MXPA98008663A - Laundry additive particle having multiple surface coatings - Google Patents

Abstract

A laundry additive particle having multiple coatings and compositions employing the particle are provided. The laundry additive particle comprises a porous carrier core material;a first encapsulating material coated on the core material to form an intermediate layer, the first encapsulating material comprising a glassy material derived from one or more at least partially water-soluble hydroxylic compounds having an anhydrous, nonplasticized, glass transition temperature, Tg, of at least about 0°C;and a second encapsulating material coated on the intermediate layer to form an outer layer, the second encapsulating material comprising a carbohydrate material having an anhydrous, nonplasticized, glass transition temperature, Tg, of at least about 130°C;and the laundry additive particle has a hygroscopicity value of less than about 80%. Preferably, a laundry or cleaning agent such as a perfume is supported on or contained in the porous carrier.

Description

ADDITIVE PARTICLE FOR LAUNDRY THAT HAS MULTIPLE SURFACE COATINGS FIELD OF THE INVENTION The present invention relates generally to laundry additive particles having surface coatings and, more particularly, to zeolite particles loaded with perfume having multiple surface coatings.

BACKGROUND OF THE INVENTION Most consumers have waited for perfumed laundry products, and that fabrics that have been washed have a pleasant fragrance as well. The perfume additives make the laundry compositions aesthetically more pleasant to the consumer and, in some cases, the perfume imparts a pleasant fragrance to the fabrics treated therewith. However, the amount of perfume carried from an aqueous laundry solution to the fabric is often marginal. Therefore, the industry has long sought an effective perfume release system for use in laundry products that provides a durable and stable fragrance in product storage, as well as fragrance to washed fabrics.

Compositions for laundry and other compositions for the care of fabrics containing perfume mixed with, or sprinkled on, the compositions, are well known in commercial practice. Because perfumes are made from a combination of volatile compounds, the perfume can be emitted continuously from simple solutions and dry mixes to which the perfume has been added. Various techniques have been developed to hinder or delay the release of perfume from the compositions, so that they remain aesthetically pleasing for much longer. However, to date, a few methods provide significant aroma benefits to fabrics after prolonged storage of the product. In addition there has been a continuous search for methods and compositions that efficiently and efficiently release perfume from a wash solution on the surface of the fabrics. As can be seen from the following descriptions, various perfume release methods have been developed which involve the protection of the perfume through the washing cycle, with the release thereof on the fabrics. The patent of E.U.A. No. 4,096,072 by Brock et al., Issued June 20, 1978, teaches a method for releasing fabric conditioning agents, including perfume, through the washing and drying cycle by a fatty quaternary ammonium salt. The patent of E.U.A. 4,402,856 by Schnoring et al., Issued September 6, 1983, teaches a microencapsulation technique involving the formulation of a shell material that allows diffusion of the perfume out of the capsule only at certain temperatures. The patent of E.U.A. 4,152,272 per Young, issued lo. May 1979 teaches the incorporation of perfume into waxy particles to protect the perfume during storage in dry compositions and through the washing process. The perfume diffuses affirmatively through the wax on the fabric in the dryer. The patent of E.U-A. No. 5,066,419 by Walley et al., Issued November 19, 1991, teaches perfume dispersed with a non-polymeric water insoluble carrier material and encapsulated in a protective shell by coating with a friable coating material insoluble in water. The patent of E.U.A. No. 5,094,761 by Trinh et al., Issued March 10, 1992, teaches a clay-protected perfume / cyclodextrin complex which provides perfume benefits to at least partially wetted fabrics. Another method for releasing the perfume in the wash cycle involves combining the perfume with an emulsifier and water-soluble polymer, forming the mixture into particles, and adding them to a washing composition, as described in US Pat. 4,209,417 by Whyte, issued June 24, 1980; the patent of E.U.A. 4,339,356 by Whyte, issued July 13, 1982; and the patent of E.U.A. No. 3,576,760 by Gould et al., Issued April 27, 1971. However, even with the substantial work done by the industry in this area, there is still a need for a simple, more efficient and effective perfume release system than can be mixed with laundry compositions to provide initial and lasting perfume benefits to fabrics that have been treated with the laundry product. The perfume can also be adsorbed on a porous carrier material, such as a polymeric material, as described in UK Patent Pub. 2,066,839 by Bares et al., Published July 15, 1981. Perfumes have also been adsorbed. on a clay or zeolite material which is then mixed into particulate detergent compositions. Generally, the preferred zeolites have been type A or 4A zeolites, with a nominal pore size of approximately 4 Angstrom units. It is now thought that with zeolite A or 4A, the perfume is adsorbed on the surface of the zeolite, relatively little perfume being actually absorbed into the pores of the zeolite. While the adsorption of the perfume on the zeolite or polymeric carriers may perhaps provide some improvement over the addition of pure perfume mixed with the detergent compositions, the industry is still seeking improvements in the storage time duration of the laundry compositions without loss of the characteristics of the perfume, in the intensity or amount of fragrance released to the fabrics, and in the duration of the fragrance of perfume on the surface of treated fabrics.

Therefore, there is a need for a perfume release system that provides a satisfactory perfume aroma during use and then from the dried fabric, but which also provides prolonged storage benefits and reduced flavor intensity of the product.

TECHNICAL BACKGROUND The patent of E.U.A. No. 4,539,135 by Ramachandran et al., Issued September 3, 1985, discloses particulate laundry compounds comprising a clay or zeolite material bearing perfume. The patent of E.U.A. 4,713,193 by Tai, issued December 15, 1987, discloses a free-flowing particulate detergent additive comprising a liquid or oily adjunct material with a zeolite material. Japanese Patent HEI 4C1992] -218583 by Nishishiro, published on August 10, 1992, discloses controlled release materials including perfumes plus zeolites. The patent of E.U.A. 4,304,675 by Corey et al., Issued December 8, 1981, teaches a method and composition comprising zeolites for deodorant articles. Other patents are East German Patent Publication No. 248,508, published August 12, 1987; East German Patent Publication No. 137,599, published September 12, 1979; publication of European applications No. 535,942, published on April 7, 1993, and publication No. 536,942, published on April 14, 1993, by Unilever PLC; patent of E.U.A. 5,336,665, issued August 9, 1994 to Garner-Gray et al .; WO 94/28107, published December 8, 1994; patent of E.U.A. 5,258,132, issued November 2, 1993, and the patent of E.U.A. 5,230,822, issued July 27, 1993, both to Kamel and others; patent of E.U.A. 5,141,664, issued August 25, 1992 to Corring and others; and patent of E.U.A. 2,809,895, issued October 15, 1957 to S isher.

BRIEF DESCRIPTION OF THE INVENTION This need is covered by the present invention, in which an additive particle is provided for laundry. The additive laundry particle can be used to release several useful cleaning and laundry agents to or through the wash cycle. The additive laundry particle of the present invention essentially comprises a porous carrier material as a particle core, and multiple surface or encapsulation coatings on the porous core. The additive laundry particle of the present invention is particularly effective for releasing perfume ingredients through washing to the surface of a fabric. In traditional perfume release systems, more than 50% of the perfume material is "lost" due to diffusion of the product's volatile perfume materials, as well as by dissolution in the water, and is never released to the surface of the cloth. In the present invention, multiple coatings efficiently transport the perfume material loaded on, or in, the zeolite core. Thus, the perfume material is released at a higher rate through washing to the surface of the fabric, than with traditional perfume release systems. In accordance with a first embodiment of the present invention, an additive particle is provided for laundry. The additive laundry particle comprises: (i) a porous vehicle core material; (ii) a first encapsulating material coated on the core material to form an intermediate layer, the first encapsulating material comprising a vitreous material derived from one or more at least partially water-soluble hydroxyl compounds having a glass transition temperature, Tg, anhydrous, non-plasticized, of at least about 0 ° C; and (iii) a second encapsulating material coated on the intermediate layer to form an outer layer, the second encapsulating material comprising a carbohydrate material having a glass transition temperature, Tg, anhydrous, unplasticized, of at least about 130. ° C; and the additive particle for laundry has a hygroscopicity value of less than about 80%.

Preferably, the porous vehicle core material is selected from the group consisting of amorphous silicates, non-layered crystalline silicates, layered silicates, calcium carbonates, calcium / sodium carbonate double salts, sodium carbonates, clays, zeolites, sodalites, alkali metal phosphates, macroporous zeolites, chitin microspheres, carboxyalkylcelluloses, carboxyalkyl starches, cyclodextrins, porous starches, and mixtures thereof, and more preferably is a zeolite selected from the group consisting of zeolite X, Y zeolite, and mixtures of the same. The additive laundry particle further comprises a cleaning or laundry agent contained in or supported on the porous vehicle core. The cleaning or laundry agent is selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, anti-scale agents, dye transfer inhibitors, photobleaches, enzymes, antibodies catalysts, brighteners, substantive fabric colorants, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, pH leap systems, and mixtures thereof, and is preferably a perfume that is contained in a zeolite.

The first encapsulating material is a carbohydrate material having a dextrose equivalent, DE, of about 75 or less, and is preferably a hydrogenated starch hydrolyzate. The second encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 7.5 or less, preferably a modified starch or starch or a maltodextrin. The second encapsulating material may further include an ingredient selected from the group consisting of plasticizers, anti-agglomeration agents, and mixtures thereof, in conjunction with the carbohydrate. In addition, the additive particle for laundry has a hygroscopicity value of less than about % In accordance with a second embodiment of the present invention, a detergent composition for cleaning or laundry is provided. The cleaning or laundry composition comprises from about 0.001% to about 50% by weight of the composition of the additive laundry particle as described above, and from about 50% to about 99.999% by weight of the ingredient composition for laundry. laundry selected from the group consisting of detersive surfactants, detergency builders, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof. Preferably, the composition includes at least one detersive surfactant and at least one builder. Accordingly, an object of the present invention is to provide an additive laundry particle having multiple surface coatings. Another object of the present invention is to provide a cleaning or laundry composition having an additive laundry particle with multiple surface coatings thereon. Finally, an object of the present invention is to provide an additive laundry particle that can provide improved fabric flavoring benefits, prolonged storage life capabilities, and reduce the flavor intensity of the product. These and other objects, features and advantages of the present invention will be recognized by those skilled in the art from the following description and the appended claims. All percentages, ratios and proportions herein are on a weight basis, unless otherwise indicated. All documents cited herein are incorporated herein by reference.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The present invention relates to an additive particle for laundry and to compositions for cleaning and laundry using said particle. Cleaning and laundry compositions include traditional granular laundry detergents, as well as granular bleaching compositions, automatic dishwashing, hard surface cleaning, and fabric softening compositions. The additive laundry particle of the present invention provides superior perfume release capabilities through washing, and minimizes product scent due to the release of volatile perfume ingredients. While not wishing to be limited by theory, it is also thought that the multiple coatings of the particle of the present invention increase the stability of said particle. The laundry particle of the present invention comprises a core material that is a porous carrier. This porous vehicle core is then coated in a first encapsulating material to form an intermediate layer. The intermediate layer is then coated with a second encapsulating material that forms an outer layer on the particle. Thus, the laundry particle comprises a core with an intermediate layer of a first material, and an outer layer on the intermediate layer of a second material. The laundry particles of the present invention have a hygroscopicity value of less than about 80%. The "hygroscopicity value", as used herein, means the level of moisture uptake by vitreous particles, as measured by the percentage increase in weight of the particles under the following test method. The hygroscopicity value required for the vitreous particles of the present invention is determined by placing 2 grams of particles (particles of approximately 500 microns size that have no moisture barrier coating) in an open container petri dish under 32.2 conditions. ° C and 80% relative humidity over a period of 4 weeks. The percent increase in weight of the particles at the end of this period is the hygroscopicity value of the particles as used herein. The preferred particles of the present invention have a hygroscopicity value of less than about 50%, more preferably less than about 30%. The laundry additive particles of the present invention typically comprise from about 10% to about 95% of the encapsulating materials, preferably from about 20% to about 90%, and more preferably from about 20% to about 75% with typical of the first encapsulating material: second encapsulating material, from about 1: 1 to about 10: 1, preferably from about 5: 1 to about 2: 1. The particulate compositions of the present invention typically also comprise from about 0% to about 90% useful agents for cleaning or laundry compositions, preferably from about 10% to about 80%, and more preferably from about 25% by weight. approximately 80%. Porous Vehicle Core Material The porous vehicle core material, as used herein, means any material capable of supporting (eg, by surface absorption or pore adsorption) a releasable agent such as a cleaning agent or laundry. Such materials include porous solids selected from the group consisting of amorphous silicates, non-layered crystalline silicates, layered silicates, calcium carbonates, calcium / sodium carbonate double salts, sodium carbonates, clays, zeolites, sodalites, alkali metal phosphates, macroporous zeolites, chitin microspheres, carboxyalkylcelluloses, carboxyalkyl idones, cyclodextrins, porous starches, and mixtures thereof. The preferred porous carrier materials are zeolite X, Y zeolite, and mixtures thereof. The term "zeolite", as used herein, refers to a crystalline aluminosilicate material. The structural formula of the zeolite is based on the unit cell of crystal, the unit of smaller structure represented by Mm / n [(A102) m (Si02) and JxH20 where n is the valence 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 from 1 to 100. More preferably, y / m is from 1 to 5. The M cation can be elements of group IA and Group IIA, such as sodium, potassium, magnesium and calcium. The zeolite useful herein is a faujasite-type zeolite, including X-type zeolite or Y-type zeolite, both having a nominal pore size of about 8 Angstrom units, typically in the range of about 7.4 to about 10 Angstrom units. The aluminosilicate zeolite materials useful in the practice of this invention are commercially available. The methods for producing type X and type Y zeolites are well known and are available in common texts. Preferred synthetic crystalline aluminosilicate materials useful herein are available under the designation type X or type Y. For purposes of illustration, and not by way of limitation, in a preferred embodiment, the crystalline aluminosilicate material is of type X and It is selected from the following: (I) Nase CA102 reads * (Si02)? Oe] * xH20, (II) K86CA102] 86 * (S02) l06] * XH20, (III) [AIO2] 86 * (SIO2) l06] "xH2 ?, (IV ) Sr2lBa22 CA102] 86 * (YES02) 106 r XH20; and mixtures thereof, wherein x is from about 0 to about 276. The zeolites of formula (I) and (II) have a nominal pore size or aperture of 8.4 Angstrom units.

The zeolites of formula (III) and (IV) have a nominal pore size or opening of 8.0 Angstrom units. In another preferred embodiment, the crystalline aluminosilicate material is of type Y and is selected from the following: (V) Na56 CA102 356 * (YES02) l36] * XH20, (VI) K66 CA102] 56 F (YES02) l36] * XH20, and mixtures thereof, wherein x is from about 0 to about 276. The zeolites of formula (V) and (VI) have a nominal pore size or opening of 8.0 Angstrom units. The zeolites used in the present invention are in particle form, and have an average particle size of about 0.5 microns to about 120 microns, preferably about 0.5 microns to about 30 microns, as measured by standard size analysis technique. particle. The size of the zeolite particles allows them to be transported in the fabrics with which they come into contact. Once established on the surface of the fabric (with its coating matrix having been entrained during the laundry process), the zeolites can begin to release their incorporated laundry agents, especially when subjected to hot or humid conditions. First encapsulating material The first encapsulating material of the present invention is a vitreous material derived from one or more hydroxyl compounds at least partially water soluble. The at least partially water soluble hydroxylic compounds useful herein are preferably selected from the following groups of materials. 1. Carbohydrates, which can be any or a mixture of: i) simple sugars (or monosaccharides); ii) oligosaccharides (defined as carbohydrate chains consisting of 2 to 35 molecules of monosaccharide); iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 molecules of monosaccharide); iv) starches, including modified starches and starch hydrolysates; and v) hydrogenated from i), ii), iii) and iv). Both linear and branched carbohydrate chains can be used. In addition, starches and chemically modified poly- / oligo-saccharides can be used. Typical modifications include the addition of hydrophobic portions of the alkyl, aryl, etc. form, identical to those found in surfactants to impart some surfactant activity to these compounds. Preferred carbohydrate materials are hydrogenated and, in particular, hydrogenated starch hydrolysates. More preferred are hydrogenated starch hydrolysates which are derived from carbohydrates having an equivalence of dextrose, (DE), of less than 45, and are typically produced by hydrogenation of starch hydrolysates with an ED of less than 45. Suitable examples of Hydrogenated starch hydrolysates include those available under the trade names of POLYSORB and LYCASIN, from Roquette America of Keokuk, Iowa, and HYSTAR, of Lonza of Fairlawn, NJ 2. All natural or synthetic gums, such as alginate esters, carrageenan , agar-agar, pectic acid, and natural gums such as gum arabic, tragacanth gum and k-ray gum. 3. Chitin and chitosan. 4. Cellulose and cellulose derivatives. Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropylmethylcellulose (HPMC); iii) carboxymethylcellulose (CMC); and iv) all the enteric / aquatic coatings, and mixtures thereof. 5. Silicates, phosphates and borates. 6. Polyvinyl alcohol (PVA). 7. Polyethylene glycol (PEG). 8. Plasticizers. Materials included within these groups that are not at least partially water-soluble and that have glass transition temperatures, Tg, lower than the lower limit of the present, of about 0 ° C, are useful herein only when they are mixed in such amounts with the hydroxylic compounds useful herein that have the upper Tg required, so that the glassy particle produced has the required hygroscopicity value of less than about 80%. The glass transition temperature, commonly abbreviated as "Tg", is a well-known and easily determined property for vitreous materials. This transition is described as equivalent to the liquefaction, after heating through the Tg region, of a material in the vitreous state to one in the liquid state. It is not a phase transition such as fusion, vaporization or sublimation. [See William P. Brennan. "What is a Tg? ' A review of the scanning calorimetry of the glass transition. " Thermal Analysis Application Study # 7. Perkin-Elmer Corporation, March 1973.]. The measurement of Tg is easily obtained by the use of a differential scanning calorimeter (sweep). For the purposes of the present invention, the Tg of the hydroxy compounds is obtained for the anhydrous compound that does not contain any plasticizer (which will affect the measured Tg value of the hydroxy compound). The glass transition temperature is also described in detail in P. Peyser, "Glass Transition Te peratures of Polymers", Polymer Handbook, Third Edition, J. Brandrup and E. H. Im ergut (Wiley-Interscience; 1989), pp. VI / 209-VI / 277. At least one of the hydroxyl compounds useful in the vitreous particles of the present invention should have an anhydrous Tg, not plasticized, of at least 0 ° C, and for particles that do not have a moisture barrier coating, of 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 also preferred that these compounds be processable at low temperatures, preferably within the range of about 50 ° C to about 200 ° C, and more preferably within the range of about 60 ° C to about 180 ° C. Preferably, the hydroxy compound is a carbohydrate material having an equivalence of dextrose, DE, of about 75 or less, more preferably of about 65 or less, and most preferably between about 7.5 and about 45. As used in present, the term "dextrose equivalence" and abbreviated "DE", refers to the total amount of reducing sugars expressed as dextrose that is present, calculated as a percentage of the total dry substance. The amount is measured on a scale from 0 to 100, with 100 being the amount present in a pure sugar. The usual technique for determining the dextrose equivalence is a volumetric alkaline copper method. Both dextrose equivalence and methods for measuring same are well known in the art, particularly in the food and syrup industries. Preferred carbohydrate materials of the first encapsulating material of the present invention include sucrose, hydrogenated starch hydrolysates, glucose, lactose and starch hydrolysates, such as corn syrup.

Second Encapsulating Material According to the present invention, the second encapsulating material forming the outer layer is a carbohydrate material having a glass transition temperature, Tg, anhydrous, unplasticized, of at least about 130 ° C, and more preferably of at least about 150 ° C, and most preferably about 175 ° C. The carbohydrate of the second encapsulating material can be any or a mixture of: i) simple sugars (or monosaccharides); ii) oligosaccharides (defined as "carbohydrate chains consisting of 2 to 35 molecules of monosaccharide), iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 molecules of monosaccharide), iv) starches, including modified starches; and v) hydrogenated from i), ii), iii) and iv) Both linear and branched carbohydrate chains can be used, and starches and chemically modified poly- / oligo-saccharides can be used, Typical modifications include the addition of hydrophobic portions of the alkyl, aryl, etc. form, identical to those found in surfactants to impart some surfactant activity to these compounds The carbohydrate of the second encapsulating material preferably has an equivalence of dextrose, DE, of about 7.5 or less, more preferably about 5 or less Preferably, the carbohydrate of the second encapsulating material is a modified starch or starch, a maltodextrin, or hydrogenated starch hydrolysates, as described above. Suitable odextrins include Maltrin M040 ™, commercially available from Grain Products Processing, and suitable modified starches or starches include Capsul E ™ and Amiogum 23 ™, which are commercially available from National Starch Chemical Co. and American Maze Co ., respectively. The second encapsulating material may include optional additive ingredients such as plasticizers, anti-agglomeration agents, and mixtures thereof. Optional plasticizers include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates, and the like, the most preferred being a mixture of sorbitol and polyethylene glycol and low molecular weight polyols. The plasticizer is used at levels of about 0.01% to about 5%. Anti-agglomeration agents according to the present invention are preferably a surfactant, and low levels of less than 1% of the second encapsulating material are included. Suitable surfactants for use in the present invention include TWEEN 80 ™ commercially available from Imperial Chemicals, Inc. (ICI).

Cleaning and laundry agents Cleaning and laundry agents are included in the particle of the present invention. These agents are supported on, or contained in, the porous vehicle core material, as described above. The agents useful in the present invention are selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, anti-scale agents, minimal-value inhibitors, dye transfer inhibitors. , photobleaching res, enzymes, catalytic antibodies, brighteners, substantive dyes of fabrics, antifungals, antimicrobials, insect repellents, dirt release polymers, fabric softening agents, dye fixatives, pH jump systems, and mixtures thereof . As can be appreciated for the present invention, these agents that are incorporated in the particles of the present invention can be the same as, or different from, those agents that are used to formulate the rest of the cleaning and laundry compositions containing the particle . For example, the particle may comprise a perfume agent, and the same or different perfume can also be mixed in the final composition (by techniques such as spraying) together with the particle containing perfume. These agents are selected as desired for the type of composition being formulated, such as granular laundry detergent compositions, granulated automatic dishwashing compositions, or hard surface cleaners. The different types of agents useful in the present invention are described below. The laundry particle of the present invention can, in fact, be included in a composition that can contain other ingredients. Compositions containing laundry additive particles may optionally include one or more other adjunct detergent materials or other materials to facilitate or improve the cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition. (for example, by perfumes, dyes, dyes, etc.).

Perfume In accordance with the present invention, the preferred cleaning or laundry agent is a perfume material.

As used herein, the term "perfume" is used to indicate any odoriferous material that is subsequently released in the aqueous solution and / or on the fabrics that come in contact therewith. More often, the perfume will be liquid at room temperature. A wide variety of chemicals are known for use as a perfume, including materials such as aldehydes, ketones, alcohols and esters. More commonly, oils and exudates of plants and animals, which occur naturally and which comprise complete mixtures of various chemical components, are known to be used as perfumes. The perfumes herein may be relatively simple in their compositions, or may comprise highly sophisticated complete mixtures of natural and synthetic chemical components, all selected to provide some desired aroma. Typical perfumes may comprise, for example, woody / terrestrial bases containing exotic materials such as sandalwood, civet and patchouli oil. The perfumes can be of a light floral fragrance, for example, rose extract, violet extract, and lilac. Perfumes can also be formulated to provide convenient fruit flavors, for example, lime, lemon and orange. Any chemically compatible material that exudes a pleasant or otherwise convenient scent can be used in the perfumed compositions herein. The perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances (e.g., digeranyl succinate), hydrolyzable inorganic-organic pro-fragances, and mixtures thereof. These pro-fragrances can release the perfume material as a result of simple hydrolysis, or they can be promragans triggered by a change in pH (e.g., decrease in pH), or they can be enzymatically releasable pro-fragrances. Preferred perfume agents useful herein are defined as follows. For the purposes of the compositions of the present invention exposed to the aqueous medium of the washing process, several characteristic parameters of perfume molecules are important to identify and define: their longer and wider measurements; Cross-sectional area; molecular volume; and molecular surface area. These values are calculated for individual perfume molecules using the CHEMX program (from Chemical Design, Ltd.) for molecules in a minimal energy conformation determined by the standard geometry optimized in CHEMX and using standard atomic van der Waals radii. The definitions of the parameters are the following: "Longest": the largest distance (in Angstroms) between atoms in the molecule, augmented by their van der Waals radii. "Wider": the largest distance (in Angstroms) between atoms in the molecules, augmented by their van der Waals radii in the projection of the molecule on a plane perpendicular to the "longest" axis of the molecule. "area of cross section": area (in square Angstrom units) covered by the projection of the molecule in the plane perpendicular to the longest axis. "Molecular volume": the volume (in cubic Angstrom units) covered by the molecule in its minimum energy configuration. "Molecular surface area": arbitrary units given in Angstroms squared (for calibration purposes, the molecules methyl beta naphthyl ketone, benzyl salicylate and camphor gum have surface areas measuring 128 ± 3, 163.5 ± 3 and 122.5 ± 3 units, respectively). The shape of the molecule is also important for the incorporation of the latter. For example, a perfectly spherical symmetric molecule that is too small to be included in the zeolite channels has no preferred orientation, and is incorporated from any alternative direction. However, for molecules that have a length that exceeds the pore size, there is a preferred "alternative orientation" for inclusion. The calculation of the volume / surface area ratio of a molecule is used herein to express the "configuration index" of a molecule. The higher the value, the more spherical the molecule.

For the purposes of the present invention * the perfume agents are classified according to their ability to be incorporated into the pores of the preferred zeolite vehicle, and hence their utility as components for the release of the preferred zeolite vehicle through a watery environment Graphing these agents in a ratio of volume / surface area against the area plane in cross section, conveniently classifies the agents into groups according to their incorporation capacity in the zeolite. In particular, for the zeolite X and Y vehicles according to the present invention, the agents are incorporated if they are located below the line (referred to herein as the "incorporation line") defined by the equation: y = - 0.01068X + 1.497 where x is the cross sectional area, and y is the volume / surface area ratio. Agents that fall below the line of incorporation are referred to herein as "releasable agents"; the agents that are located above the line are referred to herein as "non-releasable agents". For containment through washing, the releasable agents are retained in the zeolite vehicle as a function of their affinity for the vehicle with respect to the competent release agents. Affinity is influenced by size, hydrophilicity, functionality, volatility, etc. of the molecule, and can be effected by interaction between the releasable agents within the zeolite vehicle. These interactions allow for improved characteristics through the containment of the wash for the mixture of incorporated releasable agents. Specifically, for the present invention, the use of releasable agents having at least one dimension that closely matches the pore size of the zeolite vehicle retards the loss of other releasable agents in the aqueous wash environment. The releasable agents that function in this manner are referred to herein as "blocking agents", and are defined herein in the ratio of volume / surface area against the plane of cross-sectional area, with those releasable agent molecules. which are located below the "line of incorporation" (as defined above), but above said line (referred to herein as the "blocker line") defined by the equation: y = -0.01325X + 1.46 where x is the cross-sectional area, and y is the volume / surface area ratio. For the compositions of the present invention using X and Y zeolites as carriers, all of the releasable agents below the "line of incorporation" can be assorted and released from the compositions of the present invention, with the preferred materials being those below. of the "blocker line". Mixtures of blocking agents and other releasable agents are also preferred. The laundry perfume agent blends useful in the laundry particles of the present invention preferably comprise from about 5% to about 100% (preferably from about 25% to about 100%, more preferably about 50% by weight). about 100%) of releasable agents; and preferably comprise from about 0.1% to about 100% (preferably from about 0.1% to about 50%) of blocking agents, by weight, of the laundry agent mixture. Obviously for the compositions of the present invention, according to which the perfume agents are being released by the compositions, sensory perception is required for a benefit to be seen by the consumer. For the compositions of the present invention, the most preferred perfume agents useful herein have a minimum perception value (measured as minimum aroma detection values ("ODT") under carefully controlled GC conditions as described in more detail. forward) less than, or equal to, 10 parts per billion, ("ppb") (= 10 parts per billion). Agents with ODTs between 10 parts per billion and 1 part per million ("ppm") are less preferred. Preferably, agents with ODTs greater than 1 ppm are avoided. Laundry agent perfume blends useful for the laundry particles of the present invention preferably comprise from about 0% to about 80% releasable agents with ODTs between 10 parts per billion and 1 ppm, and about 20 % to approximately 100% (preferably from about 30% to about 100%, more preferably from about 50% to about 100%) of releasable agents with ODTs less than, or equal to, 10 parts per billion. Also preferred are perfumes carried through the laundry process and then released into the air around the dried fabrics (eg, such as the space around the fabric during storage). This requires the movement of the perfume out of the pores of the zeolite, with subsequent separation in the air around the fabric. Therefore, preferred perfume agents are further identified based on their volatility. The boiling point is used herein as a measure of the volatility, and the preferred materials have a boiling point of less than 300 ° C. Laundry agent perfume blends useful in the laundry particles of the present invention preferably comprise at least about 50% releasable agents with a boiling point of less than 300 ° C (preferably at least about 60%), more preferably at least approximately 70%). In addition, preferred laundry particles herein comprise compositions wherein at least about 80%, and more preferably at least about 90%, of the releasable agents, have a "ClogP value" greater than about 1.0. The ClogP values are obtained in the following manner.

Calculation of ClogP These perfume ingredients are characterized by their separation coefficient P in octanol / water. The octanol / water separation coefficient of a perfume ingredient is the ratio between its equilibrium concentration in octanol and water. Since the separation coefficients for most of the perfume ingredients are large, they are most conveniently given in the form of their logarithm of base 10, logP. The logP of many perfume ingredients has been reported, for example, the Pomona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), contains many logPs, along with quotes from the original literature. However, the logP values are more conveniently calculated using the "CLOGP" program also available from Daylight CIS. This program also gives a list of experimental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo (see A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sa mens, J. B. Taylor and C.

A. Ramsden, Eds., P. 295, Pergamon Press, 1990). The focus of the fragment is based on the chemical structure of each perfume ingredient, and takes into account the number and types of atoms, the union of them, and the chemical bonds. The ClogP values, which are the most reliable and widely used estimates for this physicochemical property, can be used in place of the experimental logP values for the selection of the perfume ingredients.

Determination of minimum aroma detection values The gas chromatograph is used to determine the exact volume of material injected by the syringe, the precise separation ratio, and the hydrocarbon response using a standard hydrocarbon of known concentration and chain distribution. The air flow rate is accurately measured and, assuming that the duration of a human inhalation lasts 0.2 minutes, the volume sampled is calculated. Since the precise concentration in the detector is known at any point of time, the mass per inhaled volume and, consequently, the concentration of the material is known. To determine if a material has a minimum value of less than 10 parts per billion, the solutions are supplied to the aspiration orifice at the concentration calculated above. A panelist aspirates the effluent from GC, and identifies the retention time when the aroma is perceived.

The average over all panel members determines the minimum perception value. The required amount of analyte is injected into the column until a concentration of 10 parts per billion is reached in the detector. Following is a list of the typical parameters of the gas chromatograph to determine the minimum values of aroma detection.

GC: 5890, Series II with FID detector Sampler 7673 Column: Scientific DB-1 J &W Length, 30 meters; ID, 0.25 mm; film thickness, 1 miera Method: Separation injection: separation ratio 17/1 Automatic sampler: 1.13 microliters per injection Column flow: 1.10 ml / minute Air flow: 345 ml / minute Inlet temperature, 245 ° C detector: 285 ° C Temperature information: Initial temperature: 50 ° C Speed: 5C / minute Final temperature: 280 ° C Final time: 6 minutes Main assumptions: 0.02 minutes per aspiration; GC air is added for dilution of the sample.

Perfume fixative Optionally, the perfume can be combined with a perfume fixative. The perfume fixing materials used herein are characterized by several criteria that make them especially suitable in the practice of this invention. Dispersible additives are used, toxicologically acceptable, non-irritating to the skin, inert to the perfume, degradable and / or available from renewable resources, and relatively odorless. It is thought that perfume fixatives retard the evaporation of the most volatile components of the perfume. Examples of suitable fixatives include members selected from the group consisting of diethyl phthalate, musks, and mixtures thereof. If used, the perfume binders comprise from about 10% to about 50%, preferably from about 20% to about 40%, by weight, of the perfume.

Incorporation of the perfume into the pre-ferided zeolite carrier The X-type or Y-type zeolites to be used as preferred carrier herein preferably contain less than about 15% removable water, more preferably less than about 8% removable water , and most preferably less than about 5% of removable water. Said materials can first be obtained by activation / dehydration by heating to about 150 to 350 ° C, optionally with reduced pressure (from about 0.001 to about 20 Torr.) After activation, the agent is slowly and completely mixed with the zeolite activated and, optionally, heated to about 60 ° C or up to about 2 hours to accelerate the absorption equilibrium within the zeolite particles.The perfume / zeolite mixture is then cooled to room temperature, and is in the form of a powder The amount of laundry agent incorporated in the zeolite vehicle is less than about 20%, typically less than about 18.5%, by weight, of the charged particle, given the limits on the pore volume of the zeolite. However, it will be recognized that the particles of the present invention may exceed this level of laundry agent by weight of the particle. a, but recognizing that excessive levels of laundry agents will not be incorporated into the zeolite, even if only releasable agents are used. Therefore, the particles of the present invention can comprise more than 20% by weight laundry agents. Since any excess laundry agents (as well as any non-releasable agents present) are not incorporated into the pores of the zeolite, it is likely that these materials will be immediately released into the wash solution after coming in contact with the media. aqueous wash. In addition to its function of containing / protecting the perfume in the particles, of zeolite, the carbohydrate material also conveniently functions to agglomerate multiple particles of perfumed zeolite into agglomerates having a general particle size in the range of 200 to 1000 microns., preferably from 400 to 600 microns. This reduces the dust formation capacity (dusty state). In addition, the tendency of the smaller individual scented zeolites to filter to the bottom of containers filled with granular detergents that, by themselves, typically have particle sizes in the range of 200 to 1000 microns, decreases.

Attached ingredients for cleaning or laundry The adjunct ingredients useful for (or with) the cleaning or laundry compositions according to the present invention, are selected from the group consisting of surfactants, perfumes, bleaches, bleach promoters, bleach activators, bleaching catalysts, chelating agents, anti-scale agents, minimal-value inhibitors, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, substantive fabric colorants, antifungals, antimicrobials, insect repellants, release polymers of dirt, fabric softening agents, dye fixatives, pH jump systems, and mixtures thereof. As can be appreciated in the present invention, these agents useful in cleaning or laundry compositions that are incorporated in the particulate compositions of the present invention may be the same as, or different from, those agents that are used to formulate the remainder of the composition. cleaning and laundry compositions containing the particulate compositions produced by the present process. For example, the particulate compositions may comprise a perfume agent, and the same or different agent may also be mixed in the final composition together with the particulate composition containing perfume. These agents are selected as desired for the type of composition being formulated, such as granular laundry detergent compositions, granulated automatic dishwashing compositions, or hard surface cleaners. The different types of agents useful in the compositions for cleaning and laundry are described below. The compositions containing particulate compositions may optionally include one or more other adjunct detergent materials or other materials to facilitate or improve the cleaning performance, the treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.

Detersive Surfactant The granules and / or agglomerates include surfactants at the levels stated above. The detersive surfactant can be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, switterionic surfactants, and mixtures thereof. Non-limiting examples of surfactants useful herein include the conventional Cn-Ciß alkylbenzene sulphonates ("LAS"), and the primary, branched-chain and branched C10-C20 alkyl ("AS") sulfates, the alkyl sulfates (2,3) ) secondary Cío-Cis of the formula CH3 (CH2) x (CH0S03 ~ M +) CH3, and CH3 (CH2) y (CH0S03 ~ M + H2CH3, where xy (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, Cι-Ciß alkylalkoxysulfates ("AExS", especially EO-1-7 ethoxysulfates), Cι-Ciß alkylalkoxycarboxylates. (especially EO 1-5 ethoxycarboxylates), C10-C18 glycerol ethers, Cio-Ciß alkyl polyglycosides and their corresponding sulfated polyglycosides, and C12-C18 alphasulfonated fatty acid esters, If desired, nonionic surfactants and amphoteric conven such as the C12-C18 alkyl ethoxylates ("AE") including the so-called narrow-spiked alkyl ethoxylates and the C6-C12 alkyl phenolalkoxylates (especially ethoxylates and ethoxy / mixed propoxy), betaines and sulfobetaines ("sultaines") of C12- C18, Cio-Cis amine oxides, and the like, can also be included in the overall compositions. The N-alkyl polyhydroxolic fatty acid amides of Cio-Cis can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9, 206,154. Other surfactants derived from sugars include the N-alkoxy-polyhydric acid fatty acid amides, such as N- (3-methoxypropyl) glucamide from Cio-Ciß. The N-propyl to N-hexylglucamides of Ci2-C? S can be used for low foaming. Conventional C10-C20 soaps can also be used. If high foaming is desired, Cío-Cie branched-chain soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are included in usual textbooks. The alkylalcoxy sulfates "AExS" from Cio-Cis (especially EO-1-7 ethoxysulfates) and the C12-C18 alkyl ethoxylates ("AE") are most preferred for the cellulase-containing detergents described herein.

Detersive Detergency Enhancer Granules and agglomerates preferably include a builder at the levels set forth above. For this purpose, both inorganic and organic builders can be used. In the same way, both crystalline and amorphous builder materials can be used. Builders are typically used in fabric washing compositions to facilitate the removal of particulate soils and to remove water hardness. Inorganic or P-containing builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate builders are required in certain places. Importantly, the compositions herein work surprisingly well even in the presence of so-called "weak" builders (as compared to phosphate builders) such as citrate, or in the so-called "lower detergency breeding" situation. , which can occur with stratified zeolite or silicate builders. Examples of silicate builders are alkali metal silicates, particularly those that have a Si? 2: a2? Ratio. in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in the U.S. Patent. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the SKS-6 Na silicate builder does not contain aluminum. NaSKS-6 has the morphological form of stratified silicate delta-Na2Si0e. It can be prepared by methods such as those described in German Application DE-A-3, 417,649 and DE-A-3,742,043. SKS-6 is a highly preferred stratified silicate for use herein, but other layered silicates, such as those having the general formula NaMSix? 2? +? and H 2 ?, 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. Several other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as the alpha, beta and gamma forms. As indicated above, the a-Na2Si0s (NaSKS-6) form is most preferred for use herein. Other silicates can also be used, such as for example magnesium silicate, which can serve as a tightening agent in granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are the alkali metal and alkali metal carbonates, as described in German Patent Application No. 2,321,001, published November 15, 1973. As mentioned above, the builders of aluminosilicate are builders useful in the present invention. Aluminosilicate builders are of great importance in most commercially available heavy duty granular detergent compositions, and can also be an important detergent builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: Mz (zA102) and] xH20 where z and y are integers of at least 6, the molar ratio of z: y is on the scale of about 1.0 to about 0.5 , and x is an integer of around 15 to approximately 264. Useful aluminosilicate ion exchange materials, are commercially available. These aluminosilicates may be of crystalline or amorphous structure, and may be aluminosilicates that occur naturally or that are synthetically derived. A method for producing aluminosilicate ion exchange materials is described in the U.S. Patent. 3,985,669, Kru mel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein, are available under the designations of Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Nai2 C (A102) 12 (S02) 12] xH20 where x is from about 20 to about 30, especially about 27. The The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals, such as sodium, potassium and lithium or alkanolammonium salts are preferred. Included among the polycarboxylate builders are a variety of useful material categories. An important category of polycarboxylate builders comprises ether polycarboxylates, including oxydisuccinate, as described in Berg, U.S. 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" detergency builders of U.S. Patent 4,663,071, issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in US Pat. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxy-ethyloxy-succinic acid, the different alkali metal salts , ammonium and substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, poly-aleic acid, benzene-1,3,5-tricarboxylic acid, carboxy-ethyl-oxisuccinic acid, and soluble salts thereof. Citrate builders, for example, citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations because of their availability from renewable resources, and also because of its biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinates are also especially useful in said compositions 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 described in US Pat. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids, and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in the patent application. European Patent No. 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are described in U.S. Patent No. 4,144,226, Crutchfield et al., Issued March 13, 1979, and in the EU-A Patent. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, U.S. Patent. 3,723,322.

Fatty acids, for example, C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional activity of detergency builder Such use of fatty acids will generally result in decreased foaming, which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, and especially in bar formulations used for hand-washing operations, various alkali metal phosphates, such as the well-known sodium tripolyphosphites, pyrophosphate, can be used. of sodium and sodium orthophosphate. Phosphonate builders, such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates, can also be used (see, for example, U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Other Attached Ingredients The composition of the present invention may also include enzymes, enzyme stabilizers, brighteners, dispersion (i.e., polyacrylates) polymeric agents, vehicles, hydrides, foam enhancers or suppressants, soil release agents, soil release inhibitors. dye transfer, and processing aids.

Granulated compositions The cleaning and laundry compositions of the present invention can be used in granular compositions of both low density (less than 550 grams / liter) and high density, in which the density of the granule is at least 550 grams / liter. The granular compositions are typically formulated to provide in the wash a pH of from about 7.5 to about 11.5, more preferably from about 9.5 to about 10.5. The low density compositions can be prepared by standard spray drying procedures. There are several methods and equipment to prepare high density compositions. Common commercial practice in the field uses spray-drying towers to make compositions having a density of less than about 500 g / l. Accordingly, if spray drying is used as part of the general procedure, the resulting spray dried particles must be further densified using the means and equipment described below. In the alternative, the formulator can eliminate spray drying by using commercially available mixing, densifying and granulating equipment. The following is a non-limiting description of such equipment suitable for use herein.

Various means and equipment are available to prepare high density granular detergent compositions (ie, greater than about 550, preferably greater than about 650, grams / liter or "g / l"), high solubility and free flowing, in accordance with the present invention. Current commercial practice in the field employs spray-drying towers to make granular laundry detergents that often have a density less than about 500 g / l. In this process, an aqueous suspension of various thermosetting ingredients in the final detergent composition is formed into homogeneous granules by passing it through a spray-drying tower, using conventional techniques, at temperatures from about 175 ° C to about 225 ° C. . However, if spray drying is used as part of the general procedure herein, other steps of the process should be used as described below to obtain the density level (ie> 650 g / l) required by the products. compact, modern detergents with low dosage. For example, spray-dried granules of a tower can be further densified by charging a liquid such as water or a non-ionic surfactant into the pores of the granules., and / or by submitting them to one or more high speed mixers / densifiers. A high speed mixer / densifier suitable for this process is a device marketed under the trade name "Lódige CB 30" or "Lódige CB 30 Recycler", which comprises a static cylindrical mixing tub having a central rotation arrow with blades of mixing / cutting mounted on it. During use, the ingredients for the detergent composition are introduced into the tub and the arrow / blade assembly is rotated at speeds in the range of 100-2500 rpm to provide complete mixing / densification. See Jacobs et al., Patent of E.U.A. 5,149,445, issued September 22, 1992. The preferred residence time in a high-speed mixer / densifier is about 1 to 60 seconds. Another apparatus of this type includes the devices marketed under the trade name "Shugi Granulator" and under the trade name "Drais K-TTP 80". Another step of the process that can be used to further densify the spray dried granules is to spray and agglomerate or deform the spray-dried granules in a moderate speed mixer / densifier to obtain particles having lower intra-particle porosity. Equipment such as that marketed under the trade name of "L? Dige KM" (Series 300 to 600), or "Lódige Ploughshare", of mixer / densifiers, is suitable for this step of the procedure. Said equipment operates typically at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer / densifier is around 0-1 to 12 minutes. Other useful equipment includes the device that is available under the trade name of "Drais K-T 160". This method step employing a moderate speed mixer / densifier (e.g., Lódige KM) can be used as such or sequentially with a previously mentioned high speed mixer / densifier (e.g., Lódige CB) to achieve the desired density. Other types of apparatus for manufacturing granules useful herein include the apparatus described in the E-U.A patent. 2,306,898 by G.L. Heller, December 29, 1942. While it may be more appropriate to use the high speed mixer / densifier followed by the low speed mixer / densifier, the reverse sequential mixer / densifier configuration is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer / densifiers, equipment operating temperatures, temperature and / or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used for optimizing the densification of the spray-dried granules in the process of the invention. By way of example, see the procedures in Appel et al., U.S. Patent. 5,133,924, issued July 28, 1992 (the granules are brought to a deformable state before densification); Delwel et al., Patent of E.U.A. 4,637,891, issued January 20, 1987 (granulation of spray-dried granules with a liquid binder and aluminosilicate); Kruse et al., Patent of E.U.A. 4,726,908, issued February 23, 1988 5 (granulation of spray-dried granules with a liquid binder and aluminosilicate); and Bortolotti et al., Patent of E.U.A. 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate). 0 In those situations in which detergent ingredients that are particularly sensitive to heat or highly volatile are to be incorporated into the final detergent composition, procedures that do not include towers are preferred. ^ spray drying. The formulator can eliminate the step of spray drying by feeding, in a continuous or intermittent, starting detergent ingredients directly into the mixing / densification equipment that is commercially available. A particularly preferred embodiment involves charging a surfactant paste and anhydrous builder material in a high speed mixer / densifier (e.g., Lódige CB), followed by a moderate speed mixer / densifier (e.g., Lódige KM). ), to form high density detergent agglomerates. See Capeci et al., Patent of E.U-A. 5,366,652, issued November 22, 1994, and Capeci et al., Patent of E.U.A. 5,486,303, issued January 23, 1996. Optionally, the liquid / solids ratio of the starting detergent ingredients in said process can be selected to obtain high density agglomerates that are freer and crisp. Optionally, the method may include one or more recirculation streams of undersized particles produced by the process, which are realized to the mixer / densifiers for subsequent agglomeration or accumulation. The oversized particles produced by this process can be sent to a grinding apparatus and then fed back to the mixing / densification equipment. These additional steps of the recirculation process facilitate the agglomeration by accumulation of the starting detergent ingredients, which results in a finished composition having a uniform distribution of the desired particle size (400-700 microns) and density (> 550). g / l). See Capeci et al., Patent of E.U.A. 5,516,448, issued May 14, 1996, and Capeci et al., Patent of E.U-A. 5,489,392, issued February 6, 1996. Other suitable methods that do not require the use of spray drying towers are described by Bollier et al., U.S. 4,828,721, issued May 9, 1989; Beerse et al., Patent of E.U.A. 5,108,646, issued April 28, 1992; and Jolicoeur, patent of E.U.A. 5,178,798, issued on January 12, 1993.

In still another embodiment, the high density detergent composition of the invention can be produced using a fluidized bed mixer. In this process, the different ingredients of the finished composition are combined in an aqueous suspension (typically 80% solids content) , and they are sprayed in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, this method may optionally include the step of mixing the suspension using the aforementioned Lódige CB mixer / densifier, or a "Flexomix 160" mixer / densifier, available from Shugi. In such processes, fluidized beds or moving beds of the type available under the trade name of "Escher Wyss" can be used. Another suitable method that can be used herein involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (eg, sodium carbonate) and optionally other detergent ingredients into a high speed mixer / densifier (residence time of 5-30 seconds) to form agglomerates containing a partially or fully neutralized anionic surfactant salt, and the other starting detergent ingredients. Optionally, the contents in the high speed mixer / densifier can be sent to a moderate speed mixer / densifier (eg, Lódige KM) for further agglomeration, resulting in a finished high density detergent composition. See Appel et al., Patent of E.U.A. 5,164,108, issued November 17, 1992. Optionally, the high density detergent compositions according to the invention can be produced by mixing densified or conventional spray dried detergent granules with detergent agglomerates in various proportions (for example, a ratio of 60:40 weight of granules: agitated), produced by one or a combination of the methods described herein.I read.

Other adjunct ingredients such as enzymes, perfumes, brighteners and the like, may be sprinkled or mixed with the agglomerates, granules or mixtures thereof, produced by the methods described herein. Bleaching compositions in granulated form typically limit the water content, for example, to less than about 7% free water, for better storage stability.

Deposition of perfume on the surface of the fabric The method for washing fabrics and depositing perfume therein comprises contacting said fabrics with an aqueous washing solution comprising at least about 10 ppm of conventional detersive ingredients described above, as well as also at least about 0.1 ppm of the additive laundry particle described above. Preferably, said aqueous solution comprises from about 500 ppm to about 20,000 ppm of the conventional detersive ingredients, and from about 10 ppm to about 200 ppm of the additive laundry particle. The additive laundry particle works under all circumstances, but is particularly useful in providing aroma benefits on fabrics during storage, drying or ironing. The method comprises contacting the fabrics with an aqueous solution containing at least about 100 ppm of conventional detersive ingredients, and at least about 1 ppm of the additive laundry particle, so that the perfumed zeolite particles are transported in the fabrics; Store the dried fabrics in line under environmental conditions with humidity of at least 20%; drying the fabric in a conventional automatic dryer; or applying heat to fabrics that have been dried in line or machine dried, at a low heat content (less than about 50 ° C) by conventional ironing means (preferably with steam or pre-wet). The following non-limiting examples illustrate the parameters and compositions used within the invention. All percentages, parts and relationships are by weight, unless otherwise indicated.

EXAMPLE I An additive laundry particle according to the present invention is produced by the following procedure. A solution of 75% of solid carbohydrate material (hydrolyzed hydrogenated starch POLYSORB RA-1000 from Roquette America) and the water balance, are premixed in a stirred mixing flask with 1.5% by weight of Ti? 2 powder (marketed) under the tradename of Tronox by the Kerr McGee Chemical Corporation) to form a carbohydrate encapsulation fluid solution. The carbohydrate fluid is dried to a moisture content of approximately 2.0% in a Wiped Film evaporator ("WFE") Luwa ™. Then, the carbohydrate fluid and zeolite X charged with 16% by weight perfume ("PLZ") are fed at a weight ratio of 1: 1 in a twinworm extruder ("TSE") ZSK 30 Werner & 12 barrel Pferer ™ without die plate for constriction, to form agglomerates. The barrels 1 to 4 of the TSE are maintained at a temperature of 80 ° C, while the barrels 5 and 6 are maintained at a temperature of 90 ° C, the barrels 7 and 8 at a temperature of 130 ° C, the barrels 9 and 10 at a temperature of 135 ° C, and barrels 11 and 12 at a temperature of 130 ° C. The carbohydrate fluid is fed at a temperature of 160 ° C to the TSE in the barrel 7, while the PLZ is added in the barrel 11 and intimately mixed with the carbohydrate fluid before leaving the TSE as an extruded product having a discharge temperature of 145 ° C and a speed of 500 g / min.- The product is cooled to room temperature to form free-flowing particles that are ground in a Fitz ™ mill (commercially available from Fitzpatrick Company) and sized by sieving to produce particles in the scale of 150 microns to 1180 microns. The sized particles are then sent to a Wurster fluid bed coater in which an aqueous mixture containing 22.5% Maltrin 040 ™ (having a dextrose equivalent of 5) commercially available from Grain Processing Corp is added., 1.0% of D-Sorbitol ™ commercially available from J.T. Baker, 1.0% polyethylene glycol (PEG 600 Carbowax ™ commercially available from Union Carbide), and 0.5% surfactant (TWEEN 80 ™) commercially available from Imperial Chemicals, Inc. (ICI)). The coated particles are dried to produce an extremely suitable particulate composition for use as an additive laundry composition. The particles formed unexpectedly have a superior "pure product aroma" ("NPO"), and emit only minimal detectable aromas on the flavor of the base product observed by a statistically significant number of classifiers of a panel. This provides solid evidence of the lack of displacement of the perfume from the vehicle's particles.

EXAMPLE II Next, various detergent compositions made in accordance with the invention and specifically for top-loading washing machines incorporating the perfume particle prepared in Example I are exemplified.

Granule base A B C Aluminosilicate 18.0 22.0 24.0 Sodium sulfate 10.0 19.0 6.0 Sodium Polyacrylate Polymer 3.0 2.0 4.0 Polyethylene Glycol (P.M. = 400) 2.0 1.0 Sodium Alkylbenzenesulfonate linear C12-13 6.0 7.0 8.0 Secondary sodium alkyl sulphate of C14-16 3.0 3.0 Sodium alkyl ethoxylated sulfate of C14-15 3.0 9.0 - - Sodium silicate 1. 0 2. 0 3.0 Rinse aid 24/47 * 0.3 0.3 0.3 Sodium carbonate 7.0 26.0 Carboxymethylcellulose - - 1. 0 DTPMPA2 - - 0.5 DTPA3 0.5 Mixed agglomerates C14-15 sodium alkyl sulphate 5.0 C12-13 linear sodium alkylbenzene sulfonate 2.0 Sodium carbonate 4.0 Polyethylene glycol (P.M. = 4000) 1.0 Sodium carbonate mixture * • * • "" * "• *" "" 13.0 C12-15 alkyl ethoxylate (E0 = 7) 2.0 0 - 5 2.0 Alkyl ethoxylate of C12-IS (E0 = 3) - - 2.0 Perfume spray 0.3 0.4 0. 3 Perfume particles4 0.5 0.5 0.5 Polyvinylpirolidone 0.5 - - N-oxide of polyvinyl pyridine 0.5 - - Polyvinylpirolidone-polyvinylimidazole 0.5 - - Diestearila ina and Cumeno 2.0 - - Sulphonic acid Dirt release polymer5 0.5 - Lipase lipolase (100,000 LU / D * 0.5 - 0.5 Thermamil amylase (60 KNU / g) * 0.3 - 0.3 CAREZYMER cellulase (1000 CEVU / g) * 0.3 Protease (40mg / g)? 0.5 0-5 0.5 N0BS8 5.0 TAED * 3.0 Sodium percarbonate 12.0 Sodium perborate 22.0 Polydimethylsiloxane monohydrate 0.3 - 3.0 Sodium Sulfate - 3.0 Ingredientee divereoe (water, etc.) Balance sheet balance Total 100 100 100 1. Acquired from Ciba-Geigy 2. Diethylenetriaminepentamethylenephosphonic acid 3. Diethylenetriaminepentaacetic acid 4. From Example I 5- Obtained in accordance with the Patent of E.U-A. 5,415,807, issued May 16, 1995 to Gosselink and others 6. Acquired from Novo Nordisk A / S 7. Acquired from Genencor 8. Nonanoiloxybenzenesulfonate 9. Tetraacetylethylenediamine.

EXAMPLE III The following detergent compositions containing the perfume particle of Example I according to the invention are especially suitable for front loading washing machines. (% by weight) Granule base A B Aluminosilicate 15.0 Sodium sulfate 2.0 Sodium alkyl linear alkylbenzene sulfonate C12-13 3.0 DTPMPA * 0.5 Carboxymethylcellulose 0.5 Acrylic acid / maleic acid copolymer 4.0 Mixed grades C14-15 sodium alkyl sulfate 11.0 C12-13 linear sodium alkylbenzene sulfonate 5.0 C18-22 sodium alkylsulphate 2.0 Sodium silicate 4.0 Aluminosilicate 12.0 13.0 Carboxymethylcellulose 0.5 Acrylic acid / maleic acid copolymer 2.0 Sodium carbonate 8.0 7.0 Mix Perfume spray 0.3 0-5 Perfume particles2 0.5 0.5 C12-I S alkyl ethoxylate (E0 = 7) 4.0 4. 0 Ci2-? E alkyl ethoxylate (E0 = 3) 2.0 2.0 Acrylic acid / maleic acid copolymer - 3.0 Stratified crystalline silicate - 12.0 Sodium citrate 5-0 8.0 Baking soda 5-0 5.0 Sodium carbonate 6.0 15.0 Polyvinylpyrrolidone 0.5-0-5 Alkasease4 protease (3.0 AU / g) 0-5 1.0 Lipase lipolasa4 (100,000 LU / 1) 0.5 0.5 Amylase thermamil * (60KNU / g) 0.5 0.5 Cellulase CAREZYME ** (1000 CEVU / g) 0.5 0.5 Sodium Sulfate 4.0 0.0 Various ingredients (water, etc.) balance balance Total 100.0 100.0 1. Diethylenetriaminepentamethylenephosphonic acid 2. From Example I 3. SKS6 commercially available from Hoechst 4. Acquired from Novo Nordisk A / S.

EXAMPLE IV r The following detergent compositions according to the invention are suitable for top-load washing machines of low wash volume. (% by weight) Granule base A Aluminosilicate 7.0 10 Sodium sulphate 3.0 Polyethylene glycol (MW = 4000) 0.5 Copolymer of acrylic acid / maleic acid 6.0 Cationic surfactant agent1 0.5 Eodium alkylene sulfate, C14-16 7.0 7.0 Sodium linear alkylenebenzene sulfonate -i3 13.0 C14-15 sodium ethoxylated alkylsulfate 6.0 Crystalline silicate eet ratified2 6.0 Sodium silicate 2.0 Sodium oleic acid acid 1.0 20 Brightener 493 0.3 Sodium carbonate 28.0 DTPA * 0.3 Mixture 25 Alkyl ethoxylate C12-15 (E0 = 7) 1.0 Aspe rsion of pe rfume 1.0 Pe rfume pa rticles5 1.0 Dirt release polymer6 0.5 Polyvinyl pyrrolidone 0.3 N-oxide polyvinylpyridine 0.1 Polyvinyl pyrrolidone-polyvinylimidazole 0.1 Lipase lipolase (100,000LU / g) 7 0.3 Amylase te rmamil (60KNU / g) 7 0.1 CAREZYMER Cellulase (1000 CEVU / g)? 0.1 Savinasa (4.0 KNPU / g)? 1.0 N0BS8 4.0 Sodium perborate monohydrate 5.0 Various ingredients (water, etc.) balance Total 100.0 1. Compound of dimethylhydroxyethyl ammonium quaternary of C12-14 2. SKS6 commercially available from Hoechst 3. Acquired from Ciba-Geigy 4. Diethylenetriaminepentaacetic acid 5. From Example I 6. Obtained in accordance with the US Patent , 5,415,807, issued May 16, 1995 to Gosselink and others 7. Acquired from Novo Nordisk A / S 8. Nonanoyloxybenzenesulfonate.

EXAMPLE V The following detergent compositions according to the invention are suitable for hand and machine washing operations. The base granule is prepared by a conventional spray drying process, in which the starting ingredients are formed in a suspension and passed through an asperion drying tower having a hot air stream (200-400). ° C) countercurrent which results in the formation of porous granules. The remaining adjunct detergent ingredients are sprinkled or added in eeco.

Base granule A B C Eodium alkylbenzene sulfonate of C12-13 19.0 18.0 19.0 Cationic tenective agent1 0.5-0-5 - DTPMPA2 0.3 - - DTPA3 - 0-3 - Tripolipus fato of eodium 25.0 19.0 29.0 Acrylic acid / maleic acid copolymer 1.0 0.6 - Carboxymethylcellulose 0.3 0.2 0.3 Rinse aid 49/15/33 * 0.2 0.2 0.2 Sodium sulphate 28.0 39.0 15.0 Sodium silicate (2.0R) 7.5 - __ Sodium silicate (1.6R) - 7.5 6.0 Quantum mixture (zinc phthalocyanine-sulfonate) 2.0 2.0 2.0 Sodium carbonate 5.0 6.0 20.0 C12-13 alkyl ethoxylate (E0 = 7) 0.4 - 1.2 Protease Savinasa5 (4KNPY / g) 0.6 - 1.0 Amylase thermamil5 (60KNU / g) 0.4 __ __ Lipase lipolase5 (100,000 LU / I) '0.1 0.1 0.1 Sav / Ban5 (6KNPU / 100 KNU / g) - 0.3 CAREZYMER5 cellulase (1000 CEVU / g) - 0.1 Dirt release polymer6 0.1 0.1 0.3 Perfume spray 0.4 0.4 0.4 Perfume particles7 1.5 1.5 2.0 Miscellaneous ingredients (water, etc.) balance sheet balance Total 100.0 100.0 100.0 1. Compound of dimethylhydroxyethyl quaternary ammonium of C12-14 2. Diethylenetriaminepenta ethylene phosphonic acid 3. Diethylenetriaminepentaacetic acid 4. Acquired from Ciba-Geigy 5. Acquired from Novo Nordisk A / S 6. Obtained in accordance with the Patent of E.U.A. 5,415,807, issued May 16, 1995 to Gosselink and others 7. From example I.

EXAMPLE VI The following detergent composition according to the invention is in the form of a wash bar which is particularly suitable for hand washing operations. % in weigh Coconut Alkyl Sulfate 30.0 Sodium Tripolyphosphate 5.0 Tetrasodium Pyrophosphate 5.0 Sodium carbonate 20.0 Sodium Sulfate 5.0 Sodium carbonate 5.0 Na? .9Ko.? Ca (C? 3) 2 15.0 Aluminosilicate 2.0 Coconut fatty alcohol 2.0 Perfume particle1 1.0 Perfume spray 1.0 Various ingredients (water, etc.) Total balance 100.0 1. From example I.

Having thus described the invention in detail, it will be clear to those skilled in the art that various changes can be made without departing from the scope of the invention, and that it should not be considered that the scope is limited to what is described in the specification.

Claims (20)

1. NOVELTY OF THE INVENTION CLAIMS 1. - An additive laundry particle, characterized in that it comprises: (i) a porous vehicle core material; (ii) a first encapsulating material coated on said core material to form an intermediate layer, said first encapsulating material comprising a vitreous material derived from one or more at least water-soluble hydroxyl compounds having a glass transition temperature, Tg, anhydrous, non-plasticized, of at least about 0 ° C; and (iii) a second encapsulating material revetted on said intermediate layer to form an outer layer, said second encapsulating material comprising a carbohydrate material having a glass transition temperature, Tg, anhydrous, non-plasticized, of at least about 130. "C" wherein said additive laundry particle has a hygroscopicity value of less than about 80%
2. 2. The additive laundry particle according to claim 1, characterized in that said porous vehicle core material is selected from the group which consists of amorphous silicates, non-stratified silicate silicates, layered silicates, calcium carbonates, calcium / sodium carbonate double salts, sodium carbonates, clays, zeolites, eodalites, alkali metal foefatoe, macroporous zeolites, chitin microspheres, carboxyalkylcelluloses , carboxyalkylal idones, cyclodextrins, porous starches, and mixtures of the same
3. 3. The additive laundry particle according to claim 2, characterized in that said porous vehicle core material is a zeolite, and said zeolite is selected from the group consisting of zeolite X, zeolite Y, and mixtures thereof. same.
4. 4. The additive laundry particle according to claim 1, characterized in that said additive laundry particle further comprises a cleaning or laundry agent contained in or supported on said porous vehicle core; said cleaning or laundry agent being selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, anti-scale agents, minimal value inhibitors, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, substantive fabric dyes, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, pH leap systems, and mixtures thereof.
5. 5. - The additive laundry particle according to claim 4, characterized in that said cleaning or laundry agent is a perfume material.
6. 6.- The additive particle for laundry of 5 according to claim 5, characterized in that said porous vehicle core is a zeolite selected from the group consisting of zeolite X, Y zeolite, and mixtures thereof, and said perfume material is contained in said zeolite.
7. 7. The additive laundry particle according to claim 1, characterized in that said first encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 75 or less.
8. 8. The additive laundry particle according to claim 1, characterized in that said »second encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 7. 5 or less.
9. 9. The additive particle for laundry according to claim 8, characterized in that said second encapsulating material is a starch, modified starch or starch hydrolyzate.
10. 10. The additive laundry particle according to claim 8, characterized in that said second encapsulating material is a maltodextrin.
11. 11. - The additive laundry particle according to claim 1, characterized in that said additive particle for laundry has a hygroscopicity value of less than about 30%.
12. 12. The additive laundry particle according to claim 8, characterized in that said second encapsulating material further includes an ingredient selected from the group consisting of plasticizers, anti-agglomeration agents, and mixtures thereof.
13. 13. A detergent composition for cleaning or laundry, characterized in that it comprises: (i) from about 0.001% to about 50% by weight of the composition of an additive laundry particle comprising a porous vehicle core material; a first encapsulating material coated on said core material to form an intermediate layer, said first encapsulating material comprising a vitreous material derived from one or more at least partially water-soluble hydroxyl compounds having a glass transition temperature, Tg, anhydrous, not plasticized, of at least about 0 ° C; and a second encapsulating material coated on said intermediate layer to form an outer layer, said second encapsulating material comprising a carbohydrate material having a glass transition temperature, Tg, anhydrous, non-plasticized, of at least about 130 ° C; wherein said additive laundry particle has a hygroscopicity value of less than about 80%; and ii) from about 50% to about 99.999% by weight of the laundry ingredient composition selected from the group consisting of detersive surfactants, detergency builders, bleaching agent, enzymes, soil release polymers, transfer inhibitors. of dye, fillers, and mixtures thereof.
14. 14. The detergent composition for cleaning or laundry according to claim 13, characterized in that it also includes at least one detergent surfactant and at least a detergency builder.
15. 15. The detergent composition for cleaning or laundry according to claim 13, characterized in that said porous vehicle core material is a zeolite, and said zeolite is selected from the group consisting of zeolite X, zeolite Y, and mixtures thereof. the same.
16. 16. The detergent composition for cleaning or laundry according to claim 13, characterized in that said additive laundry particle further comprises a cleaning or laundry agent contained in or supported on said porous vehicle core; said cleaning or laundry agent being selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, flaking agents, and minimal value inhibitors, dye transfer inhibitors , photobleaches, enzymes, catalytic antibodies, brighteners, subetantive dyes of telae, 5 anti icóticae, anti icrobianoe, insect repellents, dirt release polymers, fabric softening agents, dye fixatives, pH jump systems, and mixtures of the miemos.
17. 17.- The composition for cleaning or laundry of 10 according to claim 13, characterized in that said first encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 75 or less.
18. 18. The cleaning or laundry composition according to claim 13, characterized in that said second encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 7.5 or less.
19. 19. The cleaning or laundry composition according to claim 14, characterized in that said second encapsulating material is a modified starch or starch.
20. 20. The cleaning or laundry composition according to claim 18, characterized in that said second encapsulating material is a maltodextrin. kr $ 21.- The composition for cleaning or laundry according to claim 13, characterized in that said additive particle for laundry has a hygroecopicity value of less than about 30%.