CN102046766B - Detergent composition comprising a triggered release system - Google Patents

Abstract

There is provided a detergent composition, especially a laundry detergent composition, comprising a particle for triggered release of a rinse benefit agent, said particle comprising: a) a rinse benefit agent, b) an enzyme, and c) a substrate for said enzyme, wherein the rinse benefit agent and the enzyme are surrounded by a barrier layer comprising the substrate. The use of the enzyme-triggered release system can retain a rinse benefit agent during the wash stage and release it during the subsequent rinse stage.

Description

Detergent composition comprising triggered release system

technical field

The present invention relates to detergent compositions, particularly laundry detergent compositions, comprising detergent granules comprising a triggered release system for rinse benefit agents. The invention further relates to the production of said detergent composition and its use. In a further aspect, the present invention relates to dishwashing detergent compositions comprising said particles and their use for dishwashing. the

Background of the invention

It is known in the art to prepare granules comprising different types of release systems to release the active compound or benefit agent at the correct point in time to obtain the best possible application of the active ingredient. the

For many years, making laundry, dishwashing or cleaning products available to consumers in bulk-packaged products and, when using the products, at the consumer's The cleaning product is dispensed to the appropriate needs specific to the application (which is determined by the hardness of the water, the nature, amount and/or degree of soiling of the laundry, dishes etc. or items to be cleaned, the amount of liquid in the laundry, dishwashing or cleaning bath or other parameters decision), is routine practice. the

Given consumers' desire for laundry, dishwashing or cleaning products that can be more easily and conveniently dispensed, these products have increasingly been made in forms that result in separate dispensing redundancy: Laundry, dishwashing or cleaning products are prepared to contain laundry, Measured portions of all components needed in a dishwashing or cleaning cycle. In the case of solid products, such fractions are usually formed into shaped bodies (sometimes containing more than one phase), such as pellets, beads, tablets ("tabs"), blocks, cakes, etc., which are added to the wash liquor as a complete product middle. It has also been proposed to encapsulate liquid products within water-soluble capsules which dissolve on contact with an aqueous bath and release their contents into the bath. the

One disadvantage of some of these products is that all the components needed during the laundry, dishwashing or cleaning cycle go into the water bath at the same time. Not only does this lead to problems with certain components of laundry, dishwashing or cleaning products being incompatible with others, but it becomes impossible to selectively introduce specific components into the bath at defined points in time. Another disadvantage is that even if a delayed release mechanism is incorporated into the regimen, it is not particularly effective and it is difficult to provide the desired release profile. the

In the context of the prior art, means have recently been described whereby individual laundry, dishwashing or cleaning product components can be dispensed selectively at defined points in time during their application. For example, temperature-controlled release of active ingredients has been described such that actives such as surfactants, bleaches, detersive polymers, etc. are released during the main wash, cleaning cycle or even in a post-treatment cycle, such as in the case of machine dishwashing Release in the final rinse. the

The use of paraffin waxes with a melting point above 50° C. has been described on numerous occasions. One commercially available product uses a wax wick as the carrier or matrix for the tablet so that the final rinse surfactant ("rinse aid") incorporated therein is not released during the cleaning cycle and until the end of the dishwasher. The rinse cycle is released. If released too early, eg in the cleansing cycle, the final rinse surfactant will mostly be drained in the middle rinse and will then have little or no effect in the final rinse. The use of a matrix material with a melting point at the final rinse cycle temperature ensures that the final rinse surfactant emulsified in the matrix (or ideally, molecularly dispersed in the matrix) remains encapsulated in the matrix during the cleaning cycle, which at maximum A temperature of 55°C was run and was not released until the matrix material melted in the final cleaning cycle, in which a temperature of up to about 65°C was reached. the

This solution for protecting the final rinse surfactant has proven effective in practice. However, a disadvantage is that in a dishwashing tablet core composed of paraffin wax and final rinse surfactant, the amount of matrix material is 30-95% of the total mass of the core, typically about 50% of the total mass. The matrix material, especially in this amount, may leave residues on cleaned articles such as crockery or glassware, and may otherwise interfere with the action of the final rinse surfactant it contains and is released when the paraffin melts. One reason for this may be that after the paraffin has melted, the final rinse surfactant remains bound to the interface between the lipophilic carrier material and the rinse bath, thus failing to produce the desired effect. the

Another disadvantage of temperature-controlled release of active ingredients in laundry or dishwashing products is that typical domestic laundry and dishwashers have a large number of programs that vary greatly, especially with regard to their temperature and time profiles. For example, the most commonly employed programs in modern dishwashers have a peak temperature of 50-60°C or 60-70°C during the cleaning cycle; the exact temperature level can vary according to the manufacturer and the type of machine. the

WO 01/44434 (Henkel) relates to the combination of physico-chemical and enzymatic triggers which lead to particle perforation due to enzymatic activity in the wash solution. However, the presence of enzymes in the wash water has certain disadvantages; this technology necessitates that the detergent contains the necessary enzymes to perforate the particles. The detergent needs to be formulated in such a way that it is not hostile to enzymes. In addition, it is difficult to ensure the proper enzyme activity in the detergent to guarantee the release of the payload at the right moment during the washing process. the

WO 9937746 (Procter & Gamble) relates to multilayer detergent tablets comprising a core, a first encapsulating layer containing detergent actives and a second encapsulating layer containing a rupture system, which results in a delayed release of detergent actives. the

EP-A-971 024 (Procter & Gamble) discloses laundry cleaning compositions comprising cleaning ingredients, and reaction products between primary amines and fragrance components. It documents that the active ingredient is released over a longer period of time than when the active ingredient itself is used alone. the

Further examples of granules for use in detergents are disclosed in the following documents: US 2003/0191043, US 2005/003980, WO 99/29820, WO 97/22680, EP 1 388 585, EP 304332, EP 458845, US 5,733,763. the

Summary of the invention

There is a continuing need for alternative or improved viable triggered release technologies for laundry and dishwashing applications. Due to price and technical challenges, detergent producers are limited in their choice of use of eg fragrance and fabric care ingredients. The present invention provides the ability to formulate more effective delivery systems for use in the rinse phase of a laundry or dishwashing process in a cost effective manner. the

We have unexpectedly found in our studies of improved release systems for detergent granules that the combination of an enzyme substrate and an enzyme capable of facilitating the modification of said substrate provides a triggered release system that works very well. We have found that the use of an enzyme triggered release system enables the retention of rinse benefit agents during the wash phase and their release during the subsequent rinse phase. The enzyme is triggered by a lower surfactant concentration during the rinse and it will start to react with the substrate whereby the particle will become destabilized, degrade and/or rupture releasing the rinse benefit agent into the rinse solution. The surfactant concentration is typically decreased from a level above the critical micelle concentration (CMC) of the surfactant to a level below the CMC. the

It is an object of the present invention to provide a system that releases rinse benefit agents into the rinse liquor at desired process stages or points in use during dishwashing or laundry methods. In use, such a triggered release system does not require the composition of the liquid to be specifically adapted to the release system. the

We have unexpectedly found that particles comprising a rinse benefit agent and said enzyme surrounded by a barrier layer comprising an enzyme substrate provide the most suitable system for delivering rinse benefit agents such as fragrances into the laundry or dishwashing process . the

The particles of the present invention comprise an enzyme-triggered release system comprising a rinse benefit agent and an enzyme-substrate pair that enables the rinse-triggered release of the rinse benefit agent during the rinse phase of a laundry or dishwashing process. The enzyme-substrate pairs used in the present invention form part of an effective triggered release system for delivering rinse benefit agents to obtain a suitable release profile during application. the

Thus, the laundry detergent compositions of the present invention comprise detergent granules comprising:

a) rinse benefit agent,

b) enzymes, and

c) a substrate for said enzyme,

wherein said rinse benefit agent and said enzyme are enclosed within (surrounded by) a barrier layer comprising said substrate. the

The invention further relates to processes for the preparation of laundry detergent compositions comprising said granules, dishwashing detergent compositions comprising said granules, and uses of said granules. Finally, the present invention provides a method of washing kitchenware comprising a washing step wherein soiled kitchenware is contacted with an aqueous composition comprising the dishwashing detergent composition of claim 12, followed by wherein said rinse benefit agent is removed from said Rinse step in which particles are released into the rinse liquid. the

Specifically, the present invention relates to the following aspects:

1. Laundry detergent compositions comprising particles for triggering release of rinse benefit agents, said particles comprising:

a) rinse benefit agent,

b) enzymes, and

c) a substrate for said enzyme,

wherein said rinse benefit agent and said enzyme are surrounded by a barrier layer comprising said substrate, wherein said substrate is insoluble in water. the

2. A detergent composition according to item 1, wherein the rinse benefit agent is selected from the group consisting of fragrances, masking agents, chemical odor neutralizers, physical odor neutralizers, pro-perfumes, fiber lubricants, antistatic agents , anti-wrinkle agent, defoamer, photoprotectant, optical brightener, soil release polymer, stain repellant, anti-fouling agent, fabric softening compound, antibacterial agent, insecticide, fungicide, insect repellant, Antioxidants, shading dyes, color fixing agents, second enzymes and mixtures thereof. the

3. Detergent composition according to item 1, wherein said enzyme acting on said substrate is selected from the group consisting of amylases, lipases, cellulases, cutinases and mixtures thereof. the

4. The detergent composition of item 1, wherein the water-insoluble substrate is selected from the group consisting of monoglycerides, diglycerides, triglycerides, wax esters and mixtures thereof. the

5. A detergent composition according to any one of clauses 1-4, wherein said particle comprises a core comprising said rinse benefit agent, and a layer comprising said substrate surrounding said core. the

6. The detergent composition of item 5, wherein the core comprises carrier particles. the

7. A laundry detergent composition comprising particles for triggering release of rinse benefit agents, said particles comprising:

a) rinse benefit agent,

b) enzymes, and

c) a substrate for said enzyme,

Where said particle comprises a core comprising said rinse benefit agent and a layer surrounding said core comprising said substrate, said rinse benefit agent, substrate and enzyme may be present together in the core and/or in the same layer, said The substrate is insoluble in water. the

8. A laundry detergent composition comprising particles for triggering release of rinse benefit agents, said particles comprising:

a) rinse benefit agent,

b) enzymes, and

c) a substrate for said enzyme,

wherein said rinse benefit agent and said enzyme are surrounded by a barrier layer comprising said substrate; said particle comprises a first layer comprising said rinse benefit agent, and a second layer comprising said substrate; said substrate Substances are insoluble in water. the

9. The method for preparing the detergent composition of item 1, comprising the following steps:

a) preparing a core comprising said benefit agent,

b) apply one or more layers,

wherein each layer comprises the enzyme or a substrate for the enzyme. the

10. The method of item 9, wherein the granules are prepared in a mixer, fluidized bed, fluidized bed spray dryer, spray dryer or extruder. the

Detailed description of the invention

All percentages and ratios are by weight unless otherwise indicated. All percentages are calculated based on the total composition unless otherwise stated. A substance is considered insoluble if it has a solubility in water at 25°C of less than 1 g/l, in particular less than 0.5 g/l, less than 0.2 g/l or less than 0.1 g/l. the

Herein, the inventors do not wish to be limited by the materials of a particular trade name. Materials equivalent to those mentioned by trade names (eg, those obtained from different sources under different names or catalog (reference) numbers) may be substituted and used in the compositions herein. the

All documents mentioned herein, including all patents, patent applications, and printed publications, are hereby incorporated by reference in their entirety. the

particles

In a particular embodiment, the particles of the present invention comprise a core comprising a rinse benefit agent and a layer surrounding the core. The core may comprise inert carrier particles consisting, for example, of Na ₂ SO ₄ , carbonates or silicates. The rinse benefit agent, substrate and enzyme may be present together in the core and/or in the same layer.

The particles comprise a barrier layer. The benefit agent, enzyme and substrate may be present mixed together homogeneously in a matrix, wherein the matrix is a layer or the core of the particle. the

The particle may comprise a first layer and a second layer. The first layer may comprise the enzyme, and the second layer may comprise a substrate for the enzyme present in the first layer. the

In a particular embodiment, the enzyme and the substrate are present in the particle in such a manner that they are in physical contact, either in the same layer or matrix, or in layers adjacent to each other. There may be a thin water-soluble layer between the layer containing the enzyme and the layer containing the substrate. the

In a specific embodiment of the invention, the particles include:

a) a core comprising a rinse benefit agent,

b) optionally a protective layer,

c) an enzyme-containing layer, and

d) Barrier layer comprising a substrate for the enzyme in c). the

The particles may further comprise one or more additional coatings. the

The granules of the present invention are preferably in the range of 0.001 mg to 10000 mg. In a more particular embodiment of the invention, said granules weigh from 0.005 mg to 1000 mg. In an even more specific embodiment, the average grain weight is between 0.01 mg and 100 mg. the

In a particular embodiment, the average particle size is from 0.1 to 2000 μm. In a more specific embodiment, the average particle size is 50-1400 μm. In a most preferred embodiment of the invention, the average particle size is 100-1000 μm. In a further embodiment, the average particle size of the present invention is 100-800 μm. the

For use in dishwashing, the particles should be chosen to be sufficiently large that they are not released to a significant extent during discharge after the main cleaning cycle. Thus, the average particle size may be greater than 1 mm or greater than 3 mm, for example in the range 3-20 mm or 5-15 mm. In a particular embodiment of the invention, the particles of the invention release more than 60% of the rinse benefit agent during the rinse stage of the wash process. In a more specific embodiment of the particles of the invention, more than 70% of the rinse benefit agent is released during the rinse phase. The release of the rinse benefit agent can be measured by the method described in Example 6. the

core

The detergent particles may comprise a core surrounded by one or more layers. The core of the particle may comprise a rinse benefit agent, alone or in combination with other components. the

The core may comprise a pre-formed core, such as an inert core on which the rinse benefit agent is deposited, or a core made of a porous material with the rinse benefit agent deposited therein. In a preferred embodiment, the rinse benefit agent is deposited into the core. the

The benefit agent can be incorporated into the core at the time of preparation of the core particle. In a preferred embodiment, the core is prepared by pelletization of a filler component in the presence of a rinse benefit agent and optionally additional binder material. the

Preformed cores can also be referred to as carrier particles; cores, placebo cores (cores not containing active compound) or seeds are inert particles on which a mixture comprising the active compound can be deposited. The preformed core may comprise inorganic salts, starches, sugars, sugar alcohols, small organic molecules such as organic acids or salts such as carbonates, minerals such as clays, zeolites or silicates, or two or more of these The combination. the

In a particular embodiment of the invention, the core may be prepared by applying a mixture comprising a rinse benefit agent to a preformed core. the

barrier layer

The particles of the invention include a barrier layer. The barrier layer provides a physical barrier and/or transport barrier (including encapsulation) to the rinse benefit agent in question. The barrier layer thereby prevents, reduces, delays and/or inhibits the passage of rinse benefit agent from the particle. the

The barrier layer prevents leakage or undesired migration or delivery of rinse benefit agent from the particle into the wash liquor during the wash phase. The barrier layer can also improve particle stability, facilitating formulation, storage and application. the

The barrier layer may function as a scaffold for the substrate. The substrate may itself act as a barrier layer, or it may be a second component that affects the properties of the barrier material due to enzymatic activity. the

The barrier layer comprises the substrate and may comprise the enzyme. In a particular embodiment of the invention, the substrate present in said barrier layer is present in an amount of said layer whereby said enzyme promotes the alteration of said substrate to such an extent that the barrier layer loses its integrity properties, thereby releasing the rinse benefit agent into the wash liquor. The barrier layer may comprise 1-100% w/w substrate. Thus, the amount of substrate may be at least 10% w/w of the barrier layer, in particular at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80% of the barrier layer w/w. The amount of substrate in the barrier layer may especially be 30-100% w/w of the barrier layer, such as 40-90% w/w, 50-80% w/w, less than 90% w/w, less than 80%, or less than 70%. the

The barrier layer should comprise a water insoluble continuous layer which is preferably hydrophobic and which may contain suspended particles. The main component of the continuous layer may be the substrate, or it may be inert. Thus, the main component may be a triglyceride such as a fat or oil, paraffin, tripalmitin, palm oil, beeswax, jojoba wax, polyester, ester wax, polycaprolactone (PCL), polymers such as polystyrene and polybutylene oxide, and mixtures thereof, or polymers such as polystyrene or polycarbonate. The suspended particles, if present, may contain the enzyme or the substrate, or they may be inert, such as fillers, kaolin, talc, clay, silica, dye particles or calcium carbonate. the

Conventional coatings and methods known in the art may suitably be used, for example the coatings described in WO 89/08694, WO 89/08695, 270 608 B1 and/or WO 00/01793. Other examples of conventional coating materials can be found in US 4,106,991, EP 170360, EP 304332, EP 304331, EP 458849, EP 458845, WO 97/39116, WO 92/12645A, WO 89/08695, WO 89/08694, WO 87/ 07292, WO 91/06638, WO 92/13030, WO 93/07260, WO 93/07263, WO 96/38527, WO 96/16151, WO 97/23606, US 5,324,649, US 4,689,297, EP 206417, EP DE 193829, 4344215, DE 4322229 A, DD 263790, JP 61162185 A and/or JP 58179492. the

During the rinse it is important that the detergent particles do not dissolve or break down before the rinse benefit agent will be released into the wash process. To maintain the structural integrity of the particles, the barrier layer may comprise a material that does not melt or disintegrate when exposed to temperatures above 35°C such that it significantly impairs the properties of the barrier layer, or is not particularly soluble in washing liquid or other aqueous solvents. In another embodiment, the enzyme substrate does not have a melting point in the range of 35°C to 50°C. the

rinse benefit agent

The rinse benefit agents are compounds that perform their function during the rinse cycle of a laundry or dishwasher, either by improving the outcome of the wash process or by delivering a user perceived benefit. In particular, rinse benefit agents include fragrances, encapsulated fragrances, perfumes, pro-fragrances, chemical odor neutralizers, physical odor neutralizers, fiber lubricants, antistatic agents , anti-wrinkle agents, defoamers, photo-protective agents (photo-protective agents), optical brighteners, soil release polymers, stain repellents, anti-fouling agents, fabric softening compounds, antibacterial agents, insecticides, fungicides insect repellents, antioxidants, moisture management agents, shading dyes and pigments, color fixing agents, fabric conditioners, silicone oils, secondary enzymes, and mixtures thereof. For use in dishwashing detergent compositions, the particles of the present invention may include rinse benefit agents such as clear rinsing agents, antibacterial compositions, silver protectants, fragrances, disinfectants, odor masking agents and second enzyme. the

Perfumes useful in the perfume granules of the present invention are those which are effectively released from the perfume granules in sufficient dosage over the desired period of time. It may be selected from, for example, natural essential oils or synthetic fragrances and blends thereof. Many fragrances are polar in nature due to the presence of large amounts of alcohols and other polar compounds. Typical aromatic materials include natural oils such as lemon, orange, clove leaf, cedarwood, rose, or jasmine; natural resins such as labdanum or frankincense; single aromatics that can be isolated from natural sources or synthesized artificially Chemicals such as alcohols such as geranol, nerol, citronellol, linalool, tetrahydrogeranol, betaphenylathyl alcohol, methylphenylcarbinol, dimethylbenzylcarbinol , menthol, or cedrol; acetates and other esters derived from these alcohols; aldehydes, such as citral, citronellal, hydroxycitronellal, lauric aldehyde, undecenal, cinnamaldehyde, amylcinnamaldehyde , vanillin, or piperonal; acetals derived from these aldehydes; ketones, such as methylhexylketone, ionones, and methylionones; phenolic compounds, such as eugenol and isoeugenol; synthetic musks, such as Musk xylene, muscone and ethylene tridecanedioate, etc. the

Fragrances or fragrances can be added to laundry, dishwashing or cleaning compositions to enhance the overall aesthetic appeal of the product and to provide the consumer with not only performance (fabric softness, cleansing) but also a product that can't be wrong. For aromatic oils or perfumes, individual odorant compounds can be used, examples of which are synthetic products of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons. Ester odorant compounds are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylmethyl acetate, phenylethyl acetate, benzoic acid Linalyl, Benzyl Formate, Ethyl Methyl Phenyl Glycinate, Allyl Cyclohexyl Propionate, Phenyl Methyl Methyl Propionate, and Benzyl Salicylate. Such ethers include, for example, benzyl ethyl ether. The aldehydes include, for example, linear normal aldehydes having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and Bojiehong aldehyde. The ketones include, for example, ionones, α-isomethylionone and methyl cedryl ketone. Such alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. the

Preference is given to using mixtures of different odorants, which are mixed so that together they produce an appealing aroma. Such fragrance oils may also contain a mixture of natural odorants obtainable from vegetable sources. Examples are pine oil, citrus oil, jasmine oil, patchouli oil, rose oil or ylang-ylang oil. Also suitable are nutmeg oil, sage oil, chamomile oil, clove oil, nepeta oil, peppermint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil , Frankincense, Gepong and Labdanum Oils, Orange Blossom Oil, Neroli Oil, Orange Peel Oil and Sandalwood Oil. the

In a particular embodiment, the level of perfume is up to 2% by weight of the total detergent composition. The fragrance is typically present in an amount of 10-85% of the total weight of the granules, preferably 20-75% of the total weight of the granules. the

The fragrance suitably has a molecular weight of 50-500. the

Top notes are defined by Poucher (Journal of the Society of Cosmetic Chemists 6(2):80[1955]). Examples of well-known top-notes include citrus oil, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide, and cis-3-hexanol. the

Typical fragrance components which are advantageously encapsulated include those with lower boiling points, preferably those with a boiling point below 300 degrees Celsius, preferably 100-250 degrees Celsius. the

It is also advantageous to encapsulate fragrance components with a low LogP, preferably with a LogP of less than 3.0 (those that are to be partitioned into water). These lower boiling point and lower LogP materials are known as "delayed blooming" fragrance ingredients and include the following materials:

Allyl Caproate, Amyl Acetate, Amyl Propionate, Anisaldehyde, Anisole, Benzaldehyde, Benzyl Acetate, Benzyl Acetone, Benzyl Alcohol, Benzyl Formate, Benzyl Isovalerate, Propionic Acid Benzyl esters, βγ-hexenol, camphor gum, L-carvone, d-carvone, cinnamyl alcohol, cinnamyl formate, cis-jasmone, cis-3-hexenyl acetate , cuminyl alcohol, CyclalC, dimethyl benzyl carbinol, dimethyl benzyl carbinol acetate, ethyl acetate, ethyl acetoacetate, ethyl amyl ketone, ethyl benzoate, ethyl butyrate, ethyl Hexyl Ketone, Ethyl Phenyl Acetate, Eucalyptol, Eugenol, Fenchyl Acetate, Flor Acetate (Tricyclodecenyl Acetate), Frutene (Tricyclodecenyl Propionate), Geranium Alcohol, Hexanol, Hexenyl Acetate, Hexyl Acetate, Hexyl Formate, Hydroxytropol, Hydroxycitronellal, Indanone, Isoamyl Alcohol, Isomenthone, Isopulegyl Acetate, Isoquinoline Ketone, privet aldehyde, linalool, linalool oxide, linalyl formate, menthone, menthyl acetphenone, methyl amyl ketone, methyl anthranilate, methyl benzoate, methyl benzyl ethyl Ester, methyl eugenol, methyl heptenone, methyl heptyne carbonate, methyl heptyl ketone, methyl hexyl ketone, methyl phenylmethyl acetate, methyl salicylate, N-methyl Methyl anthranilate, nerol, capryllactone, octanol, p-cresol, p-cresol methyl ether, p-methoxyacetophenone, p-methylacetophenone, phenoxyethanol , phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethyl dimethyl carbinol, prenyl acetate, propyl bornate, menthol, rose ether, sassafras, 4-terpine Alcohol, alpha-terpineol and/or viridine. the

Some or all of the fragrances may be in pro-perfume form. For the purposes of the present invention, a pro-perfume is any material comprising a pro-perfume that can be converted into a perfume. the

Suitable pro-perfumes are those which yield a fragrance component which is an aldehyde. Aldehydes that can be used in fragrances include, but are not limited to, phenylacetaldehyde, p-methylphenylacetaldehyde, p-cymenealdehyde, methylinonylacetaldehyde, phenylpropanal, 3-(4-tert-butylphenyl)-2- Methylpropanal, 3-(4-tert-butylphenyl)propanal, 3-(4-methoxyphenyl)-2-methylpropanal, 3-(4-isopropylphenyl)- 2-methylpropanal, 3-(3,4-methylenedioxyphenyl)-2-methylpropanal, 3-(4-ethylphenyl)-2,2-dimethylpropanal Aldehyde, phenylbutyraldehyde, 3-methyl-5-phenylpentanal, hexanal, trans-2-hexenal, cis-hex-3-enal, heptanal, cis-4-heptanal Enal, 2-ethyl-2-heptenal, 2,6-dimethyl-5-heptenal, 2,4-heptadienal, octanal, 2-octenal, 3,7- Dimethyloctanal, 3,7-dimethyl-2,6-octadiene-1-al, 3,7-dimethyl-1,6-octadiene-3-al, 3,7- Dimethyl-6-octenal, 3,7-dimethyl-7-hydroxyoct-1-al, nonanal, 6-nonenal, 2,4-nonadienal, 2,6-nonanal Dienal, decanal, 2-methyldecenal, 4-decenal, 9-decenal, 2,4-decenal, undecanal, 2-methyldecenal, 2-methyl Undecanal, 2,6,10-trimethyl-9-undecenal, undec-10-enyl aldehyde, undec-8-enal, dodecanal, tridecanal, tetradecanal, Anisaldehyde, bourgenonal, cinnamaldehyde, a-amylcinnamaldehyde, a-hexylcinnamaldehyde, methoxy-cinnamaldehyde, citronellal, hydroxycitronellal, isocyclic citral, citronellyloxyacetaldehyde, cortexaldehyde, cumminic aldehyde, cyclamen aldehyde, cyanaldehyde, piperonal, hydrotropic aldehyde, lilial, vanillin, ethyl vanillin, benzaldehyde, p-tolualdehyde, 3,4- Dimethoxybenzaldehyde, 3- and 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 2,4-dimethyl-3-cyclohexene-1 - Formaldehyde, 1-methyl-3-(4-methylpentyl)-3-cyclohexene-carbaldehyde, p-methylphenoxyacetaldehyde and mixtures thereof. the

Suitable fabric softening and/or finishing agents are preferably selected from those of the cationic detergent active type, clays and silicones. Those of the cationic detergent active type are preferably selected from quaternary ammonium cationic molecules, for example those having a solubility in water of less than 10 g/l at pH 2.5 and 20°C. the

Fabric softening compounds that may be included in the particles of the present invention may be cationic, such as substantially water-insoluble quaternary ammonium materials comprising a single alkyl or alkenyl group having an average chain length greater than or equal to _C20 chain, or more preferably, a compound comprising a polar head group and two alkyl or alkenyl chains having an average chain length greater than or equal to _C14 . Preferably, the fabric softening compound has two long chain alkyl or alkenyl chains each having an average chain length greater than or equal to _C16 . Most preferably, at least 50% of said long chain alkyl or alkenyl groups have a chain length of C ₁₈ or higher. It is preferred if the long chain alkyl or alkenyl groups of the fabric softening compound are predominantly linear. Silicones with similar functional properties may also be preferred.

It is preferred that the ester-linked quaternary ammonium compound contains two or more ester groups. In monoester and diester quats, it is preferred if the ester group is the linkage between the nitrogen atom and the alkyl group. The ester group is preferably attached to the nitrogen atom via another hydrocarbyl group. the

If the fabric softening and/or finishing category is silicone, suitable materials include: non-volatile silicone fluids such as poly(di)alkylsiloxanes, especially polydimethylsiloxanes and carboxylated or ethyl Oxylated variant. They can be branched, partially crosslinked or preferably linear aminosilicones, including any organosilicones with amine functionality. the

Suitable silicones include dimethyl, methyl(aminoethylaminoisobutyl)siloxane, which typically has a dynamic viscosity (when measured at 25°C and a shear rate of about 100s) of 100 mPas to 200,000 mPas, and an average amine content of about 2 mol%. the

The second enzyme may be used for: bacterial control (such as protease or lysozyme), as fabric care active agent (such as cellulase), as activator (such as lipase degrading pro-fragrance or pro-bleach molecules), Used to prevent biofilm or to prevent odors in washing machines that always wash at low temperatures. the

The rinse benefit agent may be present in the particle in an amount of 1-95%, preferably 10-95%, more preferably 30-90%. the

enzyme acting on a substrate

The enzyme may hydrolyze the enzyme substrate or assist in a process that alters its properties such that its barrier properties are disrupted and thus the structural integrity of the particle is destabilized. In the context of the present invention, the enzyme may be any enzyme or a combination of different enzymes. Thus, when an "enzyme" is mentioned, it will generally be understood not only as a single enzyme, but also as a combination of more than one enzyme. the

The particles of the invention may comprise at least one, at least two or at least three enzymes. the

It is to be understood that enzyme variants (eg produced by recombinant techniques) are included within the meaning of the term "enzyme". Examples of such enzyme variants are disclosed, for example, in EP 251,446 (Genencor), WO 91/00345 (Novo Nordisk), EP 525,610 (Solvay) and WO 94/02618 (Gist-Brocades NV). the

The classification of enzymes adopted in the specification and claims of the present invention is based on Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Academic Press, Inc., 1992. the

Thus, enzyme types that may be suitably incorporated into the granules of the invention include oxidoreductases (EC 1.-.-.-), transferases (EC 2.-.-.-), hydrolases (EC 3.-.- .-), lyase (EC 4.-.-.-), isomerase (EC 5.-.-.-) and ligase (EC 6.-.-.-). the

Preferred oxidoreductases in the context of the present invention are peroxidases (EC 1.11.1) and laccases (EC 1.10.3.2). the

Preferred hydrolases in the context of the present invention are: carboxylate hydrolases (EC 3.1.1.-), such as lipases (EC 3.1.1.3); phytases (EC 3.1.3.-), for example 3 - phytases (EC 3.1.3.8) and 6-phytases (EC 3.1.3.26); glycosidases (EC 3.2, which fall within the group denoted herein by "sugarases"), such as alpha-amylases ( EC 3.2.1.1). the

In the context of the present invention, the term "glycosidase" is used not only to denote enzymes (i.e. glycosidases, EC3. Used to denote enzymes capable of isomerizing carbohydrates, for example six-membered ring structures such as D-glucose to five-membered ring structures such as D-fructose. the

Related carbohydrases include the following (EC numbers are in brackets):

α-amylase (EC 3.2.1.1), β-amylase (EC 3.2.1.2), dextran 1,4-α-glucosidase (EC 3.2.1.3), endo-1,4-β- Glucanase (cellulase, EC 3.2.1.4), endo-1,3(4)-β-glucanase (EC 3.2.1.6), endo-1,4-β-xylanase ( EC 3.2.1.8), dextranase (EC 3.2.1.11), chitinase (EC 3.2.1.14), polygalacturonase (EC 3.2.1.15), lysozyme (EC 3.2.1.17) , β-glucosidase (EC 3.2.1.21), α-galactosidase (EC 3.2.1.22), starch-1,6-glucosidase (EC 3.2.1.33), xylan 1,4-β -xylosidase (EC 3.2.1.37), endoglucan-1,3-β-D-glucosidase (EC 3.2.1.39), endo-dextrin-1,6-α-glucosidase ( EC 3.2.1.41), endoglucan-1,3-α-glucosidase (EC 3.2.1.59), endoglucan 1,4-β-glucosidase (EC 3.2.1.74), endoglucan -1,6-β-glucosidase (EC 3.2.1.75), intra-arabinan-1,5-α-L-arabinosidase (EC 3.2.1.99), chitosanase (EC 3.2.1.132) . the

Examples of commercially available lipases include Lipoprime ^™ , Lipolase ^™ , Lipolase ^™ Ultra, Lipozyme ^™ , Palatase ^™ , Novozym ^™ 435 and Lecitase ^™ (all obtained from Novozymes A/S).

Other commercially available lipases include Lumafast ^™ (Pseudomonas mendoza lipase from Genencor International Inc.); Lipomax ^™ (Ps. pseudoalcaligenes lipase from Gist-Brocades/Genencor Int. Inc.); and Solvay Bacillus sp. lipase enzymes. Other lipases are available from other suppliers.

Examples of commercially available carbohydrases include Alpha-Gal ^™ , Bio-Feed ^™ Alpha, Bio-Feed ^™ Beta, Bio-Feed ^™ Plus, Bio-Feed ^™ Plus, Novozyme ^™ 188, Celluclast ^™ , Cellusoft ^™ , Ceremyl ^™ , Citrozym ^TM , Denimax ^TM , Dezyme ^TM , Dextrozyme ^TM , Finizym ^TM , Fungamyl ^TM , Gamanase ^TM , Glucanex ^TM , Lactozym ^{TM , Maltogenase TM , Pentopan TM , Pectinex TM} , Promozyme ^TM , Pulpzyme ^TM , Termamyl ^{TM ,} Novamyl AM ^™ (Amyloglucosidase Novo), Maltogenase ^™ and Aquazym ^™ (all available from Novozymes A/S). Other carbohydrases are available from other suppliers.

Enzyme substrate

The enzyme substrates used in the present invention are materials that can be modified, degraded and/or altered by the enzymes used in the present invention. In a particular embodiment of the invention, said enzyme and said substrate are present in said particle in such an amount that the structure of said substrate is altered such that said particle loses its integrity and The extent to which the rinse benefit agent is thereby released into the rinse liquor. The substrate is preferably water insoluble. the

enzyme-substrate pair

The term "enzyme-substrate pair" is used in relation to the enzyme and substrate contained in the particle, and wherein the "substrate" is a substrate of the enzyme, meaning that the enzyme will recognize the the substrate and will react with it. the

The enzyme is used to alter the substrate to release the rinse benefit agent into the process. This means that if an enzyme is selected, a substrate set is given for selection and vice versa. the

If lipase is chosen, examples of lipase substrates, which do not have to be natural, include but are not limited to lipids, mono-, di-, and triglycerides such as tripalmitin, palm oil, beeswax, jojoba Jojoba wax, polyester, ester wax, polycaprolactone (PCL) and mixtures thereof. the

If cutinases are selected, examples of cutinase-degradable materials, which need not be natural, include, but are not limited to, triglycerides, waxes, polyesters, and mixtures thereof. In a particular embodiment of the invention, said enzyme is cutinase, and said enzyme substrate is selected from tripalmitin, palm oil, beeswax, jojoba wood wax, polyester, ester wax, polycaprolactone Esters (PCL) and their mixtures. the

If cellulase is selected, examples of cellulase substrates include, but are not limited to, cellulose, methylcellulose, ethylcellulose, propylcellulose, carboxymethylcellulose, cellulose monoacetate, cellulose diacetate , cellulose triacetate, rayon, cuprammonium rayon, crystalline cellulose, amorphous cellulose, β-1,3-1-4-glucan and mixtures thereof. the

If a polysaccharide lyase or polysaccharide hydrolase is selected, a polysaccharide-containing material is given as an enzyme substrate. Examples of polysaccharide-containing materials include, but are not limited to, gellan gum, xanthan gum, schizophillan gum, sclerodextran gum, alginates, carageenan gum, and pectins such as protopectin or pectic acid. the

In a particular embodiment of the invention, said enzyme is pectin lyase, and said enzyme substrate is selected from pectins with various modifications. the

If xylanase is selected, xylan-containing material is given. Examples of xylan-containing enzyme substrates include, but are not limited to, xylan and carboxymethylxylan. the

In a specific embodiment of the present invention, said enzyme is xylanase, and said enzyme substrate is selected from birch wood xylan, wheat xylan, oat chiffon xylan, corncob xylan. the

If an amylase is selected, a starch-containing enzyme substrate is given. Starch is a mixture of amylose and amylopectin. The ratio of these two components can vary. The naturally occurring form is in the range of 20:80-30:70. For the purposes of the present invention, an amylase may mean any enzyme capable of altering the intermolecular bonds present in amylose or amylopectin. the

Mixtures of the enzyme substrates mentioned in the above sections are possible and can provide unique barrier properties. Furthermore, the barrier properties of such mixtures can be partially or completely destroyed by using enzymes acting on the components of said mixtures. the

Other non-limiting examples of enzyme substrate-enzyme pairs are:

Polyhydroxyalkanoate (PHA), such as polyhydroxybutyrate (PHB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), Polyhydroxycaprylate (PHO) and their copolymers. These compounds were first discovered in bacteria such as Alcaligenes eutrophus. PHAs. Enzymes that can modify PHA have been identified, such as polyhydroxybutyrate depolymerase (EC 3.1.1.75). the

Non-limiting examples of enzymes related to modified starches and starch-based biopolymers are: amylases, glucoamylases ((EC 3.2.1.3) and EC 3.2.1.20), amylases (EC 3.2.1.1); Pullulanase (EC 3.2.1.41); (producing) maltoamylase (EC 3.2.1.133); neopullulanase (EC 3.2.1.135); maltotetraose-forming a-amylase (EC 3.2.1.60); isoamylase (EC 3.2.1.68); gluco-dextranase (gluco-dextranase) (EC 3.2.1.70); maltohexaose-forming a-amylase (EC 3.2.1.98); Maltopentaose-forming a-amylase (EC 3.2.1.-). the

Suitable substrates for amylases include thermoplastic starches, which are raw starches to which flexibilisers and plasticizers such as sorbitol or glycine are added. The amount of plasticizer added affects the properties of the thermoplastic starch. the

Recently, blending starch with degradable synthetic aliphatic polyesters such as PLA and PCL has become the focus of research and development of biodegradable plastics. Biodegradable plastics can be prepared by blending up to 45% starch with degradable PCL. This new material is suitable for coating payload particles since the melting temperature is typically only 60°C and it softens at temperatures above 40°C. The following are non-limiting examples of such blends: Mater-Bi™ (manufactured by Novamont, Italy) and Bioflex™ (manufactured by Biotech Germany). the

Other polyesters that are blended with starch to improve the mechanical properties of the material are polybutylene succinate (PBS) or polybutylene succinate adipate (PBSA). A small amount (5% by weight) of a compatibilizer (maleic anhydride functionalized polyester) can be added to impart phase stability to these starch based polymer blends. At higher starch contents (>60%), such sheets may become brittle. For this reason, plasticizers are usually added to reduce brittleness and improve flexibility. Starch content and addition of plasticizers can be used to modify physical properties or melting temperature. the

An enzyme capable of modifying chitin is for example chitinase (EC 3.2.1.14). Chitin is a polysaccharide synthesized from N-acetylglucosamine units. These units form covalent β-1,4-bonds (similar to the bonds between glucose-forming cellulose units). The acetamide groups allow for increased hydrogen bonding between adjacent polymers, imparting increased strength to the chitin-polymer matrix. The chitin layer does exhibit barrier properties that can be tuned by degree of acetylation or other modifications. Other known modifications include, but are not limited to: phosphated chitin (P-chitin), phosphorylated-sulfated chitin (PS-chitin), and sulfated chitin (S-chitin). Chitin). the

In addition to hydrolysis of the chitin barrier layer, chitin can also be deacetylated by the action of enzymes such as chitin deacetylase (EC-3.5.1.41). Complete deacetylation results in the conversion of chitin to chitosan. Chitosan can be gel-like, water- and fat-absorbent, and is indeed mechanically less strong than chitin. Therefore, one method of the present invention consists in using chitin as a barrier substance and chitin deacetylase as an enzyme pair. In formulated particles, complete or even partial deacetylation of chitin will enable the release of the payload. In addition, chitosan has a bioadhesive effect such that conversion of all or some of the chitin in the barrier layer can also affect the binding of the particles to components in the chosen application. the

DLN Dispersion W 50，其为Bayer生产的阴离子脂肪族聚酯-聚氨酯分散体(Bayer MaterialScience AG，D-51368 Leverkusen，Germany  www.bayercoatings.com)。可将所述含水分散体施加至颗粒，在那里聚酯可形成阻隔层。Bionolle是Showa Highpolymer Co.，Ltd，Japan生产的可生物降解树脂。Ecoflex 

为BASF的可完全生物降解和可堆肥的塑料。BAK1095是Bayer的热塑性聚酯酰胺。  Bioplastics; polyester resins such as Impranil can be used

DLN Dispersion W 50, which is an anionic aliphatic polyester-polyurethane dispersion produced by Bayer (Bayer MaterialScience AG, D-51368 Leverkusen, Germany www.bayercoatings.com ). The aqueous dispersion can be applied to particles where the polyester can form a barrier layer. Bionolle is a biodegradable resin produced by Showa Highpolymer Co., Ltd, Japan. Ecoflex

Fully biodegradable and compostable plastic for BASF. BAK1095 is Bayer's thermoplastic polyester amide.

Polyester wax is a synthetic wax (Nature, 1957, 1791345). It has a low melting point of 37°C. the

The wax is soluble in most organic solvents, including alcohols, ethers, esters, ketones and hydrocarbons; heating to 25°C facilitates dissolution. the

Ester wax 1960 is a synthetic wax (Quarterly Journal of Microscopical Science, Vol. 101, 459-462, 1960). This wax is a typical blend of ester waxes, consisting of:

Diethylene glycol distearate 60g

Glyceryl Monostearate 30g

300 macrogol distearate 10g

Ester Wax 1960 has a melting point of 48°C. Adjustment of the melting temperature is achieved by adjusting the relative component concentrations. the

Polycaprolactone (PCL) is a biodegradable polyester with a low melting point of about 60°C and a glass transition temperature of about -60°C. PCL can be prepared by ring-opening polymerization of ε-caprolactone using a catalyst such as stannous octoate. As mentioned in the previous section, PCL can be blended with starch to form thermoplastic starch. Amylose degrading enzymes can be used to degrade this blend. In addition, PCL itself is degradable by serine esterase. In the following non-limiting examples, lipase (EC 3.1.1.3) and cutinase (EC 3.1.1.74) have been shown to degrade PCL plastic (US Patent US 6255451 B1). In addition, commercial products such as Impranil, Bionolle and Ecoflex are also degradable by serine esterase. Ester waxes and polyester waxes are also degradable by the same enzymes. the

In addition to the waxes and plastics mentioned above, the following natural products can also be degraded by serine esterases such as lipase and cutinase: rosin gum, beeswax, jojoba wood wax. Essentially any natural fat or oil can be used as a barrier material in the present invention, and these materials can be degraded by serine esterases such as lipase or cutinase. the

Auxiliary Granular Components

The granules may further comprise conventional materials known for use in the formulation of active ingredients as auxiliary granule components, such as binders, solvents, fillers, etc., e.g. as in WO 89/08694, WO 89/08695, EP 270608 B1 and /or as described in WO 00/01793. Other examples of conventional coating materials can be found in US 4,106,991, EP 170360, EP 304332, EP304331, EP 458849, EP 458845, WO 97/39116, WO 92/12645A, WO 87/07292, WO 91/06638, WO 92/13030 , WO 93/07260, WO 93/07263, WO 96/38527, WO 96/16151, WO 97/23606, US 5,324,649, US 4,689,297, EP 206417, EP 193829, DE 4344215, DE 43226229A, DD 26379 /or in JP 58179492. the

filler

Suitable fillers are water-soluble and/or inorganic salts such as finely ground alkali metal sulfates, alkali metal carbonates and/or alkali metal chlorides), clays such as kaolin (for example Speswhite ^™ , English China Clay), bentonite, Talc, zeolites such as zeolite 4A or zeolite A24, chalk, calcium carbonate, silicates and/or silicon dioxide.

binder

Suitable binders are those with a high melting point or no melting point at all and of non-waxy nature, for example polyvinylpyrrolidone, polyvinyl alcohol, high melting point ethoxylated alcohols, high melting point Polyethylene glycol or polyoxyethylene, cellulose derivatives such as hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose or carboxymethylcellulose, carbohydrate binders such as starch, dextrin, Maltodextrins, pregelatinized starches, sugars and polyols such as sucrose, mannitol, lactose and sorbitol, gums such as acacia, pectin or alginates, protein type binders such as gelatin, or art Any other binder known. Suitable binders are carbohydrate binders such as Glucidex 21D available from Roquette Freres, France, or Avedex W80 available from Avebe, Netherlands. the

Granule preparation

The invention further provides a process for preparing the particles of the invention. the

The granules can be prepared by methods known to those skilled in the art of granulation, including mixer granulation, fluid bed coating, prilling, disc granulation, pan drum coating, spraying Drying, extrusion, fluid bed spray drying, high shear agglomeration, spheronization or combinations of these techniques. the

Relevant particles may be, but are not limited to, layered products, absorbent products, pelletized products and prilled products. The granules may optionally be dried after granulation. After granulation the granules can be further sieved. the

Methods for preparing such particles can be found in Handbook of Powder Technology; Particle size enlargement, C.E. Capes; Vol. 1; 1980; Elsevier. Preparation methods include known granulation techniques, namely:

a) A spray-dried product wherein a solution comprising a liquid rinse benefit agent is atomized within a spray drying tower to form small droplets which dry during their descent down the drying tower to form particulate material containing a rinse benefit agent . In this way, extremely small particles can be prepared (Michael S. Showell (editor); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker). the

b) layered products, wherein the rinse benefit agent is applied as a layer around a pre-formed inert core particle, wherein a solution containing the rinse benefit agent is atomized, typically a stream in which the pre-formed core particle is fluidized in a bed apparatus, and the solution containing the active ingredient is attached to the core particle and dried to leave a layer of dry active ingredient on the surface of the core particle. Particles of the desired size can be obtained in this manner if available core particles of the desired size can be found. Such products are described, for example, in WO 97/23606. the

c) Absorbent core particles wherein, rather than coating the rinse benefit agent as a layer around the core, the rinse benefit agent is absorbed to and/or into the surface of the core. Such methods are described in WO 97/39116. the

d) Extruded or pelletized products, where the rinse benefit agent containing paste is compressed into pellets, or extruded under pressure through a small orifice and cut into pellets, which are then dried. Such particles are usually of considerable size because the material from which the extrusion orifice is made (usually a plate with drilled holes) sets limits on the allowable pressure drop across the extrusion orifice (Michael S. Showell (ed.) ; Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker). the

e) Pelletized products where the rinse benefit agent in powder form is suspended in molten wax and the suspension is sprayed, for example by means of a rotating disk atomizer, into a cooling chamber where the droplets solidify rapidly (Michael S. Showell (ed. ); Powdered detergents; Surfactant Science Series; 1998; Vol. 71; pp. 140-142; Marcel Dekker). The resulting product is one in which the rinse benefit agent is evenly distributed throughout the inert material rather than being concentrated on its surface. In addition, US 4,016,040 and US 4,713,245 are also documents related to this technology. the

f) Mixer granulated products where the liquid containing the rinse benefit agent is added to a dry powder composition of conventional granulated ingredients. The liquid and powder are mixed in appropriate proportions, and as the moisture of the liquid is drawn into the dry powder, the components of the dry powder will begin to adhere and agglomerate and will build up the particles, forming particles containing the rinse-off benefit agent. Such methods are described in US 4,106,991 (NOVO NORDISK) and related documents EP 170360 B1 (NOVO NORDISK), EP 304332 B1 (NOVO NORDISK), EP 304331 (NOVO NORDISK), WO 90/09440 (NOVO NORDISK) and WO 90/09428 (NOVO NORDISK). the

g) size reduction, wherein the core is prepared by grinding or crushing larger granules, pellets, flakes, cakes, etc. containing the rinse benefit agent. The desired core particle fraction is obtained by sieving the ground or broken product. Both oversized and undersized particles can be recovered. Pulverization is described in (Martin Rhodes (editor); Principles of Powder Technology; 1990; Chapter 10; John Wiley & Sons). the

h) Fluidized bed granulation. Fluidized bed granulation involves suspending particles in a stream of air and spraying a liquid onto the fluidized particles through nozzles. Particles hit by spray droplets become wet and sticky. The sticky particles collide with other particles and adhere to them and form agglomerates. the

i) The core and granules may be dried, for example in a fluid bed drier. Other known methods of drying pellets in the feed or enzyme industry can be used by those skilled in the art. The drying is preferably carried out at a product temperature of 25-90°C. After drying, the core preferably comprises 0.1-10% w/w water. the

A layer may be applied to the granules comprising the active ingredient by atomization onto the granules in a fluidized bed or fluidized bed spray dryer, which layer may further be applied in a mixer, dragee type Coating machines (pan-drum coaters), equipment for coating seeds, equipment containing rotating bottoms (eks. Roto Glatt, CF granulators (Freund), torbed processors (Gauda) or in rotating flow Apply in a chemical bed processor such as Omnitex (Nara).

After applying the barrier layer, the particles can optionally be dried. Drying of the particles can be achieved by any drying method available to the skilled person, such as spray drying, freeze drying, vacuum drying, fluid bed drying, drum coating and microwave drying. Drying of the granules can also be combined with granulation methods which include, for example, the use of fluidized beds, fluidized bed spray dryers (FSD) or multi-stage dryers (MSD). the

Conventional coatings and methods known in the art may suitably be used, such as the coatings described in Danish PA2002 00473, WO 89/08694, WO 89/08695, 270608 B1 and/or WO 00/01793. Other examples of conventional coating materials can be found in US 4,106,991, EP 170360, EP304332, EP 304331, EP 458849, EP 458845, WO 97/39116, WO 92/12645A, WO 89/08695, WO 89/08694, WO 87/07292 , WO 91/06638, WO 92/13030, WO 93/07260, WO 93/07263, WO 96/38527, WO 96/16151, WO 97/23606, WO 01/25412, WO 02/20746, WO 02/28369 , US 5879920, US 5,324,649, US 4,689,297, US 6,348,442, EP 206417, EP 193829, DE 4344215, DE4322229A, DE 263790, JP 61162185A and/or JP 58179492. the

In a particular embodiment, the base coating is applied by hot melt coating in a fluidized bed. This method is well known in the art. Molten coating material is sprayed onto the core in a fluidized bed. The fluidizing gas has a temperature below the solidification temperature of the coating material (see for example Teunou & Poncelet, "Fluid Bed Coating" in "Encapsulated And Powdered Foods", edited by Onwulata, CRC Press 2005). the

In a specific embodiment, the method for preparing particles of the present invention comprises the following steps:

a) preparing a core comprising a benefit agent;

b) optionally applying a protective layer to the core of a);

c) applying an enzyme-containing layer; and

d) applying one or more barrier layers comprising a material degradable by the enzyme in c). the

Optional other coatings

The particles may comprise other layers or coatings in addition to the barrier layer to provide further improved properties to the particles. the

Optionally, prior to applying the coating of the present invention, the particles may be precoated by applying a protective precoat to the core comprising the rinse benefit agent. The pre-coat may serve to protect and retain the rinse benefit agent during further processing and may consist of, for example, a fat or oil. the

Compositions comprising said particles and their applications

The particles of the present invention may be added to cleaning compositions for textile and hard surface treatment, including fabric and household care detergent products. the

detergent

The granules of the present invention are useful as components of detergent compositions. The detergent composition may, for example, be formulated as a laundry or dishwashing detergent composition for hand or machine washing, including a cleaning additive composition or a fabric softener composition suitable for pre-treatment of soiled fabrics, or for general household use. Detergent compositions for hard surface cleaning operations, or compositions for hand or machine dishwashing operations. the

The detergent composition may be in any convenient dry form such as bars, tablets, powder, granules or paste. It may also be a liquid detergent, especially a low aqueous (less than 70% by weight) or non-aqueous liquid detergent. the

The detergent composition comprises one or more surfactants, which may be nonionic (including semi-polar) and/or anionic and/or cationic and/or zwitterionic. The level of surfactant is typically from 0.1% to 60% by weight. In dishwashing detergents it is typically 0.1-15%, especially 2-12%. the

When included therein, the detergent will generally contain from about 1% to about 40% of anionic surfactants such as linear alkylbenzene sulfonates, alpha-olefin sulfonates, alkyl sulfates (fatty alcohol sulfates) salts), alcohol ethoxy sulfates, secondary alkyl sulfonates, alpha-sulfo fatty acid methyl esters, alkyl or alkenyl succinic acids or soaps. the

When included therein, the detergent will generally contain from about 0.2% to about 40% of nonionic surfactants such as alcohol ethoxylates, nonylphenol ethoxylates, alkyl glycosides, alkyl dimethyl Amine oxides, ethoxylated fatty acid monoethanolamides, fatty acid monoethanolamides, polyhydroxyalkyl fatty acid amides, or N-acyl-N-alkyl derivatives of glucosamine ("glucamides"). In dishwashing detergents, the level of nonionic surfactants is typically 2-12%. the

The detergent may contain 0-65% of detergent builders or complexing agents such as zeolites, diphosphates, triphosphates, phosphonates, carbonates, citrates, nitrilotriacetic acid, Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, alkyl or alkenyl succinic acids, soluble or layered silicates (such as Hoechst's SKS-6). In dishwashing detergents, the level of builder is typically 40-65%, especially 50-65%. the

The detergent composition may comprise one or more other enzymes, such as protease, lipase, cutinase, amylase, carbohydrase, cellulase, pectinase, mannanase, arabinase, galactase Glycanases, xylanases, oxidases, such as laccases and/or peroxidases. the

The detergent may comprise one or more polymers. Examples are carboxymethylcellulose, poly(vinylpyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylic acid Esters/salts such as polyacrylates/salts, maleic/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers. the

The detergent may comprise a bleaching system which may comprise a _source of _H202 such as perborate or percarbonate which can form with peracids a bleach activator such as tetraacetylethylenediamine or nonanoyloxybenzenesulfonate salt binding. Alternatively, the bleaching system may comprise, for example, peroxyacids of the amide, imide or sulfone type. Dishwashing detergents typically contain 10-30% bleach system.

The detergent may also contain other conventional detergent ingredients such as fabric conditioners including clays, suds boosters, suds suppressors, corrosion inhibitors, soil suspending agents, anti-soil redeposition agents, dyes, bactericides, optical brighteners additives, hydrotropes, tarnish inhibitors or fragrances. the

washing process

The term "rinse cycle" refers to the cycle following the main wash cycle in a laundry wash or dishwashing process in which the wash load is treated with rinse water to remove wash load detergent. the

For detergents such as laundry or dishwashing detergents, it is desirable that the particles release one or more rinse benefit agents into one or more rinse cycles following the main wash cycle to maximize the effectiveness of the rinse benefit agents. It is envisioned that the present invention may be used in a wide range of wash cycles, whereby it may be necessary to adjust the composition and/or morphology of the particles to optimize their release characteristics. the

A typical washing process will involve the use of a front-loading automatic machine, which may include an extra-long, high-temperature wash cycle with high levels of mechanical agitation, followed by two, three or four short rinse cycles. Top loading automatic or semi-automatic machines can be employed which will involve the use of a short, low temperature main wash cycle followed by only one or two rinse cycles. It is also contemplated that the present invention will be used in hand washing processes where the wash cycle is at ambient temperature and of varying duration and involves variable levels of mechanical agitation. During this manual washing process, the number of rinse cycles can vary from one to seven. the

In a preferred embodiment, the triggered release particles are incorporated into the main detergent composition and thus added to the wash process in a manner typically associated with a particular wash process and well known to those skilled in the art. the

In another embodiment, the trigger release particles are incorporated in an additional detergent component, wherein the additional detergent component is contained within a dosing device so as to remain separate from the main detergent composition until both Contacts the liquid of the main wash cycle and helps keep the particles intact from one cycle to the next in the wash container. the

Example

Example 1

This example describes screening assays to assess the activity profiles of enzyme and substrate pairs or combinations (enzyme activity under wash versus rinse conditions, respectively, in a laundry process). The purpose of this analysis is to select enzyme and substrate pairs that exhibit the desired activity profile, ie low enzyme activity during wash conditions relative to enzyme activity during rinse. the

For demonstration (Table 1 below), we give an activity index (score parameter) from a series of data comparisons. For a given enzyme-substrate pair, enzyme activity is quantified under wash and rinse conditions, respectively. The activity index is obtained by multiplying the difference between rinse and wash period net activities by the sum of wash and rinse period activities. Table 1 below lists the activity indices calculated for a series of preferred hydrophobic substrates with two esterases - cutinase and lipase. Note that the polyester system exhibited a negative activity index, indicating that these combinations of enzymes and potential substrates hydrolyze faster under wash conditions than under rinse conditions. Very high activity indices were recorded for combinations of glycerides with lipases, especially mono-, di- and tripalmitin. the

The particular experiments described were performed in beaker format at room temperature; alternatively, such analyzes could take the form of HTS assays in microtiter plates. The potential substrates were suspended in a buffer solution adjusted to pH 9 with the nonionic surfactant TX-100. We assessed enzyme activity in this assay by monitoring the pH change resulting from hydrolysis using a standard pH meter. Alternative methods include, but are not limited to, light scattering, calorimetry, ultrasonic velocimetry, and spectrophotometry. the

Table 1

Example 2

A 4 kg Na ₂ SO ₄ core (350-500 μm) sample was transferred to a GEA MP 3/2/3 conventional fluid bed unit. Using the bottom spray/Wurster coating technique, with an air inlet temperature of about 65°C, an air outlet temperature of about 43°C and an air volume of 250kg/hour, the following steps are carried out in sequence:

(蛋白酶)水溶液(浓缩物)，将含酶层施加在Na₂SO₄芯上。每千克芯施加约250g Savinase 

浓缩物。添加浓缩物后，使水从涂覆的芯蒸发(直至在流化床中温度迅速升高)。  a) by spraying Savinase at a rate of 30g/min

(protease) aqueous solution (concentrate), the enzyme-containing layer was applied on _{a Na2SO4} core. Approx. 250g Savinase per kg core

concentrate. After adding the concentrate, the water was allowed to evaporate from the coated core (until the temperature rose rapidly in the fluidized bed).

浓缩物在1kg水中)喷雾至a)的产物上，施加0.02g脂肪酶(Lipex )/kg芯的额外酶层。  b) by spraying lipase aqueous solution (0.6g Lipex

Concentrate in 1 kg of water) was sprayed onto the product of a), 0.02 g of lipase (Lipex )/kg core of additional enzyme layer.

c) Apply the final coat by spraying 200 g molten (heated to about 100° C.) tripalmitin/kg product at a spray rate of 30 g/min. the

Subsequently, the completed enzyme-containing granules were cooled to room temperature for 20 minutes. the

Example 3

Enzyme-containing granules were produced as in Example 2, except that no lipase coating was applied to the product. the

Example 4

Enzyme-containing granules were produced as in Example 2, except that no lipase coating was applied, and PEG4000 was used instead of tripalmitin as the final coating. the

Example 5

Enzyme-containing granules were produced as in Example 2, except that palm oil was used instead of tripalmitin as the substrate, and spray-dried lipase was mixed into palm granules before applying a coating comprising substrate and lipase to the core granules. inside the oil. the

Example 6

The release profiles of the granules produced according to Examples 2, 3 and 4 during wash and rinse conditions were investigated by using the following analysis:

a) Mix 0.6g of liquid detergent (containing 30% water, 20% Neodol 25-7EO [ex Shell Chemicals], 14% alkylbenzenesulfonic acid, 9% monopropylene glycol, 7% sodium lauryl triethoxysulfate, 5% glycerol, 5% Prifac 5908 [ex Uniqema], 3% triethanolamine, 3% sodium hydroxide, 1% citric acid) were added to 100 ml of water (dH° 12) in a glass beaker. the

b) Transfer 20 mg of the granulate into a tea bag (with 160 μm mesh size, allowed to flow through) which is then placed in the glass beaker of a). the

c) Stir the glass beaker and take 2ml samples every 5 minutes. Immediately after the sample was taken, the sample was placed in the refrigerator. the

d) After 40 minutes under wash conditions, the teabags with granules were transferred to a new glass beaker with 100ml of tap water. Stirring was applied and 2 ml samples were taken every 5 minutes. the

e) After 10 minutes under rinse conditions, transfer the teabag with granules to a new glass beaker with 100ml of tap water. Stirring was applied and 2 ml samples were taken every 5 minutes. The rinse conditions were repeated 4 times in total. the

)活性。  f) Analysis of enzyme (Savinase) on all samples taken from wash and rinse solutions

)active.

释放的百分数给出。  The results are shown in Table 2, where the enzymatic activity of the samples is represented by the total Savinase of each particle

The percentage released is given.

Table 2

the release during washing release during rinsing Granules (Example 1) 20% 80% Granules (Example 2) 2% 8% Granules (Example 3) 100% - Granules (Example 5) 20% 80%

From the results it is evident that the desired release profile is obtained when the enzyme and substrate are present in the granules. The results show that it is possible to prepare particles where during the wash the ingredients that will be used in the rinse cycle will be released as they were during the rinse. the

Example 7

Fragrance-containing particle cores were produced intermittently by adding 1.86 kg of zeolite A24 to a Roto Junior mixer (ex Zanchetta). Turn on the impeller and chopper, and slowly add 250 g of fragrance (containing 11.3% 2-(1,1-dimethylethyl)-cyclohexanol 1-acetate, 1.6% 1-(2,6 , 6-trimethyl-3-cyclohexen-1-yl)-2-buten-1-one, 6.6% of lauric aldehyde, 6.7% of 4-(2,6,6-trimethyl-1 -cyclohexen-1-yl)-3-buten-2-one, 6.7% of 4,7-methylene-1H-inden-6-ol, 3a,4,5,6,7,7a- Hexahydro-,6-acetate, 6.7% of 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol , 6.7% of 1-(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthyl)ethanone, 6.7% of 2 -(phenylmethylene)-octanal, 6.7% of oxacyclohexadecan-2-one, 6.7% of 2-phenylethyl phenylacetate, 6.7% of ethyl 2-methylpentanoate, 6.7% octanal, 6.7% 3,7-dimethyl-3-octanol, 6.7% benzyl acetate, 6.7% 3,7-dimethyl-,3-acetate-1, 6-octadien-3-ol). When fully mixed, molten lauryl ethoxylate (80EO) at 70°C was slowly added to the mixer until approximately the correct particle size was obtained (by eye). This requires about 250 g of the alcohol ethoxylate. The contents of the mixer were then sieved, retaining the 355-710 micron particle size fraction. The lower diameter fraction was returned to the mixture and the process was repeated until a sufficient amount was prepared. the

Example 8

A 3 kg sample of the fragrance-containing particle cores prepared according to Example 7 was transferred to a GEA MP3/2/3 conventional fluidized bed unit. Using bottom spray/Wurster coating technology, with an air inlet temperature of about 65°C, an air outlet temperature of about 43°C, and an air volume of 250kg/hour, the following steps are implemented in sequence:

水溶液(0.6g Lipex 

浓缩物在1kg水中)，将含酶层施加在团聚的沸石芯(350-700μm)上。每千克芯施加约0.02g Lipex 

。添加所述浓缩物后，使水从涂覆的芯蒸发(直至在流化床中温度迅速升高)。  a) by spraying Lipex at a rate of 35g/min

Aqueous solution (0.6g Lipex

concentrate in 1 kg of water), the enzyme-containing layer was applied on an agglomerated zeolite core (350-700 μm). Apply about 0.02g Lipex per kg core

. After adding the concentrate, the water was allowed to evaporate from the coated wick (until the temperature rose rapidly in the fluidized bed).

b) The final coat was applied by spraying 200 g molten (heated to about 100° C.) tripalmitin/kg product at a spray rate of 30 g/min. the

Subsequently, the completed enzyme-containing pellet was cooled to RT for 20 min. the

Example 9

Core granulation

diger混合器中。铲速为约180rpm，刀速为3000rpm，和混合器温度为约40℃。通过缓慢添加约2.5kg熔融(75℃)PEG4000至所述沸石粉末中，产生粒状颗粒。筛选300-800微米的所述颗粒。  Transfer a 10kg sample of zeolite powder to a conventional L

diger mixer. The shovel speed was about 180 rpm, the knife speed was 3000 rpm, and the mixer temperature was about 40°C. Granulated particles were produced by slowly adding about 2.5 kg of molten (75°C) PEG4000 to the zeolite powder. The particles were screened at 300-800 microns.

fragrance filling

diger混合器中。铲速为约180rpm，和混合器温度保持在室温。通过缓慢添加芳香剂，将1kg AKK芳香剂吸收到所述颗粒中。  Transfer a 5 kg sample of screened zeolite/PEG4000 particles to L

diger mixer. The spatula speed was about 180 rpm, and the mixer temperature was maintained at room temperature. 1 kg of AKK fragrance was absorbed into the granules by slow addition of fragrance.

Precoat in mixer

diger混合器中。铲速为约180rpm，和混合器温度保持在室温。通过缓慢添加0.3kg熔融(75℃)棕榈油(Palmotex 16T，Aarhus Oliefabrik A/S，Aarhus，Denmark)至所述颗粒，施加预涂层。  A 3 kg sample of zeolite/PEG4000 particles with absorbed fragrance was transferred to L

diger mixer. The spatula speed was about 180 rpm, and the mixer temperature was maintained at room temperature. A pre-coat was applied by slowly adding 0.3 kg of molten (75°C) palm oil (Palmotex 16T, Aarhus Oliefabrik A/S, Aarhus, Denmark) to the granules.

Final coating in fluidized bed

Four different samples were prepared by applying the coating as follows. the

Final coat 1 (reference):

A 0.75 kg sample of pre-coated granules was transferred to a STREA conventional fluidized bed. Using a top spray technique with an air inlet temperature of about 30°C, an air outlet temperature of about 40°C and an air volume of 70 kg/hour, by spraying 0.25 kg of molten (80°C) tripalmitin at a spray rate of 25 g/min, the Final coat. the

Final Coat 2 (Invention):

A 0.75 kg sample of pre-coated granules was transferred to a STREA conventional fluidized bed. Using the top spray technique with an air inlet temperature of about 30° C., an air outlet temperature of about 40° C. and an air volume of 70 kg/hour, by spraying with 0.3 g of spray-dried lipase (having a total of 591 KLU) at a spray rate of 25 g/min. 0.25 kg of molten (80° C.) tripalmitin of active Thermomyces lanuginosus lipase) to apply the final coating (1 KLU = 1000 LU, unit defined in WO 00/32758). the

Final Coat 3 (Invention):

A 0.75 kg sample of pre-coated granules was transferred to a STREA conventional fluidized bed. Using the top spray technique with an air inlet temperature of about 30° C., an air outlet temperature of about 40° C. and an air volume of 70 kg/hour, the final coating is carried out in the following order: first, an aqueous solution of lipase (1.1 g thermophilic fungal lipase concentrate (Lipolase ^™ , thermophilic fungal lipase with a total activity of 2200 KLU) in 0.1 kg of water) was sprayed onto the product, then 0.25 kg of melt (80° C.) was sprayed at a spray rate of 25 g/min Tripalmitin.

Final coat 4 (reference):

A 0.75 kg sample of pre-coated granules was transferred to a STREA conventional fluidized bed. The final coat was applied by spraying 0.25 kg of molten (80° C.) PEG4000 at a spray rate of 25 g/min using a top spray technique with an air inlet temperature of about 30° C., an air outlet temperature of about 40° C. and with an air volume of 70 kg/hour. the

Example 10

To 190 g of the screened zeolite/PEG4000 granules prepared in Example 9 was added 10 g of AKK fragrance, pre-coated with 20 g of Palmotex 16T and then coated with 50 g of tripalmitin. In one sample, 0.07 g of spray-dried lipase was added to the tripalmitin and in another sample, 0.07 g of spray-dried lipase was added to the Palmotex. the

Two other samples were prepared in the same manner, except that PEG4000 was used instead of Palmotex. the

Example 11

Enzyme-containing granules were produced as in Example 2, except that pectate lyase was used instead of lipase, and 5% (w/w) polygalacturonic acid was used as substrate before applying the coating to the core granules. Mix with tripalmitin. the

Example 12

Enzyme-containing granules were produced as in Example 2, except that cellulase was used instead of lipase, and 5% (w/w) barley β-glucan as substrate was mixed with Tripalmitin Blend. the

Example 13

Enzyme-containing granules were produced as in Example 2, except that amylase was used instead of lipase, and 5% (w/w) of potato starch and tripalmitin were added as substrates before the coating was applied to the core granules. mix. the

Claims (10)

CLAIMS 1. A laundry detergent composition comprising particles for triggering release of rinse benefit agents, said particles comprising: a) rinsing the benefit agent, b) enzymes, and c) a substrate for said enzyme, wherein said rinse benefit agent and said enzyme are surrounded by a barrier layer comprising said substrate, wherein said substrate is insoluble in water. 2. A detergent composition according to claim 1, wherein said rinse benefit agent is selected from the group consisting of fragrances, masking agents, chemical odor neutralizers, physical odor neutralizers, pro-perfumes, fiber lubricants, antistatic agents , anti-wrinkle agent, defoamer, photoprotectant, optical brightener, soil release polymer, stain repellant, anti-fouling agent, fabric softening compound, antibacterial agent, insecticide, fungicide, insect repellant, Antioxidants, shading dyes, color fixing agents, second enzymes and mixtures thereof. 3. A detergent composition according to claim 1, wherein said enzyme acting on said substrate is selected from the group consisting of amylases, lipases, cellulases, cutinases and mixtures thereof. 4. The detergent composition of claim 1 wherein said water-insoluble substrate is selected from the group consisting of monoglycerides, diglycerides, triglycerides, wax esters and mixtures thereof. 5. A detergent composition according to any one of claims 1 to 4, wherein said particle comprises a core comprising said rinse benefit agent, and a layer comprising said substrate surrounding said core. 6. A detergent composition according to claim 5, wherein the core comprises carrier particles. 7. A laundry detergent composition comprising particles for triggered release of rinse benefit agents, said particles comprising: a) rinsing the benefit agent, b) enzymes, and c) a substrate for said enzyme, Where said particle comprises a core comprising said rinse benefit agent and a layer surrounding said core comprising said substrate, said rinse benefit agent, substrate and enzyme may be present together in the core and/or in the same layer, said The substrate is insoluble in water. 8. A laundry detergent composition comprising particles for triggered release of rinse benefit agents, said particles comprising: a) rinsing the benefit agent, b) enzymes, and c) a substrate for said enzyme, wherein said rinse benefit agent and said enzyme are surrounded by a barrier layer comprising said substrate; said particle comprises a first layer comprising said rinse benefit agent, and a second layer comprising said substrate; said substrate Substances are insoluble in water. 9. A process for preparing the detergent composition of claim 1, comprising the steps of: a) preparing a core comprising said benefit agent, b) apply one or more layers, wherein the layer comprises said enzyme or said enzyme's substrate or both. 10. The method of claim 9, wherein the granules are prepared in a mixer, fluidized bed, fluidized bed spray dryer, spray dryer or extruder.