CN1237163C - Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes - Google Patents

Abstract

The present invention relates to a delivery system for additives, which are incorporated in 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 moist environment. Specifically, the present additive delivery system is a particle comprising a core of porous carrier material containing an additive, such as a perfume, in its pores; a first coating of a hydrophobic oil encapsulating said core; and a second coating of a water-soluble or water-dispersible, but oil-insoluble, material, such as starch or modified starch, encapsulating the hydrophobic-oil coated core. The present delivery particle can be used to deliver laundry and cleaning agents either to or through the wash cycle. A laundry additive delivery particle according to the present invention effectively delivers perfume ingredients through the wash to a fabric surface.

Description

Delivery system for encapsulated porous carriers loaded with additives, especially detergent additives such as perfumes

field of invention

The present invention relates to delivery particles, in particular to particles for delivering detergent additives such as perfume, and to detergent compositions, especially granular detergents, comprising delivery particles.

Technical Background of the Invention

Most consumers have come to expect scented laundry products and desire a pleasant scent from laundered fabrics. In many parts of the world, hand washing is the predominant way of washing fabrics. When hand washing soiled fabrics, users are constantly exposed to wash solutions and in close proximity to the detergent products used in them. Hand wash solutions also give off a nasty smell when put in soiled fabrics. Accordingly, it is desirable and commercially advantageous to add flavors to such products. Perfume additives provide detergent compositions that are aesthetically pleasing to the user and, in some cases, perfumes impart a pleasant fragrance to fabrics treated with their compositions. However, the amount of perfume carried over from the aqueous wash solution to the fabric is usually very small. Accordingly, the industry has long sought an efficient fragrance delivery system for detergent products that provides long-lasting, shelf-stable fragrance to the product, and releases fragrance during use to mask the odor of wet solutions , and deliver fragrance to washed fabrics.

Also, after drying the fabric in the sun, the fabric had a "sun-dried" smell. Consumers tend to prefer this scent over standard fragrances. Also, they often think fabrics with this scent are cleaner. Because consumers love the scent, they like to dry fabrics in the sun. However, in some countries, consumers cannot dry fabrics outside because the air is not clean or it rains too much. Therefore, they have to dry the fabric indoors and thus cannot enjoy the benefit of the fabric having a "sun dry type" smell.

Detergent compositions have now been found which contain perfumes which provide a "sun dry" scent.

Laundry and other fabric care compositions containing perfumes which are mixed with or sprayed onto the compositions are well known from commercial practice. Because fragrances are made up of combinations of volatile compounds, there is a continual flow of fragrances from both plain solutions and dry mixes to which fragrances have been added. Various techniques have been developed to impede or delay the release of fragrances from compositions so that the fragrances remain aesthetically pleasing and pleasant for an extended period of time. However, to date, only a few approaches offer the advantage of significant fabric fragrance after long-term storage of the product.

In addition, there is a continuing search for methods and compositions which are effective and efficient in delivering fragrance from wash solutions to fabric surfaces. As can be seen from the following publications, various perfume delivery methods have been developed which involve protecting the perfume during the wash cycle while releasing the perfume onto fabrics. US 4 096 072 to Brock et al., published June 20, 1978, describes a method of delivering fabric conditioners, including perfume, by means of fatty quaternary ammonium salts through the wash and dry cycle. US 4 402 856 to Schnoring et al., published September 6, 1983, describes a microencapsulation technique involving the formulation of shell materials that allows for the diffusion of fragrances outside the capsule only at certain temperatures. US 4 152 272 to Young, published 1 May 1979, describes the incorporation of perfume in waxy microparticles to protect the perfume during storage of the dry composition and during washing. The fragrance is said to diffuse on the fabric through the wax in the dryer. US 5 066 419, Walley et al., published November 19, 1991, describes fragrances dispersed with a water-insoluble non-polymeric carrier material and coated with a water-insoluble friable coating in a protective shell middle. US 5 097 761, Trinh et al., published March 10, 1992, describes a clay-protected perfume/cyclodextrin complex which provides fragrance to at least partially wetted fabrics.

As described in US 4 209 417 of Whyte published June 24, 1980, US 4 339 356 of Whyte published July 13, 1982, and US 3 576 760 of Gould et al published April 27, 1971 Yes, another method for delivering fragrance in the wash cycle involves mixing the fragrance with an emulsifier and a water soluble polymer, allowing the mixture to form microparticles, and incorporating these microparticles into the wash composition. Despite the extensive work done by industry in this field of technology, there remains a need for a simple, more efficient and highly effective perfume delivery system that can be mixed with a detergent composition to treat fabrics treated with the detergent product. , provides an onset and lingering fragrance.

Fragrances may also be adsorbed on porous carrier materials, such as polymeric materials, as described in British Patent Publication No. 2 066839, Bares et al., published July 15, 1981. These perfumes have also been adsorbed on clay or zeolitic materials which are then mixed with the particulate detergent composition. Generally, the preferred zeolites are Type A or Type 4A zeolites having nominal pore sizes of about 4 Angstrom units. It is now believed that when using zeolites of type A or 4A, the fragrance is adsorbed on the surface of the zeolite, in fact a relatively small amount of the fragrance is adsorbed in the pores of the zeolite. While zeolite or polymeric supports provide some improvement in the adsorption of fragrances over pure fragrances mixed with cleaning compositions, the industry is still seeking to increase the shelf life of cleaning compositions without losing their fragrance characteristics, and to improve the performance of the fragrance in the washing process. The intensity or amount of fragrance released or delivered to the fabric modifies the duration of the fragrance fragrance on the treated fabric surface.

It is also shown in the art that fragrances are often used in combination with larger pore size X and Y zeolites. East German Patent Publication No. 248508, published August 12, 1987, relates to perfume dispersants (eg, air fresheners) containing perfume-loaded faujasite-type zeolites (eg, X and Y zeolites). The critical molecular diameter of fragrance molecules is said to be 2-8 Angstroms. Also, East German Patent Publication No. 137 599 published on September 12, 1979 describes compositions for powder detergents which release fragrance under temperature control. Zeolites of type A, X and Y are described for use in these compositions. More recent European Patent Publication Nos. 539 942, Published April 7, 1993, 536 942, Published Apr. 14, 1993 by Unilever PLC, and Published 9 August 1994 by Garner-Gray et al. US 5 336 665, both repeat these earlier statements.

Effective perfume delivery compositions are described in WO94/28107 published December 8, 1994 by The Procter & Gamble Company. These compositions comprise a zeolite with a pore size of at least 6 angstroms (e.g., type X or Y zeolite), a fragrance-releasing substance incorporated into the pores of the zeolite, and a substrate coated on the zeolite containing a water-soluble (washable and removable ) composition consisting of about 0-80% by weight of at least one solid polyol containing 3 or more hydroxyl moieties, and about 20-100% by weight of a fluid diol or polyol, wherein the perfume is substantially insoluble , and the solid polyol is essentially soluble.

Other perfume delivery systems are described in WO 97/34982 and WO 98/41607 published by The Procter & Gamble Company. WO 97/34982 discloses microparticles comprising a perfume-loaded zeolite and a release barrier which is a wax-derived agent whose size (ie cross-sectional area) is larger than the size of the pore openings of the zeolite support. WO 98/41607 discloses glassy microparticles comprising agents for washing or cleaning compositions and consisting of a glass body derived from one or more at least partially water-soluble hydroxyl compounds. A preferred agent is a fragrance in a zeolite carrier.

Another problem that can arise when providing perfumed products is excessive fragrance intensity associated with the product. Therefore, there is a need for a perfume delivery system which provides a satisfactory perfume fragrance both in use and thereafter to dry laundered fabrics, but which also provides long-term storage and reduces product fragrance intensity.

The present inventors have now found that porous perfume-loaded carrier particles (such as zeolite particles) are coated with a hydrophobic oil and then encapsulated with a water-soluble or water-dispersible but oil-insoluble material, such as starch or modified starch. The oil-coated perfume-loaded carrier particles are effective in preventing premature release of perfume from the perfume-loaded carrier. For such fabrics to deposit sufficient perfume on the fabric to give off a noticeable fragrance even after the fabric has dried, there are many porous carrier options available.

The present invention addresses a long felt need for a simple, effective, shelf-stable fragrance delivery system that provides the consumer with a distinct fragrance both during and after the wash cycle while product odors present during storage. In particular, fabrics treated with the fragrance delivery system of the present invention have a higher fragrance intensity and retain their fragrance for extended periods of time after washing and drying.

The present invention also provides a delivery system for other additives which satisfactorily prevents release until the product containing such additives is exposed to a wet or humid environment.

brief description of the invention

The present invention relates to a delivery system for additives that are added to a variety of consumer products, including detergent and cleaning compositions, room deodorizers, insecticide compositions, carpet cleaners and deodorants, in which to prevent Additives are released until exposed to moisture or humidity. In particular, the additive delivery system of the present invention is a microparticle comprising a core of a porous carrier material containing an additive such as a fragrance in its pores; a first hydrophobic oil coating encapsulating the core, and a second Layer A coating of water-soluble or water-dispersible, but oil-insoluble material, such as starch or modified starch encapsulation coated with a hydrophobic oil core. The delivery particles of the present invention can be used to deliver detergent or cleaning agents to or through the wash cycle. The laundry additive delivery particles of the present invention are effective in delivering perfume components to the surface of fabrics during the wash process.

In typical perfume delivery systems, more than 50% of the perfume is "lost" and not delivered to the fabric surface due to diffusion of volatile perfume from the product or due to dissolution in the wash. In the present invention, these coatings are effective to trap the fragrance within the pores of the carrier. Thus, during the wash, the perfume is delivered to the fabric surface through the wash at a higher rate than conventional perfume delivery systems.

Porous support materials are typically selected from zeolites, large pore zeolites, amorphous silicates, crystalline non-layered silicates, layered silicates, calcium carbonate, calcium carbonate/sodium carbonate double salts, sodium carbonate, clays, Sodalite, alkali metal phosphates, chitin microbeads, carboxyalkyl cellulose, carboxyalkyl starch, cyclodextrin, porous starch, and mixtures thereof. Preferably, the support material is a zeolite such as X-type zeolite, Y-type zeolite and mixtures thereof.

Particularly preferred porous supports are zeolite microparticles having a nominal pore size of at least about 6 Angstroms to facilitate the incorporation of flavorants into their pores. Without wishing to be bound by theory, it is believed that these zeolites provide channel-like or cage-like structures in which perfume molecules can be trapped. Unfortunately, such perfume-loaded zeolites do not have sufficient storage stability for commercial application in granular fabric care products such as detergents, especially due to premature release of perfume upon absorption of water. However, it has now been found that perfume-loaded zeolites can first be coated with a hydrophobic oil to protect the zeolite particles by forming a protective barrier capable of trapping and retaining the perfume in the pores of the zeolite, after which the encapsulation has a water-soluble or water-dispersible Oil-coated particles of non-oil-soluble, but non-oil-soluble materials. Thus, the fragrance remains substantially within the pores of the zeolite particles. It is also believed that since the fragrance is incorporated into the relatively large zeolite pores, they retain the fragrance better during washing than other smaller pore zeolites where the fragrance is adsorbed primarily on the zeolite surface.

The hydrophobic oil coating may be a fragrance-free oil, but is preferably of the same or a different fragrance than the fragrance oil carried in the carrier. It is believed that when the encapsulated microparticles of the present invention are added to water, such as during washing, the water-soluble or water-dispersible encapsulating material dissolves and begins to release the oil coating. When the oil coating is perfumed, the scent of the perfume is released from the wash solution, advantageously providing a moist scent. The perfume-laden carrier particles are released into the wash solution and deposited onto the fabrics. After the fabric is dried, when the moisture in the air replaces the perfume contained in the pores of the carrier, the carrier releases the perfume, which is beneficial to provide a dry smell.

The additives contained in the porous carrier core are preferably selected from the group consisting of perfumes, bleaches, bleach accelerators, bleach activators, bleach catalysts, chelating agents, antiscalants, threshold inhibitors, dye transfer inhibitors, photobleaches, enzymes, Catalytic antibodies, brighteners, fabric substantive dyes, antifungals, antimicrobials, insect repellants, soil release polymers, fabric softeners, color fixatives, pH gradient systems and mixtures thereof.

Preferred detergent additives carried on the porous carrier material are perfumes. Preferably, the particulate core is perfume loaded zeolite (PLZ).

When the preferred oil coating material is a fragrance oil, the preferred encapsulating material is starch, modified starch or starch hydrolyzate. The outer lagging material may also contain components selected from the group consisting of plasticizers, anti-blocking agents, and mixtures thereof.

In another embodiment of the present invention there is provided a washing or cleaning detergent composition. The washing or cleaning composition contains from about 0.001 to 50% by weight of the detergent additive particulate composition as described above, and from about 50 to 99.999% by weight of a detergent component composition selected from the group consisting of detergent surfactants, builders, bleach agents, enzymes, soil release polymers, dye transfer inhibiting agents, fillers and mixtures thereof. Preferably, the composition comprises at least one detersive surfactant and at least one builder.

It is therefore an object of the present invention to provide an additive delivery particle having a core loaded with an additive, preferably a detergent additive such as a perfume, and at least two surface coatings, the coating Consists of an intermediate hydrophobic oil coating and an outer cover layer of water soluble or water dispersible material. Another object of the present invention is to provide a washing and cleaning composition having said detergent additive particles therein. Another object of the present invention is to provide a detergent additive microparticle which provides improved fabric odor, extended shelf life and reduced product odor intensity. These and other objects, features and advantages of the present invention will be appreciated by those skilled in the art from the following description and appended claims.

All percentages, ratios and proportions herein are by weight unless otherwise indicated. All documents cited here are incorporated herein by reference.

Brief description of the figure

Figure 1 shows a scanning electron microscope image of intact average size detergent additive particles comprising encapsulated perfume-loaded zeolite particles of the present invention.

Figure 2 shows a scanning electron microscope image of a cross-section of a microparticle of the invention comprising zeolite microparticles loaded with fragrance within a starch coating.

Detailed Description of the Preferred Embodiment

The present invention relates to a detergent additive microparticle, preferably a perfume-containing microparticle, and to washing and cleaning compositions containing such detergent additive microparticle. Washing and cleaning compositions include conventional granular detergents as well as granular bleaches, automatic dishwashing agents, hard surface cleaners and fabric softening compositions. The laundry additive microparticles of the present invention provide superior perfume delivery during the wash and minimize product odor due to the release of volatile perfume components. While not wishing to be bound by theory, it is believed that the particular coating of the microparticles of the present invention increases the stability of the microparticles.

Preferred detergent microparticles of the present invention comprise a perfume-loaded porous carrier core which is first coated with a hydrophobic oil material, followed by a water-soluble or water-dispersible, but non-oil-soluble material, such as starch or modified Encapsulation with permanent starch to form the final microparticles.

Preferably, the detergent additive particles of the present invention have a moisture absorption value of about 80% or less. As used herein, "Moisture Absorption Value" means the amount of moisture absorbed by a particle, as measured as a percent increase in weight of the particle according to the test method described below. The required moisture absorption values for the particles of this invention can be determined by placing 2 grams of the particles in an open container petri dish for 4 weeks at 90°F and 80% relative humidity. At the end of this time period, the increase in the weight percent of the particles is the particle moisture absorption value as used herein. Preferred microparticles of the invention have a moisture absorption value of less than about 50%, more preferably less than about 30%.

The detergent additive particles of the present invention typically contain about 5-50% by weight of a perfume-loaded central core particle which itself is about 60-99% by weight of the porous carrier and about 1-40% by weight of perfume or other detergent additive material, about 1-40% by weight hydrophobic oil midcoat material, and about 10-94% by weight outer lagging material.

Preferred detergent additive particles of the present invention contain about 10-40 wt. starch or modified starch.

loaded central core particles

As already indicated, the central core of the additive granule comprises a porous carrier material and the detergent additive loaded in said carrier material. The two center core materials can be mixed in many different ways.

On a laboratory scale, basic equipment for this purpose could be a 10-20 gram coffee grinder, a 100-500 gram food processor, or even a 200-1000 gram kitchen mixer. The procedure involves placing the carrier material particles (zeolite) in the device and pouring the detergent additive while mixing. The mixing time is 0.5-15 minutes. The loaded support material (zeolite) is then left for 0.5-48 hours before further processing. A cooling jacket can optionally be used for heating during loading. At pilot plant scale, suitable equipment is a Littleford type mixer, which is a batch type mixer with a stirrer bar and chopper blades, operated at high RPM (revolutions per minute) to Or the powder mixture is continuously mixed while the liquid fragrance oil is sprayed on the powder mixture.

porous carrier material

Porous carrier material as used herein means any material capable of supporting (eg by adsorption into the pores) a deliverable agent such as a detergent or cleaning agent. Such materials include porous solids such as zeolites.

Preferred zeolites are selected from type X zeolites, type Y zeolites and mixtures thereof. The term "zeolite" as used herein refers to crystalline aluminosilicates. The structural formula of zeolites is based on the crystal unit cell, the smallest structural unit represented by the formula:

Mn/m[(AlO2)m(SiO2)y] xH2O

When n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1-100. Most preferably, y/m is 1-5. The cation M may be a group IA and IIA element such as sodium, potassium, magnesium and calcium.

The zeolites useful herein are faujasite-type zeolites, including X-type zeolites or Y-type zeolites, which typically have a pore size of about 4-10 angstrom units, preferably about 8 angstrom units.

Aluminosilicate zeolite materials useful in the practice of this invention are commercially available. Methods for producing X and Y zeolites are well known and available in standard texts. Preferred synthetic crystalline aluminosilicate materials for use herein are available under either the Type X or Type Y designations.

By way of illustration and not limitation, in a preferred embodiment, the crystalline aluminosilicate material is of type X and is selected from the following:

(I)Na ₈₆ [AlO ₂ ] ₈₆ ·(SiO ₂ ) ₁₀₆ ]xH ₂ O,

(II) K ₈₆ [AlO ₂ ] ₈₆ ·(SiO ₂ ) ₁₀₆ ]xH ₂ O,

(III)Ca ₄ 0Na ₆ [AlO ₂ ] ₈₆ ·(SiO ₂ ) ₁₀₆ ]xH ₂ O,

(IV) Sr ₂₁ Ba ₂₂ [AlO ₂ ] ₈₆ ·(SiO ₂ ) ₁₀₆ ]xH ₂ O, and mixtures thereof, wherein x is about 0-276. The zeolites of formula (I) and (II) have a nominal pore size or opening of 8.4 Angstrom units. The zeolites of formula (III) and (IV) have a nominal pore size or opening of 8.0 Angstrom units.

In another preferred embodiment, the crystalline aluminosilicate material is Y-type and is selected from the group consisting of:

(V)Na ₅₆ [AlO ₂ ] ₅₆ ·(SiO ₂ ) ₁₃₆ ]xH ₂ O,

(VI) K ₅₆ [AlO ₂ ] ₅₆ ·(SiO ₂ ) ₁₃₆ ]xH ₂ O, and mixtures thereof, wherein x is about 0-276. The zeolites of formulas (V) and (VI) have a nominal pore size or opening of 8.0 Angstrom units.

In another embodiment, the class of zeolites known as "MAP zeolites" may also be used in the present invention. Such zeolites are disclosed and described in US Application No. 08/716,147, filed September 16, 1996, entitled "MAP Zeolite and Alcalase for Improved Textile Finishing".

The zeolites used in the present invention are in particulate form, having an average particle size of from about 0.5 to 120 microns, preferably from about 0.5 to 30 microns, as measured by standard particle size analysis techniques.

The size of the zeolite particles allows their entrainment into fabrics with which they come into contact. Once set on the surface of the fabric (along with the coating that washes off during the wash), the zeolite can begin to release the detergent added to it, especially when exposed to hot or humid conditions.

intermediate oil coating material

The intermediate oil coating material of the present invention forms a coating on the central core particle. The midcoat provides a barrier layer that minimizes the release or leakage of any deliverable agents, such as fragrances, added to the porous carrier material. Intermediate coating materials include hydrophobic oils such as fragrance oils, which may be the same or different from the fragrance carried in the carrier, or non-perfume oils such as mineral oils. The hydrophobic oil may be an organic compound or a mixture of organic compounds, preferably having a weighted average ClogP value lower than the weighted ClogP value of the additive material or mixture loaded in the pores of the carrier. The ClogP value is typically used to characterize a perfume ingredient, ie by its octanol/water partition coefficient P. The octanol/water partition coefficient of a perfume ingredient is the ratio of the equilibrium concentration of that ingredient in octanol to water. The more hydrophobic the material, the higher its ClogP value. Therefore, the intermediate oil coating material is preferably less hydrophobic than the additive material contained in the porous carrier.

More preferably, the highest ClogP value of the material containing the hydrophobic oil coating is lower than the ClogP value of the material containing the additive loaded in the porous support. Even more preferably, the difference between the highest ClogP value of the hydrophobic oil coating material and the lowest ClogP value of the additive loaded material is at least one unit, most preferably two units.

External lagging material

The outer encapsulating material is coated on the middle coating material which in turn is coated on the core particle, the outer covering material providing the outer layer of the final particle. The outer coating material provides a substantially tack-free or non-stick coating to the final particle. Preferably, the exterior coating provides a particle surface that is non-tacky under highly humid conditions such as 80% relative humidity at 90°F.

The outer coating is a material derived from one or more at least partially wash-soluble or dispersible compounds. That is, the outer coating is either soluble in an aqueous wash environment or dispersible in that aqueous wash environment. The compounds usable here are preferably selected from the following classes of materials.

1. Carbohydrates, which may be any one or mixture of the following compounds: i) starches including modified starches or starch hydrolysates; ii) oligosaccharides (defined as being composed of 2-35 monosaccharides carbohydrate chains composed of molecules); iii) polysaccharides (defined as carbohydrate chains composed of at least 35 monosaccharide molecules); and (iv) monosaccharides (or monosaccharides); and v) i), ii), Hydrides of iii) and iv).

Either straight or branched carbohydrate chains can be used. Additionally, chemically modified starches and poly/oligosaccharides can be used. Typical modifications include the addition of hydrophobic moieties in the form of alkyl, aryl groups, etc., which are the same as those found in surfactants, in order to impart certain surface activity to these compounds.

2. All natural or synthetic gums, such as alginates, carrageenan, agar-agar, pectic acid and natural gums such as acacia, tragacanth and karaya.

3. Chitin and chitosan.

4. Cellulose and cellulose derivatives. Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropylmethylcellulose (HPMC); iii) carboxymethylcellulose (CMC); iv) all enteric coatings /aquateric paints and mixtures thereof.

5. Silicates, phosphates and borates.

6. Water soluble polymers including polyacrylates, caprolactone, polyvinyl alcohol (PVA) and polyethylene glycol (PEG).

7. Waxes, including silicone waxes, paraffin waxes and microcrystalline waxes.

8. Plasticizers.

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

10. Natural proteins, including gelatin, casein and ovalbumin.

Of these types of materials which are not at least partially wash soluble or dispersible, these materials can only be used here if they are mixed with the compounds used here in such amounts that the preferred hygroscopicity values of the resulting particles are less than about 80%. It is also preferred that these compounds are low temperature processable, preferably in the temperature range of about 50-220°C, more preferably about 60-180°C.

Preferred encapsulating materials are starches or modified starches such as those commercially available from National Starch under the name CAPSUL ^™ , cellulose and cellulose derivatives such as hydroxypropylmethylcellulose, other celluloses such as sucrose and fructose. Carbohydrates, natural polymers like acacia and guar gum, natural proteins, and water-soluble polymers like polyethylene glycol.

The exterior lagging coating may also include additive components such as plasticizers, anti-blocking agents, and mixtures thereof. Plasticizers which may also be present include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates and the like, with mixtures of sorbitol and polyethylene glycol and low molecular weight polyols being most preferred. The amount of plasticizer used is about 0.01-5%. The anti-blocking agent of the present invention is preferably a surfactant which is present at less than 1% in the exterior coating. Surfactants suitable for use in the present invention include TWEEN ^(TM ) products available from Imperial Chemicals, Inc (ICI).

Washing and Cleaning Additives

The microparticles of the present invention contain washing and cleaning additives or agents. These agents are contained in a porous carrier material as previously described. As assessed herein, the agents incorporated into the microparticles of the present invention may be the same or different from those conventionally used to formulate the remainder of washing and cleaning compositions containing the microparticles. For example, the microparticles may contain a fragrance agent, and the (same or different) fragrance may also be incorporated into the final composition (eg by spraying techniques) with the fragrance-containing microparticles. These agents can be selected as desired for the type of composition being formulated, eg granular detergent compositions, granular automatic dishwashing compositions or hard surface cleaners.

Compositions which may contain other ingredients can of course contain the detergent particles of the present invention. Compositions containing detergent additive microparticles may also contain one or more other detergent adjunct materials or other materials to facilitate or enhance cleaning, treat the substrate to be cleaned, or modify the detergent composition (e.g., fragrances, pigments, dyes etc.) beauty.

spices

Preferred washing or cleaning additives according to the invention are perfume materials. The term "perfume" as used herein is used to denote any scented material which is subsequently released into an aqueous solution and/or onto fabrics or other surfaces in contact therewith. Spices are usually liquid at room temperature. A large number of chemicals are known for use in fragrances, including such substances as aldehydes, especially C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof, ketones, alcohols and esters. More generally, naturally occurring vegetable and animal oils and exudates that contain complex mixtures of various chemical constituents are known to be useful as perfumes. The fragrances herein can be relatively simple in their composition, or can contain very advanced complex mixtures of natural and synthetic chemical components, all of which are selected to provide any desired scent. For example, typical fragrances can include woody/earthy bases with exotic substances such as sandalwood, musk, and patchouli oil. Fragrances can have slightly floral scents such as rose extract, violet extract, and clove scent. Perfumes can also be formulated to provide desired fruity aromas such as lime, lemon and orange. Any chemically compatible material that imparts a pleasant or otherwise desirable odor can be used in the scented compositions of the present invention.

If a "sun-dried" scent is the preferred scent, the perfume component is selected from the group consisting of _C6 - _C14 aliphatic aldehydes, _C6 - _C14 acyclic terpene aldehydes and mixtures thereof. Preferably, the fragrance component is selected from C ₈ -C ₁₂ aliphatic aldehydes, C ₈ -C ₁₂ acyclic terpene aldehydes and mixtures thereof. Most preferably, the fragrance component is selected from the group consisting of citral, neral, isocitral, dihydrocitral, citronellal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-Methyldecylaldehyde, Methylnonylacetaldehyde, 2-Nonen-1-al, Decylaldehyde, Undecenal, 2,6 Dimethyloctylaldehyde, 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, mixtures containing 30% by weight of 2-nonen-1-al, 40% by weight of undecenal and 30% by weight of citral, or 20% by weight of methylnonylacetaldehyde, 25% by weight % lauryl aldehyde, 35% by weight heptanal and 20% by weight 2-nonen-1-al.

By selecting perfume ingredients from among the above compounds, a "sun dry smell" can be imparted on fabrics even though the fabrics have not actually been sun dried. "Sun-dried" odors are produced by selecting at least one of such aldehydes which is naturally present in cotton fabrics after the fabrics have been sun-dried, and whose aldehyde is thus a component of the sun-dried odor.

Perfumes also include original fragrances, such as acetal ortho-fragrances, ketal ortho-fragrances, ester ortho-fragrances (eg, digeranylsuccinate), hydrolyzable inorganic-organic ortho-fragrances, and mixtures thereof. These pro-fragrances may release aroma substances as a result of simple hydrolysis, or may be pH-change-triggered pro-fragrances (eg pH drop), or may be pro-fragrances released enzymatically.

Preferred fragrance agents for use herein are defined below.

For the present invention, fragrance agents are those that have the ability to be incorporated into the pores of the carrier, and thus have utility as components delivered by the carrier through an aqueous environment. Commonly owned WO98/41607 describes characteristic physical parameters of fragrance molecules which can affect their ability to incorporate into the pores of a support such as a zeolite. Obviously, for a composition to deliver fragrance through the composition of the present invention, the consumer also needs to have a sensory perception to see the benefit. For the fragrance delivery microparticles of the present invention, preferred fragrance agents have a significant threshold (measured as Odor Detection Threshold ("ODT") under strictly controlled GC conditions as described in detail hereinafter) less than or equal to ten Fifty parts per billion ("50 ppb"). Agents with an ODT of 50 ppb up to 1 part per million ("1 ppm") are less preferred. Agents with an ODT in excess of 1 ppm are preferably avoided. Detergent fragrance blends for use in the fragrance delivery microparticles of the present invention contain about 0-80% deliverable agents with an ODT greater than 50 ppb up to 1 ppm, and about 20-100% (preferably about 30-100%, more preferably about 50-100%) %) with an ODT less than or equal to 50 ppb deliverables.

It is also preferred that the perfume is carried through the washing process and thereafter released into the air surrounding the dried fabric (eg like the space around the fabric during storage). This requires the fragrance to migrate out of the pores of the zeolite and then be dispersed in the air surrounding the fabric. Therefore, preferred fragrance agents were further identified based on the volatility of the fragrance. Where boiling point can be used as a measure of volatility, it is preferred that materials have a boiling point below 300°C. Detergent fragrance blends for use in the detergent microparticles of the present invention preferably contain at least about 50% of the deliverable agent having a boiling point below 300°C (preferably at least about 60%; more preferably at least about 70%).

Additionally, preferred perfume delivery microparticles for use in detergents herein comprise compositions wherein at least about 80%, more preferably at least about 90%, of the deliverable perfume has a weighted average ClogP value of from about 1.0 to 16, more preferably about 2.0-8.0. Most preferably, the deliverable fragrance agent or mixture has a weighted average ClogP value of 3-4.5. While not wishing to be bound by theory, it is believed that perfumes with preferred ClogP values remain sufficiently hydrophobic within the pores of the zeolite support to allow their perfume to deposit on fabrics during laundering and to dry at a reasonable rate. The pores of the zeolite in the fabric release it, providing a pronounced fragrance. The ClogP value can be obtained by the following method.

Calculation of ClogP :

These perfume ingredients are characterized by their octanol/water partition coefficient P. The octanol/water partition coefficient of a perfume ingredient is the ratio of its equilibrium concentration in octanol to water. Since the partition coefficients of most perfume ingredients are large, these coefficients are more conveniently expressed in base 10 logarithmic (logP) form.

The logP of many perfume ingredients has been reported; for example the Pomona92 database obtained by Daylight Chemical Information Systems, Inc (Daylight CIS) includes the logP of many perfume ingredients, and the original literature is also cited.

However, logP values are most conveniently calculated using the "CLOGP" program from Daylight CIS. The program also lists experimental logP values when logP values are obtained from the Pomona92 database. The "calculated logP" (ClogP) can be determined using the fragment approach of Hansch and Leo (cf. A. Leo, in Comprehensive Medicinal Chemistry, Chapter 4, C. Hansch, P.G. Sammens, J.B. Taylor and C.A. Ramsden, Eds. , p. 295, Pergamon Press, 1990). This fragment approach is based on the chemical structure of each fragrance component, also taking into account the number and type of atoms, atom connectivity and chemical bonding. ClogP values are the most reliable and widely used estimates of this physicochemical property, and these ClogP values can be used instead of experimental logP values when selecting fragrance components.

Determination of odor detection threshold:

Gas chromatograph analysis is characterized by determination of the exact volume of material injected with a syringe, accurate split ratios, and hydrocarbon response determined with hydrocarbon standards of known concentration and chain length distribution. The volume of the sample can be calculated by accurately measuring the air flow rate and assuming that the human inhalation time lasts 0.2 minutes. Since the exact concentration at the detector is known at any point in time, the mass of each suction volume and thus the concentration of the available material is known. To determine whether the material threshold is below 10 ppb, the solution is sent to the suction port at the back-calculated concentration. The GC effluent was aspirated by an expert panelist, and when smelled, the retention time was determined. The average of all reviewers determines the visibility threshold.

The necessary amount of analyte is injected into the column to achieve a concentration of 10 ppb at the detector. Typical GC analysis parameters used to determine odor detection thresholds are listed below.

GC: 5890 Series II with FID detector

7673 Autosampler

Column: J&W Scientific DB-1

Length 30 meters, ID 0.25 mm, film thickness 1 micron

method:

Split injection: 17/1 split ratio

Auto-sampling: 1.13 microliters per injection

Column flow rate: 1.10 ml/min

Air flow rate: 345ml/min

Inlet temperature: 245°C

Detector temperature 285°C

Temperature data:

Initial temperature: 50°C

Speed: 5C/min

Final temperature: 280°C

Final time: 6 minutes

Main assumptions: (i) 0.02 minutes per inhalation

(ii) GC gas added to sample dilution

Particularly preferred fragrances for use in the present invention are those known as high potency fragrances, characterized in that they have:

(1) Standard B.P. of about 275°C or less at 760 mm Hg, and;

(2) ClogP, or experimental logP of about 2 or higher, and;

(3) ODT is less than or equal to 50ppb and greater than 10ppb.

Fragrance fixative

Optionally, fragrances can be combined with fragrance fixatives. The deodorant materials used herein are characterized by several criteria that make these materials particularly suitable for the practice of the present invention. Additives that are dispersed, toxicologically acceptable, non-irritating to the skin, inert to fragrance, degradable and/or available from renewable resources, and relatively odorless may be used. Fragrance fixatives are believed to slow down the evaporation of the more volatile components of the fragrance.

Examples of suitable deodorants include those selected from diethyl phthalate, musk and mixtures thereof. If a fragrance fixative is used, the content of the fragrance fixative is about 10-50% by weight of the fragrance, preferably about 20-40% by weight.

Incorporation of fragrance in preferred zeolite carrier

Zeolites of type X or Y for use as preferred supports herein preferably contain less than 15% desorbable water, more preferably less than 8% desorbable water, most preferably less than about 5% desorbable water. To obtain such materials, activation/dehydration can first be performed by heating to about 150-350°C, also under reduced pressure (about 0.001-20 Torr). After activation, the reagents are slowly and thoroughly mixed with the activated zeolite, which may then also be heated to about 60°C or for about 2 hours to accelerate the absorption equilibrium within the zeolite particles. The fragrance/zeolite mixture was then cooled to room temperature and was in the form of a free flowing powder.

Assuming a limit to the pore volume of the zeolite, the amount of perfume or other detergent additive added to the zeolite support is typically from 1 to 40%, preferably at least about 10%, more preferably at least about 18.5% by weight of the loaded particulate. It is recognized, however, that the microparticles of the present invention may exceed this detergency additive level on a microparticle weight basis, but it is also recognized that excess detergency additive will not enter the zeolite, even if only deliverable agents are used. Thus, the microparticles of the present invention may contain greater than 40% detergent. Since any excess detergent (and any non-deliverable agents present) do not enter the pores of the zeolite, these materials may be released into the wash solution immediately upon contact with the aqueous wash medium.

Coated and Encapsulated Supported Zeolite Microparticles

In one embodiment of the invention, the perfume-loaded zeolite particles in the form of a free-flowing powder are substantially coated with a hydrophobic oil such as mineral oil or fragrance oil. Microparticles coated with hydrophobic oil were mixed with a solution of modified starch (CAPSUL ^™ , National Starch & Chemicals) and stirred to form an emulsion. The emulsion is then spray dried using a spray dryer with a spray system such as parallel flow with a rotating disk, impellerless disk, impeller disk or wheel or with a dual fluid mist nozzle. Typical conditions include an inlet temperature of about 120-220°C and an outlet temperature of about 50-220°C.

The detergent additive delivery particles of the present invention are discrete particles having a particle size of about 3-100 microns when measured using standard particle size analysis techniques. Figure 1 shows the SEM of the intact average gummed perfume-loaded zeolite microparticles of the present invention. Figure 2 shows a cross-section of a microparticle of the present invention containing perfume-loaded zeolite microparticles within a starch coating.

Stability Test of Encapsulated Fragrance-Loaded Zeolite Microshort

Samples of perfume-loaded encapsulated zeolite microparticles were stored in open jars at 80°F and 70% relative humidity, and in sealed plastic bags at 120°F for up to 10 days. After this period, samples were removed and evaluated organoleptically. The microparticle size is homogenized and metered according to the local actual wash conditions. They are mixed with odorless base granules, which have been previously confirmed in tests. As in the reference, primary microparticles (microparticles not subjected to stability test conditions) were included. The fragrance intensity score of the microparticles is recorded according to DryFabric Odor. The particles of the perfume-loaded zeolite outperformed the perfume-intensity scale by 5-20 points compared to the control sprayed on the perfume only.

Auxiliary washing or cleaning agents

Adjunct ingredients for use in the washing or cleaning compositions of the present invention include surfactants, adjuvants and agents such as those incorporated in the delivery particles of the present invention. Various agents useful for washing and cleaning compositions are described below. Compositions containing particulate compositions may also include one or more other detergent adjunct materials, or other materials that facilitate or enhance cleaning, treat the substrate to be cleaned, or improve the aesthetic characteristics of the detergent composition.

detergent surfactant

The particles and/or agglomerates include surfactants in the amounts previously indicated. Detersive surfactants may be selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants and mixtures thereof. Non-limiting examples of surfactants used herein include common C ₁₁ -C ₁₈ alkylbenzene sulfonate (“LAS”) and native, branched and random C ₁₀ -C ₂₀ alkyl sulfate (“LAS”) _{AS " ) ,} ^C _{10 -C} ¹⁸ _{secondary ( 2} ^{_ _} _{_ _ _ _} , 3) Alkyl sulfates, wherein x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, specifically sodium, an unsaturated cation such as oleyl sulfate, Saturated sulfates, C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO 105 ethoxy carboxylate), C ₁₀ -C ₁₈ glyceryl ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₀ -C ₁₈ alkyl-α-sulfonated fatty acids esters. Common nonionic and amphoteric surfactants such as C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including so-called narrow-peak alkyl ethoxylates, may also be present in the overall composition, if desired. Alkoxylates, and C ₆ -C ₁₂ alkylphenol alkoxylates (in particular ethoxylates and mixed ethoxy/propoxy), C ₁₂ -C ₁₈ betaines and sultaines ("sultaines"), C ₁₀ -C ₁₈ amine oxides, etc. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methyl glucamides. See WO 9 206 154 . Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ alkyl N-(3-methoxypropyl) glucamides. N-propyl through N-hexyl C ₁₂ -C ₁₈ glucamide can be used for less foaming. The usual C ₁₀ -C ₁₈ fatty acid salts can also be used. If more foaming is required, branched chain C ₁₀ -C ₁₆ fatty acid salts can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other commonly used surfactants are listed in standard texts.

For the cellulase-containing detergents described herein, C ₁₀ -C ₁₈ alkyl alkoxy sulfates ("AExS"; specifically EO 1-7 ethoxy sulfates) and C ₁₂ -C ₁₈ alkyl Ethoxylates ("AE") are most preferred.

Detergent

The microparticles and aggregates preferably contain the auxiliaries in the amounts indicated above. For this purpose, inorganic as well as organic auxiliaries can be used. Crystalline as well as amorphous auxiliaries can be used. Adjuncts are typically used in fabric washing compositions to aid in the removal of particulate soils, and to de-harden water.

Inorganic or P-containing detergent builders include, but are not limited to, polyphosphates (such as tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acids, silicates, Alkali metal, ammonium and alkanolate salts of carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate additives are required in some places. Importantly, even in the presence of so-called "weak" builders (compared to phosphates) such as citrates, or in the case of so-called "slave builders" that may arise with zeolite or layered silicate builders The composition here also works surprisingly well.

Examples of silicate builders are alkali metal silicates, especially alkali metal silicates and phyllosilicates with a SiO ₂ :Na ₂ O ratio of 1.6:1 to 3.2:1, as described in May 1987 The layered sodium silicate described in US 4 664 839 of HP Riech published on the 12th. NaSKS-6 is the trademark for a crystalline layered silicate sold by Hoechst (often abbreviated herein as "SKS-6"). Unlike zeolite builders, Na SKS-6 silicate builders do not contain aluminum. NaSKS-6 is available in the delta-Na ₂ SiO ₅ morphological form of phyllosilicates. It can be prepared as described eg in German DE-A-3 417 649 and DE-A-3 742 043 . SKS-6 is a very preferred phyllosilicate for this application, but other such phyllosilicates such as those having the general formula NaMSi _x O _2x+1 yH ₂ O can also be used here , wherein M is sodium or hydrogen, x is a number from 1.9-4, preferably 2, and y is a number from 0-20, preferably 0. Various other phyllosilicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in alpha, beta and gamma forms. As mentioned above, δ-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred for use here. Other silicates can also be used, like for example magnesium silicate, which can be used as a crispening agent in microparticle formulations, as a stabilizer for oxygen bleaches, as a component of foam control systems.

Examples of carbonate builders are the alkaline earth metal and alkali metal carbonates described in German Patent Application No. 2321001 published on November 15, 1973. As previously mentioned, aluminosilicate builders are useful builders in the present invention. Aluminosilicate builders play an important role in recently marketed durable granular detergent compositions and are an important builder component in fluid detergent formulations. Aluminosilicate builders include compounds with the following empirical formula:

M _z (zAlO ₂ ) _y ]·xH ₂ O

wherein z and y are integers of at least 6, the molar ratio of z to y is about 1.0-0.5, and x is an integer of about 15-264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or amorphous in structure and may be naturally occurring or synthetically derived. US 3 985 669 to Krummel et al., published October 12, 1976, describes a process for the production of aluminosilicate ion exchange materials. Preferred synthetic crystalline aluminosilicate ion exchange materials for use herein are available under the designations Zeolite A, Zeolite P(B), Zeolite MAP, and Type X Zeolite. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O wherein x is about 20-30, especially about 27. This material is called zeolite A. Dehydrated zeolites (x=0-10) can also be used here. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. The polycarboxylate builder is usually added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in salt form, alkali metal salts such as sodium, potassium and lithium or alkanolammonium salts are preferred.

A large number of useful materials are included in polycarboxylate builders. An important class of polycarboxylate builders includes ether polycarboxylates, including hydroxydisuccinates, such as US 3 128 287, Berg, published April 17, 1964 and published January 18, 1972 Described in published US 3 635 830 by Lamberti et al. See also the "TMS/TDS" adjuvant described in US 4 663 071, Bush et al., published May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, in particular cycloaliphatic compounds, such as those described in US Pat.

Other useful detergent builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and Carboxymethoxysuccinic acid, various alkali metal polyacetates, ammonium and substituted ammonium salts such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, Salts of hydroxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethoxysuccinic acid, and soluble salts thereof.

Citrate builders, such as citric acid and its soluble salts (particularly the sodium salt), are particularly important polycarboxylic acids in durable liquid detergent formulations due to their availability from renewable resources and their biodegradability Salt additives. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Hydroxydisuccinates are also particularly useful in such compositions and combinations.

Also suitable for use in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US 4 566 984 Bush, published January 28, 1986 described in. Useful succinic acid builders include _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: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecene succinate Esters etc. Lauryl succinate is a preferred adjuvant of this group and is described in European patent application 86200690.5/0 200 263 of 5 November 1986.

Other suitable polycarboxylates are described in US 4 144 226, Crutchfield et al., published March 13, 1979, and in U.S. Patent 3, 308 067, Diehl, published March 7, 1967. See also US 3 723 322 by Diehl.

Fatty acids, such as C ₁₂ -C ₁₈ monocarboxylic acids, may also be added to the composition alone, or together with the aforementioned adjuvants, in particular citrate and/or succinate adjuvants, to provide additional additive effect. Such use of fatty acids will generally result in reduced foaming and should be taken into account by the formulator.

Where phosphorus-based builders can be used, especially in bar formulations for hand wash operations, various alkali metal phosphates such as the well-known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used . Phosphate builders such as ethane-1-hydroxy-1,1-diphosphate and other known phosphates can also be used (see for example US 3 159 581, 3 213 030, 3 422 021, 3 400 148 and 3 422 137).

other auxiliary components

The compositions of the present invention may also contain enzymes, enzyme stabilizers, brighteners, polymeric dispersants (i.e. polyacrylates), carriers, hydrotropes, foam boosters and inhibitors, soil release agents, dye transfer inhibiting agents agents and processing aids.

granular composition

The washing and cleaning compositions of the present invention can be used in the form of low density (less than 550 g/l) and high density granular compositions wherein the particle density is at least 550 g/l. Granular compositions are typically designed to provide an in-wash pH of about 7.5-11.5, more preferably about 9.5-10.5. Low density compositions can be prepared by standard spray-drying methods. High density compositions can be prepared using a variety of methods and equipment. In the art, current commercial practice employs spray-drying towers to produce compositions having a density of less than about 500 grams per liter. Therefore, if spray-drying is used as part of the overall process, the resulting spray-dried microparticles should be further densified using the methods and apparatus described hereinafter. In another approach, the formulator can use commercially available mixing, densification and granulation equipment and omit the spray-drying process. The following is a non-limiting description of equipment suitable for this application.

Various methods and equipment are available for preparing high density (i.e. above about 550, preferably above about 650 grams per liter or "g/l"), high solubility, free-flowing, granular detergent compositions of the present invention things. In the art, current commercial practice uses spray-drying towers to produce granular detergents, which often have densities below about 500 grams per liter. In this process, an aqueous slurry of the various thermally stable ingredients of the final detergent composition is passed through a spray-drying tower at a temperature of about 175-225°C to form uniform particles using conventional techniques. However, if spray-drying is used here as part of the overall process, additional process steps as will be described later must be used to obtain the density levels required for modern compact, low metered detergent products (i.e. > 650 g/l ).

For example, spray-dried particles from the tower can be further densified by adding liquids such as water or nonionic surfactants to the pores of the particles and/or passing them through one or more high-speed mixers/densifiers . A high-speed mixer/densifier suitable for this method step is the equipment sold under the trade names "Lodige CE 30" or "Lodige CB 30 Recycler" and consists of a static cylindrical mixing drum with a central axis of rotation and its There are mixing/cutting paddles. In use, the components of the detergent composition enter the drum and the shaft/paddle assembly rotates at a speed of 100-2500 rpm to provide adequate mixing/densification. See US 5 149 455, Jacobs et al., published 22 September 1992. The preferred residence time in the high speed mixer/densifier is about 1-60 seconds. Other such devices include those sold under the tradename "Shugi Granulator" and under the tradename "Drais K-TTP80."

Other treatments that can be used to further densify the spray-dried microparticles include grinding and agglomerating or deforming the spray-dried microparticles in a moderate speed mixer/densifier to obtain particle of. Equipment such as those sold under the trade names "Lodige KM (300 or 600 series)" or "Lodige Ploughshare" mixer/densifier are suitable for this processing step. Typically, such devices operate at a speed of 40-160 revolutions per minute. The residence time of the detergent components in the mixer/densifier at moderate speed is about 0.1-12 minutes. Other available equipment includes that sold under the trade designation "Drais K-T 160". This process step using a moderate speed mixer/densifier (e.g. Lodige KM) can be used alone or in succession with the above mentioned high speed mixer/densifier (e.g. Lodige CB) to achieve the required density. Other types of particle production equipment that may be used herein include that described in US 2 306 898, published December 29, 1942 to G.L. Heller.

While it may be appropriate to use a high speed mixer/densifier followed by a low speed mixer/densifier, the invention also contemplates the use of the reverse order mixer/densifier configuration. One or a combination of parameters may be used, including residence time in the mixer/densifier, operating temperature of the equipment, temperature and/or composition of the particles, use of materials such as liquid binders and flow aids, etc. Auxiliary components in order to achieve optimum densification of the spray-dried microparticles in the process of the invention. As an example, see: US 5 133 924 of Appel et al published on July 28, 1992 (make particles reach a deformable state before densification); US 4 of Dewel et al published on January 20, 1987 637 891 (granulation of spray-dried microparticles with liquid binder and aluminosilicate); US 4 726908 (with liquid binder and aluminosilicate) spray-dried microparticle granulation); and US 5 160 657 (coating densified microparticles with liquid binder and aluminosilicate) to Bortolotti et al., published Nov. 3, 1992.

In those cases where particularly heat sensitive or highly volatile detergent ingredients are added to the final detergent composition, processes which do not involve spray drying towers are preferred. Formulators can dispense the spray-drying step by feeding raw detergent ingredients directly into commercially available mixer/densifiers either in a continuous or batch mode. A particularly preferred embodiment involves charging the pasty surfactant and anhydrous builder materials into a high speed mixer/densifier (e.g. Lodige CB) followed by a moderate speed mixer/densifier (e.g. Lodige KM ), forming high-density detergent aggregates. See US 5 366 652, Capeci et al., published November 22, 1994 and US 5 486 303, Capeci et al., published January 23, 1996. It is also possible in such a process to select the liquid/solid ratio of the raw detergent components to obtain a more free flowing yet friable high density aggregate.

The process may also include one or more recycle streams of undersized fines produced by the process which are returned to the mixer/densifier for further aggregation or bulking. The oversize particles produced by this process can be sent to a comminution unit and then back to the mixer/densifier unit. These additional recycle process steps facilitate bulk agglomeration of the raw detergent composition resulting in a product composition having the desired uniform particle size distribution (400-700 microns) and density (>550 g/l). See US 5 516 448, Capeci et al., published May 14, 1996 and US 5 489 392, Capeci et al., published February 6, 1996. In US 4 828 721, published May 9, 1989 to Bollier et al; US 5 108 646, published April 28, 1992 to Beerse et al; and US 5178 798, published January 12, 1993 to Jolicoeur Other suitable methods that do not require the use of a spray-drying tower are described.

In another embodiment, the high density detergent compositions of the present invention can be produced using a fluid bed mixer. In this process, the various components of the finished composition are combined in an aqueous slurry (typically 80% solids) and sprayed into a fluidized bed to give the finished detergent granules. Prior to the fluidized bed, the process may also include the step of mixing the aqueous slurry using the aforementioned Lodige CB mixer/densifier or the "Flexomix 160" mixer/densifier available from Shugi. Fluidized or moving beds available under the tradename "Escher Wyss" may be used in such processes.

Another suitable method that can be used here involves adding a liquid acidic precursor of anionic surfactant, a basic inorganic material (such as sodium carbonate) and optionally other detergent ingredients to a high speed mixer/densifier (residence time 5-30 seconds) to form aggregates containing partially or fully neutralized anionic surfactant salts and other raw detergent components. The contents of the high speed mixer/densifier can also be sent to a moderate speed mixer/densifier (eg Lodige KB) for further agglomeration to give a finished high density detergent composition. See US 5 164 108, Appel et al., published Nov. 17, 1992.

It is also possible to blend conventional or densified spray-dried detergent particles with detergent aggregates obtained in combination with one or more of the methods discussed herein (for example, the weight ratio of particles to aggregates is 60:40), the high density detergent composition of the present invention can be produced. Additional adjunct components such as enzymes, fragrances, brighteners, etc. may be sprayed on or mixed with the agglomerates, microparticles or mixtures thereof produced by the methods discussed herein. For optimum storage stability, the water content of bleaching compositions in granular form is typically limited to, for example, less than about 7% free water.

Deposition of fragrances on fabric surfaces

A method of laundering fabrics and depositing perfume thereon comprising contacting said fabrics with an aqueous wash liquor comprising at least about 100 mmp of the aforementioned typical detergent ingredients, and at least about 0.1 ppm of the above disclosed detergent additive particulates. Preferably, the aqueous wash liquor contains about 500-20,000 ppm typical detergent ingredients and about 10-200 ppm detergent additive particulates.

Laundry additive microparticles can be useful in any situation, but are particularly useful for providing fragrance during the wash and on wet and dry fabrics. The method comprises contacting fabrics with an aqueous wash liquor containing at least about 100 ppm of normal detergency components and at least about 1 ppm of detergent additive particulates, such that the perfume-containing zeolite particulates are carried onto the fabrics under ambient conditions of at least 20% humidity The fabric is line dried, dried in a conventional automatic dryer, or heated at low temperature (less than about 50° C.) after being line dried or machine dried by conventional ironing methods, preferably with steam or pre-wetting.

The following non-limiting examples illustrate the compositional parameters used in the present invention. All percentages, parts and ratios are by weight unless otherwise indicated.

Example I

The 13X zeolite and perfume were mixed in an 85/15 weight ratio to prepare a perfume-loaded zeolite ("PLZ"). PLZ is thoroughly mixed with intermediate coating oil (ICO) at a ratio of PLZ:ICO of 1:0.5 to 1:1. The mixture is then poured into a solution of about 4 times the weight of the mixture and containing about 25% solid starch. This second mixture is kept under agitation throughout the process using a mixer or a high speed homogenizer such as a tissue homogenizer. The mixture was then poured into a spray dryer at 180-220°C. The process yields a fine powder which is suitable for use as a detergent additive in detergent compositions. The fragrance loaded in the zeolite has the following composition: material name % Violiff 2.5 Frutene 15.0 methyl isobutenyl tetrahydropyran 7.5 Cymal 10.0 Florhydral 15.0 Delta Turkone (Damascone) 15.0 ionone beta 25.0 PTBucinal 10.0

The microparticles formed surprisingly had a superior "net product odor" ("NPO"), and emitted only a minimal detectable odor compared to the base product odor as observed by statistical method mass evaluation grading. This provides strong evidence that the fragrance has not migrated from the carrier particles.

Example II

Several examples of detergent compositions incorporating the perfume particles prepared in Example 1 are given below. Matrix particles 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 (MW=400) 2.0 1.0 -- C _12-13 linear alkylbenzene sulfonate Na 6.0 7.0 8.0 C _14-16 Secondary Alkyl Sulfate Na 3.0 3.0 -- Ethoxylated _C14-15 Alkyl Sulfate Na 3.0 9.0 -- Sodium silicate 1.0 2.0 3.0 Brightener 24/47 ¹ 0.3 0.3 0.3 Sodium carbonate 7.0 26.0 carboxymethyl cellulose -- -- 1.0 DTP MPA ² -- -- 0.5

table (continued) DTPA ³ 0.5 -- -- mixed agglomerates C _14-15 Alkyl Sulfate Na 5.0 -- -- C _12-13 linear alkylbenzene sulfonate Na 2.0 -- -- Sodium carbonate 4.0 -- -- Polyethylene glycol (MW=4000) 1.0 -- -- mix Sodium carbonate -- -- 13.0 C _12-15 Alkyl Ethoxylate (EO=7) 2.0 0.5 2.0 C _12-15 Alkyl Ethoxylate (EO=3) -- -- 2.0 spice spray 0.3 0.4 0.3 Spice Particles ⁴ 0.5 0.5 0.5 polyvinylpyrrolidone 0.5 -- -- Polyvinyl-N-pyridine oxide 0.5 -- -- Polyvinylpyrrolidone-polyvinylimidazole 0.5 -- -- Distearylamine & cumene sulfonate 2.0 -- -- Dirt Release Polymer ⁵ 0.5 -- -- Lipolase (100.000LU/I) ⁶ 0.5 -- 0.5 Termamyl Amylase (60KNU/g) ⁶ 0.3 -- 0.3 CAREZYME® Cellulase (1000CEVU/g) ⁶ 0.3 -- -- Protease (40 mg/g) ⁷ 0.5 0.5 0.5 NOBS ⁸ 5.0 -- -- TAED ⁹ -- -- 3.0 sodium percarbonate 12.0 -- -- Sodium perborate monohydrate -- -- 22.0 Polydimethylsiloxane 0.3 -- 3.0 sodium sulfate -- -- 3.0 Other (water, etc.) margin margin margin Total 100 100 100

1. Buy from Ciba-Geigy

2. Diethylenetriaminepentamethylenephosphonic acid

3. Diethylenetriaminepentaacetic acid

4. From Example I

5. Produced according to US 5 415 807 published on May 16, 1995 by Gosselink et al.

6. Buy from Novo Nordisk A/S

7. Buy from Genencor

8. Nonanoyloxybenzenesulfonate

9. Tetraacetylethylenediamine

Example III

The detergent compositions of the present invention described below are suitable for use in both machine and hand washing operations. The matrix particles are prepared by the usual spray drying method, in which the raw material components are made into a slurry and passed through a spray drying tower with hot air convection (200-400° C.) to form porous particles. The remaining adjunct detergent ingredients are sprayed on the granules, or added to the dry granules. Matrix particles A B C C _12-13 Alkylbenzenesulfonate Na 19.0 18.0 19.0 Cationic Surfactant ¹ 0.5 0.5 -- DTPMAP ² 0.3 -- -- DTPA ³ -- 0.3 -- sodium tripolyphosphate 25.0 19.0 29.0 Acrylic/maleic acid copolymer 1.0 0.6 -- carboxymethyl cellulose 0.3 0.2 0.3 Brightener 49/15/33 ⁴ 0.2 0.2 0.2 sodium sulfate 28.0 39.0 15.0 Sodium silicate (2.0R) 7.5 -- -- Sodium silicate (1.6R) -- 7.5 6.0 mix Quantum (zinc phthalocyanine sulfonate) 2.0 2.0 2.0 Sodium carbonate 5.0 6.0 20.0 C _12-13 Alkyl Ethoxylate (EO=7) 0.4 -- 1.2

table (continued) Sayinase ⁵ protease (4KNPY/g) 0.6 -- 1.0 Termamyl ⁵ Amylase (60KNU/g) 0.4 -- -- Lipolase ⁵ lipase (100 000LU/I) 0.1 0.1 0.1 Sav/Ban5(6KNPU/100KNU/g) -- 0.3 -- CAREZYME®5 Cellulase (1000CEVU/g) -- 0.1 -- Dirt Release Polymer ⁶ 0.1 0.1 0.3 spice spray 0.4 0.4 0.4 Spice Particles ⁷ 1.5 1.5 2.0 Other (water, etc.) margin margin margin Total 100.0 100.0 100.0

1. C _12-14 dimethyl hydroxyethyl quaternary ammonium compound

2. Diethylenetriaminepentamethylenephosphonic acid

3. Diethylenetriaminepentaacetic acid

4. Buy from Giba-Geigy

5. Buy from Novo Nordisk A/S

6. Produced according to US 5 415 807 published on May 16, 1995 by Gosselink et al.

7. From Example I

Example IV

The following detergent compositions according to the invention are in the form of washing bars which are especially suitable for use in hand washing operations.

%weight

Coconut Fatty Alkyl Sulfates 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(CO ₃ ) ₂ 15.0

Aluminosilicate 2.0

Coconut Fatty Alcohol 2.0

Spice Particles ¹ 1.0

Fragrance Spraying 1.0

Other (water, etc.) balance

Total 100.0

1. From Example I

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 should not be considered limited to the description. described in the content.

Claims (37)

1. An additive delivery particle comprising: (i) 5-50% by weight of central core particles, the core particles contain a porous carrier material, and additives contained in the pores of the porous carrier material; the additives are selected from the group consisting of perfumes, bleaching agents, Bleach Accelerators, Bleach Activators, Bleach Catalysts, Chelating Agents, Antiscalants, Threshold Inhibitors, Dye Transfer Inhibitors, Photobleaches, Enzymes, Catalytic Antibodies, Brighteners, Direct Fabric Dyeing Dyes, Antifungal Agents, Antimicrobials, insect repellants, soil release polymers, fabric softeners, color fixatives, pH gradient systems and mixtures thereof; (ii) 1-40% by weight of an intermediate coating material coated on the central core particle, the intermediate coating material containing a hydrophobic oil material; and (iii) 10-94% by weight of an outer lagging material coated on said intermediate coating material; said outer lagging material containing one or more wash-dissolving or dispersing 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, C ₁₀ -C ₃₅ fatty compounds and mixtures thereof. 2. The additive delivery particle of claim 1, wherein said intermediate hydrophobic oil coating material has a calculated logP lower than the calculated logP of the additive material contained in the porous carrier material. 3. The additive delivery particle of claim 2 comprising: (i) 5-50% by weight of the central core particle comprising 60-99% porous carrier material and 1-40% additive material by weight of the core particle, (ii) 1-40% by weight of said intermediate hydrophobic coating material, and (iii) 10-94% by weight of the external lagging material. 4. Additive delivery particles according to claim 3, wherein said porous support material is a zeolite selected from the group consisting of type X zeolites, type Y zeolites and mixtures thereof. 5. The additive delivery particle according to claim 3, wherein said additive carried in said carrier is a fragrance. 6. The additive delivery particle of claim 3, wherein said intermediate hydrophobic coating material is perfume oil. 7. The additive delivery particle of claim 3, wherein said outer coating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. 8. The additive delivery particle of claim 3, comprising: (i) 5-50% by weight of the central core particle containing 60-99% zeolite as the porous carrier material based on the weight of the core particle, and 1-40% fragrance, (ii) 1-40% by weight perfume oil as an intermediate coating material, and (iii) 10-94% by weight of starch or modified starch as the external encapsulation material. 9. The additive delivery particle of claim 8, wherein the weighted average calculated logP value of said fragrance loaded on said zeolite support is 1.0-16.0. 10. The additive particle according to claim 9, wherein the weighted average calculated logP value of said fragrance loaded on said zeolite support is 3.0-4.5. 11. The additive delivery microparticle of claim 9, wherein the weighted average calculated logP value of the perfume oil used as an intermediate coating material is lower than the weighted average calculated logP value of the perfume loaded in the porous carrier. 12. The additive delivery microparticle of claim 11, wherein the mid-coat perfume oil material has a highest calculated logP value that is lower than the lowest calculated logP value of the perfume loaded in the porous carrier. 13. The additive delivery microparticle of claim 12, wherein the difference between the highest calculated logP value of the mid-coat perfume oil material and the lowest calculated logP value of the perfume loaded in the porous carrier is at least one unit. 14. The additive delivery microparticle of claim 13, wherein the difference between the highest calculated logP value of the mid-coat perfume oil material and the lowest calculated logP value of the perfume loaded in the porous carrier is at least two units. 15. The additive delivery particle of claim 8 wherein said fragrance loaded in said zeolite carrier comprises a high potency fragrance characterized by: (1) A normal boiling point of 275°C or less at 760 mm Hg; and (2) Calculated logP or experimental logP of 2 or higher; and (3) The odor detection threshold is less than or equal to 50ppb, but greater than 10ppb. 16. The additive delivery particle of claim 8, wherein said perfume oil used as an intermediate coating material contains a high potency perfume characterized by: (1) A normal boiling point of 275°C or less at 760 mm Hg; and (2) Calculated logP or experimental logP of 2 or higher; and (3) The odor detection threshold is less than or equal to 50ppb, but greater than 10ppb. 17. The additive delivery particle of claim 8 comprising: (i) 10-40% by weight of said central core particle; (ii) 10-30% by weight of perfume oil as an intermediate coating material; and (iii) 30-80% by weight of starch or modified starch as external encapsulating material. 18. A washing or cleaning detergent composition comprising a) 0.001-50% by weight of the composition of additive delivery particles containing (i) 5-50% by weight of central core particles, the core particles contain a porous carrier material and additives contained in the pores of the porous carrier material; the additives are selected from perfumes, bleaching agents, bleach accelerators , bleach activators, bleach catalysts, chelating agents, anti-fouling agents, low limit inhibitors, dye transfer inhibitors, photobleaching agents, enzymes, catalytic antibodies, brighteners, fabric direct dyes, antifungal agents, antibacterial agents, Insect repellants, soil release polymers, fabric softeners, color fixatives, pH gradient systems and mixtures thereof; (ii) 1-40% by weight of an intermediate coating material coated on the central core particle; the intermediate coating material contains a hydrophobic oil material; and (iii) 10-94% by weight of an outer lagging material coated on said intermediate coating material; said outer coating material containing one or more wash-dissolving or dispersing 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, C ₁₀ -C ₃₅ fatty compounds and mixtures thereof; as well as b) From 50 to 99.999% by weight of the composition, a detersive component selected from detersive surfactants, builders, bleaches, enzymes, soil release polymers, dye transfer inhibiting agents, fillers and mixtures thereof. 19. A washing or cleaning detergent composition according to claim 18 comprising at least one detersive surfactant and at least one builder. 20. A washing or cleaning detergent composition according to claim 18 wherein said porous support material is a zeolite selected from the group consisting of X zeolites, Y zeolites and mixtures thereof. 21. A washing or cleaning detergent composition according to claim 18, wherein said external encapsulating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. 22. A washing or cleaning detergent composition according to claim 18 wherein said central core particle is a perfume loaded zeolite. 23. A washing or cleaning detergent composition according to claim 22 wherein said perfume carried in said zeolite carrier comprises a high potency perfume characterized by: (1) A normal boiling point of 275°C or less at 760 mm Hg; and (2) Calculated logP or experimental logP of 2 or higher; and (3) The odor detection threshold is less than or equal to 50ppb, but greater than 10ppb. 24. A washing or cleaning detergent composition according to claim 23, wherein said intermediate coating on the core particle comprises a perfume oil. 25. A washing or cleaning detergent composition according to claim 24 wherein said mid-coat perfume oil comprises a high potency perfume characterized by: (1) A normal boiling point of 275°C or less at 760 mm Hg; and (2) Calculated logP or experimental logP of 2 or higher; and (3) The odor detection threshold is less than or equal to 50ppb, but greater than 10ppb. 26. A washing or cleaning detergent composition according to claim 25, wherein said external encapsulating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. 27. A washing or cleaning detergent composition according to claim 22, wherein said perfume carried by said zeolite carrier has a weighted average calculated logP value of 1.0-16.0. 28. A washing or cleaning detergent composition according to claim 27, wherein said perfume carried by said zeolite carrier has a weighted average calculated logP value of 3.0-4.5. 29. A washing or cleaning detergent composition according to claim 24, wherein said perfume oil used as an intermediate coating material has a weighted average calculated logP value which is lower than the weighted average calculated logP value of the perfume carried in said zeolite carrier. LogP values were averaged. 30. A washing or cleaning detergent composition according to claim 29, wherein the highest calculated logP value of said mid-coat perfume oil material is lower than the lowest calculated logP value of the perfume loaded in said zeolite carrier. 31. A washing or cleaning detergent composition according to claim 30, wherein the difference between the highest calculated logP value of said mid-coat perfume oil material and the lowest calculated logP value of the perfume loaded in said zeolite carrier for at least two units. 32. The additive delivery microparticle of claim 1, wherein said additive contained in the pores of said porous support material is selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes spices and mixtures thereof. 33. The additive delivery microparticle of claim 1, wherein said intermediate coating material is a perfume selected from the group consisting of _C6 - _C14 aliphatic aldehydes, _C6 - _C14 membered ring terpene aldehydes, and mixtures thereof. 34. The additive delivery microparticle of claim 1, wherein said fragrance is selected from the group consisting of _C6 - _C14 aliphatic aldehydes, _C6 - _C14 acyclic terpene aldehydes, and mixtures thereof. 35. The additive delivery microparticle of claim 6, wherein said fragrance oil is selected from the group consisting of _C6 - _C14 aliphatic aldehydes, _C6 - _C14 acyclic terpene aldehydes, and mixtures thereof. 36. A washing or cleaning detergent composition comprising: a) 0.001-50% by weight of the composition of additive delivery microparticles containing (i) 5-50% by weight of central core particles, the core particles contain a porous carrier material and additives contained in the pores of the porous carrier material; the additives are selected from the group consisting of C ₆ -C ₁₄ aliphatic Fragrances of aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof; (ii) 1-40% by weight of an intermediate coating material coated on the central core particle; the intermediate coating material contains a hydrophobic oil material; and (iii) 10-94% by weight of an outer lagging material coated on said intermediate coating material; said outer coating material containing one or more wash-dissolving or dispersing 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, C ₁₀ -C ₃₅ fatty compounds and mixtures thereof; as well as b) 50-99.999% by weight of the composition of a detersive component selected from detersive surfactants, builders, bleaches, enzymes, soil release polymers, dye transfer inhibiting agents, fillers and mixtures thereof. 37. A washing or cleaning detergent composition according to claim 36, wherein the intermediate coating material is selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof spices.

Images