosed in Gemian Patent Application No. 2,321,001 published on November 15, 1973.As mentioned previously, aluminosilicate builders are useful builders in the presentinvention. Aluminosilicate builders are of great importance in most currently marketedheavy duty granular detergent compositions, and can also be a significant builder ingredientin liquid detergent formulations. Aluminosilicate builders include those having theempirical formula:MZ(zAlO2)y]-xH2Owherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 toabout 0.5, and x is an integer from about 15 to about 264.Useful aluminosilicate ion exchange materials are commercially available. Thesealuminosilicates can be crystalline or amorphous in structure and can be naturally-CA 02265804 l999-03- 16W0 98/ 12298 PCTIU S97/ 1563022occurring aluminosilicates or synthetically derived. A method for producingaluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, etal, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchangematerials useful herein are available under the designations Zeolite A, Zeolite P (B),Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystallinealuminosilicate ion exchange material has the fonnula:N812[(A|02)12(Si02)12]-xH20wherein x is from about 20 to about 30, especially about 27. This material is known asZeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, thealuminosilicate has a particle size of about 0.1-10 microns in diameter.Organic detergent builders suitable for the purposes of the present inventioninclude, but are not restricted to, a wide variety of polycarboxylate compounds. As usedherein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups,preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of a neutralized salt. Whenutilized in salt form, alkali metals, such as sodium, potassium, and lithium, oralkanolammonium salts are preferred.Included among the polycarboxylate builders are a variety of categories of usefulmaterials. One important category of polycarboxylate builders encompasses the etherpolycarboxylates, including oxydisuccinate, as disclosed 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 Patent 4,663,071, issued to Bush et al, on May 5,1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicycliccompounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635;4,120,874 and 4,102,903.Other useful detergency builders include the ether hydroxypolycarboxylates,copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxybenzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkalimetal, ammonium and substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates suchas 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 detergentformulations due to their availability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially in combination with zeoliteCA 02265804 l999-03- 16W0 98/12298 PCT/US97/1563023and/or layered silicate builders. Oxydisuccinates are also especially useful in suchcompositions and combinations.Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa—l,6-hexanedioates and the related compounds disclosed in U.S. Patent4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compoundof this type is dodecenylsuccinic acid. Specific examples of succinate builders include:laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2—dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of thisgroup, and are described in European Patent Application 862006905/0,200,263, publishedNovember 5, 1986.Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfieldet 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., C12-C18 monocarboxylic acids, can also be incorporated into thecompositions alone, or in combination with the aforesaid builders, especially citrate and/orthe succinate builders, to provide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken into account by theformulator.In situations where phosphorus-based builders can be used, and especially in theformulation of bars used for hand-laundering operations, the various alkali metalphosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate andsodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1, l-diphosphonate and other known phosphonates (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.Other Adjunct IngredientsThe detergent composition may also include enzymes, enzyme stabilizers,brighteners, polymeric dispersing agents (i.e. polyacrylates), carriers, hydrotropes, sudsboosters or suppressers, soil release agents, dye transfer inhibitors, and processing aids.In order to make the present invention more readily understood, reference is madeto the following examples, which are intended to be illustrative only and not intended to belimiting in scope.Example 1A solution of 82% solid carbohydrate material (having a dextrose equivalence 62)and the balance water is premixed in an agitated mixing vessel with 1.5% by weight TiO2powder (commercially sold under the trade name Tronox by the Kerr McGee ChemicalCorporation) to form a carbohydrate encapsulation fluid solution. The carbohydrate fluid isCA 02265804 l999-03- 16wo 98/12298 PCT/US97/15630‘ 24dried to a moisture level of 2% in a LuwaTM Wiped Film Evaporator ("WFE") and is thencooled to form a solid glassy material. The resulting carbohydrate fluid has a moisturelevel of 2.0%. Thereafter, the carbohydrate fluid and zeolite X loaded with 16% perfumeby weight ("PLZ") are inputted at a weight ratio of 1:1 into a 12 barrel, Werner &PfleidererTM ZSK 30 twin screw extruder ("TSE") without a constricting die plate to fonnagglomerates. Barrels 1 through 4 of the TSE are maintained at a temperature of 80°Cwhile barrels 5 and 6 are maintained at a temperature of 90°C, barrels 7 and 8 at atemperature of 130°C, barrels 9 and 10 at a temperature of 135°C, and barrels 11 and 12 ata temperature of 13°C. The carbohydrate fluid is fed at a temperature of 160°C to the TSEin barrel 7, while the PLZ is added in barrel 11 and intimately mixed with the carbohydratefluid prior to leaving the TSE as an extmdate having a discharge temperature of 145°C anda rate of 500 g/min. The product is cooled at room temperature to form free flowingparticles which are ground in a Fitz Mi1lTM (commercially available from the FitzpatrickCompany) and sized via screening to result in particles in the size range of 150 microns to1180 microns. The sized particles are then sent to a Wurster fluid bed coater in which anaqueous mixture containing 22.5% of Maltrin M040” commercially available from GrainProcessing Corporation, 1.0% of D-Sorbitolm commercially available from J.T. Baker,1.0% of polyethylene glycol (Carbowaxm PEG 600 commercially available from UnionCarbide), and 0.5% of surfactant (TWEEN 80"‘ commercially available from ImperialChemicals, Inc.(ICI)) is added. The coated particles are dried to produce a particulatecomposition extremely suitable for use as a laundry additive composition.The particles formed unexpectedly have a superior "Neat Product Odor" ("NPO")in that it does not emit any detectable odor over the base product odor as observed by astatistically significant number of panelist graders. This provides strong evidence of thelack of perfume displacement from the carrier particles.Example 11Several detergent compositions made in accordance with the invention andspecifically for top-loading washing machines are exemplified below incorporating theperfume particle prepared in Example I.% WeightBase Granule A E QAluminosilicate 18.0 22.0 24.0Sodium Sulfate 10.0 19.0 6.0Sodium Polyacrylate Polymer 3.0 2.0 4.0Polyethylene Glycol (MW=400) 2.0 1.0 --C12-13 Linear Alkylbenzene Sulfonate, Na 6.0 7.0 3.0€14-16 Secondary Alkyl Sulfate, Na 3.0 3.0 --CA 02265804 l999-03- 16W0 98/12298 PCT/US97/1563025C14-15 Alkyl Ethoxylated Sulfate, Na 3.0 9.0 --Sodium Silicate 1.0 2.0 3.0Brightener 24/471 0.3 0.3 03Sodium Carbonate 7.0 26.0Carboxymethyl Cellulose -- -- 1.0DTPMPA2 -- -- 0.5DTPA3 0.5 -- --Admixed AgglomeratesC14-15 Alkyl Sulfate, Na 5.0 -- --C12-13 Linear Alkylbenzene Sulfonate, Na 2.0 -- --Sodium Carbonate 4.0 -- --Polyethylene Glycol (MW=4000) l.0 -- --;A_d_II_I£Sodium Carbonate -- -- 13.0Cl2—l5 Alkyl Ethoxylate (EO=7) 2.0 0.5 2.0C12-15 Alkyl Ethoxylate (EO=3) —~ -- 2.0Perfume Spray-On 0.3 0.4 0.3Perfume Particles4 0.5 0.5 0.5Polyvinylpyrrilidone 0.5 -- --Polyvinylpyridine N-oxide 0.5 -- --Polyvinylpyrrolidone-polyvinylimidazole 0.5 -- --Distearylamine & Cumene Sulfonic Acid 2.0 -- --Soil Release Polymer5 0.5 -- --Lipolase Lipase (1oo,ooo LU/I)6 0.5 -— 0.5Termamyl Amylase (60 KNU/g)5 0.3 -- 0.3CAREZYME® Cellulase (1000 CEVU/g)5 0.3 -- --Protease (40mg/g)7 0.5 0.5 0.5NOBS3 5.0 -— --TAED9 -- -- 3.0Sodium Percarbonate l2.0 -- --Sodium Perborate Monohydrate -- -- 22.0Polydimethylsiloxane 0.3 -- 3.0Sodium Sulfate -- -- 3.0Miscellaneous (water, etc.) gaging; _l;a_l_g1_c_e ga_la_n_9_gTotal 100.0 100.0 100.01 Purchased from Ciba—Geigy2 Diethylene Triamine Pentamethylene Phosophonic AcidCA 02265804 l999-03- 16W0 98/ 12298 PCT/US97/15630263 Diethylene Triamine Pentaacetic Acid4 From Example I5 Made according to U.S. Patent 5,415,807, issued May 16, 1995 to Gosselink et al6 Purchased from Novo Nordisk A/S7 Purchased from Genencor8 Nonanoyloxybenzenesulfonate9 Tetra Acetyle Ethylene DramineExample 111The following detergent compositions containing a perfume particle from Example1 in accordance with the invention are especially suitable for front loading washingmachines.% WeightBase Granule A QAluminosilicate 15.0 --Sodium Sulfate . 2.0 --C12-13 Linear Alkylbenzene Sulfonate, Na 3.0 --DTPMPA1 0.5 --Carboxymethylcellulose 0.5 --Acrylic Acid/Maleic Acid Co-polymer 4.0 --Admixed Agglomerates 5C 14-15 Alkyl Sulfate, Na -- 11.0C 12-13 Linear Alkylbenzene Sulfonate, Na 5.0 --C18-22 Alkyl Sulfate, Na 2.0 --Sodium Silicate 4.0 --Aluminosilicate 12.0 13.0Carboxymethylcellulose -- 0.5Acrylic Acid/Maleic Acid Co-polymer —- 2.0Sodium Carbonate 8.0 7.0A_dI£i§Perfume Spray-On A 0.3 0.5Perfume Particlesz 0.5 A 0.5C012-15 Alky1Ethoxylate(EO=7) 4.0 4.0C12-15 Alkyl Ethoxylate (EO=3) 2.0 2.0Acrylic Acid/Maleic Acid Co-polymer -- 3.0Crystalline Layered Silicate3 -- 12.0Sodium Citrate 5.0 8.0Sodium Bicarbonate 5.0 5.0CA 02265804 l999-03- 16W0 98/1229827Sodium CarbonatePolyvinylpyrrilidoneAlcalase protease4 (3.0 AU/g)Lipolase Lipase4 (l00,000 LU/1)Termamyl Amy|ase4 (60KNU/g)CAREZYME® Cellulase4 (IOOOCEVU/g)Sodium SulfateMiscellaneous (water, etc.)Total6.00.50.50.50.50.54.0balance100.01 Diethylene Triamine Pentamethylenephosphonic Acid2 From Example I3 SKS 6 commercially available from Hoechst4 Purchased from Novo Nordisk A/SPCTIU S9711 563015.00.51.00.50.50.50.0P212222100.0CA 02265804 l999-03- 16W0 98/ 12298 PCT /U S97/ 1563028Example IVThe following detergent compositions according to the invention are suitable forlow wash volume, top loading washing machines.(% Weight)Base Granules AAluminosilicate 7.0Sodium Sulfate 3.0Polyethylene Glycol (MW=4000) 0.5Acrylic Acid/Maleic Acid Co-polymer 6.0Cationic Surfactantl 0.5C1446 Secondary Alkyl Sulfate, Na 7.0C1243 Linear Alkylbenzene Sulfonate, Na 13.0C1445 Alkyl Ethoxylated Sulfate, Na 6.0Crystalline Layered Silicatez 6.0Sodium Silicate 2.0Oleic Fatty Acid, Na 1.0Brightener 493 0.3Sodium Carbonate 28.0DTPA4 0.3A_<1m_ixC12-15 Alkyl Ethoxylate (EO=7) 1.0Perfume Spray-On 1.0Perfume Partic1es5 1_0Soil Release Polymer5 0.5Polyvinylpyrrilidone 0.3Polyvinylpyridine N-Oxide 0.1Polyvinylpyrrilidone-polyvinylimidazole 0.1Lipolase Lipase (l00.000LU/g)7 0.3Termamyl Amylase (60KNU/g)7 0.1CAREZYME® Cellulase (1000 CEVU/g)7 0.1Savinase (4.0 KNPU/g)7 1.0NOBS3 4.0Sodium Perborate Monohydrate 5.0Miscellaneous (water, etc.) Qal_21n_ceTotal 100.01 C1244 Dimethyl Hydroxyethyl Quaternary Ammonium Compound2 SKS 6 commercially available from I-loechstCA 02265804 l999-03- 16WO 98112298 PCT/US97/15630293 Purchased from Ciba-Geigy4 Diethylene Triamine Pentaacetic Acid5 From Example I6 Made according to U.S. patent 5,415,807 issued May 16, 1995 to Gosselink et a17 Purchased from Novo Nordisk A/S3 NonanoyloxybenzenesulfonateExample VThe following detergent compositions according to the invention are suitable formachine and handwashing operations. The base granule is prepared by a conventionalspray drying process in which the starting ingredients are formed into a slurry and passedthrough a spray drying tower having a counter current stream of hot air (200-400°C)resulting in the formation of porous granules. The remaining adjunct detergent ingredientsare sprayed on or added dry.(% Weight)Base Granule A EC12_1 3 Alkylbenzene Sulfonate, Na 19.0 18.0Cationic Surfactant] 0.5 0.5DTPMPA2 0.3 --DTPA3 -- 0.3Sodium Tripolyphosphate 25.0 19.0Acrylic/Maleic Co-polymer 1.0 0.6Carboxymethylcellulose 0.3 0.2Brightener 49/15/334 0.2 0.2Sodium Sulfate 28.0 39.0Sodium Silicate (2.0R) 7.5 --Sodium Silicate (1 .6R) -- 7.5MgSodium Carbonate 5.0 6.0(312.13 A1kylEthoxy1ate(EO=7) 0.4 --Savinase5 Protease (4KNPY/g) 0.6 --Tennamyl5 Amylase (60KNU/g) 0.4 --Lipolase5 Lipase (l00,000 LU/I) 0.1 0.1Sav/Ban5 (6 KNPU/100 KNU/g) -- 0.3CAREZYME®5 Cellulase (1000 CEVU/g) -- 0.1Soil Release Po1ymer5 0.1 0.1Perfume Spray-On 0.4 0.4Quantum(zinc phthalocyanine sulfonate) 2.0 2.015.06.020.0CA 02265804 l999-03- 16W0 98/ 12298 PCT/U S97/ 1563030Perfume Particles7 1.5 1.5 2,0Miscellaneous (water, etc.) balance balance balanceTotal 100.0 100.0 100.01 C12_ 14 Dimethyl Hydroxyethyl Quaternary Ammonium Compound2 Diethylene Triamine Pentamethylenephosphoric Acid3 Diethylene Triamine Pentaacetic Acid4 Purchased from Ciba-Geigy5 Purchased from Novo Nordisk A/S6 Made according to U.S. patent 5,415,807 issued May 16, 1995 to Gosselink et al7 From Example IExample VIThe following detergent composition according to the invention is in the fonn of alaundry bar which is particularly suitable for handwashing operations.(% Weight)ACoconut Fatty Alkyl Sulfate 30.0Sodium Tripolyphosphate 5.0Tetrasodium Pyrophosphate 5.0Sodium Carbonate 20.0Sodium Sulfate 5.0Calcium Carbonate 5.0Na1_9K0_1Ca(CO3)2 15.0Aluminosilicate 2.0Coconut Fatty Alcohol 2.0Perfume Particles] 1.0Perfume Spray-On 1.0Miscellaneous (water, etc.) IggyTotal 100.01 From Example I.Having thus described the invention in detail, it will be clear to those skilled in theart that various changes may be made without departing from the scope of the inventionand the invention is not to be considered limited to what is described in the specification.

Claims (10)

WHAT IS CLAIMED IS:

1. A process for producing a particulate laundry additive composition characterized by the steps of:
(a) inputting a first encapsulating material and porous carrier particles into an extruder, said porous carrier particles having a perfume absorbed therein;
(b) extruding said porous carrier particles and said first encapsulating material so as to form an extrudate containing said porous carrier particles enrobed with said first encapsulating material;
(c) cooling said extrudate;
(d) grinding said extrudate into granules; and (e) coating said granules with a second encapsulating material, thereby forming said particulate laundry additive composition.

2. The process according to claim 1 wherein said first and second encapsulating materials are substantially free of water.

3. The process according to claims 1-2 wherein said first and second encapsulating materials are in the glass phase and have a glass transition temperature in the range of from 30°C to 200°C.

4. The process according to claims 1-3 wherein said first and second encapsulating materials are 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.

5. The process according to claims 1-4 further characterized by the step of adding a pigment to said extruder.

6. The process according to claim 5 wherein said pigment is selected from the group consisting titanium dioxide, silica, sodium alumina silicate, ultramarines, optical brighteners and mixtures thereof.

7. The process according to claims 1-6 wherein said cooling step includes cooling said extrudate to be within a temperature range of from 20°C to 100°C.

8. The process according to claims 1-7 wherein said cooling step is completed within 1 second to 120 seconds.

9. The process according to claims 1-8 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 m 2/g.

10. A process for producing a particulate laundry additive composition characterized by the steps of:
(a) inputting a first carbohydrate material and porous carrier particles into an extruder, said porous carrier particles having a perfume absorbed therein;
(b) mixing said porous carrier particles and said first C material so as to form a particulate mixture containing said porous carrier particles enrobed with said first encapsulating material;
(c) cooling said particulate mixture;
(d) grinding said particulate mixture into granules; and (e) coating said granules with a second carbohydrate material, thereby forming said particulate laundry additive composition.