HUP0203565A2 - Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes - Google Patents

Abstract

57) The invention relates to an additive release system incorporated into a variety of consumer products, including detergents and cleaning products, room deodorizers, insect repellents, carpet cleaners and deodorizers, in which the additive is protected from release until exposed to a wet or humid environment. The additive release system according to the invention specifically includes a porous carrier material core containing an additive, such as a perfume, in its pores; the first material comprising said core-encapsulating hydrophobic oil; and a water-soluble or dispersible but oil-insoluble second material encapsulating the hydrophobic oil-coated core, such as starch or modified starch. The emitting particle according to the invention can be used to release washing and cleaning materials either into the wash or through the wash cycle. The washing additive-emitting particle according to the invention effectively transports perfume components through the washing solution to the fabric surface. HE

Description

S. B. G. & K.

Patent Attorney's Office H-1062 Budapest, Andrássy út 113. Phone: 461-1000, Fax: 461-1099 ρ 0203565 . ·’ :74.-78Q7BE . ·· · ·· · •/NY

A delivery system comprising an encapsulated porous carrier filled with additives, in particular detergent additives, such as perfumes

The invention relates to carrier particles, in particular particles for releasing laundry additives, such as perfumes, and to detergent compositions, in particular granular detergents, comprising the carrier particles.

Most consumers expect scented laundry products and require the washed fabrics to have a pleasant scent. In many parts of the world, hand washing is the predominant method of washing fabrics. When washing soiled fabrics, the user often comes into contact with the wash solution and comes into close contact with the detergent product used for the wash. Hand wash solutions can also develop an unpleasant odor when added to soiled fabrics. Therefore, the addition of perfume materials to such products is desirable and commercially advantageous. Perfume additives make such compositions more aesthetically pleasing to the consumer, and in some cases the perfume imparts a pleasant scent to the fabrics treated with it. However, the amount of perfume transferred from the aqueous wash solution to the fabrics is often small. The industry has therefore long sought an effective perfume delivery system for use in detergent products that provides a long-lasting, storage-stable fragrance to the product, releases fragrance during use to mask the wet solution odor, and delivers the fragrance to the washed fabrics.

Furthermore, after drying fabrics in the sun, the fabrics acquire a “sun-dried” type of scent. Consumers often prefer this over the standard perfume scent. Fabrics with this scent are also often perceived as cleaner. Because consumers like this scent, they like to dry their fabrics in the sun. However, in some countries, consumers are unable to dry their fabrics outside because the air is not clean or there is too much rain. As a result, they dry their fabrics indoors and are not expected to enjoy the benefits of the “sun-dried” type of scent on their fabrics.

We have found a detergent formulation containing a perfume that can provide a “sun-dried” type scent.

Detergent and other fabric care compositions which contain perfumes mixed with or sprayed onto the composition are well known in the art. Since perfumes are prepared from a combination of suitable compounds, it is possible to continuously release perfume from simple solutions and dry mixes to which the perfume has been added. Various techniques have been developed to inhibit or delay the release of perfumes from the composition in such a way that they remain aesthetically pleasing for a longer period of time. However, to date, few methods have provided significant fabric perfuming benefits after long-term storage of the product.

Therefore, research is underway to develop methods and compositions that effectively and efficiently deliver perfume from a wash bath to fabric surfaces. Various perfume delivery methods have been developed that incorporate protection of the perfume during the wash cycle, releasing the perfume onto the fabric, as can be seen in the following publications. USP 4,096,072 describes a fatty quaternary ammonium salt in the wash and dry cycle.

74,780/BE teaches a method of delivering fabric conditioners containing perfume. USP 4,402,856 teaches a microencapsulation technique involving the formation of a shell material that allows the perfume to diffuse out of the capsule only at certain temperatures. For the protection of perfume, in dry formulation storage and in the washing process, USP 4,152,272 teaches the incorporation of perfume into wax particles. The perfume is said to diffuse through the wax into the fabric in the dryer. USP 5,066,419 teaches a perfume dispersed in a water-insoluble non-polymeric carrier and encapsulated in a protective shell coated with a water-insoluble, powder coating material. USP 5,094,761 discloses a clay-protected perfume/cyclodextrin complex that provides fragrance benefits to at least partially wetted fabrics.

Another method for delivering perfume during the wash cycle involves combining the perfume with an emulsifier and a water-soluble polymer, forming the mixture into particles, and adding them to a detergent composition, as disclosed in USP 4,209,417; USP 4,339,356; and USP 3,576,760. Despite the extensive work in this area, there remains a need for a simple, efficient, and effective perfume delivery system that can be mixed with cleaning compositions to provide initial and sustained perfume benefits to fabrics treated with the cleaning product.

Perfume can also be absorbed onto the surface of a porous carrier material, such as a polymeric material, as described in July 1981.

74.780/BE

They are disclosed in British Patent Specification No. UK 2,066,839, published on 15 June 1991. Perfumes may also be absorbed onto the surface of a clay or zeolite material which is then incorporated into particulate detergent compositions. Preferred zeolites are generally type A or 4A zeolites having a nominal pore diameter of about 0.4 nm. It is believed that with A or 4A zeolites the perfume is absorbed onto the surface of the zeolite such that relatively little of the perfume is actually absorbed into the pores of the zeolite. Although absorption of perfume onto zeolite or polymer carriers may provide some improvement over the dosing of pure perfume mixed with detergent compositions, the industry is still seeking ways to improve the shelf life of detergent compositions without loss of perfume properties, the intensity or amount of fragrance delivered to fabrics, and the persistence of the perfume fragrance on treated fabric surfaces.

According to the teaching of the art, perfume combinations are usually mixed with larger pore size zeolites X and Y. The subject of the German Democratic Republic patent application published on August 12, 1987 under publication number 248,508 is perfume dispensers (e.g. air fresheners) containing a perfume-laden faujasite type zeolite (e.g. zeolites X and Y). The critical molecular diameter of the perfume molecules is said to be between 0.2 and 0.8 nm. Furthermore, the German Democratic Republic patent application published on September 12, 1979 under publication number 137,599 teaches compositions for use in powdered detergents for the thermally controlled release of perfume. For use in these compositions

74,780/BE teach the use of zeolites A, X and Y. These teachings are repeated in more detail in recently filed European Patent Specifications No. 535,942, published April 7, 1993, and No. 536,942, published April 14, 1993, and in USP Patent Specification No. 5,336,665.

Effective perfume delivery compositions are taught in WO 94/28107, published December 8, 1994. These compositions comprise zeolites (e.g., X or Y) having a pore diameter of at least 0.6 nm, a perfume solubilized into the pores of the zeolite, and a matrix coating on the perfumed zeolite, the matrix comprising a water-soluble (washable) matrix comprising from about 0 to about 80% by weight of at least one solid polyol containing at least 3 hydroxyl groups and from about 20 to about 100% by weight of a liquid diol or polyol in which the perfume is substantially insoluble and in which the solid polyol is substantially soluble.

Other perfume delivery systems are taught in WO 97/34982 and WO 98/41607. WO 97/34982 discloses particles comprising a perfume-loaded zeolite and a release barrier which is a material derived from a wax and has a size (i.e. cross-sectional area) larger than the pore openings of the zeolite carrier. WO 98/41607 discloses glassy particles comprising materials useful in detergent or cleaning compositions and one or more at least partially water-soluble hydroxy compounds derived from glass. A preferred material is a perfume in a zeolite carrier.

Another problem that arises is the provision of perfumed products

74.780/BE, excessive odor intensity associated with the products may occur. There is therefore a need for a perfume delivery system that provides a satisfactory perfume scent from dry washed fabrics during and after use, but which offers long shelf life benefits and reduced product odor intensity.

The invention has found that perfume loaded into porous carriers, such as zeolite particles, can be effectively protected from premature perfume release by coating the loaded carrier particles with a hydrophobic oil and then encapsulating the oil-coated perfume-loaded carrier particles with a water-soluble or water-dispersible but oil-insoluble material, such as starch or modified starch. The porous carrier can be selected to adhere to the fabrics, to be able to deposit enough perfume on the fabrics, to release a noticeable fragrance even after they have dried.

The invention addresses a long-standing need for a simple, effective, storage-stable perfume delivery system that provides consumer-perceived fragrance benefits during and after the wash process and has reduced product odor during storage of the composition. Fabrics treated with the perfume delivery system of the invention have particularly high fragrance intensity and remain fragrant for a longer period of time after washing and drying.

The invention also provides a release system for other additives which are desirably protected from release until the additive-containing product is subjected to aqueous processing.

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or exposed to a humid environment.

The present invention provides an additive delivery system that can be incorporated into a variety of consumer products, including detergents and cleaning compositions, room deodorizers, insecticidal compositions, carpet cleaners and deodorizers, wherein the additive is protected from release until exposed to a wet or humid environment. The additive delivery system of the present invention typically comprises a porous carrier core containing an additive, such as a perfume, in its pores, a hydrophobic oil coating encapsulating said core, and a water-soluble or water-dispersible but oil-insoluble second coating material, such as a starch or modified starch, encapsulating the hydrophobic oil-coated core.

In conventional perfume delivery systems, more than 50% of the perfume material is "lost by diffusion of the matching perfume material from the product or dissolution in the wash solution and does not reach the fabric surface. In the invention, the coatings effectively keep the perfume material confined within the carrier core. The perfume material thus reaches the fabric surface in a greater proportion than with conventional perfume delivery systems.

The porous support material is typically zeolites, macro-porous zeolites, amorphous silicates, crystalline non-layered silicates, layered silicates, calcium carbonates, calcium/sodium carbonate double salts, sodium carbonates, clays, sodalites, alkali metal phosphates, chitin microbeads, carboxyalkyl celluloses, carboxyalkyl starches, cyclodextrins, porous starches and

74.780/BE and mixtures thereof. The preferred carrier material is zeolite, for example Zeolite X, Zeolite Y and mixtures thereof.

Particularly preferred porous carriers for the efficient delivery of perfume into their pores are zeolite particles having a nominal pore size of at least about 0.6 nm. Without wishing to be bound by theory, it is believed that these zeolites provide a channel or lattice-like structure that entraps the perfume molecules. Unfortunately, such perfumed zeolites are not sufficiently shelf-stable for commercial use in particulate fabric care products due to premature release of the perfume, particularly upon absorption of moisture. However, we have found that in order to protect the perfume-loaded zeolite particles by forming a barrier to enclose and retain the perfume within the pores of the zeolite, the zeolite particles can be first coated with a hydrophobic oil and then the oil-coated particles are encapsulated with a water-soluble or water-dispersible but oil-insoluble material. Thus, the perfume is substantially retained within the pores of the zeolite particles. In our opinion, since the perfume is contained in relatively large zeolite pores, it has better perfume retention during the washing process than smaller pore-sized zeolites in which the perfume is predominantly adsorbed on the zeolite surface.

The hydrophobic oil coating may be a non-perfume oil, but preferably a perfume, which may be the same or different from the perfume oil incorporated into the carrier. It is believed that when the encapsulated particle of the invention is placed in water, for example during washing, the water-soluble or water-dispersible encapsulating material

74.780/BE dissolves and the oil coating begins to release. When this oil coating is a perfume, the perfume spots are released from the wash solution, providing a wet fragrance benefit. The perfume-laden carrier particles enter the wash solution and are deposited on the fabrics. After the fabrics dry, the perfume is released from the carrier as moisture in the air replaces the perfume stored in the pores of the carrier, providing a dry fragrance benefit.

The additive stored in the porous carrier core is preferably selected from the group consisting of perfumes, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, anti-scale agents, dye transfer inhibitors, light-activated bleaches, enzymes, catalytic antibodies, color enhancers, fabric fastness dyes, antifungal agents, antimicrobial agents, insect repellents, soil release polymers, fabric softeners, dye fixatives, pH-bridge systems, and mixtures thereof.

The preferred laundry additive to be loaded into the porous carrier is a perfume. The particle core is preferably a perfume-loaded zeolite (PLZ).

The preferred encapsulating material is starch, modified starch or starch hydrolysate, while the preferred oil coating material is a perfume oil. The outer encapsulating material may further comprise a component selected from the group consisting of plasticizers, anti-agglomeration agents, and mixtures thereof.

In a further embodiment of the invention, there is provided a washing or cleaning detergent composition. The washing or cleaning composition comprises from about 0.001% to about 50% by weight of the composition of a laundry additive, and from about 50% to about 99.999% by weight of the composition of a cleaning ingredient selected from the group consisting of detersive surfactants, soil builders, bleaching agents, enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof, as previously described.

The invention therefore provides a carrier particle with an additive, preferably a laundry additive, such as a perfume-loaded core, and at least two surface coatings, an intermediate hydrophobic oil coating and an outer encapsulating coating of an outer water-soluble or water-dispersible material. Another object of the invention is a detergent and cleaning composition comprising said laundry additive particle. Still another object of the invention is a laundry additive particle which can provide improved fabric fragrance benefits with long shelf life and reduced product odor intensity. These and other objects, features and advantages of the invention will be apparent to those skilled in the art from the following description and the appended claims.

All percentages, ratios and parts in the specification are by weight unless otherwise indicated. All cited documents are incorporated herein by reference in their entirety.

Figure 1 illustrates an SEM of an intact average size laundry additive particle containing an encapsulated perfume-loaded zeolite particle according to the invention.

Figure 2 shows the filled cavity inside a starch coating.

74.780/BE illustrates a cross-sectional SEM of a particle according to the invention containing zeolite particles.

The present invention relates to a laundry additive particle and a detergent and cleaning composition comprising the additive particle, preferably a perfume-containing particle. The detergent and cleaning compositions include conventional granular detergents, as well as granular bleach, machine dishwashing, hard surface cleaners, and fabric softeners. The laundry additive particle of the present invention has excellent perfume release throughout the wash cycle and minimizes product odor due to the volatile perfume components released. While not wishing to be bound by theory, it is believed that special coatings on the particle of the present invention also increase the stability of the particle.

The preferred laundry particle of the invention comprises a perfume-filled porous carrier core, which core is first coated with a hydrophobic oil material and then encapsulated with a water-soluble or water-dispersible but oil-insoluble outer coating material, such as starch or modified starch, to form the finished particle.

The preferred laundry particle of the invention preferably has a hygroscopicity value of less than about 80%. "Hygroscopicity value" as used herein means the amount of moisture absorbed by the particles as a percentage increase in the weight of the particles, as measured by the following test procedure. The hygroscopicity value required for the particles of the invention is determined by placing 2 g of the particles in an open-top Petri dish at 32.2°C and 80% relative humidity for 4 weeks.

74.780/BE for a period of time. The percentage increase in the mass of the particles at the end of this period is the hygroscopicity of the particles, as described herein. Preferred particles of the invention have a hygroscopicity of less than about 50%, more preferably less than about 30%.

The laundry additive particles of the invention consist of about 5-50% of a filled central core particle, which itself is about 60-99% porous carrier material and about 1-40% perfume and other laundry additive, about 1-40% hydrophobic oil intermediate coating material, and about 10-94% outer encapsulating material.

Charged central core particle

The central core of the additive particle comprises a porous carrier material and a laundry additive incorporated into said carrier material, as previously described. The two components of the central core may be mixed in a number of different ways.

On a laboratory scale, the basic equipment used for this purpose can vary from a 10-20 g coffee grinder to a 100-500 g food processor, or even a 200-1000 g kitchen mixer. The process consists of placing the carrier particles (zeolite) in the equipment and pouring in the laundry additive while mixing. The loaded carrier (zeolite) is then allowed to rest for 0.5-48 hours before further processing. During the loading process, when heating is carried out, a cooling jacket can be used as an option. On a semi-industrial scale, a suitable equipment is a Littleford type mixer, which is a batch type mixer, with rotating and grinding blades operating at a high speed of 74,780 rpm, continuously mixing the powder or powder mixture while spraying the liquid perfume oil onto it.

Porous substrate

As used herein, a porous support is any material capable of retaining a transportable substance, such as a detergent or cleaning agent, on a porous support (e.g., by adsorption into the pores). Such materials include porous solids, such as zeolites.

Preferred zeolites are selected from zeolite X, zeolite Y and mixtures thereof. The term "zeolite" as used herein refers to a crystalline aluminosilicate material. The structural formula of a zeolite is based on the crystal unit cell, the smallest unit of the structure being

Mm/n[(AIO2) _m (SiO2)y]xH ₂ O —wherein n is the valence of the M cation, x is the number of water molecules/unit cell, m and ya are the number of tetrahedra/unit cell, and y/m is between 1 and 100. Most preferably, y/m is between 1 and 5. The M cation may be a group IA or IIA element, such as sodium, potassium, magnesium, and calcium.

The zeolite useful in the invention is a faujasite-type zeolite, including type X or type Y zeolite, both of which typically have a nominal pore size of about 0.4-1 nm, preferably about 0.8 nm.

Aluminosilicate zeolite materials useful in the practice of the invention are commercially available. Types X and Y

74.780/BE The methods for preparing zeolites are well known and available in standard texts. Preferred crystalline aluminosilicate materials for use in the invention are available under the designations X type or Y type.

In a preferred embodiment, for illustrative and non-limiting purposes, the crystalline aluminosilicate material is of type X and is selected from the following materials:

(I) Na86l(AIO2)86(SiO2)i 061XH2O, (II) K86[( _AIO2 )86(SIO2)1 οθΐ XH2O.

(III) Ca ₄₀ Na ₆ [(AIO2)86(SiO2)i 061 xH ₂ O, (IV) 8Γ ₂₁ Β32 ₂ [(ΑΙθ2)86 (θ·θ2)ΐ06] xH2O.

wherein x is from about 0 to about 276, and mixtures thereof. The zeolites of formulae (I) and (II) have a nominal pore size or opening of 0.84 nm. The zeolites of formulae (III) and (IV) have a nominal pore size or opening of 0.8 nm.

In another preferred embodiment, the crystalline aluminosilicate material is of type Y and is selected from the following materials:

(V) Na)56[(AIO2)56SiO2)i361 XH2O, (VI) K56[(AIO2)56(SiO2)i 36] XH2O, in which the value of x in the general formulae is from about 0 to about 276, and mixtures thereof. The nominal pore size or aperture of the zeolites of general formulae (V) and (VI) is 0.8 nm.

In yet another embodiment, a group of zeolites also known as "Zeolite MAP" may be used in accordance with the invention. Such zeolites are disclosed in USSN 08/716,147.

74.780/BE

The zeolites used in the invention are in particulate form and have an average particle size of about θ' 5-120 pm, preferably about 0.5-30 pm, as measured by standard particle size analysis techniques.

The size of zeolite particles allows them to penetrate the fabrics they come into contact with. Once they have settled on the fabric surface (by washing away their coating matrix during the washing process), zeolites can begin to release the laundry detergents they contain, especially when exposed to heat or humid conditions.

Intermediate oil coating material

The intermediate oil coating material of the invention forms a coating on the central core particle. The intermediate coating provides a barrier to minimize the release or leakage of any deliverable material, such as perfume, introduced into the porous carrier. The intermediate coating material comprises a hydrophobic oil, such as a perfume oil, the same or different from the perfume oil introduced into the carrier, or a non-perfume oil, such as mineral oil. The hydrophobic oil may be an organic compound or a mixture thereof, preferably having a measured average ClogP value that is less than the measured average ClogP value of the additive or mixture introduced into the pores of the carrier. ClogP values—i.e., their octanol/water partition coefficient, P—are typically used to characterize perfume ingredients. The octanol/water partition coefficient of a perfume ingredient is the ratio of its equilibrium concentrations in octanol and water. The more hydrophobic a substance is, the higher its ClogP value. The intermediate coating material is thus preferably less hydrophobic,

74.780/BE as an additive stored in a porous carrier.

More preferably, the maximum ClogP value of the hydrophobic oil-containing material is less than the minimum ClogP value of the additive-loaded porous carrier material. More preferably, the difference between the maximum ClogP value of the hydrophobic oil-containing material and the minimum ClogP value of the additive-loaded porous carrier material is at least one unit, and most preferably two units.

Outer encapsulating material

The outer encapsulating material is placed on the intermediate coating material surrounding the core particle and provides the outer layer of the finished particle. The outer coating material essentially provides a non-sticky or non-adherent coating on the finished particle. The outer coating preferably provides a particle with a non-sticky surface under very humid conditions, such as 32.2°C at 80% relative humidity.

The outer coating is a material derived from one or more at least partially water-soluble or water-dispersible compounds. That is, the outer coating is either soluble in an aqueous washing environment or dispersible in that aqueous washing environment. The compounds useful in the invention are selected from the following groups of materials.

1. Carbohydrates, which may be any or a mixture of the following: i) Starches, including modified starches and starch hydrolysates; ii) Oligosaccharides (defined as carbohydrate chains of 2 to 35 monosaccharide molecules); iii) Polysaccharides (defined as at least 35 monosaccharide molecules)

74.780/BE . ·. .· :··. .· .· ·

Both linear and branched carbohydrate chains can be used. In addition to chemically modified starches, poly/oligosaccharides can be used. Typical modifications include the addition of hydrophobic groups to form groups identical to the alkyl, ^aryl , etc. groups found in surfactants, to impart some surface activity to these compounds.

2. All natural or synthetic gums, such as alginate esters, carrageenan, agar-agar, pectic acid and natural gums, gum arabic, gum tragacanth and karaya honey — ga.

3. Chitin and chitosan.

4. Cellulose and cellulose derivatives. For example: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) (hydroxypropylmethyl) cellulose (HPMC); iii) carboxymethyl cellulose (CMC); iv) all interior/aqueous 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. Softeners.

9. Long-chain (10-35 carbon atoms) fatty compounds, including fatty acids, fatty alcohols and fatty esters.

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10. Natural proteins, including gelatin, casein and egg albumin.

Within these groups, those materials that are not soluble or at least partially dispersible in water are useful in the invention only when mixed with compounds useful in the invention in amounts such that the resulting particle has a preferred hygroscopicity value of less than about 80%. It is also preferred that these compounds be operable at low temperatures, preferably in the range of about 50-200°C, and more preferably in the range of about 60-180°C.

Preferred encapsulating materials include starches or modified starches, such as CAPSUL™ commercially available from National Starch, cellulose and cellulose derivatives, such as hydroxypropyl methylcellulose, other carbohydrates, such as sucrose and fructose, natural polymers, such as gum arabic and guar gum, natural proteins, and water-soluble polymers, such as polyethylene glycol.

The outer encapsulating coating may contain optional additive components such as plasticizers, anti-agglomeration agents and mixtures thereof. Optional plasticizers include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates and the like, most preferably a mixture of sorbitol and polyethylene glycol and low molecular weight polyols. The plasticizer is used in amounts ranging from about 0.01 to about 5%. The anti-agglomeration agents of the invention are preferably surfactants and are preferably present in the outer coating.

74.780/BE are used in amounts less than 1% of the coating. Surfactants suitable for use in the invention include TWEEN™ 80, which is commercially available from Imperial Chemicals, Inc. (ICI).

Detergent and cleaning additives

The particles of the invention are incorporated with detergent and cleaning additives or agents. The materials are retained in the porous carrier material as previously described. The materials incorporated into the particles of the invention may be the same as or different from those typically used to form the rest of the detergent and cleaning compositions comprising the particles, as is clearly apparent from the invention. For example, the particles may contain a perfume material, and in addition to the perfume-containing particle, a perfume (the same or different) may be incorporated into the finished composition (e.g., by spray-on techniques). These materials are selected as desired for the type of composition to be formed—e.g., granular laundry detergent compositions, granular machine dishwashing compositions, or hard surface cleaners.

The detergent particle of the invention is of course incorporated into a composition containing the other ingredients. Compositions containing detergent additive particles may optionally contain one or more other cleaning additives or other materials to aid or enhance cleaning performance, treat the material to be cleaned, or modify the aesthetic properties of the detergent composition (e.g., perfumes, dyes, paints, etc.).

74.780/BE

Perfume

A preferred washing or cleaning additive according to the invention is a perfume material. As used herein, the term "perfume" is used to refer to any fragrant substance that is subsequently released into the water bath and/or onto fabrics or other surfaces in contact with it. Perfume is most often liquid at ambient temperatures. A wide variety of chemicals are known for perfume applications, including such substances as aldehydes, especially aliphatic aldehydes having 6-14 carbon atoms, acyclic terpene aldehydes having 6-14 carbon atoms and mixtures thereof, ketones, alcohols and esters. More commonly, naturally occurring plant and animal oils and secretions containing complex mixtures of various chemical components are known for use as perfumes. The perfumes of the invention may be relatively simple in composition or may comprise very sophisticated complex mixtures of natural and synthetic chemical components, each selected to provide any desired scent. Typical perfumes include woody/earthy fragrances containing exotic materials such as sandalwood, civet and patchouli oils. bases. The perfumes may have a light floral scent, such as rose extract, viola extract and acacia. The perfumes may also be formulated to provide the desired fruity scent, such as lime, lemon and orange. Any chemically compatible material which produces a pleasant fragrance or otherwise has a pleasant odor may be used in the perfumed compositions of the invention.

If the "sun-dried scent" is the preferred scent, then the perfume component is selected from the group consisting of aliphatic aldehydes having 6-14 carbon atoms, acyclic terpene aldehyde having 6-14 carbon atoms, and mixtures thereof. Preferably, the perfume component is selected from aliphatic aldehydes having 8-12 carbon atoms, acyclic terpene aldehyde having 8-12 carbon atoms, and mixtures thereof. Most preferably, the perfume component is selected from citral; neral; isocitral; dihydrocitral; citronellal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyldecanal; methylnonylacetaldehyde; 2-nonen-1-al; undecylene aldehyde; 2,6-dimethyloctanal; 2,6,10-trimethyl-9-undecen-1-al; trimethylundecanal; dodecenal, melonal; 2-methyloctanal; 3,5,5-trimethylhexanal and mixtures thereof. Preferred mixtures are, for example, a mixture of 30% by weight of 2-nonen-1-al, 40% by weight of undecylene aldehyde and 30% by weight of citral or a mixture of 20% by weight of methylnonylacetaldehyde, 25% by weight of lauric aldehyde, 35% by weight of decanal and 20% by weight of 2-nonen-1-al.

By selecting a perfume component from the above, a "sun-dried" scent can be produced on the fabric even if the fabric has not actually been sun-dried. The "sun-dried" scent can be produced by selecting aldehydes in such a way that at least one of them is a substance naturally present on the cotton fabric after sun-drying, and thus is a component of the sun-dried scent.

Preferred perfume materials for use in the invention are defined as follows.

Perfume materials for the purposes of the invention are those which can be incorporated into the pores of the carrier material and are therefore suitable for use in the transport of the carrier material through an aqueous environment.

74,780/BE as components. WO 98/41607 discloses the characteristic physical parameters of perfume molecules which influence their ability to be incorporated into a carrier material, such as a zeolite. For compositions according to the invention in which the perfume materials are carried in the compositions, a sensory perception is obviously required for a benefit to be perceived by the consumer. Preferred perfume materials for the perfume-emitting particles of the invention have a detection threshold [measured as odor detection thresholds ("ODT") under carefully controlled GC (gas chromatography) conditions, as described in more detail hereinafter] of less than or equal to 50 ppb (parts per billion). Materials with an ODT of between 50 ppb and 1 ppm (parts per million) are less preferred. Materials with an ODT of above 1 ppm are preferably avoided. Detergent perfume mixtures useful for the perfume-emitting particles of the invention preferably contain about 0-80% of an emissible material with an ODT of between 50 ppb and 1 ppm and about 20-100% (preferably about 30-100%; more preferably about 50-100%) of an emissible material with an ODT of less than or equal to 50 ppb.

Also preferred are perfumes that are transferred through the washing process and then released into the air around the dried fabrics (e.g., into the space around the fabric during storage). This requires the perfume to move out of the zeolite pores with subsequent distribution into the air around the fabric. Preferred perfume materials are therefore further identified by their volatility. Boiling point is used as a measure of volatility throughout the specification, and preferred 74.780/BE materials have a boiling point of less than 300°C. The detergent perfume mixtures useful for the laundry particles of the invention preferably contain at least about 50% (preferably at least about 60%; more preferably at least about 70%) of the delivered material having a boiling point of less than 300°C.

Additionally, for use in detergent compositions of the present invention, preferred perfume-emitting particles comprise at least about 80%, and more preferably at least about 90%, of a measured average ClogP value of from about 1.0 to about 16, and more preferably from about 2.0 to about 8.0. Most preferably, the perfume materials or mixtures to be released have a measured average ClogP value of from about 3 to about 4.5. While not wishing to be bound by theory, it is believed that perfume materials with preferred ClogP values are sufficiently hydrophobic to be stored within the pores of the zeolite carrier and deposited on fabrics during washing, yet are capable of exiting the zeolite pores at a reasonable rate to provide a noticeable benefit to the dry fabric. The ClogP values are obtained as follows.

Calculation of ClogP:

These perfume ingredients can be characterized by their octanol/water partition coefficient, P. The octanol/water partition coefficient of a perfume ingredient is the ratio of its equilibrium concentrations in octanol and water. Since most perfume ingredients have large partition coefficients, they are more conveniently expressed in their base 10 logarithmic form, logP.

Many perfume ingredients have logP values; for example, Daylight Chemical Information Systems, Inc. (Daylight CIS) has

The Pomona 92 database, available for purchase at 74.780/BE, contains a lot, in addition to original literature citations.

However, the most straightforward way to calculate logP values is with the “CLOGP” program, also available from Daylight CIS. This program also lists the experimental logP values in the Pomona92 database. The “calculated logP value (ClogP)” is determined using the fractional approach of Hansch and Leo (cf. A. Leo in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J.B. Taylor and C. A. Ramsaden, Eds., p. 295. Pergamon Press, 1990). The fractional approach is based on the chemical structure of each perfume ingredient and takes into account the number and type of atoms, the ability of the atoms to combine, and the chemical bonding. The ClogP values, which are the most reliable and widely used estimates of this physicochemical property, are used instead of the experimental logP values when selecting perfume ingredients. we can apply.

Determination of odor thresholds:

The gas chromatograph can be characterized by determining the exact volume of material injected by the syringe, the exact gap ratio, and the hydrocarbon response using a hydrocarbon standard of known concentration and chain length distribution. The air flow rate is accurately measured and, assuming a human inhalation time of 0.2 minutes, the sampled volume is calculated. Since the exact concentration at any point in the detector at any time is known, the mass/inhaled volume, and hence the concentration of the material, is known. To determine whether a material has a threshold below 10 ppb,

74.780/BE solutions with calculated concentrations are applied to the inhalation gap. A sensory panel member inhales the exhaust gas from the gas chromatograph and identifies the retention time at which the odor was detected. The average of all panel members determines the detection threshold.

The amount of test substance required to reach a concentration of 10 ppb at the detector is injected into the column. The gas chromatography parameters typical for determining odor thresholds are listed below:

GC: 5890 Series II with FID detector

7673 Autosampler

Column: J&W Scientific DB-1

Length 30 m, 0.25 mm inner diameter, 1 pm film thickness Edge:

Joint injection: 17/1 joint ratio

Autosampler: 1.13 pl/injection

Column flow: 1.10 ml/min

Air flow: 345 ml/min

Inlet temperature: 245°C

Detector temperature: 285°C

Temperature information:

Initial temperature: 50°C

Speed 5°C/min

Final temperature: 280°C

Final time: 6 minutes

Guiding assumptions: (i) 0.02 min/breath (ii) GC air is added for sample dilution

74.780/BE

Particularly preferred perfumes for use in the invention correspond to highly effective perfumes and are described as follows:

(1) a boiling point of about 275°C or lower at 101.08 kPa, and;

(2) a ClogP value or experimental logP value of about 2 or greater, and;

(3) Odor detection threshold less than or equal to 50 ppb and greater than 10 ppb.

Perfume fixing material

Optionally, the perfume can be combined with a perfume fixative. The perfume fixatives used in the invention can be characterized by several criteria that make them particularly suitable for the practice of the invention. We use additives that are dispersible, toxicologically acceptable, non-irritating to the skin, neutral to perfume, available from degradable and/or renewable sources, and relatively odorless. Perfume fixatives are believed to slow the evaporation of the more volatile components of the perfume.

Suitable fixatives include members selected from the group consisting of diethyl phthalate, musks, and mixtures thereof. The perfume fixative, if used, comprises about 10-50%, preferably about 20-40%, by weight of the perfume.

Incorporation of perfume into the preferred zeolite carrier

The type X or type Y zeolites used in the invention preferably contain less than about 15%, more preferably less than about 8%, and most preferably less than about 5%.

74.7B0/BE contain desorbable water. Such materials can be obtained by first activating/dehydrating by heating to about 150-350°C, optionally under reduced pressure (about 1.33xl0 ^-4 -2.66 kPa). After activation, the material is slowly and thoroughly mixed with the activated zeolite and optionally heated to about 60°C for up to about 2 hours to accelerate the absorption equilibrium in the zeolite particles. The perfume/zeolite mixture is then cooled to room temperature and obtained in the form of a free-flowing powder.

The amount of perfume or other laundry additive incorporated into the zeolite carrier is typically between about 1% and about 40%, preferably at least about 10%, more preferably at least about 18.5% by weight of the loaded particle, the limits being imposed by the pore size of the zeolite. It should be appreciated, however, that the particles of the invention may exceed this amount of laundry additive by weight of the particle, with the recognition that excess laundry additive cannot be incorporated into the zeolite even when only releasable materials are used. The particles of the invention may therefore contain more than 40% by weight of laundry material. Since no excess laundry material (as well as any non-releasable materials present) is incorporated into the zeolite pores, these materials are likely to be readily released into the aqueous wash solution upon contact with the aqueous wash medium.

Coating and encapsulation of filled zeolite particles

In one embodiment of the invention, the perfume-filled zeolite particles in the form of a free-flowing powder are completely

74.780/BE are coated with a hydrophobic oil, such as mineral oil or perfume oil. The hydrophobic oil coated particles are mixed with a modified starch solution (CAPSUL™, National Starch & Chemicals) and mixed to form an emulsion. The emulsion is then spray dried using an atomizing system, such as a co-current rotating disc, vaneless disc, vane disc, or two-fluid mist atomizing nozzle. Typical conditions are an inlet temperature of about 120-220°C and an outlet temperature of about 50-220°C.

Current laundry additive release particles are discrete particles with particle sizes ranging from about 3 to 100 µm, as measured by standard particle size analysis. Figure 1 illustrates an SEM of an intact, average size encapsulated, perfume-filled zeolite particle of the invention. Figure 2 illustrates a cross-section of a particle of the invention containing filled zeolite particles within a starch shell.

Stachyological investigation of encapsulated, perfume-loaded zeolite particles

The encapsulated, perfume-loaded zeolite particles are stored in an open container at 26.7°C and 70% relative humidity, and then in sealed plastic bags at 49°C for ten days. After this time, samples are taken and organoleptically evaluated. The particles are homogenized and dosed according to the actual local laundry conditions. They are pre-mixed with an odorless base particle approved for such testing. The original particles (not subjected to the stability test conditions) are included as a comparator. For the particles

74.780/BE perfume intensity scores are recorded in dry fabric scent. Zeolite particles loaded with perfume can provide a 5-20 point advantage on a perfume intensity scale compared to a control sprayed with perfume only.

Additional detergent or cleaning ingredients

Additional ingredients useful in the detergent or cleaning compositions of the invention include surfactants, soil-suspending agents and agents, for example, those incorporated into the emitting particles of the invention. The various types of materials useful in the detergent or cleaning compositions are described below. Compositions comprising particulate compositions may optionally contain one or more detersive additives or other materials to aid or enhance cleaning performance, treat the material to be cleaned or modify the aesthetic properties of the detergent composition.

Cleaning surfactants

The particles and/or agglomerates contain surfactants in the amounts previously disclosed. The detersive surfactant is selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and mixtures thereof. Non-limiting examples of surfactants useful in the present invention include conventional C11-18 alkylbenzene sulfonates ("LAS") and primary, branched, and random C10-20 alkyl sulfates ("AS"),

CH3 (CH2) _x (CHOSO3-M ⁺ )CH3 and CH3(CH2)y(CHOSO3-M ⁺ )CH2CH3 have the general formula — in which formula

74.780/BE x and (y+1) are integers, at least about 7, preferably at least about 9, and

M is a cation that promotes water solubility, especially sodium —

C10-18 secondary (2,3)alkyl sulfates, unsaturated sulfates, such as oleyl sulfate, C10-18 alkyl alkoxy sulfates ("AE _X S; especially EO 1-7 ethoxy sulfates), C10-18 alkyl alkoxy carboxylates (especially EO 1-5 ethoxy carboxylates), C10-18 glycine ethers, C10-18 alkyl polyglucosides and their corresponding sulfated polyglucosides and C12-18 α-sulfonated fatty acid esters. The overall composition may optionally include conventional nonionic and amphoteric surfactants, such as C12-18 alkyl ethoxylates ("AE") and C6-12 alkyl ethoxylates, including the so-called narrow-peaked alkyl ethoxylates. alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C12-18 betaines and sulfobetaines ("sultaines"), C10-18 amine oxides and the like can also be included in the general compositions. C10-18 N-alkylpolyhydroxy fatty acid amides can also be used. Typical examples are C12-18 N-methylglucamides. See WO 9,206,154. Other sugar derivative surfactants are N-alkoxypolyhydroxy fatty acid amides, such as C10-18

N-(3-methoxypropyl)-glucamide. N-propyl-N-hexyl-, C12-18 glucamides can be used for low foaming. C10-20 soaps can also be used. If good foaming is desired, C10-16 soaps can be used.

74.780/BE. In particular, mixtures of anionic and nonionic surfactants can be used. Other conventional surfactants that can be used are listed in standard texts.

For the cellulase-containing detergents disclosed herein, C10-18 alkyl alkoxy sulfates ("AE χ3; especially EO 1-7 ethoxy sulfates) and C12-18 alkyl ethoxylates ("AE") are most preferred.

Cleaning detergent

The particles and agglomerates contain soil-lifting agents in the amounts previously disclosed. Inorganic as well as organic soil-lifting agents may be used here. Crystalline as well as amorphous soil-lifting agents may also be used. Soil-lifting agents are typically used in fabric cleaning compositions to aid in the removal of particulate soil.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, alkali metal, ammonium, and alkanol ammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including dicarbonates and sesquicarbonates), sulfates, and aluminum silicates. However, in some applications, non-phosphate builders are required. Importantly, the compositions of the invention work surprisingly well even in the presence of so-called "weak builders" (compared to phosphates), such as citrate, or in the so-called "under-floated" situation, which can occur with zeolite or layered silicate builders.

Silicate soil-fluidizing agents include alkali metal silicates,

74.780/BE ³² ·. .· f especially those with a SiO2:Na2O ratio of between 1.6:1 and 3.2:1 and layered silicates, for example the layered sodium silicates disclosed in USP 4,664,839. The crystalline layered silicate sold by Hoechst is under the trade name NaSKS-6 (abbreviated throughout this specification as "SKS-6"). Unlike zeolite soil builders, the NaSKS-6 silicate soil builder does not contain aluminum. NaSKS-6 is a layered silicate with the morphological form 8-Na2SiO5. It can be prepared, for example, by the processes disclosed in German Patent Documents DE-A-3,417,649 and DE-A3,742,043. SKS-6 is a very preferred layered silicate for use in the invention, but other layered silicates can be used, such as

NaMSi _x O2x+j *yH 2θ —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. Various other layered silicates available from Hoechst are NaSKS-5, NaSKS-7, and NaSKS-11, as α, β, and γ forms. The most preferred for use in the present invention is δ-Na2SiO5 (NaSKS-6 form), as noted earlier in the specification. Other silicates may also be used, such as magnesium silicate, which may serve as a fritting agent in granular formulations, a stabilizer for oxygen bleaches, and a component of suds control systems.

Carbonate flotation agents are, for example, described in German patent application No. 2,321,001, published on November 15, 1973.

74.780/BE. Aluminum silicate soil builders can be used in the invention, as mentioned earlier in the description. Aluminum silicate soil builders are of great importance in the most recently marketed high-performance granular compositions and can also be significant soil builder ingredients in liquid detergent compositions. Aluminum silicate soil builders include

Compounds with the empirical formula [M _z (zAIO ₂ ) _y ]-xH ₂ O — in which z and y are integers of at least 6, the molar ratio of z to y is about 1.0 to 0.5, and x is an integer of about 15 to 264.

Suitable aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetic derivatives. A process for preparing aluminosilicate ion exchange materials is described in USP 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials for use in the present invention are available under the trade names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is

It has the general formula Nai ₂ [(AIO ₂ )i 2(SíO ₂ )i ₂ ]·χΗ ₂ O — where x is about 20-30, typically about 27. This material is known as Zeolite A.

74.780/BE is known. Dehydrated zeolites (x = 0-10) can also be used in the invention. The aluminosilicate preferably has a particle size of about 0.1-10 pm in diameter.

Suitable organic detergent builders for the purposes of the invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds containing a plurality of carboxyl groups, preferably at least 3 carboxylates. The polycarboxylate builder may generally be added to the composition in its acidic form, but may also be added in the form of a neutralized salt. When utilized in the salt form, alkali metal salts, such as sodium, potassium, and lithium salts, or alkanol ammonium salts are preferred.

Polycarboxylate builders include a wide range of useful classes of materials. An important class of polycarboxylate builders are the ether polycarboxylates, including oxydisuccinate, as disclosed in USP 3,128,287 and USP 3,635,830. See also "TMS/TDS builders" in USP 4,663,071. Suitable ether carboxylates include cyclic compounds, particularly alicyclic compounds, such as those disclosed in USP 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergent-active soil-suspending agents are ether hydroxy polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and (carboxymethoxy) succinic acid, polyacetic acid

74.780/BE acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, various alkali metal, ammonium and substituted ammonium salts, and polycarboxylates, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, (carboxymethyl)oxysuccinic acid and their soluble salts.

Citrate builders, such as citric acid and its soluble salts (especially the sodium salt), are particularly important polycarboxylate builders in high-performance liquid detergent compositions because they are available from renewable sources and are biodegradable. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

The 3,3-dicarboxy-4-oxa-1,6-hexanedionates and their related compounds disclosed in USP 4,566,984 are also suitable in the detergent compositions of the present invention. Useful succinic acid builders include C5-20 alkyl alkenyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl succinic acid. Typical succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Of this group, lauryl succinates are the preferred soil builders and are disclosed in Patent Application Serial No. 86200690.5/0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in USP 4,144,226 and USP 3,308,067. See USP

74.780/BE

Also see patent number 3,723,322.

To provide additional soil-lifting activity, fatty acids, such as C12-C18 monocarboxylic acids, alone or in combination with the aforementioned soil-lifting agents, especially citrate and/or succinate soil-lifting agents, can also be incorporated into the compositions. Such use of fatty acids generally results in a reduction in foaming, which should be taken into account.

In situations where phosphorus-based soil builders may be used, and particularly in the formation of molded parts used in hand washing operations, various alkali metal phosphates, such as the well-known sodium tripolyphosphates, sodium pyrophosphate, and sodium orthophosphate, may be used. Phosphonate soil builders, such as ethane-1-hydroxy-1,1-diphosphonate and other well-known phosphonates, may also be used (see, for example, USP 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Other additive components

The compositions of the invention may also contain enzymes, enzyme stabilizers, color enhancers, polymeric dispersants (i.e., polyacrylates), carriers, hydrotropes, suds enhancers or depressants, soil release agents, dye transfer inhibitors, and treatment aids.

Granular preparations

The detergent and cleaning compositions of the invention can be used in both low density (less than 550 grams/liter) and high density granular compositions in which the particle density is at least 550 grams/liter. The granular compositions are typically designed to provide a wash pH of about 7.5 to 11.5, more preferably about 9.5 to 10.5. Various means and equipment ^are available for producing high density compositions. Current industry practice in the field utilizes spray drying towers to produce compositions having densities less than about 500 g/liter. Accordingly, where spray drying is used as part of the overall process, the resulting spray dried particles should be further densified using the means and equipment described hereinafter. Alternatively, the manufacturer may eliminate spray drying by using commercially available mixing, thickening and granulating equipment. The following is a non-limiting description of such equipment suitable for use in the invention.

Various means and apparatus are available for preparing high density (i.e., greater than about 550, preferably greater than about 650 grams per liter or "g/L"), highly soluble, free-flowing, granular detergent compositions of the present invention. Current industry practice in the field utilizes spray drying towers to prepare compositions having densities less than about 500 g/L. In this process, an aqueous suspension of various heat-resistant ingredients is passed through a spray drying tower, using conventional techniques, at temperatures between about 175°C and 225°C, to form the finished detergent compositions into homogeneous granules. If spray drying is used in the complete preparation of the present invention,

74,780/IN

As part of the Ό :* process, however, we must apply the additional operations described later in the specification to obtain the density level (i.e. >650 g/l) required by a modern compact, low-dose detergent product.

For example, the spray-dried particles from the tower can be further densified by introducing a liquid, such as water or a nonionic surfactant, into the pores of the particles. A suitable high speed mixer/shredder for this process is a device sold under the trade name 'Lödige CB 30' or 'Lödige CB 30 Recycler' which comprises a static cylindrical mixing drum with a central rotating shaft equipped with mixing/shredding blades. In use, the ingredients for the detergent composition of the invention are introduced into the drum and the shaft/blade assembly is rotated at a speed of 100-2500 rpm during mixing/shredding. See USP 5,149,455. The preferred residence time in the high speed mixer/shredding device is between about 1 and 60 seconds. Other such devices include devices sold under the trade names 'Shugi Granulator' and 'Drais K-TTP 80'.

Another operation that can be used to further densify the spray-dried granules includes milling and agglomerating or deforming the spray-dried granules in a medium speed mixer/densifier to obtain particles with reduced intraparticle porosity. Suitable equipment for this operation includes, for example, the mixer/thickeners commercially available under the trade names "Lödige KM (300 or 600 series) ^and "Lödige Ploughshare". Such equipment typically operates at 40-160 rpm. The residence time of the detergent ingredients in the medium speed mixer/thickener is approximately 0.1-12 minutes. Another suitable equipment includes a device sold under the trade name "Drais KT 160". This operation, which uses a medium speed mixer/thickener (e.g. Lödige KM), can be used alone or in sequence with the high speed mixer/thickener (e.g. Lödige CB) described above to achieve the desired density. Other granule production equipment suitable for the invention includes the equipment described in USP 2,306,898.

Although it may be more appropriate to use a high speed mixer/densifier followed by a low speed mixer/densifier, the reverse sequential mixer/densifier configuration is also contemplated in the present invention. Various parameters, including residence times in the mixer/densifier, operating temperatures of the equipment, temperature and/or composition of the granules, and additive components such as liquid binders and flow aids, can be used in the process of the present invention to optimize densification of spray-dried granules, one or a combination thereof. See, for example, USP 5,133,924 (granules are brought to a deformable state prior to densification); USP 4,637,891 (spray-dried granules are granulated with a liquid binder and aluminosilicate); USP 4,726,908 (spray-dried granules are granulated with a liquid binder and aluminosilicate); and USP 5,160,657 74.780/BE (densified granules are coated with a liquid binder and aluminosilicate).

In situations where it is intended to incorporate particularly heat-sensitive or highly compatible detergent ingredients into the finished detergent composition, processes that do not involve spray drying towers are advantageous. The spray drying step can be eliminated by feeding the starting detergent ingredients continuously or batchwise directly into a commercially available mixer/thickener. A particularly advantageous process for forming high density detergent agglomerates involves feeding a surfactant paste and an anhydrous soil-suspending agent to a high speed mixer/thickener (e.g., Lödige CB) followed by a medium speed mixer/thickener (e.g., Lödige KM). See USP 5,366,652 and USP 5,486,303. In such a process, the liquid/solid ratio of the starting detergent ingredients can be selected to produce more fluid and friable high density agglomerates, if desired.

Optionally, the process includes one or more recycle streams of undersized particles resulting from the process being fed back to the mixer/thickener for further agglomeration or build-up. The oversized particles produced by this process may be sent to a grinding device and then fed back to the mixer/thickener. These additional recycle operations assist in achieving the desired particle size (400-700 pm) and density (>550 g/l) of the starting detergent ingredients.

74.780/BE to a uniformly distributed finished product. See USP 5,516,448 and USP 5,489,392. Other suitable processes not requiring the use of spray drying towers are disclosed in USP 4,828,721; USP 5,108,646 and USP 5,178,798.

In yet another embodiment, the high density detergent composition of the invention is prepared using a fluidized bed mixer. In this process, the various components of the finished composition are combined in an aqueous suspension (typically 80% solids content) and sprayed onto a fluidized bed to provide the finished detergent granules. This process may optionally include mixing the suspension prior to the fluidized bed using the aforementioned Lödige CB mixer/thickener or the “Flexomix 160” mixer/thickener available from Shugi. In such processes, a fluidized bed or moving bed type available under the trade name “Escher Wyss” may be used.

Another suitable process for use in the present invention involves feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detersive ingredients into a high speed mixer/thickener (residence time 5-30 seconds) to form agglomerates containing partially or completely neutralized anionic surfactant salt and the other starting detergent ingredients. Optionally, the material in the high speed mixer/thickener can be transferred to a medium speed mixer/thickener (e.g. Lödige KM) to form the finished high density detergent composition.

74.780/BE for further agglomeration. See USP 5,164,108.

The high density detergent compositions of the present invention may optionally be prepared by mixing conventional or densified spray-dried granules with detergent agglomerates prepared by one or a combination of the processes discussed hereinabove in varying proportions (e.g., 60:40 granule/agglomerate weight ratio). Additional additive ingredients, such as enzymes, perfumes, color enhancers, and the like, may be sprayed onto or mixed with the agglomerates, granules, or mixtures thereof prepared by the processes discussed herein. Bleach compositions in granular form typically have a limited water content, e.g., less than about 7% water for best storage stability.

Perfume deposits on fabric surfaces

The fabric washing and fabric perfume deposition process comprises contacting said fabrics with an aqueous washing solution comprising at least about 100 ppm of the conventional detergent ingredients as described above and at least about 0.1 ppm of the laundry additive particles as described above. Preferably, said aqueous solution comprises from about 500 to 20,000 ppm of conventional detergent ingredients and from about 10 to 200 ppm of the laundry additive particles.

The laundry additive particle works in all conditions, but is particularly useful for providing fragrance benefits during washing and on wet and dry fabrics. The process for fabrics

74.780/BE comprises contacting the fabric with an aqueous solution containing at least about 100 ppm of conventional detergent ingredients and at least about 1 ppm of laundry additive particles, applying the perfumed zeolite particles to the fabric, storing the line-dried fabric in an ambient humidity of at least 20%, drying the fabric in a conventional automatic dryer or applying heat with a conventional iron (preferably with steam or pre-wetting) to the line-dried or low heat (less than about 50°C) machine-dried fabric.

The following non-limiting examples illustrate the parameters and compositions employed within the invention. All percentages, parts and ratios are by weight unless otherwise indicated.

Example 1

Perfume-loaded zeolite ("PLZ") is prepared by mixing Zeolite 13X and perfume in a ratio of 85/15 by weight. The perfume-loaded zeolite is mixed with the intermediate coating oil (ICO) in a ratio of 1:0.5 to 1:1 PLZ:ICO. The mixture is then poured into a solution containing about 25% solid starch by weight, four times the mixture, during the entire process. This second mixture is mixed using a mixer or a high-speed homogenizer, such as a fabric homogenizer, during the entire process. The mixture is then pumped into a spray dryer at a temperature of between 180-220°C. The process results in a fine powder suitable for use in laundry detergent formulations.

74.780/BE for use as an additive. The perfume charge in the zeolite has the following composition:

Name of the substance % Violiff 2.5 Fruten 15.0 Methylisobutenyl tetrahydropyran 7.5 Cymal 10.0 Fluorhydral 15.0 Δ- Damascus 15.0 β-Ionone 25.0 P.T. Bucinal_________ 10.0

The particles formed unexpectedly have an excellent "pure product odor" ("NPO") and emit only minimal detectable odor other than the base product odor, as observed by a statistically significant number of panelists. This is strong evidence of the lack of perfume emission from the carrier particles.

Example 2

The following are some examples of detergent compositions containing the perfume particle prepared in Example 1.

____Base grain The B C Aluminosilicate 18.0 22.0 24.0 Sodium sulfate__________ 10, 0 19, 0 _ 6.0

74.780/BE

Sodium polyacrylate polymer 3, 0 2, 0 4.0 Polyethylene glycol (Molecular weight=400) 2, 0 1.0 C12-13 linear alkyl -benzenesulfonate sodium salt_____ 6, 0 7.0 8, 0 C14-16 secondary alkyl sulfate, sodium salt 3, 0 3.0 — C14-15 alkyl -ethoxylated sulfate sodium salt 3, 0 9, 0 - Sodium silicate 1.0 2.0 3.0 Color Enhancer 24/471 0, 3 0, 3 0, 3 Sodium carbonate 7, 0 26.0 (Carboxymethyl)cellulose _ horse DTPMPA ² __________________________ _ — 0, 3 DTPA ³ 0.5 — Mixed agglomerates C14-15 alkyl sulfate sodium salt 5, 0 - - C12-13 Linear Alkyl- -Benzenesulfonate Sodium Salt 2, 0 - - Sodium carbonate 4.0 _ _ Polyethylene glycol (Molecular weight=400) 1, p. - - ______________Mixture Sodium carbonate__________ — _ 13, 0 C12-15 alkyl ethoxylate (E0=7)_______ __________ 2, 0 0.5 2.0 C12-15 alkyl ethoxylate (E0=7)_________ - - 2.0 Perfume Spray 0, 3 o, 4 0.3 Perfume particles ⁴ ___________ 0.5 0.5 0.5 Poly(vinylpyrrolidone)____________ 0.5 — —

74.780/BE

Poly(vinylpyridine)-N-oxide 0.5 _ _ Poly(vinylpyrrolidone)poly(vinylimide z ο1) 0.5 - - Distearylamine & Cumenesulfonic acid______________ 2.0 - - Dirt-relieving polymer^ 0.5 _ _ Lipolase lipase (100,000 LU/I) ⁶ 0.5 — 0.5 Termamyl amylase (60 KNU/g) ⁶ 0.3 0, 3 CAREZYME® cellulase (1000 CEVU/q) ⁶ 0.3 _ _ Protease (40 mg/q) ⁷ 0.5 0.5 0.5 NOBS ⁸ ________ 5, 0 _ TAED ⁹ — _ 3, 0 Sodium percarbonate 12, 0 _ _ Sodium perborate monohydrate — 22.0 Dimethylpolysiloxane 0.3 3.0 Sodium sulfate — 3, 0 Other materials (water, etc.) supplement supplement supplement Total 100 ___100 100

1. Obtained from Ciba-Geigy

2. Diethylenetriaminepentamethylenephosphonic acid

3. Diethylenetriaminepentaacetic acid

4. As per example 1

5. Manufactured in accordance with USP 5,415,807.

6. Obtained from Novo Nordisk A/S

7. Obtained from Genencor

8. Nonanoyloxybenzenesulfonate

9. Tetraacetylethylenediamine

74.780/BE

Example 3

The following detergent compositions of the invention are suitable for both machine and hand washing operations. The base granules are prepared by a conventional spray drying process in which the starting ingredients are suspended and passed through a hot air (200-400°C) countercurrent spray drying tower to form porous granules. The remaining additive cleaning ingredient is sprayed on or dry added.

Basic granule The B c C12-13 alkylbenzenesulfonate sodium salt 19, 0 18.0 19.0 Cationic surfactant 0.5 0.5 - DTPMPA ² 0.3 — _ DTPA ³ — 0.3 _ Sodium tripolyphosphate 25, 0 19, 0 29, 0 Acrylic/maleic copolymer 1.0 0.6 _ (Carboxymethyl)cellulose 0.3 0.2 0.3 Color Enhancer 49/15/33^ 0.2 0.2 0.2 Sodium sulfate 28.0 39.0 15, 0 Sodium silicate (2,OR) 7.5 _ Sodium silicate (1.6 R) — 7.5 6.0 Mixture Quantum (zinc phthalocyanine- -sulfonate)________ 2.0 2.0 2.0 Sodium carbonate 5, 0 6.0 20, 0 C12-13 alkyl ethoxylate (EO=7) 0.4 - 1.2

74.780/BE

Savinase^ protease (4KNPY/g) 0.6 _ 1, p. Termamyl ⁵ amylase (60KNU/g) 0.4 _ Lipolase ⁵ lipase (100000 LU/g) 0.1 0.1 0.1 Acid/Ban ⁵ (6KNPU/100 KNU/q) — 0.3 _ CAREZYME ⁵ cellulase (1000 CEVU/g) - 0.1 - Dirt-relieving polymer^ o, 1 o, 1 0.3 Spraying perfume 0, 4 0.4 0, 4 Perfume particles? 1.5 1.5 2.0 Other materials (water, etc.) supplement supplement supplement Total 100, 0 100, 0 100, 0

1. 12-14 carbon dimethyl-hydroxyethyl quaternary ammonium compound

2. Diethylenetriaminepentamethylenephosphonic acid

3. Diethylenetriaminepentaacetic acid

4. Obtained from Ciba-Geigy

5. Obtained from Novo Nordisk A/S

6. Manufactured in accordance with USP 5,415,807.

7. As in example 1.

Example 4

The following detergent composition according to the invention is in the form of a laundry bar, which is particularly suitable for hand washing operations.

74.780/BE

% by weight Coconut Fat Alkyl Sulfate 30.0 Sodium tripolyphosphate 5, 0 Tetrasodium pyrophosphate 5.0 Sodium carbonate 20, 0 Sodium sulfate 5.0 Calcium carbonate 5, 0 ^Na 1.9 ^K 0.1 Ca(C0 ₃ )2 15.0 Aluminosilicate 2.0 Coconut fatty alcohol 2.0 Perfume particle^ 1.0 Perfume Spray 1, p. Other materials (water, etc.) Addition Total 100.0

1. As in example 1.

Having thus described the invention in detail, it will be apparent to those skilled in the art that various changes may be made without departing from the scope of the invention, and the invention is not to be construed as limited to what is set forth in the description.

74.780/BE

Claims (3)

Patent claims 1. Additive emitting particle which: (i) a central core particle comprising a porous carrier and an additive stored in the pores of said porous carrier, said additive being selected from the group consisting of perfume, bleach, bleach promoter, bleach activator, bleach catalyst, chelating anti-scale agent, threshold inhibitor, dye transfer inhibitor, light-activated bleach, enzyme, catalytic antibody, color brightener, fabric fastness dye, antifungal agent, antimicrobial agent, insect repellent, soil release polymer, fabric softener, dye fixing agent, pH buffering system, and mixtures thereof; (iii) an intermediate coating material applied to said central core particle, said intermediate coating material comprising a hydrophobic oil material; and (iii) an outer encapsulating material applied to said intermediate coating material, said outer encapsulating material providing an additive-releasing particle with a substantially non-stick surface; said outer encapsulating material comprising one or more of the following, at least partially soluble or dispersible in the washing solution: carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, water-soluble polymers, fatty compounds, 74.780/BE si ·.:· :· ^: ::· / / tai and mixtures thereof. 2. The additive-releasing particle of claim 1, wherein the intermediate hydrophobic oil coating material has a ClogP value lower than the ClogP value of the additive stored in the porous carrier material. 3- The additive emitting particle according to claim 2, which: (i) 5-50% of said central core particle, said core particle comprising about 60-99% of porous carrier material and about 1-40% of additive by weight of said core particle; (ii) about 1-40% of a disclosed intermediate hydrophobic coating material; and (iii) about 10-94% of a disclosed encapsulating material. 4. The additive release particle of claim 3, wherein said porous carrier material is a zeolite selected from the group consisting of Zeolite X, Zeolite Y, and mixtures thereof. 5. The additive-releasing particle of claim 3, wherein said additive incorporated into said carrier is a perfume material. 6. The additive-releasing particle of claim 3, wherein said intermediate hydrophobic coating material is a perfume oil. 7. The additive-releasing particle of claim 3, wherein said outer coating material is a carbohydrate selected from starch, modified starch, or starch hydrolysate. 74.780/BE θ· Additive emitting particle according to claim A3, which: (i) 5-50% of said central core particle, said core particle comprising about 60-99% zeolite as a porous carrier material, and about 1-40% perfume material by weight of said core particle; (ii) about 1-40% perfume oil as an intermediate coating material; and (iii) about 10-94% starch or modified starch as an external encapsulating material. θ* The additive release particle of claim 8, wherein the said perfume material incorporated into said zeolite carrier has a measured average ClogP value of between about 1.0 and about 16.0. 10. The additive release particle of claim 8, wherein the perfume material incorporated into said zeolite carrier comprises a highly effective perfume which typically: (1) a boiling point of about 275°C or less at 101.08 kPa, and; (2) ClogP or experimental logP value is about 2 or greater, and; (3) ODT value less than or equal to 50 ppb and greater than 10 ppm. 11. The additive-releasing particle of claim 8, wherein the perfume oil used as the intermediate coating material comprises a highly effective perfume, which typically: (1) having a boiling point of about 275°C or less at 101.08 kPa, and; 74.780/BE 53 . ·. .· :··. .· .· • · · · · · · (2) ClogP or experimental logP value of approximately 2 or greater, and; (3) ODT value less than or equal to 50 ppb and greater than 10 ppm. 12. The additive emitting particle of claim 8, which: (i) about 10-40% of the central core particle; (ii) about 10-30% perfume oil as an intermediate coating material; and (iii) about 30-80% starch or modified starch as an external encapsulating material. 13. A washing or cleaning preparation which: a) about 0.001-50% by weight of the composition of an additive-releasing particle, which: (i) a θ9Υ central core particle comprising a porous carrier and an additive stored in the pores of said porous carrier, said additive being selected from the group consisting of perfume, bleach, bleach promoter, bleach activator, bleach catalyst, chelating anti-scale agent, threshold inhibitor, dye transfer inhibitor, light-activated bleach, enzyme, catalytic antibody, color brightener, fabric fastness dye, antifungal agent, antimicrobial agent, insect repellent, soil release polymer, fabric softener, dye fixing agent, pH buffering system, and mixtures thereof; 74.780/BE (ii) an intermediate coating material applied to said central core particle, said intermediate coating material comprising a hydrophobic oil material; and (iii) an outer encapsulating material applied to said intermediate coating material, said outer encapsulating material providing an additive-releasing particle with a substantially non-stick surface; said outer encapsulating material comprising one or more compounds selected from the group consisting of carbohydrates, cellulose and cellulose derivatives, natural and synthetic gums, silicates, borates, phosphates, chitin and chitosan, water-soluble polymers, fatty compounds, and mixtures thereof, at least partially soluble or dispersible in the washing solution; and (iv) about 50-99.999%, by weight of the composition, of a detergent ingredient selected from the group consisting of detersive surfactants, soil builders, bleaches, enzymes, soil release polymers, dye transfer inhibitors, fillers, and mixtures thereof. swarm/ The authorized person: 74.780/BE