KR100466468B1 - Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes - Google Patents

Abstract

The present invention relates to additive delivery systems that are protected from release until exposed to a wet or damp environment, which is incorporated into a variety of consumer products including detergents and cleaning compositions, indoor deodorants, pesticide compositions, carpet cleaners and deodorants. In particular, the additive delivery system of the present invention encapsulates a core of a porous carrier material containing an additive such as a fragrance in a pore of the porous carrier material, a first coating of hydrophobic oil encapsulating the core and a hydrophobic oil coated core, Particles comprising a second coating of a water soluble or water dispersible but oil insoluble material such as starch or modified starch. The delivery particles of the invention can be used to deliver laundry and detergents into or through the wash cycle. The laundry additive delivery particles according to the present invention effectively deliver the perfume component to the fabric surface through washing.

Description

Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes}

Most consumers have expected that fragrant laundry products and washed fabrics also have a pleasant orientation. In many parts of the world, hand washing is a major means of washing textiles. In the case of handwashing soiled fabrics, the user often comes into contact with the cleaning solution and is in close proximity to the detergent product used. Hand wash solutions can also cause unpleasant odors when adding soiled clothing. Therefore, it is desirable to add fragrance material to the article and it is commercially advantageous. Fragrance additives make the laundry composition more aesthetically pleasing to the consumer, and in some cases, fragrances provide a pleasant aroma to the treated fabric. However, the amount of perfume delivered to the fabric in an aqueous laundry bath is often not enough. Thus, the industry is not only providing sustained storage-stable aromas to the product, but also releasing the aromas during use to block odors of the wettable solution and to deliver the aromas to the washed fabric, which is an effective aroma for use in detergent products. We have long studied the delivery system.

In addition, after the fabric has been sun dried, the fabric has a "sun-dried type" odor. Consumers often prefer this odor as the standard fragrance odor. Consumers also often think of fabrics with this smell as cleaner. Since the consumer likes the smell, the consumer prefers to dry the fabric in daylight. However, in some countries, consumers cannot dry the fabric outdoors because the air is not clean or it rains too much. As a result, they have to dry the fabrics indoors and cannot expect to enjoy the benefit of having a "sun-dried type" odor on their fabrics.

It has now been found a detergent composition comprising a fragrance that can provide an "sun-dried type" odor.

Laundry and other fiber protection compositions containing fragrances mixed with or sprayed onto the composition are well known from commercial practice. Since fragrances are prepared in combination of volatile compounds, fragrances can be continuously released from simple solutions and dry mixtures to which the fragrance is added. The composition will remain esthetically pleasing for a longer period of time as various techniques have been developed to prevent or delay the release of perfume from the composition. However, to date, there are few ways to deliver significant fabric odor benefits even after the extended storage period of the product.

In addition, ongoing research has been conducted on methods and compositions for effectively and efficiently delivering perfume from the wash bath to the fabric surface. As can be appreciated from the specification that follows, various methods of perfume delivery have been developed with regard to protecting perfume and releasing it onto fabric during the wash cycle. US Pat. No. 4,096,072, issued to Brock et al. On June 20, 1978, teaches a method of delivering textile conditioning agents, including fragrances, through fatty quaternary ammonium salts during washing and drying cycles. US Pat. No. 4,402,856, issued to Schnoring et al. On September 6, 1983, teaches microencapsulation techniques related to the formulation of shell materials that diffuse perfume out of capsules only at certain temperatures. US Pat. No. 4,152,272, issued to Young on May 1, 1979, teaches the introduction of perfume into waxy particles to protect the perfume during storage and during the laundry process as a dry composition. The fragrance is reliably diffused into the fabric through the wax in the dryer. US Pat. No. 5,066,419, issued to Walley et al. On November 19, 1991, is encapsulated in a protective sheath by dispersing with a water-insoluble nonpolymeric carrier material and coating with a water-insoluble brittle coating material. Teaching the aroma. US Pat. No. 5,094,761, issued to Trinh et al. On March 10, 1992, teaches clay protected perfume / cyclodextrin complexes that at least partially provide a fragrance benefit to the wettable fabric.

Another method of delivering perfume during the wash cycle involves mixing the perfume with an emulsifier and a water soluble polymer, forming the mixture into particles and adding it into the laundry composition, which is described in US Pat. No. 4,209,417, 1980. Granted to Whyte on 24th of February; US Patent No. 4,339,356, issued to Whyte on July 13, 1982; And US Patent No. 3,576,760, issued to Gould et al. On April 27, 1971. However, in practical work performed industrially in the art, for a simple, more efficient and effective perfume delivery system that can be blended with the laundry composition to provide a long lasting perfume benefit from the fabric treated with the laundry product. The need still exists.

Fragrances may also be adsorbed onto porous carrier materials, such as polymeric materials, as described in British Patent Publication No. 2,066,839, published by Bares et al., July 15, 1981. The fragrance is also adsorbed onto clay or zeolite material and then mixed into the particulate detergent composition. Generally, preferred zeolites are type A or 4A zeolites having a nominal pore size of about 4 mm 3 units. Currently, when using zeolite A or 4A, the fragrance is adsorbed on the zeolite surface, but the fragrance that is substantially adsorbed into the zeolite pores is considered relatively small. While adsorption of fragrances onto zeolites or polymeric carriers may provide some improvement to the addition of pure fragrances mixed with detergent compositions, the industry has shown that in the strength and amount of fragrance released during the cleaning process and delivered to the fabric, And in the duration of the fragrance odor on the treated fabric surface, there is still a study for improvement in extending the shelf life of the laundry composition without losing the fragrance properties.

It is also taught in the art to mix fragrances with zeolites X and Y of generally larger pore sizes. German Patent Publication No. 248,508, published August 12, 1987, discloses a fragrance dispenser (e.g., containing a faujasite-type zeolite (e.g., zeolites X and Y) filled with a fragrance. Air purifier). Critical molecular diameters of the perfume molecules are mentioned on the order of 2 to 8 mm 3. Further, East German Patent Publication No. 137,599, published on Sep. 12, 1979, teaches compositions for use in powdered detergents that provide temperature controlled release of fragrances. Zeolites A, X and Y are taught for use in such compositions. These early teachings are published in European Publication Application No. 535,942, published April 7, 1993, and 536,942, published April 14, 1993, more recently by Unilever PLC; And US Pat. No. 5,336,665, issued August 9, 1994 to Garner-Gray et al.

Effective perfume delivery compositions are taught in WO 94/28107, published December 8, 1994 by The Procter & Gamble Company. Such compositions include zeolites having a pore size of at least 6 mm 3 (eg zeolite X or Y), fragrances releasably introduced into the pores of the zeolites, and matrices coated on the fragrance introduced zeolites, wherein the matrix is 3 A water soluble (washable) composition comprising 0% to about 80% by weight of at least one solid polyol containing at least one hydroxyl moiety and from about 20% to about 100% by weight of a fluid diol or polyol, wherein said The fragrance is substantially insoluble and the solid polyol is substantially soluble.

Other perfume delivery systems are taught in WO 97/34982 and WO 98/41607 published by The Procter & Gamble. WO 97/34982 describes particles comprising fragrance filled zeolites and release blockers, wherein the release blockers are derived from wax and have a larger size (ie cross-sectional area) than the pore size of the zeolite carrier. Having a formulation. WO 98/41607 describes glassy particles comprising formulations useful in laundry or cleaning compositions and glass derived from at least one hydroxyl-based compound that is at least partially water soluble. Preferred formulations are fragrances in zeolite carriers.

Another problem that may arise when providing a perfume filled product is the excessive odor strength associated with the product. Accordingly, there is a need for a perfume delivery system that provides satisfactory fragrance odor during and after use, but also from dried laundry fabrics, but also provides extended storage benefits and reduced product odor strength.

According to the present invention, a perfume filled into a porous carrier, such as a zeolite particle, is now coated with a hydrophobic oil and then the oil-coated perfume-filled carrier particle is water soluble or water dispersible, but oil-insoluble. It has been found that by encapsulating with a phosphorus material, for example starch or modified starch, it can effectively protect the fragrance against early release. The porous carrier may be chosen to penetrate directly into the fabric to allow sufficient deposition of perfume on the fabric to deliver a noticeable odor benefit even after the fabric has dried.

The present invention addresses the long-term need for a simple, effective and storage-stable fragrance delivery system that provides a odor benefit recognizable to consumers during and after the laundry process and that reduces product odor during storage of the composition. Solve. In particular, fabrics treated with the perfume delivery system of the present invention have a higher odor intensity and retain fragrance for longer periods of time after washing and drying.

The present invention also provides a delivery system for other additives, wherein the product comprising the additive is protected from desirably releasing until exposed to a wet or moist environment.

Summary of the Invention

The present invention relates to a delivery system for additives introduced into a variety of consumer products, including detergents and cleaning compositions, indoor deodorants, pesticide compositions, carpet cleaners and deodorants, wherein the additives may be exposed to a wet or moist environment. Protected from release until In particular, the additive delivery system of the present invention comprises a core of a porous carrier material containing an additive such as a fragrance in its aperture, a first coating of hydrophobic oil encapsulating the core, and a starch or modification encapsulating the hydrophobic oil coated core. Particles comprising a second coating of a water soluble or water dispersible but oil-insoluble material such as starch. The delivery particles of the invention can be used to deliver laundry and detergent into or during the wash cycle. The laundry additive delivery particles according to the present invention effectively deliver the fragrance components to the fabric surface via washing.

In conventional perfume delivery systems, at least 50% of the perfume material is "waste" by diffusion of volatile perfume material from the product or by dissolution during washing and is not delivered to the fabric surface. In the present invention, the coating effectively encapsulates the perfume material into the carrier core. Thus, the perfume material is delivered to the fabric surface at a higher level through washing than using conventional perfume delivery systems.

Porous carrier materials typically include zeolites, macroporous zeolites, amorphous silicates, crystalline non-layered silicates, layered silicates, calcium carbonate, calcium carbonate / sodium carbonate double salts, sodium carbonate, clay, sodalite, alkali metal phosphates, chitin fine beads, carboxy Alkylcelluloses, carboxyalkyl starches, cyclodextrins, porous starches, and mixtures thereof. Preferably, the carrier material is a zeolite such as zeolite X, zeolite Y and mixtures thereof.

Particularly preferred porous carriers are zeolites having a nominal pore size of at least about 6 mm 3 for the effective introduction of the fragrance into its pores. Without being limited by theory, such zeolites are believed to provide a channel or cage-type structure in which perfume molecules are encapsulated. Unfortunately, the perfume filled zeolites are not sufficiently storage-stable for commercial use in granular fabric protection products such as laundry detergents, especially due to premature release of the perfume upon moisture absorption. However, up to the present application, the perfume-filled zeolite is first coated with a hydrophobic oil to form a barrier for encapsulating and maintaining the perfume in the zeolite pores, and then the oil coating with a water soluble or water dispersible but oil-insoluble material. It has been found that the zeolite particles can be protected by encapsulating the particles. Thus, the fragrance remains substantially in the pores of the zeolite particles. In addition, because the fragrance is introduced into relatively large zeolite pores, the fragrance retention is better during the laundering process than the smaller pore size zeolites where the fragrance is mainly adsorbed on the zeolite surface.

The hydrophobic oil coating may be a non-aromatic oil, but is preferably a fragrance which may be the same as or different from the aromatic oil filled into the carrier. When the encapsulated particles of the invention are added to water, such as during washing, the water soluble or water dispersible encapsulation material dissolves and begins to release the oil coating. If this oil coating is a perfume, the perfume component is released from the wash solution to provide a wettable odor benefit. Carrier particles filled with perfume are released into the wash solution and deposited on the fabric. After the fabric is dried, the fragrance is released from the carrier when moisture in the atmosphere displaces the fragrance contained in the carrier hole, providing a dry odor benefit.

Additives contained in the porous carrier core are preferably fragrances, bleaches, bleach promoters, bleach activators, bleach catalysts, chelating agents, antiscalants, dye transfer inhibitors, photobleaches, enzymes, catalytic antibodies, brighteners, textiles -Dye dyes, antifungal agents, antimicrobial agents, insect killers, stain release polymers, fabric softeners, dye fixatives, pH raising systems, and mixtures thereof.

Preferred laundry additives filled into the porous carrier material are fragrances. Preferably, the particle core is a perfume-filled zeolite (PLZ).

Preferred encapsulating materials are starch, modified starch or starch hydrolysates, while preferred oil coating materials are aromatic oils. The outer encapsulating material may further comprise a component selected from the group consisting of plasticizers, anti-aggregates, and mixtures thereof.

In a further specific embodiment of the present invention, a laundry or cleaning detergent composition is provided. The laundry or cleaning composition comprises about 0.001% to about 50% of the laundry additive agent particles as described above per weight of the composition, and a detergent surfactant, builder, bleach, enzyme, stain release polymer, dye transfer inhibitor, filler and mixtures thereof. Washing components selected from about 50% to about 99.999% by weight of the composition. Preferably, the composition comprises at least one detergent surfactant and at least one builder.

It is therefore an object of the present invention to deliver additives having at least two surface coatings comprising a core filled with an additive, preferably a laundry additive such as a fragrance, and an intermediate hydrophobic oil coating and an outer encapsulation coating of a water soluble or water dispersible material. To provide particles. Another object of the present invention is to provide a laundry and cleaning composition having laundry additive particles on its surface. It is a further object of the present invention to provide laundry additive additive particles which can provide improved fabric odor benefits, extend shelf life and reduce product odor strength. 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 the appended claims.

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

The present invention relates to delivery particles, in particular particles for the delivery of laundry additives such as fragrances, and detergent compositions, in particular granular detergents, comprising said delivery particles.

1 shows an SEM for a full average sized laundry additive particle comprising encapsulated perfume-filled zeolite particles according to the present invention.

FIG. 2 shows an SEM of the cross section of a particle according to the invention, containing zeolite particles packed into a starch coating.

The present invention relates to laundry and cleaning compositions comprising laundry additive particles and laundry additive particles, preferably perfume-containing particles. Laundry and cleaning compositions include granular bleach, automatic dishwashing, hard surface cleaning, and fabric softening compositions as well as conventional granular laundry detergents. The laundry additive particle of the present invention provides excellent perfume delivery capability through washing and minimizes product odor due to the release of volatile fragrance components. Without being bound by theory, it is also believed that the specified coatings of the particles of the present invention increase the stability of the particles.

Preferred laundry particles of the present invention comprise a core of a porous carrier filled with a fragrance, the filled core being first coated with a hydrophobic oil material and then of a water soluble or water dispersible but oil-insoluble material such as starch or modified starch. Encapsulated with an outer coating to produce final particles.

Preferably, the laundry additive agent particles of the present invention have a hygroscopic value of about 80% or less. As used herein, "hygroscopicity value" means the degree of moisture uptake by the particles, as measured by the percent increase in weight of the particles under the following test method. The hygroscopic value required for the particles of the present invention is determined by placing 2 g of particles in an open container petri dish under conditions of 90 ° F. and 80% relative humidity for 4 weeks. The percent increase in weight of the particles at the end of this period is the hygroscopic value of the particles as used herein. Preferred particles of the invention have a hygroscopic value of about 50% or less, more preferably about 30% or less.

Laundry additive additive particles of the invention are themselves from about 60% to about 90% of porous carrier and from about 1% to about 40% of fragrance or other laundry additive material, typically from about 5% to about filled core core particles. 50%, about 1% to about 40% hydrophobic oil intermediate coating material, and about 10% to about 94% external encapsulation material.

Filled Center Core Particles

As mentioned above, the central core of the additive particles comprises a porous carrier material and a laundry additive added to the carrier material. The two components of the central core can be mixed in many different ways.

On a laboratory scale, the basic apparatus used for this purpose can vary from 10 to 20 g coffee grinder to 100 to 500 g food processor or even 200 to 1000 g kitchen mixer. The process consists of placing and mixing carrier material particles (zeolites) in the apparatus while simultaneously pouring laundry additives. Mixing time is 0.5 to 15 minutes. The charged carrier material (zeolite) is then left for a period of 0.5 to 48 hours before further processing is carried out. During the charging process in which exotherm occurs, a cooling shroud can optionally be used. At the small test plant level, a suitable device is a Littleford type mixer, which is used to plow and ax blades operated at high RPM to continuously mix the powder or mixture of powders while the liquid aromatic oil is sprayed on it. Having a kind of batch type mixer.

Porous carrier material

Porous carrier materials as used herein are all materials capable of supporting (eg, absorbing into a pore) a deliverable formulation such as laundry or detergent. The material includes a porous solid such as zeolite.

Preferred zeolites are selected from zeolite X, zeolite Y and mixtures thereof. As used herein, the term “zeolite” means a crystalline aluminosilicate material. The structural formula of the zeolite is the minimum unit structural formula Mm / n [(AlO ₂ ) m (SiO ₂ ) y] .xH ₂ O (where n is the valence of the cation M and x is the number of water molecules per unit cell). Number, m and y are the total number of tetrahedrons per unit basal tissue, and y / m is from 1 to 100). Most preferably, y / m is 1-5. The cation M can be a Group IA and Group IIA element such as sodium, potassium, magnesium and calcium.

Zeolites useful herein are pozacite-type zeolites, including X-type zeolites or Y-type zeolites, which typically have a pore size in the range of about 4 to about 10 microns, preferably about 8 microns.

Aluminosilicate zeolite materials useful in the practice of the present invention are commercially available. Methods for preparing X and Y zeolites are known and available in standard textbooks. Preferred synthetic crystalline aluminosilicate materials useful herein are available under the designation Form X or Form Y.

In an illustrative and non-limiting manner, in a preferred specific embodiment, the crystalline aluminosilicate material is Form X and is selected from:

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

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

(III) Ca ₄₀ Na ₆ [AlO ₂ ] _86. (SiO ₂ ) ₁₀₆ ] .xH ₂ O,

(IV) Sr ₂₁ Ba ₂₂ [AlO ₂ ] _86. (SiO ₂ ) ₁₀₆ ] .xH ₂ O, or mixtures thereof, wherein x is from about 0 to about 276. Zeolites of formulas (I) and (II) have a nominal pore size or opening in units of 8.4 mm 3. Zeolites of formulas (III) and (IV) have nominal pore sizes or openings in units of 8.0 mm 3.

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

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

(VI) K ₅₆ [AlO ₂ ] ₅₆占 (SiO ₂ ) ₁₃₆ ] xH ₂ O and mixtures thereof, wherein x is from about 0 to about 276. Zeolites of formulas (V) and (VI) have a nominal pore size or opening in units of 8.0 mm 3.

In another specific embodiment, the zeolite class known as “zeolite MAP” may also be used in the present invention. Such zeolites are described and described in US Patent Application Serial No. 08 / 716,147, entitled "Zeolite MAP and Alcalase for Improved Fabric Care," filed September 16, 1996.

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

The size of the zeolite particles allows for incorporation of these particles into the fabric into which the particles come into contact. Once settled on the fabric surface (with the coating removed by washing during the washing process), the zeolites can initiate the release of their introduced laundry detergents, especially when exposed to heat or wet conditions.

Intermediate oil coating material

The intermediate oil coating material according to the invention forms a coating on the central core particles. Intermediate coatings provide a barrier that minimizes the release or leakage of any deliverable agent, such as a perfume, incorporated into the porous carrier. The intermediate coating material may comprise a fragrance oil, which may be the same as or different from the fragrance filled into the carrier, or a hydrophobic oil such as a non-aromatic oil such as mineral oil. The hydrophobic oil may preferably be one or a mixture of organic compounds having a metered average ClogP which is lower than the metered average ClogP of the adduct material or mixture filled in the pores of the carrier. ClogP values are typically used to characterize the perfume component by its octanol / water partition coefficient P. The octanol / water partition coefficient of the perfume component is the ratio between its equilibrium concentration in octanol and water. The higher the hydrophobic material, the higher its ClogP. Thus, the intermediate oil coating material is preferably less hydrophobic than the additive material contained in the porous carrier.

More preferably, the highest ClogP of the material comprising the hydrophobic oil coating is lower than the lowest ClogP of the material comprising the additive added to the porous carrier. Even more preferably, there is a difference of at least one unit and most preferably two units between the highest ClogP of the hydrophobic oil coating material and the lowest ClogP of the filled additive material.

Outer encapsulation material

The outer encapsulation material is coated on the intermediate coating material coated on the core particles to provide an outer layer of the final particles. The outer coating material provides a substantially non-tacky or non-tacky coating for the final particle. Preferably, the outer coating provides particles that will have a non-viscous surface at high humidity conditions such as 80% relative humidity at 90 ° F.

The outer coating is a material derived from one or more compounds that are at least partially wash-soluble or dispersible. That is, the outer coating will be soluble or dispersible in an aqueous washing environment. Compounds useful herein are preferably selected from the class of the following materials.

1.i) starch comprising modified starch and starch hydrolysate, ii) oligosaccharides (defined as carbohydrate chains of 2 to 35 monosaccharide molecules), iii) polysaccharides (comprising at least 35 monosaccharide molecules) Carbohydrates, which may be defined as carbohydrate chains), iv) simple sugars (or monosaccharides) and hydrides of v) i), ii), iii) and iv) or mixtures thereof.

Both linear and branched carbohydrate chains can be used. Additionally, chemically modified starches and poly / oligo-saccharides can be used. Typical modifications include the addition of hydrophobic moieties in the form of alkyl, aryl, and the like as found in surfactants to impart specific surface action to the compound.

2. All natural or synthetic rubbers such as alginate esters, carrageenan, agar-agar, pectinic acid, and natural rubbers (eg, gum arabic, tragacanth and karaya rubbers).

3. Chitin and Chitosan.

4. Cellulose and Cellulose Derivatives. Examples include i) cellulose acetate and cellulose acetate phthalate (CAP), ii) hydroxypropyl methyl cellulose (HPMC), iii) carboxymethylcellulose (CMC), iv) all enteric / aqueous coatings and mixtures thereof.

5. Silicates, phosphates and borates.

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

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

8. Plasticizer.

9. Long chain (C _10-35 ) fatty compounds comprising fatty acids, fatty alcohols and fatty acid esters.

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

Materials belonging to this class that are not at least partially washable or dispersible are useful herein only if the compounds useful herein and the particles resulting from mixing in such amounts have a desirable hygroscopic value of about 80% or less. It is also preferred that the compound is low temperature processable, preferably about 50 ° C to about 200 ° C, and more preferably about 60 ° C to about 180 ° C.

Preferred encapsulating materials are, for example, starches or modified starches such as CAPSUL ^™, commercially available from National Starch, cellulose and cellulose derivatives such as hydroxy propyl methyl cellulose, other carbohydrates such as sucrose and fructose, gum arabic and guar. Natural polymers such as rubber, natural proteins, and water soluble polymers such as polyethylene glycol.

The outer encapsulation coating can include any additive component such as a plasticizer, an anticoagulant, and mixtures thereof. Optional plasticizers include sorbitol, polyethylene glycol, propylene glycol, low molecular weight carbohydrates, and mixtures thereof with sorbitol and polyethylene glycol, and the like, with low molecular weight polyols being most preferred. Plasticizers are used at levels of about 0.01% to about 5%. The anticoagulant according to the invention is preferably a surfactant and comprises at low levels of 1% or less of the outer coating. Suitable surfactants for use in the present invention include TWEEN ^™ 80 (commercially available from Imperial Chemicals, Inc. (ICI)).

Laundry and cleaning additives

Laundry and cleaning additives or formulations are included in the particles of the invention. The agent is contained in the porous carrier material as described herein above. As can be appreciated for the present invention, the formulation introduced into the particles of the present invention may be the same or different than the formulation typically used to formulate the remainder of the laundry and cleaning composition containing the particles. For example, the particles may contain perfume and the (same or different) perfume may also be mixed (eg, by surface spraying techniques) into the final composition with the perfume-containing particles. The formulation is preferably selected for the type of composition to be formulated, such as granular laundry detergent compositions, granular automated dishwashing compositions, or hard surface cleaners.

The laundry particles of the present invention can of course be included in compositions that may contain other ingredients. A composition containing laundry additive particles may be used to aid or enhance cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (eg, fragrances, colorants, dyes, etc.) Detergent additives or other materials may optionally be included.

air freshener

Preferred laundry or cleaning additives according to the invention are perfume materials. As used herein, the term “fragrance” refers to all aromatic substances that are subsequently released into the aqueous bath in contact with and / or to the fabric surface or to another surface. Perfume will often be liquid at ambient temperature. A wide variety of chemicals are known for perfume use and include aldehydes, in particular C _6-14 aliphatic aldehydes, C _6-14 acyclic terpene aldehydes and mixtures thereof, ketones, alcohols and esters. More generally, the use of natural vegetable and animal oils and exudate, including complex mixtures of various chemical components, as perfumes is known. The fragrances herein can include relatively complex mixtures of all natural and synthetic chemical components selected so that their composition can be relatively simple or provide any desired odor. Typical fragrances may include woody / soil bases containing foreign substances such as, for example, sandalwood oil, musk and patchouli oil. The fragrance may be of light flower fragrance, for example rose extract, violet extract and lilac. Perfumes can also be formulated to provide the desired fruity odors such as lime, lemon and orange odors. Any chemically miscible substance that emits a pleasant or other desirable odor can be used in the perfume treated composition herein.

If the "sun dried" odor is the preferred odor, the fragrance component is selected from the group consisting of C _6-14 aliphatic aldehydes, C _{6-14 acyclic} terpene aldehydes and mixtures thereof. Preferably, the perfume component is selected from C _8-12 aliphatic aldehydes, C _8-12 acyclic terpene aldehydes and mixtures thereof. Most preferably, the fragrance component is citral, neural, iso-citral, dihydro citral, citronellal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, 2-methyl deca Nal, methyl nonyl acetaldehyde, 2-nonene-1-al, decanal, undecanal, undecylenic acid aldehyde, 2,6-dimethyl octanal, 2,6,10-trimethyl-9-undecen-1-al , Trimethyl undecanal, dodecenal, melonal, 2-methyl octanal, 3,5,5-trimethyl hexanal and mixtures thereof. Preferred mixtures are, for example, 30% by weight 2-nonene-1-al, 40% by weight undecylene-based aldehyde, and 20% by weight methyl nonyl acetaldehyde, aldehyde laurate 25 Weight percent, 35 weight percent decanal and 20 weight percent 2-nonen-1-al.

By selecting the fragrance component from the foregoing, a "sun dried odor" is produced in the fabric even when the fabric does not substantially sun dry. The "sun dried" odor is formed by selecting aldehydes so that at least one of them is naturally present in the cotton fabric after sun drying the fabric to be a component of the sun dried odor.

Perfumes also include aromatic precursors such as acetal aromatic precursors, ketal aromatic precursors, ester aromatic precursors (eg, digeranyl succinate), hydrolyzable inorganic-organic aromatic precursors, and mixtures thereof. The fragrance precursor can release fragrance material as a result of simple hydrolysis, can be a pH-change-triggered fragrance precursor (eg, a pH drop), or can be an enzymatically release fragrance precursor.

Preferred fragrances useful herein are defined as follows.

For the purposes of the present invention, fragrances are agents which have the ability to be introduced into the pores of the carrier and thereby have utility as a component for delivery from the carrier via an aqueous environment. Shared document WO 98/41607 describes characteristic physical parameters of fragrance molecules that affect the ability of a zeolite-like carrier to be introduced into pores. Obviously in the present invention where perfume is delivered by the composition, sensory perception is also required in order for the consumer to understand the benefits. For perfume delivery particles of the present invention, preferred perfumes are odor detection thresholds (" ODTs ") under carefully controlled GC conditions, as will be described in detail below, of up to 50 parts per billion (" ppb "). Measured). Less preferred are formulations having at least 50 ppb to 1 part per million (“ppm”) ODT. Formulations having an ODT of at least 1 ppm are preferably avoided. Laundry detergent fragrance mixtures useful in the fragrance delivery particles of the present invention are preferably from about 0% to about 80% deliverable formulations having an ODT of at least 50 ppb and up to 1 ppm, and from about 20% to deliverable formulations having an ODT of 50 ppb or less. About 100% (preferably about 30% to about 100%, more preferably about 50% to about 100%).

Also preferred are fragrances that are maintained during the laundering process and are released into the fabric surrounding air (eg, the space around the fabric during storage) that is dried after washing. This requires the fragrance to move out of the zeolite aperture and subsequently be dispensed into the air around the fabric. Thus, preferred fragrances are further identified based on their volatility. Boiling point is used herein as a measure of volatility and preferred materials have a boiling point of 300 ° C. or lower. Laundry detergent fragrance mixtures useful in the laundry particles of the present invention preferably comprise at least about 50% (preferably at least about 60%, more preferably at least about 70%) deliverable formulations having a boiling point below 300 ° C. .

In addition, preferred perfume delivery particles for use in laundry detergent herein range from about 1.0% to about 80%, and more preferably about 90% or more of deliverable fragrance, from about 1.0 to 16, and more preferably from about 2.0 to about 8.0 A composition having a metered average ClogP value of. Most preferably, the deliverable fragrance or mixture has a metered average ClogP value of 3 to 4.5. Without wishing to be bound by theory, the fragrance material having the desired ClogP value is sufficiently hydrophobic to remain in the pores of the zeolite carrier and to be deposited on the fabric during cleaning, but it is released from the zeolite pores in a suitable proportion from the dry fabric to provide a recognizable advantage. It is thought to be. ClogP values are obtained as follows.

Calculation of ClogP

The fragrance component is characterized by its octanol / water partition coefficient P. The octanol / water partition coefficient of the perfume component is the ratio between its equilibrium concentration in octanol and water. Since the partition coefficients of most perfume components are large, they are more easily presented in the form of their logarithm, logP, relative to base 10.

LogPs of numerous fragrance components have been reported and described in the Pomona92 database, Daylight Chemical Information Systems, Inc. Daylight CIS contains many, with citations to the original literature.

However, logP values are conveniently calculated mainly by the "CLOGP" program (Daylight CIS). The program also contains experimental logP values when useful in the Pomona92 database. "Calculated logP" (ClogP) is described in Hansch and Leo [A. Leo, in Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P.G. Sammens, J. B. Taylor and C. A. Ramsden, Eds., P. 295, Pergamon Press, 1990]. The fragment method is based on the chemical structure of each perfume component and takes into account the number and type of atoms, atomic connectivity, and chemical bonds. The most reliable and widely used evaluation method for these physicochemical properties can be used in place of experimental logP values in the selection of fragrance components.

Determination of Odor Detection Threshold

Gas chromatographs are characterized to determine the exact volume of the material injected into the syringe, the correct distribution rate, and the hydrocarbon reaction using hydrocarbon standards for known concentrations and chain-length distributions. The air flow rate is accurately measured and the sampled volume is calculated assuming a human inhalation duration up to the last 0.2 minutes. Since the exact concentration at the detector at any point in time is known, the mass per inhaled volume is known and therefore the concentration of the substance is known. To determine if the material has a threshold of 10 ppb or less, the solution is delivered to a sniff port at the back-calculated concentration. The panelist will smell the GC eluate and check the retention time for the smell to be recognized. The average for all panelists is determined as a recognizable threshold.

The required amount of analyte is injected onto the column to achieve a 10 ppb concentration in the detector. Typical gas chromatograph parameters for measuring odor detection thresholds are reported below.

GC: 5890 Series II with FID Detector

7673 Automatic Sampling Device

Column: J & W Scientific DB-1

30 meters long, ID 0.25 mm, film thickness 1 μm

Way:

Split injection: 17/1 split ratio

Automatic sampler: 1.13 μl per injection

Column flow rate: 1.10 mL / min

Air flow rate: 345ml / min

Inlet temperature: 245 ℃

Detector temperature: 285 ℃

Temperature information

Onset temperature: 50 ° C

Rate: 5 ℃ / min

Final temperature: 280 ℃

Last time: 6 minutes

Main assumption: (i) 0.02 minutes per smell

(ii) GC air is added to the sample diluent.

Particularly preferred fragrances for use in the present invention are fragrances cited as strong-effect fragrances and characterized as having:

(1) a standard boiling point (B.P.) of about 275 ° C. or less at 760 mm Hg,

(2) at least about ClogP or experimental logP, and

(3) an ODT of 50 ppb or less to 10 ppb or more.

Aroma repellent

Optionally, the fragrance can be mixed with the fragrance retention agent. As used herein, the perfume retention agent material is characterized by several criteria that make it particularly suitable for the practice of the present invention. Additives which are available from dispersible, toxicologically-acceptable, non-skin irritant, fragrance inert, degradable and / or renewable sources and relatively odorless are used. Aroma retention agents are believed to retard the evaporation of more volatile components of the perfume.

Examples of suitable retention agents are selected from the group consisting of diethyl phthalate, musk, and mixtures thereof. When used, the fragrance retention agent comprises about 10 to about 50 weight percent of the perfume, preferably about 20 to about 40 weight percent.

Introduction of Perfumes in Preferred Zeolite Carriers

Type X or Y zeolites used as preferred carriers herein are up to about 15% desorbable water, more preferably up to about 8% desorbable water, and most preferably up to about 5% desorption. Contains as much water as possible. The material may be obtained by first activation / dehydration, optionally by heating to about 150 to 350 ° C., with reduced pressure (about 0.001 to about 20 Torr). After activation, the formulation is slowly and thoroughly mixed with the activated zeolite and optionally heated to about 60 ° C. for about 2 hours to promote adsorption equilibrium in the zeolite particles. The perfume / zeolite mixture is then cooled to room temperature, which is in the form of a free-flowing powder.

The amount of fragrance or other laundry additive introduced into the zeolite carrier is typically from about 1 to 40% by weight, preferably at least about 10% by weight, more preferably, taking into account the limitations in the pore volume of the zeolite. At least about 18.5 weight percent. However, although the particles of the present invention may exceed these levels of laundry additives per weight percent of particles, it should be appreciated that even when deliverable formulations are used, excess levels of laundry additives will not be introduced into the zeolite. . Thus, the particles of the present invention may comprise at least 40% by weight of the laundry detergent. Since any excess laundry detergent (as well as non-deliverable formulations present) is not introduced into the zeolite pores, the materials are likely to be released immediately into the wash liquor upon contact with the aqueous wash medium.

Coating and Encapsulation of Filled Zeolite Particles

In a specific embodiment of the invention, the perfume-filled zeolite particles in the form of free-flowing powders are completely covered with hydrophobic oils, such as mineral or aromatic oils. The hydrophobic-oil coated particles are mixed in a modified starch (CAPSUL ^™ , National Starch & Chemicals) solution and stirred to form an emulsion. The emulsion is then spray dried using a spray dryer having a spray system commonly used with spin disks, wingless disks, winged disks or wheels or two-flow mist spray nozzles. Typical conditions relate to inlet temperatures of about 120 ° C. to about 220 ° C., and outlet temperatures of about 50 ° C. to about 220 ° C.

Laundry additive additive delivery particles of the invention are discrete particles having a particle size of about 3 to about 100 μm as measured by standard particle size analysis techniques. 1 shows an SEM of fully averaged sized encapsulated perfume-filled zeolite particles according to the present invention. 2 shows a cross section of a particle according to the invention, containing zeolite particles filled in a starch coating.

Stability Test of Encapsulated Fragrance-Filled Zeolite Particles

Samples of encapsulated fragrance-filled zeolite particles are held for 10 days in open containers at 80 ° F. and 70% relative humidity and in sealed plastic bags at 120 ° F. After this period, the sample is taken out and the sensory test is evaluated. The particles are homogenized and administered according to the zone parenchymal wash conditions. They are mixed with odorless base granules approved for this type of test. Initial particles (which do not apply to stability test conditions) are included as references. The directional strength score for the particles is reported as a term of dry fabric odor. Particles with fragrance filled zeolites can provide an advantage of about 5 to 20 points in fragrance intensity size compared to the control sprayed with fragrance alone.

Additional laundry or cleaning ingredients

Additional components useful in the laundry or cleaning composition according to the present invention include agents such as surfactants, builders, and those introduced into the delivery particles of the present invention. Various types of formulations useful in laundry and cleaning compositions are described below. The composition containing the particulate composition may optionally include one or more detergent additives or other materials to aid in and enhance cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition.

Detergent surfactant

Granules and / or aggregates comprise surfactants at the levels mentioned previously. Detergent surfactants may be selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, and mixtures thereof. Examples of non-limiting surfactants useful herein include conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates (“LSA”) and primary, branched and random C ₁₀ -C ₂₀ alkyl sulfates (“AS”), formula CH _{3 (CH 2) x (CHOSO 3} - M +) CH 3 and _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 ( wherein, x and (y + 1) is about 7 or more, and preferably Is an integer of at least about 9, M is a water soluble cation, in particular sodium, C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates, unsaturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfates (“AE _x S ", in particular EO 1-7 ethoxy sulfate), C ₁₀ -C ₁₈ alkyl alkoxy carboxylate (especially EO 1-5 ethoxycarboxylate), C ₁₀ -C ₁₈ glycerol ether, C ₁₀ -C ₁₈ alkylpoly Glycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ alpha-sulfonated fatty acid esters. If desired, C ₁₂ -C ₁₈ alkyl ethoxylates (“AEs”) and C ₆ -C ₁₂ alkyl phenols comprising conventional nonionic and amphoteric surfactants such as so-called narrow peak alkyl ethoxylates Alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines (“sultaines”), C ₁₀ -C ₁₈ amine oxides, and the like may be included in the overall composition. Can be. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamide. See WO 9,206,154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamide can be used for low foamability. C ₁₀ -C ₂₀ conventional soaps may also be used. If high foamability is desired, branched C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other commonly useful surfactants are described in standard textbooks.

C ₁₀ -C ₁₈ alkyl alkoxy sulfates (“AE _x S”, in particular EO 1-7 ethoxy sulfates) and C ₁₂ -C ₁₈ alkyl ethoxylates (“AEs”) are described in the cellulase-containing detergents described herein. Most preferred.

Detergent builder

Granules and aggregates preferably comprise builders at the previously mentioned levels. For this purpose, organic as well as inorganic builders can be used. It is also possible to use amorphous builder materials as well as crystallinity. Builders are typically used in fabric laundry compositions to promote removal of particulate contaminants and to eliminate the possibility of water curing.

Inorganic or P-containing detergent builders include ammonium and alkanolammonium salts, phosphonates, phytic acid, silicates, carbonates of alkali metals, polyphosphates (e.g., tripolyphosphates, pyrophosphates and glassy polymerizable meta-phosphates). Bicarbonates and sesquicarbonates), sulfates, and aluminosilicates, but are not limited thereto. However, non-phosphate builders are required in certain places. Importantly, the compositions herein are used in the presence of so-called "weak" builders (compared to phosphates), such as citrate, or in so-called "non-enhanced" situations that can be caused when using zeolite or layered silicate builders. Surprisingly well.

Examples of silicate builders include alkali metal silicates, especially those having SiO ₂ : Na ₂ O at a ratio of 1.6: 1 to 3.2: 1, and US Patent No. 4,664,839, issued May 12, 1987 to HP Rieck. Layered silicates such as layered sodium silicate. NaSKS-6 is a trade name for crystalline layered silicate sold by Hoechst (hereinafter commonly abbreviated as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 has the delta-Na ₂ SiO ₅ form of layered silicate. It can be prepared in the same manner as described in German patent application DE-A 3,417,649 and DE-A 3,742,043. Although SKS-6 is a highly preferred layered silicate for use herein, the general formula NaMSi _x O _{2x + 1} yH ₂ O, wherein M is sodium or hydrogen, x is from 1.9 to 4, preferably 2 Other such layered silicates, such as y having 0 to 20, preferably 0, may be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in alpha, beta and gamma forms. As noted above, delta-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. For example, other silicates, such as magnesium silicates, may also be useful, which may act as crispening agents in granular formulations, as stabilizers in oxygen bleaches, and as components of foam control systems.

Examples of carbonate builders are alkaline earth metals and alkali metal carbonates, as described in German Publication No. 2,321,001 published November 15, 1973. As mentioned above, aluminosilicate builders are useful builders in the present invention. Aluminosilicate builders are very important in most commercially available heavy particulate detergent compositions and may also be an important builder component in liquid detergent formulations. Aluminosilicate builder empirical formula M _z (zAlO _{2) y]} and xH ₂ O (wherein, z and y are the molar ratio of z for a six or more integer y is in the range of 1.0 to about 0.5 x is from about 15 to about 264 It is an integer of the range).

Useful aluminosilicate ion exchange materials are commercially available. Such aluminosilicates may be crystalline or amorphous in structure and may be natural aluminosilicates or synthetically derived. Methods for preparing aluminosilicate ion exchange materials are described in US Pat. No. 3,985,669 to Krummel et al. On October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are commercially available under the names Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material is of formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] .xH ₂ O, wherein x is from about 20 to about 30, in particular about 27. Has This material is known as zeolite A. Dehydrated zeolites (x = 0-10) may also be used herein. Preferably, the aluminosilicates have a particle size of about 0.1 to 10 μm 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" means a compound having a plurality of carboxylate groups, preferably three or more carboxylates. Polycarboxylate builders can generally be added to the composition in acid form, but can also be added in the form of neutral salts. When used in salt form, alkali metals such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Polycarboxylate builders include various categories of useful materials. One important category of polycarboxylates is described in US Pat. No. 3,128,287 to Berg on April 7, 1964, and US Pat. No. 3,635,830 to Lamberti et al. On January 18, 1972. Ether polycarboxylates, including oxydisuccinates, as shown. See also the "TMS / TDS" builder in US Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. Suitable ether polycarboxylates also include cyclic compounds, especially cycloaliphatic compounds, as described in US Pat. Nos. 3,923,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

Other useful detergent builders include ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid, and carboxymethyloxy Various alkali metal, ammonium and substituted ammonium salts of polyacetic acid, such as succinic acid and ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as melic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5 -Tricarboxylic acids, polycarboxylates such as carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders such as citric acid and soluble salts thereof (particularly sodium salts) are polycarboxylate builders that are particularly important in heavy liquid detergent formulations due to their availability from renewable sources and their biodegradability. Citrate can also be used in granular formulations, especially when used in combination with zeolites and / or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and combinations.

Suitable for the detergent compositions of the invention are also 3,3-dicarboxy-4-oxa-1,6-hexanedioate described in US Pat. No. 4,566,984 to Bush on Jan. 28, 1986 and Related compounds. Useful succinic acid builders include C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. Particularly preferred compounds of this type are dodecenyl succinic acid. Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmity succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate, and the like. Laurylsuccinate is a preferred builder of this group and is described in European Patent Application No. 86200690.5 / 0,200,263, published November 5, 1986.

Other suitable polycarboxylates are described in US Pat. No. 4,144,226 to Crutchfield et al. On March 13, 1979 and US Pat. No. 3,308,067 to Diehl on March 7, 1967. See also US Pat. No. 3,723,322 to Diehl.

Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be introduced into the composition alone or in combination with the aforementioned builders, in particular citrate and / or succinate builders, to provide additional builder activity. The use of fatty acids generally reduces foaming, which should be considered by the formulator.

In situations where a phosphorus builder can be used and especially in bar formulations used in hand washing operations, various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates [see, for example, US Pat. Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148). And 3,422,137 may also be used.

Other additional ingredients

Compositions of the present invention may also include enzymes, enzyme stabilizers, polishes, polymeric dispersants (ie, polyacrylates), carriers, perfumes, foaming accelerators or inhibitors, stain release agents, dye transfer inhibitors, and processing aids. have.

Granular composition

The laundry and cleaning compositions of the present invention can be used in both low density (550 g / l or less) and high density granular compositions having a granule density of 550 g / l or more. The particulate composition is typically designed to provide a wash pH of about 7.5 to about 11.5, more preferably about 9.5 to about 10.5. Low density compositions can be prepared by standard spray-drying methods. Various means and devices can be used to prepare the high density compositions. Currently commercially available methods in the art use spray-drying towers to produce compositions having a density of about 500 g / l or less. Therefore, when spray drying is used as part of the overall process, the spray dried particles obtained must be further densified using the means and apparatus described later. Alternatively, the formulator may omit spray-drying by using commercially available mixing, densifying and granulating devices. The following is a non-limiting description of the device suitable for use herein.

Various means and devices are used to prepare the high density (ie, greater than about 550, preferably greater than about 650 g / l), high solubility, free-flowing, granular detergent compositions according to the present invention. Currently commercially available methods in the art often use spray-drying towers to produce granular laundry detergents having a density of about 500 g / l or less. In this process, aqueous slurries of the various heat-stable components in the final detergent composition are passed through a spray-drying tower using conventional techniques at temperatures of about 175 ° C to about 225 ° C to form homogeneous granules. However, when spray drying is used as part of the overall process herein, the density level required for current dense, low dose detergent products using additional process steps as described later (ie 650 g / more than 1).

For example, spray dried granules from a tower can be added by additionally filling liquids such as water or liquids such as nonionic surfactants into the pores of the granules and / or applying the granules into one or more high speed mixers / densifiers. To increase the density. High speed mixers / densifiers suitable for this method are devices marketed under the trade names "Lodige CB 30" or "Lodige CB 30 Recycler", comprising a fixed cylindrical mixing drum having a central axis of rotation with a mixing / cutting blade mounted on its surface. In use, the components of the detergent composition are introduced into the drum and the shaft / blade parts are rotated at a speed in the range of 100 to 2500 rpm to thoroughly mix / densify. See US Pat. No. 5,149,455, issued to Jacobs et al. On September 22, 1992. The preferred residence time in the high speed mixer / densifier is about 1 to 60 seconds. Other such devices include those sold under the trade name "Shugi Granulator" and under the trade name "Drais K-TTP 80".

Another process step that can be used to further densify the spray dried granules involves grinding and agglomerating or deforming the spray dried granules in a mixer / densifier at a suitable speed to obtain particles with lower intragranular porosity. do. Devices such as mixers / densers commercially available under the trade names “Lodige KM (Series 300 or 600)” or “Lodige Ploughshare” are suitable for this process step. The device typically operates at 40 to 160 rpm. The residence time of the detergent component in the mixer / densifier at an appropriate rate is about 0.1 to 12 minutes. Other useful devices include devices useful under the trade name "Drais K-T 160". This process step using a suitable speed mixer / densifier (eg Lodige KM) can be used on its own or subsequently after using a high speed mixer / densifier (eg Lodige CB) described above. . Other types of granule manufacturing apparatus useful herein include the apparatus described in US Pat. No. 2,306,898, issued December 29, 1942 to G. L. Heller.

While it may be more suitable to use a slow mixer / densifier after the high speed mixer / densifier, the reverse mixer / densifier arrangement is also included in the present invention. Spray drying in the process of the invention using one or a combination of various variables including the residence time in the mixer / densifier, the operating temperature of the device, the temperature and / or composition of the granules, the use of additional ingredients such as liquid binders and flow aids The densification of the granulated granules can be optimized. See, eg, US Pat. No. 5,133,924 to Appel et al. On July 28, 1992 (making the granules deformable before densification); US Patent No. 4,637,891 to Delwel et al. On January 20, 1987 (spray dried granules are granulated with liquid binder and aluminosilicate); US Patent No. 4,726,908 to Kruse et al., Feb. 23, 1988 (spray dried granules are granulated with a liquid binder and aluminosilicate); And US Pat. No. 5,160,657 (covering densified granules with liquid binder and aluminosilicate) to Bortolotti et al. On November 3, 1992.

In particular in situations where a thermally sensitive or highly volatile detergent component is introduced into the final detergent composition, a method that does not include a spray drying tower is preferred. The formulator may omit the spray drying step by continuously or batchwise supplying the starting detergent component directly into a commercially available mixing / densing apparatus. One particularly preferred specific embodiment is that the surfactant paste and anhydrous builder material are charged into a high speed mixer / densifier (e.g. Lodige CB) and then packed into a suitable high speed mixer / densifier (e.g. Lodige KM) to achieve high density. Related to forming detergent aggregates. See US Patent No. 5,366,652 to Capeci et al. On November 22, 1994 and US Patent No. 5,486,303 to Capeci et al. On January 23, 1996. Optionally, the liquid / solid ratio of the starting detergent component in the process can be chosen to obtain a more free flowing and shrinking high density aggregate.

Optionally, the method may include one or more recycle streams that refeed too small particles produced by the method back into the mixer / densifier for further flocculation or augmentation. Too large particles produced by the process can be sent to the grinding apparatus and fed back to the mixing / densing apparatus. These additional recycle process steps may promote enhanced coagulation of the starting detergent components to form a finished composition having a homogeneous distribution of the desired particle size (400-700 μm) and density (greater than 550 g / l). See US Pat. No. 5,516,448 to Capeci et al. On May 14, 1996 and US Pat. No. 5,489,392 to Capeci et al. On February 6, 1996. Other suitable methods that do not require the use of spray drying towers are described in US Pat. No. 4,828,721 to Bollier et al. On May 9, 1989; US Patent No. 5,108,646 to Beerse et al. On April 28, 1992; And US Pat. No. 5,178,798, issued to Jolicoeur on January 12, 1993.

In another specific embodiment, the high density detergent composition of the present invention can be prepared using a fluidized bed mixer. In this process, the various components of the finished composition are mixed in an aqueous slurry (typically 80% solids content) and sprayed into the fluidized bed to provide the finished detergent granules. Prior to the fluidized bed step, the method may optionally include mixing the slurry using the aforementioned Lodige CB mixer / densifier or "Flexomix 160" mixer / densifier (Shugi). Commercially available fluidized or moving bed types under the trade name "Escher Wyss" can be used in this process.

Another suitable method that can be used herein is to supply a liquid acid precursor of an anionic surfactant, an alkali inorganic material (eg sodium carbonate) and optionally other detergent components to a high speed mixer / densifier (retention time 5-30 seconds). To form aggregates containing partially or fully neutralized anionic surfactant salts and other starting detergent components. Optionally, the contents in the high speed mixer / densifier can be delivered to a mixer / densifier (eg Lodige KM) at a suitable speed for further flocculation to obtain a finished high density detergent composition. See US Patent No. 5,164,108, issued to Appel et al. On November 17, 1992.

Optionally, the high density detergent compositions according to the present invention may be used in various ratios (eg, granules to agglomerates 60:40) prepared using conventional or densified spray dried detergent granules in one or a combination of the methods discussed herein. It can be prepared by mixing with the aggregates. Additional additional components such as enzymes, fragrances, brighteners and the like can be sprayed or mixed with aggregates, granules or mixtures thereof prepared by the methods discussed herein. Bleach compositions in the form of granules typically limit the water content to, for example, about 7% free water or less for best storage stability.

Deodorant Deposition on Fabric Surface

The method of washing the fabric and depositing fragrances on the fabric comprises contacting the fabric with an aqueous cleaning solution comprising at least about 100 ppm of the conventional detergent components described above as well as at least about 0.1 ppm of the laundry addition particles described above. Preferably, the aqueous solution comprises about 500 ppm to about 20,000 ppm of conventional detergent components and about 10 ppm to about 200 ppm of laundry addition particles.

The laundry addition particles work under all circumstances, but are particularly useful during the laundry process and to provide odor benefits on wet and dry fabrics. The method comprises contacting the fabric with an aqueous liquid containing at least about 100 ppm of conventional detergent components and at least about 1 ppm of laundry addition particles to allow fragranced zeolite particles to be incorporated onto the fabric and under ambient conditions having a humidity of at least 20%. Store the line-dried fabric, dry it in a conventional automated dryer, dry it in a clothesline or by conventional ironing means (preferably steam or pre-wet). Applying heat to fabrics machined at low temperatures (up to about 50 ° C.).

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

Example I

Fragrance filled zeolites ("PLZ") are made by mixing zeolite 13X and fragrances in an 85/15 weight ratio. PLZ is thoroughly mixed with intermediate coating oil (ICO) in a ratio of PLZ: ICO 1: 0.5 to 1: 1. The mixture is then poured into a solution that is about 4 times the weight of the mixture and contains about 25% solid starch. During the whole process, this second mixture is maintained under stirring using a high speed homogenizer, such as a mixer or tissue homogenizer. The mixture is then pumped into the spray dryer at 180-220 ° C. The process produces a fine powder, which is suitable for use as a laundry additive in detergent compositions. The fragrance filled into the zeolite has the following composition.

Substance % Violif 2.5 Pruten 15.0 Methyl Isobutenyl Tetrahydropyran 7.5 Shimal 10.0 Florhydral 15.0 Delta Damascon 15.0 Ionone beta 25.0 P.T. Bush blade 10.0

The particles formed have an excellent "pure product odor (" NPO ")" for the base product odor and emit only a minimal detectable odor, as unexpectedly observed by the statistically significant number of panelist scorers. This strongly proves that there is little emission of perfume from the carrier particles.

Example II

Several detergent compositions for introducing perfume particles prepared in Example I are illustrated below.

Basic granules 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 -C ₁₃ linear alkylbenzene sulfonate, Na 6.0 7.0 8.0 C ₁₄ -C ₁₆ secondary alkyl sulfates, Na 3.0 3.0 - C ₁₄ -C ₁₅ alkyl ethoxylated sulfate, Na 3.0 9.0 - Sodium silicate 1.0 2.0 3.0 Polishes 24/47 ¹ 0.3 0.3 0.3 Sodium carbonate 7.0 26.0 Carboxymethyl Cellulose - - 1.0 DTPMPA ² - - 0.5 DTPA ³ 0.5 - - Mixed Aggregates C ₁₄ -C ₁₅ alkyl sulfates, Na 5.0 - - C ₁₂ -C ₁₃ linear alkylbenzene sulfonate, Na 2.0 - - Sodium carbonate 4.0 - - Polyethylene glycol (MW = 4000) 1.0 - - mixture Sodium carbonate - - 13.0 C ₁₂ -C ₁₅ alkyl ethoxylates (EO = 7) 2.0 0.5 2.0 C ₁₂ -C ₁₅ alkyl ethoxylates (EO = 3) - - 2.0 Fragrance spray 0.3 0.4 0.3 Air freshener particles ⁴ 0.5 0.5 0.5 Polyvinylpyrrolidone 0.5 - - Polyvinylpyridine N-oxide 0.5 - - Polyvinylpyrrolidone-polyvinylimidazole 0.5 - - Distearyl and cumene sulfonic acid 2.0 - - Stain Release Polymer ⁵ 0.5 - - Lipolase Lipase (100.000LU / I) ⁶ 0.5 - 0.5 Thermamil Amylase (60 KNU / g) ⁶ 0.3 - 0.3 CAREZYME Cellulase (1000 CEVU / 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.) Remainder Remainder Remainder all 100 100 100 Purchase from Ciba-Geigy 2. Diethylene triamine pentamethylene phosphonic acid 3. Diethylene triamine pentaacetic acid4. From Example I 5. Manufactured according to US Pat. No. 5,415,807 to Grosselink et al. On May 16, 1995. Purchase from Novo Nordisk A / S 7. Purchase from Genencor 8. Nonanoyloxybenzenesulfonate 9. Tetraacetylethylenediamine

Example III

The following detergent compositions according to the invention are suitable for machine and hand washing operations. The basic granules are prepared by conventional spray drying methods in which the starting components are formed into a slurry and passed through a spray drying tower having a reverse flow stream of hot air (200-400 ° C.) to form porous granules. The remaining additive detergent component is sprayed or addition dried thereto.

Basic granules A B C C ₁₂ -C ₁₃ alkylbenzene sulfonate, Na 19.0 18.0 19.0 Cationic Surfactants ¹ 0.5 0.5 - DTPMPA ² 0.3 - - DTPA ³ - 0.3 - Sodium tripolyphosphate 25.0 19.0 29.0 Acrylic Acid / Maleic Acid Copolymer 1.0 0.6 - Carboxymethyl Cellulose 0.3 0.2 0.3 Polish 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 mixture Proton (zinc phthalocyanine sulfonate) 2.0 2.0 2.0 Sodium carbonate 5.0 6.0 20.0 C ₁₂ -C ₁₃ alkyl ethoxylates (EO = 7) 0.4 - 1.2 Savinase ⁵ protease (4KNPY / g) 0.6 - 1.0 Termanyl ⁵ Amylase (60 KNU / g) 0.4 - - Lipolase ⁵ Lipase (100,000LU / I) 0.1 0.1 0.1 Sav / Ban ⁵ (6KNPU / 100 KNU / g) - 0.3 - CAREZYME ⁵ Cellulase (1000CEVU / g) - 0.1 - Stain Release Polymer ⁶ 0.1 0.1 0.3 Fragrance spray 0.4 0.4 0.4 Air Freshener Particles ⁷ 1.5 1.5 2.0 Other (water, etc.) Remainder Remainder Remainder all 100.0 100.0 100.0 C ₁₂ -C ₁₄ dimethyl hydroxyethyl quaternary ammonium compound 2. Diethylene triamine pentamethylene phosphate 3. Diethylene triamine pentaacetic acid4. Purchase from Ciba-Geigy 5. Purchase from Novo Nordisk A / S 6. Manufactured according to US Pat. No. 5,415,807 to Grosselink et al. On May 16, 1995. From Example I

Example IV

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

weight% Coconut Fatty Alkyl Sulfate 30.0 Sodium tripolyphosphate 5.0 Sodium 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 Air freshener particles ¹ 1.0 Fragrance spray 1.0 Other (water, etc.) Remainder all 100.0 1. From Example I

Having described the present 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 present invention and that the present invention is considered not to be limited to that described.

Claims (37)

(i) a porous carrier material, and a fragrance, bleach, bleach promoter, bleach activator, bleach catalyst, chelating agent, antiscalant, threshold inhibitor, dye transfer inhibitor, photobleach, contained in the pores of the porous carrier material, Including additives selected from the group consisting of enzymes, catalytic antibodies, brighteners, fabric-dyed dyes, antifungal agents, antimicrobial agents, insect killing agents, stain release polymers, fabric softeners, dye fixatives, pH raising systems, and mixtures thereof Center core particles, (ii) an intermediate coating material comprising a hydrophobic oil material, coated on a central core particle, and (iii) carbohydrates, cellulose and cellulose derivatives, natural and synthetic rubbers, silicates, borates, phosphates, chitin and chitosan, water soluble polymers, which are coated on intermediate coating materials to provide a substantially non-viscous surface to the additive delivery particles Additive delivery particles comprising an external encapsulating material comprising at least partly one or more washable soluble or dispersible compounds selected from the group consisting of fatty compounds, and mixtures thereof. The additive delivery particle of claim 1, wherein the intermediate hydrophobic oil coating material has a lower ClogP than the ClogP of the additive material contained in the porous carrier material. The core hydrophobic coating material according to claim 2, wherein (i) 5% to 50% of the core core particles comprising 60% to 99% of the porous carrier material and 1% to 40% of the additive material per weight of the core particle, and (ii) the intermediate hydrophobic coating material Additive delivery particles comprising 1% to 40%, and (iii) 10% to 94% of the external encapsulation material. The additive delivery particle of claim 3, wherein the porous carrier material is a zeolite selected from the group consisting of zeolite X, zeolite Y, and mixtures thereof. The additive delivery particle of claim 3, wherein the additive added into the carrier is a perfume material. The additive delivery particle of claim 3, wherein the intermediate hydrophobic coating material is an aromatic oil. The additive delivery particle of claim 3 wherein the outer coating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. The core core particle according to claim 3, comprising: (i) 5% to 50% of the core core particles comprising 60% to 99% of the zeolite and 1% to 40% of the fragrance material as the porous carrier material per core particle weight, and (ii) as the intermediate coating material. Additive delivery particles comprising from 1% to 40% aromatic oil, and (iii) from 10% to 94% starch or modified starch as external encapsulating material. The additive delivery particle of claim 8, wherein the perfume material filled into the zeolite carrier has a metered average ClogP value between 1.0 and 16.0. The additive delivery particle of claim 9, wherein the perfume material filled into the zeolite carrier has a metered average ClogP value between 3 and 4.5. The additive delivery particle of claim 9, wherein the aromatic oil used as the intermediate coating material has a metered average ClogP lower than the metered average ClogP of the fragrance material filled in the porous carrier. 12. The additive delivery particle of claim 11 wherein the highest ClogP of the intermediate coated aromatic oil material is lower than the lowest ClogP of the perfume material filled in the porous carrier. The additive delivery particle of claim 12, wherein there is at least one unit difference between the highest ClogP of the intermediate coated aromatic oil material and the lowest ClogP of the perfume material filled in the porous carrier. The additive delivery particle of claim 13, wherein at least two units of difference exist between the highest ClogP of the intermediate coated aromatic oil material and the lowest ClogP of the perfume material filled in the porous carrier. The fragrance material filled into the zeolite carrier according to claim 8, wherein the fragrance material filled into the zeolite carrier comprises (1) a standard boiling point (BP) of 275 ° C. or less at 760 mm Hg, (2) ClogP or experimental logP of 2 or more, and (3) 50 ppb or less to 10 ppb or more Additive delivery particles comprising a highly effective fragrance, characterized in that it has an ODT. 9. The aromatic oil according to claim 8, wherein the aromatic oil used as the intermediate coating material comprises (1) a standard boiling point (BP) of 275 ° C. or less at 760 mm Hg, (2) two or more ClogP or experimental logP, and (3) 50 ppb or less to 10 ppb. An additive delivery particle comprising a highly effective fragrance, characterized in that it has at least ODT. The composition of claim 8, wherein (i) 10% to 40% of the core core particles, (ii) 10% to 30% of aromatic oils as intermediate coating material, and (iii) 30% to 80% of starch or modified starch as external encapsulating material. Additive delivery particles comprising a. a) (i) a porous carrier material, and a fragrance, bleach, bleach activator, bleach catalyst, chelating agent, scale inhibitor, threshold inhibitor, dye transfer inhibitor, photobleach, enzyme, contained in the pores of the porous carrier material, A central core comprising an additive selected from the group consisting of catalytic antibodies, brighteners, fabric-dyed dyes, antifungal agents, antimicrobial agents, insect killers, stain release polymers, fabric softeners, dye fixatives, pH raising systems, and mixtures thereof particle, (ii) an intermediate coating material comprising a hydrophobic oil material, coated on a core core particle, (iii) carbohydrates, cellulose and cellulose derivatives, natural and synthetic rubbers, silicates, borates, phosphates, chitin and chitosan, water soluble polymers, which are coated on intermediate coating materials to provide a substantially non-viscous surface to the laundry additive additive delivery particles. , From 0.001% to 50% of additive delivery particles (per weight of the composition) comprising an external encapsulating material comprising at least one compound that is at least partially washable or dispersible selected from the group consisting of fatty compounds, and mixtures thereof, and b) laundry or cleaning detergent composition comprising between 50% and 99.999% (per weight of the composition) of the laundry ingredients selected from the group consisting of detergent surfactants, builders, bleaches, enzymes, stain release polymers, dye transfer inhibitors, fillers and mixtures thereof . The laundry or cleaning detergent composition of claim 18 comprising at least one detergent surfactant and at least one builder. 19. The laundry or cleaning detergent composition of claim 18, wherein the porous carrier material is a zeolite selected from the group consisting of zeolite X, zeolite Y, and mixtures thereof. 19. The laundry or cleaning detergent composition of claim 18, wherein the outer encapsulating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. 19. The laundry or cleaning detergent composition of claim 18, wherein the core core particles are zeolites filled with fragrance material. The fragrance material of claim 22 wherein the fragrance material filled into the zeolite comprises (1) a standard boiling point (BP) of 275 ° C. or less at 760 mm Hg, (2) two or more ClogPs or experimental logPs, and (3) an ODT of 50 ppb to 10 ppb or more. Laundry or cleaning detergent composition comprising a very effective fragrance, characterized in that having a. 24. The laundry or cleaning detergent composition of claim 23, wherein the intermediate coating on the core particles comprises aromatic oils. The method of claim 24, wherein the intermediate coated aromatic oil has (1) a standard boiling point (BP) of 275 ° C. or less at 760 mm Hg, (2) at least 2 ClogP or experimental logP, and (3) an ODT of 50 ppb to 10 ppb or more. Laundry or cleaning detergent composition comprising a very effective fragrance, characterized in that. 27. The laundry or cleaning detergent composition of claim 25, wherein the outer encapsulating material is a carbohydrate selected from starch, modified starch or starch hydrolyzate. 23. The laundry or cleaning detergent composition of claim 22, wherein the perfume material filled into the zeolite carrier has a metered average ClogP value between 1.0 and 16.0. The laundry or cleaning detergent composition of claim 27, wherein the perfume material filled into the zeolite carrier has a metered average ClogP value between 3 and 4.5. The laundry or cleaning detergent composition of claim 27, wherein the aromatic oil used as the intermediate coating material has a metered mean ClogP lower than the metered mean ClogP of the perfume material filled into the zeolite carrier. 30. The laundry or cleaning detergent composition of claim 29, wherein the highest ClogP of the intermediate coated aromatic oil material is lower than the lowest ClogP of the perfume material filled into the zeolite carrier. 31. The laundry or cleaning detergent composition of claim 30, wherein there is at least two units of difference between the highest ClogP of the intermediate coated aromatic oil material and the lowest ClogP of the perfume material filled into the zeolite carrier. The additive according to claim 1, wherein the additive contained in the pores of the porous carrier material is a perfume selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof. Transfer particles. The additive delivery particle of claim 1 wherein the intermediate coating material is a fragrance selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof. The additive delivery particle of claim 1 wherein the fragrance material is selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof. _6. The additive delivery particle of claim 5 wherein the aromatic oil is selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof. a) (i) an additive which is a fragrance selected from the group consisting of a porous carrier material and C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof contained in the pores of the porous carrier material Core core particles, including (ii) an intermediate coating material comprising a hydrophobic oil material, coated on a core core particle, (iii) carbohydrates, cellulose and cellulose derivatives, natural and synthetic rubbers, silicates, borates, phosphates, chitin and chitosan, water soluble polymers, which are coated on intermediate coating materials to provide a substantially non-viscous surface to the laundry additive additive delivery particles. , From 0.001% to 50% of additive delivery particles (per weight of the composition) comprising an external encapsulating material comprising at least one compound that is at least partially washable or dispersible selected from the group consisting of fatty compounds, and mixtures thereof, and b) laundry or cleaning detergent composition comprising between 50% and 99.999% (per weight of the composition) of the laundry ingredients selected from the group consisting of detergent surfactants, builders, bleaches, enzymes, stain release polymers, dye transfer inhibitors, fillers and mixtures thereof . 37. The laundry or cleaning detergent composition of claim 36, wherein the intermediate coating material is a fragrance material selected from the group consisting of C ₆ -C ₁₄ aliphatic aldehydes, C ₆ -C ₁₄ acyclic terpene aldehydes and mixtures thereof.