MXPA99008579A - Laundry additive particle having multiple surface coatings - Google Patents

Abstract

A laundry additive particle having multiple coatings and compositions employing theparticle are provided. The laundry additive particle comprises a central core particle with the core particle comprising a porous carrier core material and a glassy encapsulating material intermixed with the carrier material. The glassy encapsulating material is 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. An optional intermediate encapsulating material may be coated on the central core particle. The intermediate encapsulating material may comprise a carbohydrate material having an anhydrous, nonplasticized, glass transition temperature, Tg, of at least about 130°C. Lastly, an external coating material is coated on the core particle or the intermediate encapsulating material which provides the laundry additive particle with a substantially non-tacky surface. The external coating material is derived from one or more at least partially wash soluble or dispersible compounds selected from the group consisting of waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, and mixtures thereof. 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 additive laundry particles having multiple surface coatings and, most particularly, to zeolite particles loaded with perfume having multiple surface coatings.

BACKGROUND OF THE INVENTION Many consumers have been waiting for perfumed laundry products and that fabrics that have been washed have a pleasing fragrance as well. The perfume additives make the laundry compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasing fragrance to the fabrics treated therewith. However, the amount of perfume that is originated from an aqueous laundry bath on the fabrics is commonly marginal. Therefore, the industry has long sought an effective perfume supply system for use in laundry products that provides long-lasting and stable fragrance during storage to the product, as well as fragrance to the treated fabrics.

Compositions for laundry and other types containing perfume mixed with or sprinkled on the compositions are well known from 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 prevent or delay the release of the perfume compositions to remain aesthetically pleasing for a longer period of time. However, to date, few of the methods provide significant fabric odor benefits after prolonged storage of the product. Furthermore, there has been a continuous search for methods and compositions that effectively and efficiently deliver perfume from a wash bath onto the surfaces of the fabrics. As can be seen from the following descriptions, various perfume delivery methods have been developed which include the protection of the perfume throughout the wash cycle, with the release of the perfume on the fabrics. The patent of E.U. No. 4,096,072, Brock et al., Issued June 20, 1978, teaches a method for delivering fabric conditioning agents, including perfumes, through the washing and drying cycle by means of a fatty quaternary ammonium salt. The patent of E.U. 4,402,856, Schnoring et al., Issued September 6, 1983, teaches a microencapsulation technique that includes the formulation of a shell material that will allow diffusion of the perfume out of the capsule only at certain temperatures. The patent of E.U. 4,152,272, Young, issued May 1, 1979, teaches the incorporation of perfume into waxy particles to protect the perfume during storage in dry compositions and during laundry procedures. The perfume diffuses properly through the wax on the fabric in the dryer. The patent of E.U. No. 5,006,419, Walley et al., Issued November 19, 1991, teaches a dispersed perfume with a non-polymeric, water insoluble carrier material and encapsulated in a protective shell by coating with a water-insoluble, friable coating material. The patent of E.U. No. 5,094,761, Trinh et al., Issued March 10, 1992, teaches a clay-protected perfume / cyclodextrin complex that provides perfume benefits to at least partially wetted fabrics. Another method for the supply of perfume in the wash cycle includes combining the perfume with an emulsifying and water-soluble polymer, forming the particulate mixture and adding them to a laundry composition, such as that described in the US patent. 4,209,417, Whyte, issued June 24, 1980; U.S. Patent 4,339,356, Whyte, issued July 13, 1982 and U.S. patent. No. 3,576,760, Gould et al., Issued April 27, 1971. However, even with the substantial work done by the industry in this area, there still remains a need for a simple, more efficient and effective perfume delivery 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 onto a porous carrier material, such as a polymeric material, such as described in British Patent Publication 2,066,839, Bares et al., Published July 15, 1981. Perfumes have also been adsorbed onto a clay or zeolite material which is then mixed into particulate detergent compositions. Generally, the zeolites that are preferred have been type A or 4A zeolites with a nominal pore size of approximately 4 Angstrom units. It is now believed that with zeolite A or 4A, the perfume is adsorbed on the surface of the zeolite with relatively little of the perfume actually being absorbed into the pores of the zeolite. Although the adsorption of the perfume on zeolite or polymeric vehicles may provide perhaps some improvement over the addition of concentrated perfume mixed with detergent compositions, the industry still seeks improvements in the length of storage time of the laundry compositions without the loss of the characteristics of the perfume, in the intensity or amount of fragrance supplied to the fabrics and in the duration of the perfumed aroma on the surfaces of the treated fabrics. Therefore, there remains a need for a perfume delivery system that provides a satisfactory perfumed aroma during use and subsequently of the dried fabric, but which also provides benefits of prolonged storage and reduced product odor intensity.

TECHNICAL BACKGROUND The patent of E.U. No. 4,539,135, Ramachandran et al., Issued September 3, 1985, discloses laundry compositions in particles comprising a vehicle perfume of clay material or zeolite. The patent of E.U. No. 4,713,193, Tai, issued December 15, 1987, discloses an additive for free-flowing particulate detergents comprising a liquid or oily auxiliary with a zeolite material. Japanese patent HEl 4 [1992] -218583, Nishishiro, published on August 10, 1992, discloses controlled release materials including perfumes plus zeolites. The patent of E.U. 4,304,675, Corey et al., Issued December 8, 1981, teaches a method and composition comprising zeolites to deodorize articles. The publication of the East German Patent No. 248,508, published on August 12, 1987; the publication of the East German patent No. 137,599, published on September 12, 1979; European application publication No. 535,942, published on April 7, 1993 and publication No. 536,942, published on April 14, 1993, by Unilever PLC; the patent of E.U. 5,336,665, issued August 9, 1994 to Garner-Gray et al .; WO 94/28107, published December 8, 1994; the patent of E.U. 5,258,132, issued November 2, 1993 and the US patent. 5,230,822, issued July 27, 1993, both to Kamel and others; the patent of E.U. 5,141, 664, issued August 25, 1992 to Corring et al. And the US patent. 2,809,895, issued on October 15, 1957 to Swisher BRIEF DESCRIPTION OF THE INVENTION This need is covered by the present invention, in which an additive laundry particle is provided. The additive laundry particle can be used to supply a number of laundry and cleaning agents useful either to or through the wash cycle. The additive laundry particle of the present invention essentially comprises a core of porous carrier material and multiple surface or encapsulation coatings on the core. The additive laundry particle of the present invention is particularly effective in delivering perfume ingredients through washing to a fabric surface. In traditional perfume delivery systems more than 50% of the perfume material is "lost" due to the diffusion of the volatile perfume materials of the product, as well as to the dissolution in the wash, and is never supplied to the surface of the perfume. the fabric In the present invention, multiple coatings effectively trap the perfume material loaded on or in the zeolite core. In this way, the perfume material is supplied at a higher speed during washing to the surface of the fabric than with traditional perfume delivery systems.

According to a first embodiment of the present invention, an additive laundry particle is provided. The additive laundry particle comprises a central core particle comprising a central porous vehicle material and a vitreous encapsulating material interspersed with the carrier material. The vitreous encapsulating material is derived from one or more at least partially water-soluble hydroxyl compounds having an anhydrous and unplasticized glass transition temperature (Tg) of at least about 0 ° C. An intermediate encapsulating material can then be coated on the core particle. The intermediate encapsulating material, when present, comprises a carbohydrate material having an anhydrous and unplasticized glass transition temperature (Tg) of at least about 130 ° C. An external coating material is then applied on the central particle or, when present, on the intermediate encapsulating material, which provides the additive laundry particle with a substantially non-tacky surface. The outer coating material is derived from one or more compounds at least partially soluble or dispersible in the wash selected from the group consisting of waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, quitan and chitosan, and mixtures thereof. Preferably, the porous carrier material is selected from the group consisting of amorphous silicates, non-stratified crystalline silicates, layered silicates, calcium carbonates, calcium / sodium carbonate double salts, sodium carbonates, clays, zeolites, sodalites, phosphates, alkali metal, macroporous zeolites, chitin microspheres, carboxyalkylcelluloses, carboxyalkyalmidons, cyclodextrins, porous starches and mixtures thereof, and most preferably is a zeolite selected from the group consisting of zeolite X, zeolite Y and mixtures thereof. The additive laundry particle further comprises a laundry or cleaning agent contained in or suspended on the porous vehicle core. The laundry or cleaning agent is selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelators, antiscalants, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, substantive dyes in fabrics, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, pH leap systems and mixtures thereof, and is preferably a perfume material that is contained in a zeolite. The preferred PV encapsulating material is a starch, modified starch or starch hydrolyzate, while the preferred intermediate encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of about 7.5 or less, with more preferred maltodextrin that has an ED of 5 or less. The outer coating material is preferably a cellulose or cellulose derivative, with a preference for hydroxypropylmethylcellulose. The additive laundry particle has a hygroscopicity value of less than about 80% and most preferably less than about 30%. Finally, the intermediate encapsulation material and / or the outer coating may further include an ingredient selected from the group consisting of plasticizers, anti-agglomeration agents and mixtures thereof. According to a second embodiment of the present invention, a detergent composition for laundry or cleaning is provided. The detergent composition for laundry or cleaning comprises 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 composition, of ingredients of 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 laundry and cleaning 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 flavor benefits, life capabilities during prolonged storage and reduced product odor intensity. These and other characteristic objects and advantages of the present invention will be recognizable to one 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 the cited documents are incorporated herein by reference in their entirety.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive laundry particle and to laundry and cleaning compositions employing the additive laundry particle. The laundry and cleaning compositions include granular laundry detergents, as well as granulated bleaching compositions, for automatic dishwashing, for cleaning hard surfaces and for fabric softening. The additive laundry particle of the present invention provides superior perfume delivery capabilities during washing as well as minimizes the odor of the product caused by the volatile perfume ingredients. While not wishing to be bound by theory, it is also believed that multiple coatings of the particle of the present invention increase the stability of the particle. The laundry particle of the present invention comprises a core of a porous vehicle that is coated or intermixed with a vitreous encapsulating material. In an optional step, the core particle can be coated with an intermediate encapsulating material. An outer or outer coating is then placed on the core particle or intermediate layer to form the fine particle. The laundry particles of the present invention have a hygroscopicity value of less than about 80%. The "hydroscopicity value", as used herein, means the level of moisture uptake by the particles, as measured by the percentage increase in the weight of the particles under the following test method. The hydroscopicity value required for the particles of the present invention is determined by placing 2 grams of particles (particles with a size of about 500 microns, which have no moisture barrier coating) in a wet petri dish and open under conditions of 32.2 ° C and 80% relative humidity during a period of 4 weeks. The percentage increase in the weight of the particles at the end of this time is the hygroscopicity value of the particles, as used herein. The particles that are preferred in the present invention have a hygroscopicity value of less than about 50%, most preferably less than about 30%.

The laundry additive particles of the present invention typically comprise about 30% to about 97% of the charged core particle which in turn is about 20% to about 80% vitreous encapsulating material, about 3% to about 50%. % of intermediate encapsulating material and from about 3% to about 30% of external coating material. The particulate compositions of the present invention also typically comprise about 0% to about 90% useful agents for laundry or cleaning compositions, preferably about 10% to about 80% and most preferably about 25% to about 80%.

Central core particle As already mentioned, the central core of the additive particle comprises a mixture of a porous carrier material and a glassy encapsulation material. The two core core ingredients can be .. mixed in a number of different ways, with the extrusion of the two ingredients being preferred. The central core typically comprises around % to approximately 60% of the loaded porous vehicle, the rest being vitreous encapsulation material.

POROUS VEHICLE MATERIAL As used herein, "porous carrier material" means any material capable of supporting (e.g., by surface absorption or pore adsorption) a dispensable agent such as a laundry or cleaning agent. 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 starches, cyclodextrins, porous starches and mixtures thereof. The porous carrier materials that are preferred are zeolite X, Y zeolite and mixtures thereof. The term "zeolite" used herein refers to a crystalline aluminosilicate material. The structural formula of a zeolite is based on the unitary cell of the crystal, the smallest unit of the structure represented by Mm / n [(AIO2) m (SiO2) and]. XH2O where n is the valence of the cation M, x is the number of water molecules per unit cell, my (y) is the total number of tetrahedrons per unit cell, and y / m is 1 to 100. Most preferably, y / m is 1 to 5. The M cation can be elements of group IA and group HA, 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 Y zeolites are well known and are available in normal texts. The synthetic crystalline aluminosilicate materials which are preferred and used 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 type X and is selected from the following: (I) Na86 [Al? 2] 86 (SiO2) .06] xH2 ?, (II) K86 [AIO2] 86 (SiO2) i06] xH2O, (III) Ca40Na6 [AIO2] 86 '( SiO2) 106] xH2 ?, (IV) Sr2? Ba22 [Al? 2] 86 (Si? 2)? O6] 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 aperture of 8.4 Angstrom units. The zeolites of the formula (III) and (IV) have a nominal pore size or aperture of 8.0 Angstrom units.

In another preferred embodiment, the crystalline aluminosilicate material is type Y and is selected from the following: (V) Na56 [AI02] 56 (Si02). Se] xH20, VI) K56 [AI02] 56 (Si02) .36 ] XH20 and mixtures thereof, wherein x is from about 0 to about 276. The zeoiites of formula (V) and (VI) have a nominal pore size or aperture of 8.0 Angstrom. In another modality more, the class of zeolites known as "Zeolite MAP" can also be employed in the present invention. Said zeolites are deciphered in patent application Serial No. 08 / 716,147, filed on September 16 and entitled "Zeolite MAP and Alcalase for Improved Fabric Care. "The zeolites used in the present invention are in the form of a particle 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 the analysis technique. The size of the particles of zeolite allows them to be trapped in the fabrics they come into contact with, once they are established on the surface of the fabric (with its covering matrix having been washed out during the washing process). ), zeolites can begin to release their incorporated laundry agents, especially when subjected to hot or humid conditions.

Vitreous encapsulating material The vitreous 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 hydrosoluble hydroxylic compounds useful herein are preferably selected from the following classes 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 2-35 molecules of monosaccharide); iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 molecules of monosaccharide); iv) starches including modified and hydrolyzed starches and v) hydrogenated from i), ii), iii) and iv). Both linear and branched carbohydrate chains can be used. In addition, chemically modified starches and poly- / oligo-saccharides can be used. Typical modifications include the addition of hydrophobic portions in the form of alkyl, aryl, etc., identical to those found in the surfactants to impart some surface 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 a dextrose equivalence (DE) of less than 45 and are typically produced by the hydrogenation of starch hydrolysates with an ED of less than 45. Suitable examples of hydrolysates of Hydrogenated starch include those available under the trade names POLYSORB and LYCASINE from Roquette America of Keokuk, Iowa, and HYSTAR of Lonza of Fairlawn, N.J. 2. All natural or synthetic gums such as esters of alginate, carrageenan, agar-agar, peptic acid and natural gums such as gum arabic, gum tragacanth and gum carayá. 3. Chitin and chitosan. 4. Cellulose and cellulose derivatives. Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropylmethylcellulose (HPMC); Ii) carboxymethylcellulose (CMC); iv) all enteric / aquatic coatings and mixtures thereof. 5. Silicates, phosphates and borates. 6. Polyvinyl alcohol (PVA). 7. Polyethylene glycol (PEG). 8. Plasticizers Materials within these classes that are not at least partially water-soluble and which have glass transition temperatures, Tg, below 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 having the highest Tg required, such that the vitreous particle produced has the required hygroscopicity value of less than about 80%.

The glass transition temperature, commonly abbreviated "Tg", is a property well known and easily determined for vitreous materials. This transition is described as equivalent to the liquidification, after heating through the Tg region, of a material in the vitriol 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 Analvsis Application Studv # 7, Perkin-Elmer Corporation, March 1973. ] The measurement of Tg is easily obtained using a deferential scanning calorimeter. For the purposes of the present invention, the Tg of the hydroxy compounds is obtained for the anhydrous compound which does not contain any plasticizer (which will have an impact on the measured Tg value of the hydroxylic compound). The glass transition temperature is also described in detail in P. Peyser, "Glass Trensition Temperatures of Polymers ", Polvmer Handbook, Third Edition, J.Brandrup and E. H. Immergut (Wiley-lnterscience; 1989), pp. VI / 209-VI / 277. At least one of the hydroxyl compounds useful in the present invention should have an anhydrous and unplasticized Tg of at least 0 ° C, and for particles that do not have a moisture barrier coating, at least about 20 ° C. , preferably at least about 40 ° C, most preferably at least 60 ° C and more preferably at least about 100 ° C. It is also preferred that these compounds be processable at low temperatures, preferably in the range of about 50 ° C to about 200 ° C, and most preferably in 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, most preferably about 65 or less and more preferably between about 7.5 and about 45, or the hydrogenated equivalent of these carbohydrates. As used herein, 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 of 0 to 100, with 100 being the amount present in a pure sugar. The normal technique for determining dextrose equivalence is a volumetric alkaline copper method. Both dextrose equivalence and methods for measuring dextrose equivalence 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 with hydrogenated starch hydrolysates, which are more preferred.

Intermediate encapsulating material The intermediate encapsulating material according to the present invention can form an optional coating on the central core particle. The intermediate coating can provide an additional barrier to minimize the release or spillage of any available agents incorporated in the porous carrier, such as a perfume. The intermediate layer, when present, is a carbohydrate material having an anhydrous and unplasticized glass transition temperature (Tg) of at least about 130 ° C and most preferably at least about 150 ° C and more preferably around 175 ° C. The carbohydrate material of the intermediate encapsulating material can be any or a mixture of: i) simple sugars (or monosaccharides); ii) oligosaccharides (defined as carbohydrate chains consisting of 2-35 monosaccharide molecules); iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 molecules of monosaccharide); iv) starches including modified and hydrolyzed starches and v) hydrogenated from i), ii), iii) and iv). Both linear and branched carbohydrate chains can be used. In addition, chemically modified starches and poly- / oligo-saccharides can be used. Typical modifications include the addition of hydrophobic portions in the form of alkyl, aryl, etc., identical to those found in the surfactants to impart some surface activity to these compounds.

The carbohydrate of the intermediate encapsulating material preferably has an equivalence of dextrose, DE, of about 7.5 or less, most preferably about 5 or less. The carbohydrate of the intermediate encapsulating material is preferably a modified starch or starch, a maltodextrin or a hydrogenated starch hydrolyzate as described above. Suitable maltodextrins 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 intermediate 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, with a mixture of sorbitol and polyethylene glycol and low molecular weight polyols being preferred. The plasticizer is used at levels from about 0.01% to about 5%. The anti-agglomeration agents according to the present invention are preferably a surfactant and are included at low levels of less than 1% of the intermediate encapsulating material. Suitable surfactants for use in the present invention include TWEEN 80 ™ commercially available from Imperial Chemicals, Inc. (ICI).

External coating material The outer coating material is applied to the core particle or, when present, to the intermediate encapsulation material, and provides the outer layer of the final particle. The outer coating material provides a substantially non-tacky or non-tacky coating for the final particle. Preferably, the outer coating provides a particle that will have a non-tacky surface under high humidity conditions such as 80% relative humidity at 32.2 ° C. The outer coating is a material derived from one or more compounds at least partially soluble or dispersible in the wash. That is, the outer coating will be soluble in an aqueous wash environment or will be dispersible in that aqueous wash environment. The compounds useful herein are preferably selected from the group consisting of the following classes 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 2-35 molecules of monosaccharide); iii) polysaccharides (defined as carbohydrate chains consisting of at least 35 molecules of monosaccharide); V) starches including modified and hydrolyzed starches and v) hydrogenated from i), ii), iii) and v). Both linear and branched carbohydrate chains can be used. In addition, chemically modified starches and poly- / oligo-saccharides can be used. Typical modifications include the addition of hydrophobic portions in the form of alkyl, aryl, etc., identical to those found in the surfactants to impart some surface activity to these compounds. 2. All natural or synthetic gums such as esters of alginate, carrageenan, agar-agar, peptic acid and natural gums such as gum arabic, gum tragacanth and gum carayá. 3. Chitin and chitosan. 4. Cellulose and cellulose derivatives. Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); I) hydroxypropylmethylceiulose (HPMC); iii) carboxymethylcellulose (CMC); V) all enteric / aquatic coatings and mixtures thereof. 5. Silicates, phosphates and borates. 6. Water-soluble polymers including polyacrylates, caprolactones, polyvinyl alcohol (PVA) and polyethylene glycol (PEG). 7. Waxes, including silicone waxes, paraffin waxes and microcrystalline waxes. 8. Plasticizers 9. Long chain fatty compounds (C10-C35), including fatty acids, fatty alcohols and fatty esters. Materials within these classes that are not at least partially water-soluble or dispersible are useful herein only when they are mixed in such amounts with the compounds useful herein, so that the particle produced has the required hygroscopicity value of less than about 80%. It is also preferred that these compounds be processable at low temperatures, preferably in the range of about 50 ° C to about 200 ° C, and most preferably in the range of about 60 ° C to about 180 ° C. Preferably, the hydroxy compound is cellulose or cellulose-derived materials. More preferred is hydroxypropylmethylcellulose, commercially available from Aqualori under the trade name METHOCEL. The outer coating 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, with a mixture of sorbitol and polyethylene glycol and low molecular weight polyols being preferred.

The plasticizer is used at levels from about 0.01% to about 5%. The anti-agglomeration agents according to the present invention are preferably a surfactant and are included at low levels of less than 1% of the outer coating. Suitable surfactants for use in the present invention include TWEEN 80 ™ commercially available from Imperial Chemicals, Inc. (ICI).

Laundry and cleaning agents Laundry and cleaning agents are included in the particle of the present invention. The agents are supported on, or contained in, the porous carrier material as described hereinabove. The agents useful in the present invention are selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelators, antiscaling agents, threshold inhibitors, dye transfer inhibitors, photobleaching agents, enzymes, catalytic antibodies. , brighteners, substantive dyes in fabrics, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, pH leap systems and mixtures thereof.

As can be appreciated for the present invention, these agents that are incorporated into the particles of the present invention can be the same or different from the agents that are used to formulate the rest of the laundry and cleaning compositions containing the particle. For example, the particle may comprise a perfume agent and (the same or different) agent may also be combined in the final composition together with the particle containing the 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 hereinafter. The laundry particle of the present invention can of course be included in a composition that can contain other ingredients. The compositions containing additive laundry particles may optionally include one or more auxiliary materials of detergents or other materials to assist or increase the cleaning performance, the treatment of the substrate to be cleaned or to modify the aesthetics of the detergent composition (e.g. perfumes, dyes, dyes, etc).

Perfume The preferred laundry or cleaning agent according to the present invention is a perfume material. As used herein, the term "perfume" is used to indicate any odoriferous material that is subsequently released in the aqueous bath and / or on the fabrics contacted therewith. The perfume will very commonly be liquid at room temperatures. A wide variety of chemicals are known for perfume uses, including materials such as aldehydes, ketones and esters. Most commonly, vegetable and natural animal oils and exudates comprising complex 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 complex mixtures of natural and synthetic chemical components, all chosen to provide any desired aroma. Typical perfumes may comprise, for example, woody / earthy bases containing exotic materials such as sandalwood, civet and pachuii oil. The perfumes can be a light floral fragrance, for example, rose extract, violet and lilac extract. Perfumes can also be formulated to provide desirable fruit odors, for example lime, lemon and orange. Any chemically compatible material that exudes a pleasant or otherwise desirable aroma may be used in the perfumed compositions herein. Perfumes also include pro-fragrances such as acetal pro-fragrances, ketal pro-fragrances, ester pro-fragrances (eg, digeranyl succinate), hydrolyzable inorganic-organic pro-fragrances and mixtures thereof. These pro-fragrances can release the perfume material as a result of simple hydrolysis, or they may be triggered by a change in pH (eg, pH drop) or they may be enzymatically releasable pro-fragrances. The perfume agents useful herein that are preferred are defined as follows. For the purposes of the present invention, compositions exposed to the aqueous medium of the laundry process, several characteristic parameters of perfume molecules are important to identify and define: their longest and widest measures; its cross-sectional area; molecular weight and molecular surface area. These values are calculated for individual perfume molecules using the CHEMX program (from Chemical Design, Ltd.) for molecules in a minimum energy conformation as determined by the standard geometry optimized in CHEMX and using standard van der Waal atomic radios. The definitions of the parameters are as follows: "Longer": the largest distance (in Angstroms) between atoms in the molecule increased by their van der Waal radii. "Wider": the largest distance (in Angstroms) between atoms in the molecule increased by its radii of van der Waai in the projection of the molecule on a plane perpendicular to the "longest" axis of the molecule. "Transverse area": area (in square Angstrom units) filled by the projection of the molecule in the plane perpendicular to the longest axis. "Molecular volume": the volume (in cubic Angstrom units) filled by the molecule in its minimum energy configuration. "Molecular surface area": arbitrary units that scale. as square Angstroms (for calibration purposes, the methylbetane-ethyl ketone, benzyl salicylate, and camphor gum molecules have surface areas that measure units 128 + 3, 163.5 + 3, and 122.5 ± 3, respectively). The shape of the molecule is also important for its incorporation. For example, a perfectly symmetric spherical molecule that is small enough to be included in the zeolite channels does not have a preferred orientation and is incorporated from any approaching direction. However, for molecules having a length exceeding the pore size, an "approach orientation" is preferred for inclusion. The calculation of the volume / surface area ratio of a molecule is used here to express the "shape index" for a molecule. The higher the value, the more spherical the molecule will be. For the purposes of the present invention, perfume agents are classified according to their ability to be incorporated into zeolite pores, and therefore their utility as components to be delivered from the zeolite vehicle through an aqueous environment. The plotting of these agents in a volume / surface area ratio against a cross-sectional plane allows the convenient classification of the agents into groups according to their capacity for incorporation into the zeolite. In particular, for vehicles of zeolite X and Y according to the present invention, the agents are incorporated if they fall below the line (here called "line of incorporation") defined by the equation: Y = -0.01068x + 1.497 in where x is the cross-sectional area and (y) is the volume / surface area ratio.

Agents that fall below the line of incorporation are defined here as "deliverable agents"; the agents that fall on the line are called here "non-supply agents". To be contained during washing, the available agents are retained in the zeolite vehicle as a function of their affinity for the vehicle in relation to the competent deliverable agents. The affinity is impacted by the size of the molecule, its hydrophobicity, functionality, volatility, etc., and can be affected by the interaction between agents available within the zeolite vehicle. These interactions allow for improved washing during the wash for the mixture of available dispensing agents. Specifically, for the present invention, the use of dispensing agents having at least one dimension that largely coincides with the pore size of the zeolite vehicle slows down the loss of other agents available in the wash environment. . Supplying agents that function in this manner are called "blocking agents" here, and are defined here in the volume / surface area ratio versus the cross-sectional plane as those molecules of available agents that fall below the "line of incorporation" (as defined above here) but on the line (here called the "blocking line") defined by the equation: y = -0.01325x + 1 .46 where x is the transversal area and (y) is the volume / area ratio Of surface. For the compositions of the present invention using zeolite X and Y as the carriers, all the agents available below the "line of incorporation" can be supplied and released from the compositions of the present invention, the preferred materials being those fall under the "blocking line". Mixtures of blocking agents and other available agents are also preferred. Blends of laundry perfume agents useful for the laundry particles of the present invention preferably comprise about 5% to about 100% (preferably about 25% to about 100, most preferably about 50% to about 100%) agents available and preferably comprise about 0.1% to about 100% (preferably about 0.1% to about 50%) of blocking agents, by weight of the laundry agent mixtures. Obviously for the compositions of the present invention in which the perfume agents are supplied by the compositions, sensory perception is required to observe a benefit on the part of the consumer. For the perfume compositions of the present invention, the perfume agents that are most preferred and useful herein have a threshold of notoriety (measured as odor detection thresholds ("ODT") under carefully controlled CG conditions as will be described in more detail below) of less than or equal to 10 parts per billion ("ppb"). Agents with ODTs between 10 ppb and 1 part per million ("ppm") are less preferred. Preferably, agents with ODTs of more than 1 ppm are avoided. Perfume laundry perfume blends useful for the laundry particles of the present invention preferably comprise about 0% to about 80% of agents available with ODTs between 10 ppb and 1 ppm and about 20% to about 100% (preferably about 30% to about 100%, most preferably about 50% to about 100%) of agents available with ODTs less than or equal to 10 ppb. Also preferred are perfumes included in the washing processes and subsequently released in the air around the dried fabrics (for example, such as the space around the fabric during storage). This requires the movement of perfume out of the pores of zeolite with its Subsequent separation in the air that goes around the fabric. The perfume agents that are preferred are therefore further identified on the basis of their volatility. The boiling point is used herein as a measure of volatility and the materials that are preferred have a boiling point of less than 300 ° C. Laundry agent perfume blends useful for the laundry particles of the present invention preferably comprise at least about 50% of available agents with a boiling point of less than 300 ° C (preferably at least about 60%), most preferably at least about 70%). In addition, the laundry particles that are preferred herein comprise compositions in which at least about 80%, and most preferably at least about 90% of the available agents have a "ClogP value" of more than about 1.0. The ClogP values are obtained as follows.

Calculation of CloqP These perfume ingredients are characterized by their coefficient P for the separation of octanol / water. The octanol / water separation coefficient of a perfume ingredient is the ratio between its equilibrium concentration of octanol and water. Since the separation coefficients of most of the perfume ingredients are large, they are most conveniently given in the form of their logarithm to base 10, logP. The logP of many perfume ingredients has been reported; for example, the Pomona92 database, available from Dayiight Chemical Information Systems, Inc. (Daylight CIS), contains many, along with quotes from the original literature. However, the logP values are calculated very conveniently by the "CLOGP" program, also available from Daylight CIS. This program also lists 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 (cf., A. Leo, in Comprehensive Medicinal Chemistry, Vol.4 C Hansch, PG Sammens JB Taylor and CA Ramsden, Eds., P. 295, Pergamon Press, 1990). The fragment approach is based on the chemical structure of each perfume ingredient and takes into account the numbers and types of atoms, the connectivity between atoms and the chemical bond. 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 in the selection of the perfume ingredients.

Determination of odor detection thresholds The gas chromatograph is characterized to determine the exact volume of material injected by the syringe, the precise separation ratio and the response to hydrocarbons using a hydrocarbon parameter of known chain length concentration and distribution. The air flow rate is measured accurately 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 at any point of time is known, the mass per inhaled volume is known and therefore the concentration of the material. To determine if a material has a threshold below 10 ppb, the solutions are supplied to the port of bloom at the concentration calculated earlier. A panelist smells the CG effluent and identifies the retention time when he smells. The average over all the panelists determines the threshold of notoriety capacity. The required amount of analyte is injected into the column to achieve a concentration of 10 ppb in the detector. Typical gas chromatograph parameters to determine odor detection thresholds are listed below. CG: 5890 Series II with FID detector 7673 Autosampler Column: J &W Scientific DB-1 Length 30 meters internal diameter; 0.25 mm film thickness, 1 miera. Method: Separation injection: separation ratio 17/1 Autosampler: 1.13 microliters per injection Column flow: 1.10 mL / minute Air flow. 345 mL / minute Inlet temperature: 245 ° C Detector temperature: 285 ° C Temperature information: Initial temperature: 50 ° C Speed: 5C / minute Final temperature: 280 ° C Final temperature: 6 minutes Main conclusions: 0.02 minutes per air of GC is added to the 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, toxicologically acceptable, non-irritating to the skin, inert to the perfume, degradable and / or available from renewable sources, as well as relatively inogenous additives are used. It is believed that perfume fixatives slow down the evaporation of more volatile perfume components. Examples of suitable fixatives include members selected from the group consisting of diethyl phthalate, musks and mixtures thereof. If used, the perfume fixative comprises approximately % to about 50%, preferably about 20% to about 40% by weight of the perfume.

Incorporation of perfume in the preferred zeolite vehicle The X-type or Y-type zeolites to be used herein as the preferred carrier preferably contain less than about 15% desorbable water, most preferably less than about 8% desorbable water and more preferably less than about 5% desorbable water. Such materials can be obtained by first activating / dehydrating by heating to about 150-350 ° C, optionally with reduced pressure (from about 0.001 to about 20 Torr), for at least 12 hours. After activation, the agent is slowly and carefully mixed with the activated zeolite and, optionally, heated to about 60 ° C for 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 free flowing powder. The amount of laundry agent incorporated in the zeolite carrier is less than about 20%, typically less than about 18.5% by weight of the charged particle, given the pore volume limits of the zeolite. However, it should be recognized that the particles of the present invention may exceed this level of laundry agent by weight of the particle, but recognizing that excess levels of laundry agents will not be incorporated in the zeolite, even if only agents are used. available 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-available agents present) are not incorporated into the pores of the zeolite, these materials will possibly be immediately released to the wash solution after contact with the aqueous washing medium. In addition to its function of containing / protecting the perfume in the zeolite particles, the vitreous encasing material also conveniently serves to agglomerate many perfumed zeolite particles into agglomerates having overall particle sizes in the range of 200 to 1000 microns, preferably 400 to 600 microns. This reduces the powdery character. In addition, the tendency of the smaller and more individual perfumed zeolites to move to the bottom of containers filled with granular detergents decreases, which, in turn, typically have particle sizes in the scale of 200 to 1000 microns.

Auxiliary laundry or cleaning ingredients Auxiliary ingredients useful for, or with laundry or cleaning compositions in accordance with the present invention are selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelators , antiscalants, threshold inhibitors, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, substantive dyes on fabrics, antifungals, antimicrobials, insect repellents, soil release polymers, fabric softening agents, dye fixatives, systems of pH jump and mixtures thereof. As can be appreciated for the present invention, these useful agents for laundry or cleaning compositions that are incorporated in the particulate compositions of the present invention may be the same as or different from the agents that are used to formulate the remaining laundry compositions. and cleaning containing the particulate compositions. For example, the particulate compositions may comprise a perfume agent and the same or different agent may also be combined in the final composition together with the particulate composition containing the 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 laundry and cleaning compositions are described hereinafter. The compositions containing particulate materials may optionally include one or more auxiliary materials of detergents or other materials to assist or increase 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 the agglomerates include surfactants at the levels indicated previously. The detersive surfactant can be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures. Non-limiting examples of surfactants useful herein include conventional Cj-CJ 8 alkylbenzene sulphonates ("LAS") and branched and randomized primary branched chain ("AS") alkylsulfonates, alkyl sulfates (2,3) ) secondary C-io-Ci d of the formula CH3 (CH2)? (CHOS03-M +) CH3 and CH3 (CH2) and (CHOS? 3-M +) CH2CH3 where xy (y + 1) are integers of at least 7, preferably at least 9, and M is a cation that is solubilized in water, especially sodium, unsaturated sulfates such as oleylsulfate, the alphasulfonated fatty acid esters of CJ Q-CI S ("AEXS", especially EO-1-7 ethoxysulfates), CJ QCJ S alkylalkoxycarboxylates (especially the ethoxycarboxylates EO 1 -5), the glycol ethers of C? o- -] 8- the alkyl polyglycosides of CI Q-CI SY and their corresponding sulfated polyglycosides, and alphasulfonated fatty acid esters of C-j2-Ci 8- If desired, the conventional non-ionic amphoteric surfactants such as C-alkylethoxylates of C- 2-C-] 8 ("AE") including the so-called narrow peak alkyl ethoxylates and the alkylphenolalkoxylates of CQ-C- \ 2 (especially ethoxylates and ethoxy / mixed propoxy), C-12-C18 betaines and sulfobetaines ("sultaines") "), amine oxides of CI O- -J S- and the like, can also be included in the overall compositions. The N-alkylpolychloridoxyl fatty acid amides of Q Q-8 can also be used. Typical examples include the N-methylglucamides of Ci2_Ci 8- See WO 9,206,154. Other surfactants derived from sugar include Other surfactants derived from sugar include N-alkoxy polyhydric fatty acid amides, such as N (3-methoxypropyl) glucamide of CI O- -J S- The N-propyl to N-hexyl glucamides of C -12- 18 can be used for low foaming. Conventional C10-C20 soaps can also be used. If high foaming is desired, the soaps of C- | o-C-i 6 d branched chain. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts. The alkylalkoxysulfates of C-? 0-C? 8 ("AEXS", especially EO-1 -7 ethoxysulfates) and C-? 2-C? 8 alkyl ethoxylates ("AE") are the most preferred for detergents containing cellulase described herein.

Detersive Detergency Enhancer Granules and agglomerates preferably include a builder at the levels previously indicated. Inorganic and organic builders can be used. Crystalline as well as amorphous builders can also be used. Builders are typically used in fabric washing compositions to help remove particulate soils and to remove water hardness. Inorganic or phosphate-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 sesquicarbonate), 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" detergency builders (as compared to phosphate builders) such as citrates, or in the so-called "lower detergency enhancement" situation that It can occur with zeolite builders or stratified silicate. Examples of silicate builders are alkali metal silicates, particularly those having a ratio ofYes? 2: Na2? in the scale from 1.6: 1 to 3.2: 1 and layered silicates, such as the layered sodium silicates described in the US patent. 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trade name for a crystalline layered silicate sold by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological form of delta-Na2Si? 5 layered silicate. It can be prepared by methods such as those described in the German application DE-A-3,417,649 and DE-A-3J42,043. 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 may be used herein. Some other stratified silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-1 1 as the alpha, beta and gamma forms. As indicated above, the delta-Na2Si? 5 (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 aluminosilicate builders are detergency builders useful in the present invention. Aluminosilicate builders are of great importance in the majority of the heavy duty granular detergent compositions currently commercialized, and can also be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula: Mz (zAl? 2) and] xH20 where z and y are integers of at least 6, the molar ratio of zay is in the range of about 1.0 to about 0.5 , and x is an integer from about 15 to about 264. Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically derived aluminosilicates. A method for producing aluminosilicate ion exchange materials is described in the US Patent 3,985,669, Krummel et al. Issued October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeoite X. In a Especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na «| 2 [(AIO2)? 2 (S¡O2) l 2] xH2? wherein x is from about 20 to about 30, especially about 27. The material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used herein.

Preferably, the aminosilicate 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, "polycarboxylates" 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., US patent. 3,635,830, issued January 18, 1972. See also "TMS / TDS" detergency builders of the U.S. patent.

No. 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 Patents. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, co-polymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-succinic acid, various alkali metal, ammonium and ammonium salts. substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Citrate builders, eg, citric acid and soluble salts thereof (particularly sodium sai), are polycarboxylate builders of particular importance for heavy-duty liquid detergent formulations because of their availability from renewable resources and their biodegradability. The citrates can also be used in granular compositions, especially in combination with aeolith 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-1,6-hexanodiates and the related compounds described in the U.S. patent. 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 European patent application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are described in the U.S. patent. 4,144,226, Crutchfield et al., Issued March 13, 1979 and in the US patent. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, US patent. 3,723,322. Fatty acids, e.g., C12-18 monocarboxylic acids may also be incorporated into the compositions by themselves, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional detergency builder activity. Such use of fatty acids will generally result in decreased foaming, which would be considered by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripol phosphates, 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. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

Other Auxiliary Ingredients The composition of the present invention may also include enzymes, enzyme stabilizers, brighteners, polymeric dispersing agents (ie, polyacrylates), vehicles, hydrotropes, foam boosters or suppressants, soil release agents, water transfer inhibitors, dyes and processing aids.

GRANULATED COMPOSITIONS The laundry and cleaning compositions of the present invention can be used in both low density (less than 550 grams / liter) and high density granular detergent compositions, in which the granule density is at least 550 grams / liter. The granular compositions are typically designed to provide a pH in the wash from about 7.5 to about 11.5, preferably about 9.5 to about 10.5. The low density compositions can be prepared by standard spray drying methods. Various means and equipment are available for preparing high density granular detergent compositions. Current commercial practice in the field employs spray-drying towers for making granular laundry detergents which commonly have 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 detergent particles should be densified using the means and equipment described hereinafter. Alternatively, the formulator can eliminate spray drying using mixing, densifying and granulating equipment that is commercially available. The following is a non-limiting description of such equipment suitable for use herein. Various means and equipment are available for preparing high density granular detergent compositions (ie, more than about 550, preferably more than about 650 grams / liter or "g / l"), high solubility and free flow in accordance with present invention. Current commercial practice in the field employs spray-drying towers to make granular laundry detergents that commonly have a density of less than about 500 g / l. In this process, an aqueous suspension of various heat-stable ingredients in the final detergent composition are configured to create homogeneous granules by passing them 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 overall process herein, additional processing steps such as those described hereinafter should be used to obtain the density level (ie> 650 g / l) required by the manufacturers. low dosage modern compact detergent products. For example, the spray-dried granules of a tower can be further densified by charging a liquid such as water or a nonionic surfactant into the pores of the granules and / or by subjecting them to one or more 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" comprising a static cylindrical mixing drum having a central rotating shaft with mixing blades / cut mounted on it. During use, the ingredients for the detergent composition are introduced into the drum and the arrow / blade assembly rotates at speeds in the range of 100-2500 rpm to provide thorough mixing / densification. See Jacobs et al., US patent. No. 5,149,455, issued September 22, 1992. The residence time that is preferred in the high-speed mixer / densifier is from about 1 to 60 seconds. Other devices of this type include the devices marketed under the trade name "Shugi Granuiator" and under the trade name "Drais K-TTP 80". Another processing step that can be used to densify more spray-dried granules includes grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer / densifier to thereby obtain particles having a lower particulate porosity. Equipment such as that marketed under the name mixers / densifiers "Lódige KM" (Series 300 or 600) or "Lódige Ploughshare" are suitable for this processing step. Said equipment works typically at 40-160 rpm. The residence time of the detergent ingredients in the moderate speed mixer / densifier is from about 0.1 to 12 minutes. Other useful equipment includes the device that is available under the trade name "Drais K-T 160". This processing step employing a moderate speed mixer / densifier (for example, Lódige KM) can be used by itself or sequentially with the high speed mixer / densifier mentioned above (eg, Lodige CB) to achieve the desired density. Other types of apparatus for manufacturing granules useful herein include the apparatuses described in the US patent. 2,306,898 to G.L. Heller, December 29, 1942. While it may be more appropriate to use a high-speed mixer / densifier followed by the low-speed mixer / densifier, the inverse sequential configuration of mixer / densifier is also contemplated by the invention. One or a combination of various parameters including residence times in the mixer / densifier, equipment operating temperatures, temperature and / or composition of the granules, the use of auxiliary 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., US 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. 4,637,891, issued on January 20, 1987 (training of .. granules spray dried with a liquid binder and aluminosilicate); Kruse et al., Patent of E.U. 4,726,908, issued on February 23, 1988 (formation of spray-dried granules with a liquid binder and aluminosilicate) and Bortolotti et al., US patent. 5,160,657, issued November 3, 1992 (coating densified granules with a liquid binder and aluminosilicate).

In situations where detergent ingredients that are particularly sensitive to heat or highly volatile are to be incorporated into the final detergent composition, processes that do not include spray towers are preferred. The formulator can eliminate the spray-drying step fed, either continuously or intermittently, starting detergent ingredients directly into the mixing / densification equipment that is commercially available. A particularly preferred embodiment includes charging a surfactant paste and an 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., US patent. 5,366,652, issued on November 22, 1994 and Capeci et al., Patent of E.U. 5,486,303, issued January 23, 1996. Optionally, the liquid / solid ratio of the starting detergent ingredients in said process can be selected to obtain high density agglomerates that are freer and crisper. Optionally, the method may include one or more recirculation streams of smaller sized particles produced by the process that are fed back to the mixers / densifiers for further agglomeration or accumulation. The oversized particles produced by this process can be sent to a grinding apparatus and fed back to the mixing / densifying equipment. These additional recirculation process steps facilitate the agglomeration and accumulation of the starting detergent ingredients, resulting in a finished composition having a uniform distribution of particle size (400-700 microns) and density (> 550 g / l). desired. See Capeci et al., US patent. ,516,448, issued May 14, 1996 and Capeci et al., US patent. ,489,392, issued February 6, 1996. Other suitable methods that do not make 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. 5,108,649, issued April 28, 1992 and Jolicoeur, US patent. 5,178,798, issued January 12, 1993. In yet 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 (with a solids content typically of 80%) and sprayed in a fluidized bed to provide the finished detergent granules. Prior to the fluidized bed, the method may optionally include the step of mixing the suspension using the Lódige CB mixer / densifier mentioned above or a "Flexomix 160" mixer / densifier, available from Shugi. The fluidized bed or moving beds of the type available under the trade name "Escher Wyss" can be used in such procedures.

Another suitable method that can be used herein includes feeding a liquid acid precursor of an anionic surfactant, an inorganic alkaline material (eg, sodium carbonate) and optionally other detergent ingredients into a high speed mixer / densifier ( residence 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, Lodige KM) for further agglomeration, resulting in the finished high density detergent composition. See Appel and other US patent. Do not ,164,108 issued November 17, 1992. Optionally, the high density detergent compositions according to the invention can be produced by mixing conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (for example, a weight ratio of 60% by weight). : 40 granules to agglomerates) produced by a combination of the processes described herein. Additional auxiliary ingredients such as enzymes, perfumes, brighteners and the like can be sprayed 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 stability under storage.

Deposition of perfume on fabric surfaces The method of washing fabrics and depositing perfumes thereon comprises contacting said fabrics with an aqueous washing liquid comprising at least about 100 ppm of conventional detersive ingredients described hereinbefore, as well as at least about 0.1 ppm of the additive laundry particle described above. Preferably, said aqueous liquid comprises about 500 ppm to about 20,000 ppm of the conventional detersive ingredients and about 10 ppm to about 200 ppm of the additive laundry particle. The additive laundry particle works under all circumstances, but is particularly useful for providing odor benefits on fabrics during storage, drying or ironing. The method comprises contacting the fabrics with an aqueous liquid containing at least about 100 ppm of conventional detersive ingredients and at least about 1 ppm of the additive laundry particle, such that the perfumed zeolite particles are trapped on the fabrics, store fabrics dried on clothesline under environmental conditions with humidity of at least 20%, dry the fabric in a conventional automatic dryer or apply heat to fabrics that have been dried on a clothesline or dried on a machine with low heat (less than approximately 50 ° C) by conventional ironing means (preferably with steam or pre-wetting). The following non-limiting examples illustrate the parameters and compositions employed in the invention. All percentages, parts and relationships are by weight, unless otherwise indicated.

EXAMPLE 1 An additive laundry particle is produced in accordance with the present invention by the following procedure. A solution of 75% solid carbohydrate material (hydrogenated starch hydrolyzate POLYSORB RA-1000 from Roquette America) and the remainder of water is premixed in a stirred mixing vessel with 1.5% by weight of TiO2 powder (commercially sold) under the trade name Tronox by Kerr McGee Chemical Corporation) to form a fluid carbohydrate potting solution. The carbohydrate fluid is dried to a moisture content of approximately 2.0% in a Luwa ™ Wiped Film Evaporator ("WFE"). Subsequently, the carbohydrate fluid and zeolite X charged with 16 wt.% Perfume ("PLZ") are placed at a weight ratio of 1: 1 in a Wemer &Worm twin-screw extruder. Pfleiderer ™ ZSK 30 ("TSE") with 12 drums without a constriction plate to form agglomerates. Drums 1 to 4 of the TSE are maintained at a temperature of 80 ° C while drums 5 and 6 are maintained at a temperature of 90 ° C, drums 7 and 8 at a temperature of 130 ° C, drums 9 and 10 at a temperature of 135 ° C and drums 1 1 and 12 at a temperature of 130 ° C. The carbohydrate fluid is fed at a temperature of 160 ° C to the TSE in the drum 7, while the PLZ is added to the drum 11 and is intimately mixed with the carbohydrate fluid before leaving the TSE as an extruded material having a discharge temperature of 145 ° C and a speed of 500 g / min. The product is cooled to ambient temperature to form free-flowing particles which are then sprayed on a Fitz Mili ™ (commercially available from Fitzpatrick Company) and configured by sieving to yield particles on the scale of 150 microns to 1 micron size. 180 microns. The shaped particles are then sent to a Wurster fluidized bed coating apparatus to which an aqueous mixture containing 22.5% Maltrin 040 ™ (which has a dextrose equivalent of 5) commercially available from Grain is added.

Processing Corp., 1.0% of D-Sorbitol ™ commercially available from J.T.

Baker, 1.0% polyethylene glycol (Carbowax ™ PEG 600 commercially available from Union Carbide) and 0.5% surfactant (TWEEN 80 ™, commercially available from Imperial Chemicals, Inc. (ICI)). The particles coated with Maltrin 040 ™ are then sent to a second Wurster fluidized bed coating apparatus to which an aqueous mixture containing 8.10% hydroxypropylmethylcellulose (under the tradename Methocel ™ E-15LV from Dow Chemical) is added. % titanium oxide bleaching agent and 0.90% polyethylene glycol 600 (under the trade name Carbowax ™ by Union Carbide). The coated particles are dried to produce a particulate composition suitable for use as an additive laundry composition. The particles formed unexpectedly have a "concentrated product odor" ("NPO") and emit only minimal detectable odors on the odor of the base product observed by a statistically significant number of panelist graders. This provides strong evidence of the lack of displacement of perfume from the vehicle particles.

EXAMPLE II Various detergent compositions made in accordance with the invention are exemplified below incorporating the perfume particle prepared in example 1.

Base granule 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 2.0 1.0 - (MW = 400) Alkylbenzenesulfonate 6.0 7.0 8.0 Sodium C 2-1 Linear Sodium Alkyl Sulfate 3.0 3.0 C14-16 Secondary Alkyl Sulfate sodium of 3.0 9.0 C? , -? 5 ethoxylated Sodium silicate 1.0 2.0 3.0 Brightener 24/471 0.3 0.3 0.3 Sodium carbonate 7.0 26.0 Carboxymethylcellulose - - 1.0 DTPMPA2 -._ __ 0.5 DTPA3 0.5 Mixed Agglomerates 5.0 C-14-15 Sodium Alkylsulphate 2.0 Sodium Alkylbenzenesulfonate linear C12-13 Sodium Carbonate 4.0 Poliethienglycol 1.0 (MW = 4000) Mixed Sodium Carbonate 13.0 Alquiyethoxylated 2.0 0.5 2.0 C12-15 (EO = 7) Alkyl ethoxylated 2-0 C12-? 5 (EO = 3) Perfume spray 0.3 0.4 0.3 Perfume particles4 0.5 0.5 0.5 Polyvinylpyrrolidone 0.5 - ~ N-oxide polyvinylpyridine 0.5 ~ - Polyvinylpyrrolidone-polyvinylimidazole 0.5 - - Distearylamine and acid 2.0 .. Cumene sulphonic Release polymer 0.5 dirt5 Lipase Lipolase 0.5 0.5 (100,000 LU / I) 6 Amylase Termamyl 0.3 0.3 (60 KNU / g) 6 Cellulase CAREZYME -® 0.3 (1000 CEVU / g) 6 Protease (40 mg / g) 7 0.5 0.5 0.5 NOBS8 5.0 TAED9 3.0 Sodium percarbonate 12.0 Sodium perborate 22.0 Polydimethylsuxane 0.3 3.0 monohydrate Sodium sulfate 3.0 Miscellaneous (water, etc) the remainder the rest the rest Total 100 100 100 1 . Bought from Ciba-Geigy 2. Diethylenetriaminepentamethylenephosphonic acid 3. Diethylenetriaminepentaacetic acid 4. From Example 1 5. Made in accordance with the US patent. 5,415,807, issued May 16, 1995 to Gosselink and others 6. Bought from Novo Nordisk A / S 7. Bought from Genencor 8. Nonanoyloxybenzenesulfonate 9. Tetraacetylethylenediamine EXAMPLE III The following detergent compositions according to the invention are suitable for machine and manual washing operations. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed to create a suspension and are passed through a spray-drying tower having a counter current of hot air (200-). 400 ° C), resulting in the formation of porous granules. The remaining auxiliary detergent ingredients are sprayed on, or added dry.

Granule of base B Alkylbenzenesulfonate 19.0 18.0 19.C sodium of C? 2-13 Surfactant 0.5 0.5 cationic1 DTPMPA2 0.3 - ~ DTPA3 - 0.3 - Sodium tripolyphosphate 25.0 19.0 29.I Acrylic / maleic copolymer 1 .0 0.6 - Carboxymethylcellulose 0.3 0.2 0.3 Brightener 49/15/334 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 Mixtures Cuantum (2.0 2.0 2.0 zinc phthalocyanine sulfonate) Sodium carbonate 5.0 6.0 20.0 Alkylethoxylated 0.4 1.2 C12-? 3 (EO = 7) Savinase5 protease 0.6 1.0 (4KNPY / g) Amylase Termamyl5 4.0 (60KNU / g) Lipoza Lipolase5 0.1 0.1 0.1 (100,000 LU / I) Sav / Ban5 (6 KNPU / 100KNU / g) 0.3 CAREZYME® 0.1 Cellulase (1000 CEVU / g) 6 0.1 0.1 0.3 release polymer dirt6 Perfume spray 0.4 0.4 0.4 Perfume particles7 1.5 1.5 2.0 Miscellaneous ( water, etc) the rest the rest the rest Total 100.0 100.0 100.0 1. Compound of dimethylhydroxyethylammonium quaternary of C12-14 2. Diethylenetriaminepentamethylenephosphonic acid 3. Diethylenetriaminepentaacetic acid 4. Bought from Ciba-Geigy 5. Bought from Novo Nordisk A S 6. Made in accordance with the US patent. 5,415,807, issued May 16, 1995 to Gosselink and others 7. From example 1 EXAMPLE IV The following detergent composition according to the invention is in the form of a laundry bar which is particularly suitable for manual washing operations. % by weight Coconut Fatty Alkyl Sulfate 30.0 Sodium Tripolyphosphate 5.0 Tetrasodium Pyrophosphate 5.0 Sodium Carbonate 20.0 Sodium Sulfate 5.0 Calcium Carbonate 5.0 Na1.9Ko.?Ca(C03)2 15.0 Aluminosilicate 2.0 Coconut Fatty Alcohol 2.0 Perfume Particle1 1.0 Spray of perfume 1.0 Miscellaneous (water, etc.) The rest Total 100.0 1. From Example 1. 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 the invention should not be considered limited to what is described in the specification.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1 .- An additive laundry particle comprising: i) a central core particle, said central core particle comprises a central porous vehicle material and a vitreous encapsulating material interspersed with said carrier material, said vitreous encapsulating material is derived from one or more at least partially water-soluble hydroxyl compounds having an anhydrous and unplasticized glass transition temperature (Tg) of at least 0 ° C; ii) optionally, an intermediate encapsulating material coated on said central core particle, said intermediate encapsulating material having an anhydrous and unplasticized glass transition temperature (Tg) of at least 130 ° C; and iii) an outer coating material applied on said central particle or, when present, on said intermediate encapsulating material, which provides said laundry additive particle with a substantially non-tacky surface; said outer coating material is derived from one or more compounds at least partially soluble or dispersible in the wash selected from the group consisting of waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates , borates, phosphates, removers and chitosan, and mixtures thereof; wherein said additive laundry particle has a hygroscopicity value of less than 80%.

2. A detergent composition for laundry or cleaning comprising: A) from 0.001% to 50% by weight of the composition of an additive laundry particle comprising: i) a central core particle, said central core particle comprises a central material of porous vehicle and a vitreous encapsulating material interspersed with said carrier material, said vitreous encapsulating material is derived from one or more at least partially hydrosoluble hydroxyl compounds having an anhydrous and unplasticized glass transition temperature (Tg) of at least 0 ° C; ii) an intermediate encapsulating material coated on said central core particle, said intermediate encapsulating material comprises a carbohydrate material having an anhydrous and unplasticized glass transition temperature (Tg) of at least 130 ° C; and iii) an outer coating material applied on said intermediate encapsulating material, which provides said laundry additive particle with a substantially non-tacky surface; said outer coating material is derived from one or more compounds at least partially soluble or dispersible in the wash selected from the group consisting of waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates , borates, phosphates, removers and chitosan, and mixtures thereof; wherein said additive laundry particle has a hygroscopicity value of less than 80%; and B) from 50% to 99.999% by weight of the composition, of laundry ingredients selected from the group consisting of detersive surfactants, detergency builders, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers and mixtures thereof.

3. The additive laundry particle according to any of claims 1 -2, further characterized in that said porous carrier material is a zeolite and said zeolite is selected from the group consisting of Zeolite X, Zeolite Y and mixtures thereof .

4. The laundry additive particle according to any of claims 1-3, further characterized in that said additive laundry particle further comprises a laundry or cleaning agent contained in or supported on said porous vehicle material; said laundry or cleaning agent is selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelators, anti-foulants, threshold inhibitors, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, substantive dyes on fabrics, antifungals, antimicrobials, repellents insects, dirt releasing polymers, fabric softening agents, dye fixers, pH skipping systems and mixtures thereof, and is preferably a perfume.

5. - The additive laundry particle according to any of claims 1-4, further characterized in that said vitreous encapsulating material is a starch, modified starch or starch hydrolyzate.

6. The additive laundry particle according to any of claims 1-5, further characterized in that said intermediate encapsulating material is a carbohydrate material having an equivalence of dextrose, DE, of 7.5 or less, preferably maltodextrin.

7. The additive laundry particle according to any of claims 1-6, further characterized in that said outer coating material is cellulose or cellulose derivative, preferably hydroxypropylmethylcellulose.

8. The laundry additive particle according to any of claims 1-7, further characterized in that said additive laundry particle has a hygroscopicity value of less than 30%

9. The additive laundry particle according to any of claims 1-8, further characterized in that said intermediate encapsulating material and said outer coating further include an ingredient selected from the group consisting of plasticizers, anti-agglomeration agents and mixtures thereof.

10. The additive laundry particle according to any of claims 1-9, further including at least one detersive surfactant and at least one builder. SUMMARY OF THE INVENTION An additive laundry particle is described having multiple coatings and compositions employing the particle; the additive laundry particle comprises a central core particle, which comprises a central porous vehicle material and a vitreous encapsulating material interspersed with said carrier material; the vitreous encapsulating material is derived from one or more at least partially hydrosoluble hydroxyl compounds having an anhydrous and unplasticized glass transition temperature (Tg) of at least 0 ° C; an optional intermediate encapsulating material can be coated on the core particle; the intermediate encapsulating material may comprise a carbohydrate material having an anhydrous and unplasticized glass transition temperature (Tg) of at least 130 ° C; finally, an external coating material is applied on the central particle or on the intermediate encapsulating material, which provides the additive laundry particle with a substantially non-y surface; the outer coating material is derived from one or more compounds at least partially soluble or dispersible in the wash selected from the group consisting of waxes, water-soluble polymers, fatty compounds, carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates , borates, phosphates, removers and chitosan, and mixtures thereof; the additive laundry particle has a hygroscopicity value of less than 80%; in preferred form, a laundry or cleaning agent such as a perfume is supported on, or contained in the porous carrier. * 5 J N / mvh * mmr * aom * P99 / 1204F