CN1415008A - Detergent compositions and methods for cleaning - Google Patents

Abstract

A detergent composition which produces a signal on contact with water to indicate to the user that the detergent composition is at least partially dissolved and chemical cleaning can commence. The advantage is that the user can delay the start of mechanical cleaning until this time, thereby maximising efficiency of the mechanical cleaning. The signal is preferably an audible signal. The invention also includes a method for washing using such detergent compositions and use of such detergent compositions.

Description

Detergent composition and cleaning method

field of invention

The present invention relates to detergent compositions and methods of cleaning which provide the most efficient cleaning with minimum physical washing required. The technology can find application in various cleaning compositions, especially laundry and dishwashing detergent compositions, which may be in the form of flowable, e.g. granular, liquid or flowable gels or pastes, or It may undergo additional processing steps to bring it into tablet form. The invention particularly relates to laundry detergent applications. The invention is particularly concerned with decontamination applications requiring hand washing by the user.

Background of the invention

Poor dissolution and distribution problems are well known in the detergent art. This problem has been exacerbated when producing detergents with higher bulk densities, e.g. over 600 g/l, or detergent tablets, in line with consumer demand for lower product and pack volumes and less consumption i.e. higher active washes Use the composition as needed. The problem is compounded by the use of detergent formulations which are not based on readily soluble phosphate builders, but on less soluble alternatives which overcome any environmental problems associated with phosphate builders.

In particular, in applications where hand washing is performed, it may be advantageous to wait until the detergent composition has been at least partially dissolved in the aqueous solution so that the cleaning properties of the active detergent ingredients can begin to take effect. In this way, the chemical cleaning performed can at least partially replace the need for intensive mechanical cleaning by the user when the dirt begins to decompose. However, the user will tend to start washing when detergent is added to the water, so that the chemical cleaning performance is not maximized at the start of the user's wash action. The machine washing process will also reduce energy consumption if the chemical cleaning is started when the mechanical cleaning (eg agitation) is already started.

There have been many proposals attempting to increase the dissolution and dispensing rate of detergents in aqueous solutions to overcome this problem. One such approach is the use of effervescent systems in detergents. For example, detergent compositions comprising effervescent ingredients are described in WO98/04687. In WO 98/04671, an effervescent system for detergents is disclosed wherein, in order to enhance dissolution, acidic and basic effervescent reactants which generate gas on contact with water are mixed with stabilizing agents to produce substantially anhydrous effervescent Teng particles, which have maximum efficacy when used in the wash step. Likewise, WO98/35011 also discloses particles comprising sodium bicarbonate and organic acid reactants which are interacted and formed into particles with a binder. EP-A-918 087 describes co-builder particles for incorporation into detergent compositions, comprising bicarbonate and polycarboxylic acids, which are formed by roller-compaction and which do not contain free moisture. In reality, however, the requirements to provide good storage stability and good end-use effervescence upon contact with the lotion are conflicting requirements; the use of stabilizers can prevent or reduce the effervescent reaction when water contacts the effervescent reactants during wash conditions. Efficacy at the time and slow down the reaction rate, so that the effervescence and thus dissolution aid is undesirably reduced.

Furthermore, the end user still starts the wash process before the detergent active ingredients enter the aqueous wash liquor. The present inventors now provide a washing method in which an audible signal is generated by the detergent composition to indicate to the user when the detergent composition is at least partially dissolved in the wash water to indicate that mechanical cleaning can begin. This washing method maximizes the efficiency of the washing process by ensuring that chemical cleaning begins before mechanical cleaning by the user.

Brief description of the invention

According to the present invention, there is provided a method for washing soiled articles, comprising preparing a detergent composition comprising a signaling component, adding said detergent composition to water, and initiating mechanical cleaning of soiled articles, characterized in that after A signal is generated when the detergent composition is added to water, which indicates at least partial dissolution of the detergent composition in the wash water. Preferably the signal lasts for a period of time which indicates by the at least partially dissolved detergent composition when chemical cleaning has started, so at the end of the signal the user starts mechanical cleaning. By "mechanical cleaning" is meant herein any conventional mechanical method for cleaning, such as agitation, contact with liquid or gas jets to mechanically remove dirt and/or abrasion. Preferably the signal is audible. Preferably the signal is produced by an effervescent system. Effervescence was found to be especially beneficial when it could at the same time assist in mechanical purification.

According to another aspect of the present invention, there is also provided a detergent composition comprising a signaling component such that a signal is generated when the detergent composition is contacted with water. Preferably the signal is audible. Preferably the signaling component comprises an effervescent system such that upon contact with water the effervescence is released, which is audible to the user. Preferably the time of the signal corresponds to the time it takes for the detergent composition to at least partially dissolve in the wash water, so that the user waits for the signal to be substantially over before commencing the mechanical washing step.

According to another aspect of the present invention there is also provided the use of a signaling component in a detergent composition to generate a signal which provides an indication of dissolution of the detergent composition. Preferably the signal is an acoustic signal. Detailed description of the invention

The detergent compositions of the present invention comprise a signal component such that upon contact with water a signal is generated which provides an indication that the detergent composition is at least partially dissolved. Preferably, the signal component produces an acoustic signal. Preferably the acoustic signal is produced by an effervescent system; a preferred effervescent system comprises an acid source and an alkali source which react with each other upon contact with water. In a particularly preferred embodiment of the invention, the effervescent system comprises effervescent particles. The acoustic signal generated by the signal component preferably has a noise level of at least 42dB, more preferably at least 45dB and most preferably at least 50dB during at least part of it. Preferably, the noise level generated by the acoustic signal is at least 3dB greater than the average ambient background noise level when measured over a five minute measurement period. Preferably the noise level is at least 5 dB above the surrounding background noise, more preferably at least 10 dB above the surrounding background noise. A suitable device for measuring noise levels is the CEL SoundTrack dB21 device, (Model CEL-480 Version 1.8) from CEL Instruments Ltd, using a loudspeaker and operating in Broadband SLM mode, with a frequency for RMS set at A weighted, and this frequency matches the peak at Z. A measurement range of 20-90 dB is usually suitable.

Preferably the effervescent system is designed such that the duration of the signal corresponds to the length of time required for the detergent active ingredients to at least partially dissolve in the wash water, so that in the preferred method of the invention, at the end of the audible signal, the mechanical wash process begins. Signal time is used to indicate the time delay between contact of the detergent composition comprising the signal component with the wash water and completion of the signal. The audible signal can start immediately at this point or have an initial delay before the signal is generated. Preferably the audible signal has a duration of at least 5 seconds, more preferably at least 10 seconds up to at least 30 seconds or 1 minute. Effervescent system

The effervescent system comprises one or more effervescent components such that when the effervescent system comes into contact with water, effervescence occurs. The effervescence may be the result of gases trapped in the matrix of the effervescent system being released when the particles come into contact with water, or more generally the result of a reaction between two or more reactants present in the effervescent system , which react with each other to produce gas upon contact with water. When effervescence is produced by the reaction of two or more reactants, preferably the reactants are provided by an acid source and an alkali source. acid source

Suitable acid sources include solid organic, mineral or inorganic acids, salts or derivatives thereof or mixtures thereof. Preferred acids may be mono-, di- or triprotic acids. Such acids include mono- or polycarboxylic acids, preferably citric acid, adipic acid, glutaric acid, 3-chetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, propanoic acid, Diacid. Such acids are preferably used in their acid form. Derivatives also include esters of acids. Preferred acids include citric acid and malic acid. Citric acid is especially preferred. Alkali source

Any source of alkalinity can be used in the effervescent system. Carbonate alkali sources are especially preferred and include, for example, carbonates, bicarbonates, sesquicarbonates and percarbonates, especially bicarbonates and/or carbonates. Preferred carbonates for use herein include carbonates and bicarbonates, which should be present in the effervescent system in a manner that can react with the acid source. Therefore, generally the alkali source should be water soluble or have a very fine particle size so that the reaction with the acid source readily occurs when the effervescent particles come into contact with water. Salts of alkali metals or alkaline earth metals are suitable. Water soluble salts such as potassium, lithium, sodium and the like are preferred, with sodium and potassium carbonate being especially preferred. Suitable bicarbonates for use herein include any alkali metal bicarbonate such as lithium, sodium, potassium and the like, with sodium and potassium bicarbonates being preferred. Bicarbonate may be preferred over carbonate because it is more weight efficient, ie bicarbonate is a larger _CO2 "reservoir" than carbonate at the same weight. However, overall detergent formulation requirements may lead to a more alkaline pH, resulting from carbonates, to provide a more useful overall detergent formulation, so the choice of carbonate or bicarbonate or a mixture thereof in an effervescent system may Depends on the desired pH in the aqueous medium in which the detergent composition comprising effervescent particles is dissolved. For example, where a relatively high pH (e.g., above pH 9.5) is desired in an aqueous medium, it may be preferable to use carbonate alone or a mixture of carbonate and bicarbonate, where the level of carbonate is higher than that of carbonic acid The level of hydrogen salts, typically a weight ratio of carbonate to bicarbonate is 0.1 to 10, more preferably 1 to 5 and most preferably 1 to 2.

Preferably, the detergent composition will comprise at least 0.5 wt% of the total effervescent component, more preferably at least 1 wt% of the total effervescent component and most preferably at least 5 wt% up to at least 10 or 20 wt% of the total effervescent component , based on the weight of the detergent composition.

The release of effervescence via effervescent particles may be particularly useful for the present invention because adjustment of the parameters described below can tailor the timing of the acoustic signal to the needs of the detergent composition. This is clear to those skilled in the art. Thus, for example for slower dissolving detergent compositions, effervescent particles comprising a larger proportion of non-effervescent components such as binders or other optional ingredients (which slow down dissolution) or higher compaction pressures can Used to ensure that the signal is delivered more slowly or after a delay period upon contact with the wash water so that the signal ceases after a relatively long time interval from the time the detergent composition has been in contact with the water. effervescent particles

When the effervescent system comprises the preferred effervescent particles, suitable sources of acid and alkali are as set out above. The acid source is preferably present in the effervescent particles at a level of from 0.1% to 99% by weight of the total particle, preferably from 3% to 80%, more preferably from 10% to 75% and most preferably from 15% to 70%. The carbonate source is preferably present in the effervescent particle at a level of from 0.1% to 99% by weight of the total, preferably from 20% to 95%, more preferably from 30% to 85% and most preferably from 35% to 75% of the effervescent particle weight.

It may be preferred that the number ratio of alkali source to acid source (i.e. the ratio of the number of particles of alkali source to acid source) is at least 50:1, preferably at least 100:1, more preferably at least 500:1 to at least 1000:1 and Most preferably at least 5000:1 to at least 10000:1.

Furthermore, the ratio of the median particle size of the source of alkalinity to the source of acid is preferably at least 2:1, preferably at least 8:1, more preferably at least 15:1 or at least 20:1 to at least 30:1. Preferably the particle size span of each of the acid source and alkali source is no greater than 3, more preferably no greater than 2, most preferably no greater than 1.5.

"Median particle size" herein refers to the geometric mass median diameter of a population of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving. The "geometric standard deviation" or "span" of the particle size distribution herein refers to the geometric width of the lognormal function that best matches the above particle size data, which can be determined by the diameter of the 84.13 percentile of the integral distribution curve Dividing by the ratio of diameters at the 50th percentile (D _84.13 /D ₅₀ ), see Gotoh et al., Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.

Preferably, the effervescent particles have a median particle size of from about 500 microns to about 1500 microns, more preferably from about 600 microns to about 1200 microns, and most preferably from about 700 microns to about 1000 microns. The particle size distribution is defined by a relatively neat geometric standard deviation or "span" so that there are not too many particles outside the target size range. Thus, the standard deviation of geometry is preferably from about 1 to about 2, more preferably from about 1.0 to about 1.7, more preferably from about 1.0 to about 1.4, and most preferably from about 1.0 to about 1.2.

Especially for the preparation of effervescent particles for use in the detergent compositions of the present invention, the acid source preferably has a median particle size greater than 100 μm, more preferably greater than 200 μm and most preferably greater than 300 μm. The median particle size of the source of alkalinity is preferably below 50 μm, more preferably below 25 μm and most preferably below 10 μm.

In the effervescent particle, the molar ratio of the reactive groups on the base source to the reactive groups of the acid source is preferably substantially stoichiometric so that there are substantially equimolar reactive groups. Accordingly, the molar ratio of reactive groups of the acid source to reactive groups of the alkali source is preferably 5:1 to 1:5, more preferably 3:1 to 1:3, more preferably 3:2 to 2:3 and most preferably 9:10 to 10:9.

In one aspect of the invention, when the detergent composition comprises only bicarbonate as the source of alkalinity, preferably the effervescent particles additionally comprise greater than 6 wt% citric acid, optionally in admixture with other acid source components.

Preferably the effervescent particle is substantially anhydrous such that the total moisture content (including both bound crystallization water and unbound ie free moisture) is less than 0.5 wt% of the effervescent particle. More particularly, when the effervescent component comprises both an acid source and an alkali source, preferably at least the acid source used to form the effervescent particles has an overall moisture content of less than 0.1 wt%, more preferably less than 0.05 wt% and most preferably Less than 0.01 wt%. More preferably, the source of alkalinity also has a total moisture content of less than 0.5 or less than 0.1 wt%, more preferably less than 0.05 wt% and most preferably less than 0.01 wt%.

The bulk density of the effervescent particles is preferably from 500 g/l to 1200 g/l, more preferably from 700 g/l to 1100 g/l.

The effervescent particles may optionally contain additional ingredients. Typically the effervescent particles comprise no more than 50% by weight of the particle of additional ingredients, preferably no more than 35% by weight and more preferably no more than 20% or 10%. High efficiency particles comprising not more than 5 wt% to not more than 2 wt% of additional ingredients other than components contributing to gas production/release are particularly preferred. Suitable additional ingredients may include any of the detergent ingredients described below. Particularly suitable are surfactants or organic or inorganic builder components, preferably water-soluble such as those described below.

Although not preferred for the reasons described above, optional binders or coating agents may be incorporated into the effervescent particles. Suitable materials are selected from one or a mixture of more than one of binders and surface covering agents known to those skilled in the art. Particularly suitable binders include anionic surfactants such as C6-C20 alkyl or alkylaryl sulfonates or sulfates, preferably C8-C20 alkylbenzene sulfonates, cellulose derivatives such as carboxymethylcellulose and homo- or co-polymerized polycarboxylic acids or salts thereof, nonionic surfactants, preferably C10-C20 alcohol ethoxylates, which contain 5-100 moles of ethylene oxide per mole of alcohol, and more preferably C15-C20 primary alcohol ethoxylates containing 20-100 moles of ethylene oxide per mole of alcohol. Of these, tallow alcohol ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) is preferred. Other preferred binders include polymeric materials such as polyvinylpyrrolidone with an average molecular weight of 12,000 to 700,000 and polyethylene glycol with an average weight of 600 to 10,000. Copolymers of maleic anhydride with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Other binders further include C10-C20 mono- and diglycerides and C10-C20 fatty acids. In an embodiment of the present invention, when a binder is required, especially preferred are C8-C20 alkylbenzene sulfonates.

The effervescent particles used in the present invention are preferably prepared by mixing the gas production/release-facilitating effervescent component with any additional ingredients, producing a fine mixture and then granulating the mixture to form particles. However, any mechanical comminution method may be used, and in order to maintain high activity levels in the finished effervescent granules, granulation should preferably be carried out without substantially adding any free moisture to the mixture. A preferred agglomeration step comprises a pressure agglomeration step to form a mixture of agglomerates followed, if desired, by a granulation step wherein the agglomerates form effervescent particles for use in the detergent compositions of the present invention. In the preferred pressure agglomeration process, a substantially dry mixture comprising the effervescent component and any optional additional ingredients is exposed to high external forces which bring the particles closer to each other, thereby causing bulk densification and mass densification of the particles. A bonding mechanism develops between the components in the mixture. Indeed, pressure agglomeration leads to an aggregation mechanism characterized by the presence of interparticle bonds between the primary solid effervescent particles and structures in which the effervescent particles are still recognizable, while retaining many of their properties, such as being able to react in the presence of water react with each other to release carbon dioxide.

The density increase associated with the preferred process for manufacturing the effervescent particles used in the present invention is closely related to the applied pressure. Generally, the bulk density will be increased by up to 200 g/l, preferably 10 g/l to 150 g/l, from the density of the mixture comprising the effervescent raw materials, i.e. the acid and carbonate source, and optionally the binder, before undergoing pressure agglomeration. l.

Pressure agglomeration can be performed using different processes, which can be classified by the level of force applied. The preferred process used here is roller compaction. In this process, the effervescent components, preferably the acid source and the alkali source and any optional additional ingredients after being mixed with each other are forced between two compacting rollers which apply pressure to the mixture , so that the rotation of the rollers transforms the mixture into compact sheets/flakes. The compact flakes/flakes are then broken to form effervescent particles.

A roller compactor commonly used here is, for example, the Pharmapaktor L200/ ^50P® , commercially available from Hosokawa Bepex GmbH. Process variables during the pressure agglomeration stage by roller compaction are the distance between the rolls, the feed rate, the compaction pressure and the peripheral speed of the rolls. Usually the feeding device is a screw feeder. The distance between the rollers is generally 0.5 cm to 10 cm, preferably 3 to 7 cm, more preferably 4 to 6 cm. The pressing force is generally between 20 kN and 120 kN, preferably 30 kN to 100 kN, more preferably 50 kN to 100 kN. Typically the roll speed is between 1 rpm and 180 rpm, preferably 2 rpm to 50 rpm and more preferably 2 rpm to 35 rpm. Typically, the feed rate is between 1 rpm and 100 rpm, preferably 5 rpm to 70 rpm, more preferably 8 rpm to 50 rpm. The temperature at which compaction is performed is not critical, generally it is 0°C to 40°C.

The flakes/flakes produced by the pressure agglomeration process are broken up into effervescent particles by any suitable method for reducing the size of the flakes/flakes to form particles, such as by cutting, chopping or breaking the flakes/flakes to produce the required length , and if necessary, by a method of rounding said particles, ie by preparing round or spherical particles whose diameter size complies with the above definition. In a preferred embodiment, one method of breaking up the flakes/flakes after the rolling step is by crushing the compact flakes/flakes. Crushing can generally be performed using a Flake Crusher ^FC200® , commercially available from Hosokawa Bepex GmbH.

Depending on the particle size required for the effervescent particles, the crushed material can be further sieved. Such sieving of the dry effervescent granules can be performed, for example, using the commercially available Alpine Airjet ^Screen® . Detergent base

In addition to the signal component, the detergent compositions of the present invention comprise a detergent matrix which includes all other detergent ingredients. Typically, the detergent matrix comprises at least one pre-formed detergent matrix component comprising surfactants and optionally additional detergent ingredients. Preferably the detergent matrix has an eRH of no greater than 30%. Preferably the eRH is no greater than 25%, more preferably no greater than 20% and no greater than 15% or 12% and 10%. eRH can be measured using a Rotronic™ Hygroskop DT calibrated according to the manufacturer's instructions, as stated in Rotronic Hygroskop application leaflet 2/E Spi/S date 3.1.83, using a defined saturated saline solution that covers the humidity range of the test. All assays were performed at 25°C. Furthermore, it is preferred that the detergent matrix has a free moisture content of not greater than 2 wt%, preferably not greater than 1 wt%, and even more preferably not greater than 0.5 or 0.1 or 0.05 wt%. This low free moisture content can be achieved by drying one or more or all of the components in the detergent matrix. Thus the detergent matrix component and one or more optional additional ingredients may be premixed prior to drying or may be dried after mixing. Additional detergent matrix components and/or optional additional ingredients may be mixed with the pre-dried components without an additional drying step. According to a further preferred aspect of the present invention, at least one component in the detergent matrix (detergent matrix component or additional optional detergent ingredients) is overdried, i.e. has been dried to be compatible with one or more The level at which water associated with detergent ingredients or optional additional detergent ingredients in the detergent matrix component is removed.

According to a further preferred aspect of the present invention, the detergent composition comprises an effervescent system and a low density detergent matrix component having a bulk density of less than 400 g/l. Detergent Matrix Components

The detergent matrix components include preformed particles, which may be in powder, granule, flake or other solid form, which include surfactants and optionally additional ingredients. The surfactant may be anionic, nonionic, cationic, amphoteric, zwitterionic or mixtures thereof. Preferred detergent matrix components include anionic, nonionic and/or cationic surfactants. In particular matrix components comprising anionic surfactants may be particularly useful. Suitable surfactants are described in more detail below. The content of said surfactant preforming the matrix component is preferably 5 to 80% by weight of said matrix component. It may be preferred that the amount of surfactant is higher than 10 wt%, up to higher than 20 wt% or higher than 30 wt%, based on the total amount of detergent matrix components. Surfactant levels below 70% or even below 50% may be preferred.

The detergent matrix component usually also comprises solid materials, which may be fillers, such as sulphates, especially sodium sulphate, but more preferably the detergent matrix component comprises at least one detergent ingredient, especially a builder agent or alkaline components, or mixtures of such components. Suitable examples include phosphates, aluminosilicates, crystalline layered silicates, sodium carbonate or amorphous silicates. These materials are described in more detail below. For example, each of these components, alone or in admixture, may be present in an amount greater than 5%, preferably greater than 10% or even greater than 20% by weight of the preformed matrix component. Particularly preferred builder ingredients are sodium carbonate and/or zeolites. Both zeolite A and zeolite MAP are suitable.

The preformed matrix component preferably also includes organic builders such as polycarboxylic acids and/or salts, such as citric acid, tartaric acid, malic acid, succinic acid and their salts or polymeric polycarboxylates such as acrylic or horseradish based Acid polymers or their copolymers. Such components are typically present in said matrix component at a level of less than 15 wt%, preferably less than 10 wt% of the matrix component.

Other preferred ingredients in the preformed matrix components are optical brighteners or chelating agents, such as phosphonate chelating agents NTA, DTPA and succinic acid derivative chelating agents, as described below. These components are preferably present in the preformed particle component in an amount of less than 5 wt% to less than 2 wt% of the matrix component.

The detergent matrix may comprise one or more pre-formed detergent matrix components. Suitable preformed components may be formed by spray drying, agglomeration, marumerisation, extrusion or compaction, all methods well known in the art for mixing detergent ingredients. Particularly preferred preformed matrix components are powders from spray drying, agglomeration and extrudates. Spray dried powders are particularly useful. Also preferred are detergent matrix components produced according to at least one low shear mixing step, eg in a fluidized bed, eg by fluidized bed agglomeration.

Suitable spray drying processes for forming such preformed detergent matrix components are described in, for example, EP-A-763594 or EP-A-437888. Suitable processes for forming detergent matrix component agglomerates are described, for example, in WO93/25378, EP-A-367339, EP-A-420317 or EP-A-506184. A suitable medium to low shear mixer may be, for example, a Lodige KM (trade mark) (Ploughshare) medium speed mixer, or a mixer made by Fukae, Draes, Schugi or similar brand mixers which utilize only moderate to low shear shear mixing. A preferred mixer for use in the present invention is the Lodige KM (ploughshare) medium speed mixer comprising a horizontal hollow stationary barrel with a centrally suspended shaft around which are attached several plow-shaped vanes. Preferably, the shaft rotates at a speed of about 15 rpm to about 140 rpm, more preferably about 80 rpm to about 120 rpm. Grinding or comminution is done by means of a cutter, usually small in size compared to the shaft, which preferably operates at about 3600 rpm. Other essentially similar mixers suitable for use in the process include the Lodige Ploughshare ^™ mixer and the ^Drais® KT 160 mixer. Typically, in the process of the present invention, the shear will be no greater than that produced by a Lodige KM mixer, with plow tip speeds below 10 m/s, down to 8 m/s or even lower.

Preferably, the average residence time of the various starting detergent ingredients in the low or medium speed mixer is preferably from about 0.1 minute to about 15 minutes, most preferably from about 0.5 to about 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.

Other suitable mixers for use in the present invention are low or very low shear mixers such as tumble agglomerators, drum agglomerators, pan agglomerators and fluidized bed agglomerators.

Fluidized bed agglomerators are particularly preferred. Typical fluidized bed agglomerators operate at a superficial air velocity of 0.4 to 4 m/s and can operate under positive or negative pressure. The air inlet temperature is usually -10 or 5°C up to 250°C. However, the inlet air temperature is usually lower than 200°C, even lower than 150°C. Suitable processes using fluidized bed agglomerators are described in eg WO98/58046 or WO99/03964. Suitable processes for forming detergent matrix components by extrusion are described, for example, in WO 91/02047.

The detergent matrix may comprise only one preformed component as described, or it may comprise a mixture of components, for example a mixture of different spray-dried powders or different agglomerates etc. or mixed as described above Mixtures of agglomerates, spray-dried powders and/or extrudates and the like. In order to prepare a detergent matrix with the desired low eRH, the detergent matrix components or mixtures thereof will have been subjected to drying to provide the required low moisture content. Such drying may be provided in any conventional drying step, or may be the result of more extensive drying than conventionally used conventional routes. For example, in the spray drying process, the spray drying tower can be operated at higher air inlet temperature, eg, 300°C to 350°C to 400°C. Optionally, an additional drying step may be provided wherein the agglomerates/spray dried powder/extrudate etc. are dried by any convenient method. Suitable examples include ovens and fluid bed dryers. For example, in a drying oven, the detergent base powder may be passed through the drying oven on a conveyor belt or other convenient device. Preferably the free moisture in the detergent matrix component will dry to less than 1 wt%, more preferably less than 0.5 wt%, even less than 0.1 or 0.05 wt% of the detergent matrix component. There is no necessary correlation between the free moisture content of detergent matrix components and eRH, so eRH must be measured for a particular detergent matrix to ensure that the proper eRH is achieved. In a particularly preferred aspect of the invention, the detergent matrix components are overdried (ie at least some of the bound water naturally associated with the chemical components of one or more components is at least partially removed). Particularly preferred detergent matrix components are spray dried powders.

Especially in detergent compositions which include effervescent systems in the form of effervescent particles, the incorporation of detergent matrix components comprising low-density surfactants unexpectedly promotes effervescence, and especially incipient effervescence of the detergent and effervescent duration both. This may be particularly advantageous as it enables lower amounts of effervescent particles to be used in the detergent compositions of the invention to achieve the same effervescent effect. The low density detergent matrix component preferably has a bulk density of at least 100 g/l, more preferably at least 120 g/l. Preferably the bulk density is below 350 g/l or even below 300 g/l or 250 g/l. The low bulk density detergent matrix component preferably has a median particle size of at least 50 μm, more preferably at least 75 μm and most preferably at least 100 μm. Typically, the median particle size will be below 500 μm, preferably below 450 μm and even below 400 or 350 μm.

Preferably the surfactant content in the low density detergent matrix component is at least 20 wt%, more preferably at least 25 wt% and most preferably at least 30 wt%, based on the total amount of said detergent matrix component. Any of the surfactants described below are suitable, preferably any surfactant that produces foam. Anionic and/or nonionic surfactants are particularly preferred. Cationic surfactants with good foam properties may also be preferred. As with the other described detergent matrix components, the low density detergent matrix component preferably comprises additional ingredients which may be fillers such as sulfates or more preferably additional detergent ingredients as described below. Particularly preferred additional ingredients are alkali metal carbonates, preferably sodium carbonate, silicates, which may be amorphous or crystalline, zeolites, brighteners and polymeric materials such as acrylate polymers, which may be Homopolymers or copolymers, such as acrylic and maleic copolymers, are particularly preferred.

Preferably, the low-density detergent matrix component is incorporated in the detergent composition of the present invention in an amount greater than 0.1 wt%, more preferably greater than 2 wt% to greater than 5 wt% or 10 wt%, based on the detergent composition total amount. Typically, the detergent compositions of the present invention comprise not more than 20 wt% of low density detergent matrix components, preferably not more than 15 wt%, and even not more than 10 wt%, based on the total amount of the detergent composition. Preferably, the weight ratio of effervescent component to low density detergent matrix component is from 10:1 to 1:10, preferably from 5:1 to 1:3 and most preferably from 3:1 to 1:2.

The low density detergent matrix components can be prepared by any method for making detergent matrix components, as described above, provided they can be made to a sufficiently low density. Spray drying and fluid bed agglomeration processes are particularly suitable. Spray drying is particularly preferred. additional detergent ingredients

As mentioned above, the detergent matrix may comprise one or more additional detergent ingredients. These may comprise detergent raw materials or may be pre-formed particles manufactured by processing at least one detergent ingredient with other ingredients, which may be active or inactive in the detergent, to form solid particles. When the particulate component is a detergent raw material, any granular detergent ingredient is suitable. These may be solid surfactants or soaps, or water soluble or dispersible polymeric materials, enzymes, bleaching components such as bleach activators or bleaching salts such as peroxygen salts. Surfactants and additional detergent ingredients are discussed in more detail below. Any of the following ingredients may be added to the detergent composition, either as separate solid particles or preformed microparticles or by means of a detergent matrix component. These additional detergent ingredients can be incorporated into the detergent matrix and, if desired, subjected to a drying step. Whether a drying step is required depends on the form and level of incorporation of the individual additional ingredient materials and eRH which they and the detergent matrix components and other ingredients provide in the total detergent matrix. According to a first embodiment of the invention, the final detergent matrix must have an eRH of less than 30%. detergent ingredients surfactants

Suitable surfactants for use in the present invention are the anionic, nonionic, amphoteric and zwitterionic classes of these surfactants shown in U.S.P. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Further examples are shown in "Surface ActiveAgents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is set forth in U.S.P. 4,259,217, issued March 31, 1981 to Murphy.

Preferably, the particles and detergent compositions of the invention comprise a further anionic surfactant. Virtually any anionic surfactant useful for detergent purposes can be included in the detergent composition. These may include salts of anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate and sulfonate type actives are preferred.

The anionic surfactant is present in the detergent matrix components in an amount of less than 25 wt% to less than 20 wt%, but preferably in the final composition comprising the particles from 0.1% to 60%, More preferably 1 to 40%, most preferably 5% to 30% by weight.

Other anionic surfactants include anionic carboxylate-type surfactants such as alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylates and soaps ("alkyl carboxyl") such as those selected from Water-soluble members: 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl- The water-soluble salt of 1-heptanoic acid. Certain soaps may also be included as suds suppressors. Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is a C ₅ -C ₁₇ linear or branched chain alkyl or alkenyl group and R ¹ is C ₁ -C ₄ alkyl and M is an alkali metal ion. Other anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, sulfosuccinates Monoesters (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oils.

Anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol oxirane ether sulfates, C ₅ -C ₁₇ acyl-N-(C ₁ -C ₄ alkyl) and -N-(C ₁ -C ₂ hydroxyalkyl) glucosamine sulfates, and sulfates of alkyl polysaccharides such as alkyl polyglucose Sulfates of glycosides (non-ionic non-sulfated mixtures described here). Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ branched chain alkyl sulfates and C ₁₂ -C ₁₄ linear alkyl sulfates Sulfates. Alkyl ethoxy sulphate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulphates which have been ethoxylated with 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkyl sulfate which has been treated with 0.5 to 7, preferably 15 moles of ethylene oxide/ Ethoxylated per molecule.

Preferred surfactant combinations are mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxy sulfate surfactants, optionally with cationic surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO93/18124.

Anionic sulfonate-type active agents suitable for use herein include salts of C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkyl sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oil alkenyl glycerol sulfonates and any mixtures thereof.

Virtually any alkoxylated nonionic surfactant or mixture is suitable here. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from alkylphenol nonionic condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/ Condensation products of propoxylates with propylene glycol, and condensation products of nonionic ethoxylates with propylene oxide/ethylenediamine adducts.

Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are particularly useful here. Particular preference is given to condensation products of straight-chain or branched primary or secondary alcohols having alkyl groups comprising 6 to 22 carbon atoms with 2 to 10 mol of ethylene oxide per mol of alcohol.

Polyhydroxy fatty acid amides useful herein are those of the formula R ² CONR ¹ Z, wherein: R 1 is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof, preferably C ₁ -C ₄ alkyl; and R is C ₅ -C ₃₁ hydrocarbyl; and Z is a polyhydroxyl hydrocarbyl having a linear hydrocarbyl chain of at least 3 hydroxyl groups directly attached to said chain, or an alkane Oxylated derivatives (preferably ethoxylated or propoxylated), Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl.

Alkyl polysaccharides suitable for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having hydrophobic groups and polysaccharides containing 6 to 30 carbon atoms, such as polyglycosides, hydrophilic groups containing 1.3 to 10 sugar units. Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O)t(glycosyl) _x ,

wherein ^R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains 10 to 18 carbon atoms; n is 2 or 3; t is 0 to 10 and x It is 1.3 to 8. The glycosyl is preferably derived from glucose.

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkylamphocarboxylic acids. Suitable amine oxides include those compounds having the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, amidopropyl and alkylphenyl groups or mixtures comprising 8 to 26 carbon atoms; ^R is an alkylene or hydroxyalkylene group comprising 2 to 3 carbon atoms or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R ⁵ is an alkyl or hydroxyalkyl group containing 1-3, or a polyethylene oxide group containing 1 to 3 ethylene oxide groups. Preferred are C ₁₀ -C ₁₈ alkyldimethylamine oxides, and C _10-18 amidoalkyldimethylamine oxides.

Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be clearly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaines such as C _12-18 dimethyl-ammoniohexanoate and C _10-18 amidopropane (or ethane) dimethyl (or diethyl) betaine and sultaine surfactants are exemplary in Zwitterionic surfactants used here.

Suitable cationic surfactants for use herein include quaternary ammonium surfactants. Preferably, the quaternary ammonium surfactant is a mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactant, wherein the remaining N position is represented by methyl, hydroxyethyl or hydroxypropyl group substitution. Also preferred are monoalkoxylated and dialkoxylated amine surfactants.

Cationic ester surfactants such as choline ester surfactants, such as those disclosed in US Pat. of:

wherein ^R is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, especially C ₁₀ -C ₁₄ alkyl, preferably C ₁₀ and C ₁₂ alkyl, and X is any convenient anion to provide charge balance, preferably chlorine compounds or bromides.

Cationic monoalkoxylated amine surfactants are typically present at levels in the detergent compositions of the present invention from 0.1% to 20%, preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight.

Cationic bis-alkoxylated amine surfactants such as

Also useful are those wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof. X is any suitable anion to provide charge balance, preferably chloride. bleach activator

The detergent compositions of the present invention preferably comprise a bleach activator, preferably an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxyacid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxyacid bleach precursor, as defined herein of. The production of organic peroxyacids proceeds by in situ reaction of precursors with a source of hydrogen peroxide. The bleach activators may alternatively, or additionally, comprise pre-formed peroxyacid bleaches. Preferably, the bleach activator is present in the form of separate, mixed particles.

Preferably, any bleach activator present in the particulate component has an average particle size, by weight, of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. It may be preferred that at least 80%, preferably at least 90% and at least 95% or even substantially 100% of the components or components comprising the bleach activator have a particle size of from 300 microns to 1700 microns, preferably 425 microns to 1400 microns. Preferred hydrophobic peroxyacid bleach precursors preferably comprise compounds having oxybenzenesulfonate groups, preferably NOBS, DOBS, LOBS and/or NACA-OBS. Preferred hydrophilic peroxyacid bleach precursors preferably comprise TAED. peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce peroxyacids. Typically peroxyacid bleach precursors can be represented as XC(O)-L, where L is a leaving group and X is virtually any functional group such that the structure of the peroxyacid produced in perhydrolysis is

For the purposes of the present invention, hydrophobic peroxyacid bleach precursors yield peroxyacids of the above formula wherein X is a group comprising at least 6 carbon atoms and hydrophilic peroxyacid bleach precursors yield peroxyacids of the above formula Acid bleaches wherein X is a group comprising 1 to 5 carbon atoms. The leaving group, below the L group, must be sufficiently reactive for the perhydrolysis reaction to occur within an optimal time frame (eg wash cycle). However, if L is too reactive, the activator will be difficult to stabilize for use in bleaching compositions. Preferred L groups are selected from the following and mixtures thereof:

wherein R ¹ is an alkyl, aryl, or alkaryl group containing 1 to 14 carbon atoms, R ³ is an alkyl chain containing 1 to 8 carbon atoms, R ⁴ is H or R ³ , and Y is H or solubilizing group. Any of R ¹ , R ³ and R ⁴ may be replaced by virtually any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O<--N(R ³ ) ₃ and most Preferably _-SO3 ^- M ⁺ and _-CO2 ^- M ⁺ , wherein ^R3 is an alkyl chain containing 1-4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which Provides solubility in bleach activators. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion.

The peroxyacid bleach precursor compound is preferably incorporated into the final detergent composition in an amount of 0.5 to 30% by weight, more preferably 1 to 15% by weight, most preferably 1.5 to 10% by weight. The ratio of hydrophilic to hydrophobic bleach precursors, when present, is preferably from 10:1 to 1:10, more preferably from 5:1 to 1:5 or even from 3:1 to 1:3. Suitable peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups, which precursors can be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful substances within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386.

Alkyl percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in perhydrolysis. Preferred alkyl percarboxylic acid precursor compounds of the imide type include N,N,N ¹ N ¹ tetraacetylated alkylene diamines wherein the alkylene group contains 1 to 6 carbon atoms, in particular Those compounds wherein the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred as the hydrophilic peroxyacid bleach precursor. Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose.

Amide substituted alkyl peroxyacid precursor compounds are suitable herein and include those of the general formula: or

wherein R is an aryl or alkaryl group having from about 1 to about 14 carbon ^atoms , ^R is an alkylene, arylene and alkarylene group comprising about 1 to 14 carbon atoms, and ^R5 is H or an alkyl, aryl, or alkaryl group containing 1-10 carbon atoms and L can be virtually any leaving group. R ¹ preferably contains about 6 to 12 carbon atoms. ^R2 preferably contains about 4 to 8 carbon atoms. ^R1 may be straight chain or branched chain alkyl, substituted aryl or alkylaryl, containing branching, substituents or both and may be derived from synthetic or natural sources including, for example, tallow fat. Similar structural variants are possible for ^R2 . R ² may include alkyl, aryl, wherein said R ² may also include halogen, nitrogen, sulfur and other common substituent groups or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not contain together more than 18 carbon atoms. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It may be preferred that R ¹ and R ⁵ form a ring structure together with nitrogen and carbon atoms.

Preferred examples of bleach precursors of this type include amide-substituted peroxyacid precursor compounds selected from the group consisting of (6-octylamido-caproyl)oxybenzenesulfonate, (6-decanoyl-caproyl) ) oxybenzenesulfonate, and highly preferably (6-nonamidocaproyl)oxybenzenesulfonate, and mixtures thereof, as described in EP-A-0170386.

Perbenzoic acid precursor compounds that provide perbenzoic acid in perhydrolyzed benzoxazine organic peroxyacid precursors, as disclosed for example in EP-A-332294 and EP-A-482807, and in perhydrolysis produce Cationic peroxyacid precursor compounds of cationic peroxyacids are also suitable.

阳离子过氧酸前体描述于U.S.专利4,904,406；4,751,015；4,988,451；4,397,757；5,269,962；5,127,852；5,093,022；5,106,528；U.K.1,382,594；EP475,512,4 58,396和284,292；和JP87-318,332。 Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any ammonium or alkylammonium substituted alkyl or benzoyloxybenzenesulfonates, N-acylated caprolactam and monobenzoyltetraacetylglucose benzoyl peroxide. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammoniummethylenebenzoylcaprolactams and trialkylammoniummethylenealkylcaprolactams.

The particles or compositions of the present invention may comprise, in addition to or as an alternative to the organic peroxyacid bleach precursor compound, a pre-formed organic peroxyacid, generally in an amount of from 0.1 to 15% by weight, more Preferably 1 to 10% by weight. A preferred class of organic peroxyacid compounds are the amide substituted compounds as described in EP-A-0170386. Other organic peroxyacids include diacyl and tetraacetyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperoxyazelaic acid, mono- and diperoxytridecanedioic acid and N-phthalimidoperoxycaproic acid are also suitable here. source of peroxide

Inorganic perhydrate salts are the preferred source of peroxide. Preferably, the amount of such salt is from 0.01 to 50% by weight of the composition, more preferably from 0.5 to 30% by weight.

Examples of inorganic perhydrate salts include perborates, percarbonates, perphosphates, persulfates and persilicates. Typically these materials are prepared by crystallization or fluidized bed processes. The inorganic perhydrate salts are usually alkali metal salts. The inorganic perhydrate salts may be included as crystalline solids without additional protection. However, for certain perhydrate salts, such granular compositions are preferably formed using a coating of said material, which provides better storage stability for said perhydrate salts in said granular product. Suitable coating coatings include inorganic salts such as alkali metal silicates, carbonates or borates or mixtures thereof, or organic materials such as waxes, oils or fatty soaps. Sodium perborate is _the preferred perhydrate salt and may be in the _form of the monohydrate of _the formula _NaBO2H2O2 or the _{tetrahydrate NaBO2H2O2.3H2O} . Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates here. Sodium percarbonate is _an addition compound having the formula _{2Na2CO3.3H2O2} and is commercially available as _a crystalline _solid . Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in detergent compositions herein. Chelating agent

Here, the chelating agent refers to detergent ingredients that function to capture (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferably they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper. Chelating agents are typically present in detergent matrix components and/or as dry add-ons of additional detergent ingredients such that they are present in the final detergent composition in an amount of from 0.005% to 10% of said composition or component , preferably 0.1% to 5%, more preferably 0.25% to 7.5% and most preferably 0.3% to 2% by weight.

Suitable chelating agents include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilotrimethylene phosphonates, preferably diamethylene Ethyltriaminepenta(methylenephosphonate), ethylenediaminepenta(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate) and hydroxy-ethylene 1,1 diphosphate , 1,1-hydroxyethane diphosphonic acid and 1,1 hydroxyethane dimethylenephosphonic acid.

Other suitable chelating agents for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylenediamine Disuccinic acid or any salt thereof, and iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid are described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants are described in EP-A-516,102 , is also suitable here. β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants, described in EP-A-509,382, is also suitable. EP-A 476,257 describes suitable amino-based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes suitable alkyliminodiacetic acid sequestrants. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycylamide-N,N'-disuccinic acid (GADS), ethylenediamine-NN'-diglutaric acid (EDDG), and 2-hydroxypropylenediamine-NN'-disuccinic acid (HPDDS) are also suitable. Especially preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1 hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted Ammonium salts or mixtures thereof. In particular, chelating agents comprising amino or amine groups may be bleach-sensitive and suitable for the compositions of the present invention. water soluble builder compounds

The detergent compositions herein preferably comprise water-soluble builder compounds, generally in an amount of from 1% to 80% by weight of the detergent composition, preferably from 10% to 60%, most preferably from 15% to 40% by weight.

A preferred detergent composition of the present invention comprises builder material comprising phosphate, preferably in an amount of from 0.5% to 60%, more preferably from 5% to 50%, more preferably from 8% to 40% by weight . Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphates , wherein the degree of polymerization is about 6 to 21, and phytate. Phosphate-containing builder materials preferably include tetrasodium pyrophosphate and even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or acid-formed, homo- or co-polymeric polycarboxylic acids or salts thereof, wherein said polycarboxylic acid comprises at least two carboxyl groups , separated from each other by not more than two carbon atoms, borates, and mixtures of any of the foregoing. Carboxylate or polycarboxylate builders can be of the monomeric or oligomeric type, although monomeric polycarboxylates are generally preferred for cost and performance reasons. Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, glyoxylic acid, tartaric acid, hydroxymalonic acid, and fumaric acid, and the ethers Carboxylates and sulfocarboxylates. Polycarboxylates containing three carboxy groups or their acids include, inter alia, the water-soluble citrates, aconitrates and citraconic acid salts and succinate derivatives such as carboxymethoxy as described in British Patent No. 1,379,241. Succinates, lactyloxysuccinates described in British Patent No. 1,389,732 and aminosuccinates and oxypolycarboxylates materials such as 2-oxopolycarboxylates described in British Patent No. 1,387,447 Hetero-1,1,3-propane tricarboxylate. The most preferred polycarboxylic acid containing three carboxyl groups is citric acid, preferably present in an amount of 0.1% to 15%, more preferably 0.5% to 8% by weight.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates disclosed in British Patent No. 1,261,829 Carboxylate and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000. salt. Preferred polycarboxylates are hydroxy-carboxylates containing up to three carboxyl groups per molecule, especially citrates.

Parent acids and their salts of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof, such as citric acid or citrate/citric acid mixtures are also contemplated as useful builder ingredients. Borate builders, and builders comprising borate-forming materials which can generate borate under detergent reservoir or wash conditions, find use herein as water-soluble builders.

Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acids comprise at least two carboxyl groups separated from each other by not more than two carbon atoms . Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially from 40,000 to 80,000. The polyamino compounds are also useful herein, including those derived from aspartic acid, such as disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. Partially soluble or insoluble builder compounds

The compositions herein may comprise partially soluble or insoluble builder compounds present in the detergent matrix components and/or optional additional ingredients. When present, they will generally be present in a total amount of from 0.5% to 60% by weight of the detergent composition, preferably from 5% to 50% by weight, most preferably from 8% to 40% by weight. Examples of substantially water-insoluble builders include sodium aluminosilicates. As noted above, only minor amounts of alumina silicate builder are preferably present in one embodiment of the present invention.

Suitable aluminosilicate zeolites have a unit cell of the formula Naz[(AlO ₂ ) _z (SiO ₂ ) _y ].xH ₂ O, wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate material is in hydrated form and preferably crystalline, comprising 10% to 28%, more preferably 18% to 22%, water in bound form.

The aluminosilicate zeolites may be naturally occurring materials, but are preferably of synthetic origin. Synthetic crystalline aluminosilicate ion exchange materials are available under the names Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [AIO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O

Wherein x is 20 to 30, especially 27. Zeolite X has a

Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ].276H ₂ O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP is present in an amount of 1 to 80%, more preferably 15 to 40 wt%. Zeolite MAP is described in EP384070A (Unilever). Alkali metal aluminosilicates, defined as zeolite P type, have a silicon to aluminum ratio not greater than 1.33, preferably within the range of 0.9 to 1.33 and more preferably within the range of 0.9 to 1.2. It is especially important that zeolite MAP has a silicon to aluminum ratio of no greater than 1.15 and more particularly no greater than 1.07. In a preferred aspect, the zeolite MAP detergent builder has a particle size, expressed as a median particle size _d50 value, of 1.0 to 10.0 microns, more preferably 2.0 to 7.0 microns, most preferably 2.5 to 5.0 microns . The d ₅₀ value means that 50% by weight of the particles have a diameter smaller than this number. The particle size can be determined, inter alia, by conventional analytical techniques, such as microscopic determination using a scanning electron microscope or by laser granulometers as described herein. Other methods of determining _d50 values are disclosed in EP384070A. Dyes, fragrances, enzymes, optical brighteners

Preferred ingredients of the compositions herein are dyes and dyed particles or spots, which may be bleach-sensitive. The dye used herein may be a dye or a solution of an aqueous or non-aqueous dye. It may be preferred that the dye is an aqueous solution comprising the dye in any level of dye to produce a suitable detergent particle or spot, preferably such that the level of the dye solution is prepared to be up to 2% by weight of the dye particle, or more preferably Up to 0.5% by weight, as described above. The dyes may also be mixed with anhydrous carriers, such as non-aqueous liquid materials including non-ionic surfactants. Optionally, the dye also includes other ingredients, such as an organic binder material, which may also be a non-aqueous liquid. The dye can be any suitable dye. Specific examples of suitable dyes include E104-Food Yellow 13 (Quinoline Yellow), E110-Food Yellow 3 (Sunset Yellow FCF), E131-Food Blue 5 (Patent Blue), Ultra Navy (trade name), E133- Food Blue 2 (Brilliant Blue FCF), E140-Natural Green 3 (chlorophyll and chlorphyllins), E141 and Pigment Green 7 (chlorinated Cu phthalocyanine). Preferred dyes may be Monastral Blue BV paste (trade name) and/or Pigmasol Green (trade name).

Another preferred ingredient of the compositions of the present invention is a perfume or perfume composition. Any fragrance composition can be used herein. The fragrance may also be encapsulated. Preferred fragrances comprise at least one volatile component having a low molecular weight, for example a molecular weight of 150 to 450 or preferably 350. Preferably, the fragrance component includes oxygen-containing functional groups. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or mixtures thereof.

Another highly preferred ingredient useful in the particles or compositions herein is one or more additional enzymes. Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, fruit enzymes and Gelase, Lactase and Peroxidase. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), those sold by Gist-Brocades under the trade names Maxatase, Maxacal and Maxapem, Those sold by Genencor International, and those sold by Solvay Enzymes under the trade names Opticlean and Optimase. Proteases may be incorporated into the compositions of the invention in amounts ranging from 0.0001% to 4% active enzyme by weight of the composition. Preferred amylases include, for example, alpha-amylases, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include, for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylases may be those described in PCT/US9703635 and WO95/26397 and WO96/23873. Amylase enzymes may be incorporated into the compositions of the invention in amounts ranging from 0.0001% to 2% by weight active enzyme. The lipolytic enzyme may be present at a level of 0.0001% to 2% by weight, preferably 0.001% to 1% by weight, most preferably 0.001% to 0.5% by weight of active lipolytic enzyme. The lipase may be of fungal or bacterial origin, for example, from a lipase-producing strain of Humicola species, Thermomyces species or Pseudomonas , including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens . Lipases derived from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes , which is described in granted European patent EP-B-0218272. Another preferred lipase is prepared by cloning a gene from Humicola lanuginosa and expressing a gene from Aspergillus oryzae , as a host, as described in European patent application EP-A-0258 068, which is available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. These lipases are also described in US Patent 4,810,414, Huge-Jensen et al., issued March 7,1989.

The compositions described herein also preferably contain from about 0.005 to 5% by weight of certain types of hydrophilic optical brighteners, as described above. Examples are Tinopal-UNPA-GX ^™ and Tinopal-CBS-X ^™ from Ciba-Geigy Corporation. Others include Tinopal 5BM-GX ^™ , Tinopal-DMS-X ^™ and Tinopal AMS-GX ^™ from Ciba Geigy Corporation. photobleach

Photobleaches are a preferred ingredient of the compositions or components. Preferred photobleaches include compounds having a porphine or porphyrin structure. Porphine and porphyrin, in the literature, are used as synonyms, but usually porphine stands for simple porphyrin without any substituents; where porphyrin is a subset of porphine. Porphine In this application shall include porphyrin. The porphine structure preferably comprises metal elements or cations, preferably Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Ground Zn. It may be preferred that the photobleaching compound or component is substituted with a substituent selected from alkyl groups such as methyl, ethyl, propyl, t-butyl and aromatic ring systems such as pyridyl, pyridyl- N-oxide, phenyl, naphthyl and anthracenyl moieties. The photobleaching compound or component may have solubilizing groups as substituents. Alternatively, or in addition, the photo-bleach may comprise a polymeric component capable of solubilizing the photo-bleach compound, such as PVP, PVNP, PVI or copolymers or mixtures thereof. Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, preferably having metal elements or cations as described above.

The phthalocyanine may be substituted, such as a phthalocyanine structure substituted at one or more 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atomic positions. Organic Polymerized Components

Organic polymers are additionally preferred herein and are preferably present as a component of any particulate component, such as a detergent matrix component, where they can act as a binder. According to the present invention, organic polymer refers herein to virtually any polymeric organic compound commonly used as a dispersant and anti-redeposition and soil-suspension agent in detergent compositions, including any of the high molecular weight compounds described herein as clay flocculants Organic polymers, including quaternized ethoxylated (poly)amine clay-soil release/anti-redeposition agents. Organic polymers are typically incorporated into the detergent compositions of the present invention at levels of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10% by weight of the compositions or components. Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000 to 10,000, are also suitable here. Other organic polymers suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other useful organic polymers are polyethylene glycols, especially those having a molecular weight of 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. Highly preferred polymeric components are cotton and non-cotton soil release polymers according to US Patent 4,968,451 (Scheibel et al.) and US Patent 5,415,807 (Gosselink et al.) and especially according to US Application no. 60/051517. Another organic compound useful herein, which is a preferred clay dispersant/anti-redeposition agent, can be an ethoxylated cationic monoamine and diamine of the formula:

wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0 to 20, preferably 0 to 4 (e.g. ethylene, ethylene Propyl, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, typically 20 to 35; for cationic diamines (b=1), n is at least about 12, Typical values are about 12 to about 42. Other dispersants/anti-redeposition agents useful herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Polymeric dye transfer inhibiting agents, if present, are typically present in amounts of 0.01% to 10%, preferably 0.05% to 0.5% and are preferably selected from polyamine N-oxide polymers, N-vinylpyrrolidone and N-ethylene Copolymers of imidazoles, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers may be crosslinked polymers.

Polymeric soil release agents, hereinafter "SRA", may optionally be used in the present components or compositions. If used, SRA is typically present in amounts of 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0% by weight. Preferred SRAs generally have a hydrophilic segment to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic segment to settle on hydrophobic fibers and maintain them through the wash and rinse cycle. Adhere to it, thereby playing the role of immobilizing the hydrophilic segment. This makes stains easier to decontaminate in subsequent wash steps after treatment with SBA. Preferred SRAs include oligomeric terephthalates, generally prepared by processes involving at least one esterification/oligomerization process, often utilizing metal catalysts such as titanium (IV) alkoxides. Such esters can be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely cross-linked overall structure.

Suitable SRAs are eg as described in US 4,968,451, 6 November 1990 (JJScheibel) and EP (Gosselink). Other SRAs include the nonionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters of US 4,711,730 (December 8, 1987, Gosselink et al.). Other examples of SRAs include: US4,721,580 (January 26, 1988, Gosselink) partially-and fully-anionically terminated oligoesters; US4,702,857 (October 27, 1987, Gosselink) nonionic Terminated block polyester oligomeric compounds; and anionic, especially sulfoaroyl-terminated terephthalates of US 4,877,896 (October 31, 1989, Maldonado, Gosselink, etc.). SRA also includes: block of common copolymerized ethylene terephthalate or propylene terephthalate and polyethylene oxide or polyoxypropylene terephthalate, see US3,959,230 (Hays, May 25, 1976) and US 3,893,929 (Basadur, July 8, 1975); derivatives of cellulose such as polymers of hydroxyether cellulose, available from Dow as METHOCEL; C ₁ -C ₄ Alkyl cellulose and C ₄ hydroxyalkyl cellulose, see US 4,000,093 (December 28, 1976, Nicol et al); and an average degree of substitution (methyl)/anhydroglucose unit of about 1.6 to about 2.3 and a solution viscosity of about 80 to about 120 centipoise (measured at 20°C as a 2% aqueous solution) methyl cellulose ether. Such materials are commercially available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Additional classes of SRAs include those described in US 4,201,824 (Violland et al) and US 4,240,918 (Lagasse et al); US 4,525,524 (Tung et al) and US 4,201,824 (Violland et al). foam suppression system

The detergent compositions herein, especially when formulated for use in machine washing compositions, may include a suds suppressing system present in an amount of from 0.01% to 15%, preferably 0.02%, of the composition or component to 10%, most preferably 0.05% to 3% by weight. Suitable suds suppressing systems for use herein may comprise virtually any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alcanol antifoam compounds or soaps. Antifoam compound refers herein to any compound or mixture of compounds which acts to suppress suds or suds produced by solutions of detergent compositions, especially when those solutions are agitated.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds, defined herein as any antifoam compound that includes a silicone component. Such silicone antifoam compounds typically also contain a silica component. The term "silicone" as used herein, and generally in the art, encompasses a variety of higher molecular weight polymers comprising siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are polysiloxanes, especially polydimethylsiloxanes having trimethylsilyl end capping units. Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof, as described in US Patent 2,954,347 (September 27, 1960, Wayne St. John). Other suitable antifoam compounds include, for example, high molecular weight fatty acid esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, N-alkylated fatty acid C ₁₈ -C ₄₀ ketones (such as stearyl ketone) Aminotriazines such as tri to hexaalkylmelamines or di to tetraalkyldiamine chlortriazines, which are products of cyanuric chloride with two or three moles of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide , bisstearic acid amide and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and phosphate esters.

The preferred suds suppressing system comprises an antifoam compound, preferably a silicone antifoam compound at a level of from 50% to 99%, preferably from 75% to 95%, by weight, in combination with polydimethylsiloxane; and Silica in an amount of 1% to 50%, preferably 5% to 25% by weight of the siloxane/silicone antifoam compound, wherein the silica/silicone antifoam compound is present in an amount of 5% to 50%, Preferably 10% to 40% (by weight) is combined with a dispersant compound, most preferably comprising a silicone glycol gradient (rake) copolymer having a polyoxyalkylene content of 72-78% and ethylene oxide with cyclo Propylene oxide ratio of 1:0.9 to 1:1.1, 0.5% to 10% of e.g. DCO544 from DOWConing, and an inert carrier flow compound, most preferably including _C16 - _C18 ethoxylated alcohols, which ethoxylated The degree is 5 to 50, preferably 8 to 15, and the content is 5 to 80%, preferably 10 to 70% by weight.

A highly preferred particulate foam suppression system is described in EP-A-0210731. EP-A-0210721 discloses other preferred particulate foam suppression systems. Other highly preferred suds suppressing systems include polydimethylsiloxanes or mixtures of polysiloxanes such as polydimethylsiloxanes, aluminosilicates and polycarboxylic acid polymers such as copolymers of laic and acrylic acid.

Other optional ingredients suitable for inclusion in the compositions of the present invention include pigments and filler salts, sodium sulfate being the preferred filler salt.

Highly preferred compositions contain from about 2% to about 10% by weight of an organic acid, preferably citric acid. Likewise, carbonates, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foams may preferably be present Conditioners, sunscreens, antioxidants, bactericides and dyes are described, for example, in US Patent 4,285,841 (Barrat et al., issued Aug. 25, 1981) (herein incorporated by reference).

The detergent composition may comprise, as an additional ingredient, a chlorine-based bleach. However, because the detergent compositions of the present invention are solid, most liquid chlorine-based bleaches will not be suitable for these detergent compositions and only granular or powder chlorine-based bleaches will be suitable. Alternatively, chlorine-based bleach can be added to the detergent composition by the user at the start or during the wash. The chlorine-based bleaches are bleaches that form hypochlorite species in aqueous solution. The hypochlorite ion is chemically represented by the formula OCI-. Those bleaching agents which generate hypochlorite species in aqueous solution include alkali and alkaline earth metal hypochlorites, hypochlorite adducts, chloramines, imine chlorides, amides and imides. Specific examples include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, trisodium chlorinated phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, dichloroisocyanurate Sodium Urate Dihydrate, Trichlorocyanuric Acid, 1,3-Dichloro-5,5-Dimethylhydantoin, N-Chlorosulfonamide, Chloramine T, Dichloramine T, Chloramine B, and Dichloramine B. Preferred bleaching agents for use in the compositions of the present invention are sodium hypochlorite, potassium hypochlorite or mixtures thereof. A preferred chlorine-based bleach may be Triclosan (trade name).

Most of the aforementioned hypochlorite-generating bleaches are available in solid or concentrated form and are dissolved in water during the preparation of the compositions of the invention. Some of the above materials are available in aqueous solution. laundry method

Machine laundry methods herein generally comprise treating soiled garments in a washing machine with an aqueous wash liquor which has dissolved or dispensed an effective amount of the machine laundry detergent composition of the present invention. An effective amount of a detergent composition means 10 g to 300 g of product dissolved or dispersed in a volume of 5 to 65 liters of wash liquor, such as typical product dosages and volumes of wash liquor typically used in conventional mechanical laundry methods. Preferred washing machines may be so-called low-fill machines.

In a preferred application aspect, the composition is formulated such that it is suitable for hard surface cleansing or hand washing. In another preferred aspect, the detergent composition is a pretreatment or impregnation composition for pretreating or impregnating soiled and soiled fabrics.

Example

The following examples are presented for illustrative purposes only and do not limit the scope of the appended claims in any way.

abbreviation used in examples

In detergent compositions, the abbreviated component names have the following meanings: LAS: Linear Sodium C11-13 Alkylbenzene Sulfonate TAS: Sodium Tallow Alkyl Sulfate CxyAS: Sodium C1x-C1y Alkyl Sulfate Branched AS: Branched Chloride alkyl sodium sulfate, as described in WO99/19454 C46SAS: C14-C16 secondary (2,3) alkyl sodium sulfate CxyEzS: C1x-C1y alkyl sodium sulfate CxyEz condensed with z moles of ethylene oxide : Primary linear primary of C1x-C1y condensed with average z moles of ethylene oxide

Alcohol QAS: R2.N+(CH3)2(C2H4OH), where R2=C12-C14QAS1: R2.N+(CH3)2(C2H4OH), where R2=C8-C11APA: C8-C10 aminopropyl dimethylamine soap: Linear alkyl derived from 80/20 tallow and coconut fatty acid blend

Sodium Carboxylate STS: Sodium Toluene Sulfonate CFAA: C12-C14 (Coconut) Alkyl N-Methyl Glucamide TFAA: C16-C18 Alkyl N-Methyl Glucamide TPKFA: C12-C14 Upper Integral Cut Fatty Acid STPP: Anhydrous sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate Zeolite A: Na12(AlO2SiO2)12.27H2O hydrated sodium aluminosilicate, primary particle

Subsize 0.1 to 10 microns (by weight, on anhydrous basis) NaSKS-6: Crystalline layered silicate of formula d-Na2Si2O5 Citric acid: Anhydrous citrate Borate: Sodium borate carbonate: Anhydrous carbonic acid Sodium: Particle size 200μm to 900μm Bicarbonate: Anhydrous sodium bicarbonate, particle size distribution 400μm to 1200μm Silicate: Amorphous sodium silicate (SiO2:Na2O=2.0:1) Sulfate: Anhydrous sodium sulfate magnesium sulfate : Magnesium sulfate anhydrous citrate: Trisodium citrate dihydrate, 86.4% active, particle size distribution at 425 μm

Between MA/AA and 850 μm: 1:4 maleic acid/acrylic acid copolymer, average m.wt. about 70,000 MA/from (1): 4:6 maleic acid/acrylic acid copolymer, average m.wt .About 10,000AA: Sodium polyacrylate polymer, average molecular weight 4,500CMC: Sodium carboxymethyl cellulose cellulose ether: Methyl cellulose ether, degree of polymerization 650, available from Shin Etsu

Chemicals Protease: Proteolytic enzyme with 3.3% active enzyme by weight, supplied by NOVO

Industries A/S sells Protease I under the tradename Savinase: Proteolytic enzyme with 4% by weight active enzyme, eg WO95/10591

Alcalase, sold by Genencor Int. Inc as described in: Proteolytic enzyme with 5.3% active enzyme by weight, sold by NOVO

Industries A/S sells cellulase: Cellulolytic enzyme with 0.23% by weight of active enzyme by NOVO

Industries A/S sells amylases under the tradename Carezyme: Amylolytic enzyme with 1.6% by weight of active enzyme, supplied by NOVO

Industries A/S sells lipase under the tradename Termamyl 120T: lipolytic enzyme with 2.0% by weight of active enzyme, supplied by NOVO

Industries A/S sells lipase (1) under the trade name Lipolase: lipolytic enzyme with 2.0% by weight of active enzyme, supplied by NOVO

Industries A/S sells Endoglucanase under the trade name Lipolase Ultra: Endoglucanase enzyme with 1.5% by weight of active enzyme, supplied by NOVO

Industries A/S sells PB4: Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2 PB1: Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate: of nominal formula 2Na2CO3.3H2O2 Sodium percarbonate NOBS: Nonanoyloxybenzenesulfonate in sodium salt form NAC-OBS: (6-Nonanoylhexanoyl)oxybenzenesulfonate TAED: Tetraacetylethylenediamine DTPA: Diethylene Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylene phosphonate), commercialized by Monsanto

Product name Dequest2060 Sales EDDS: Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer sodium salt Photosensitized bleaching: Sulfonated phthlocyanine zinc, encapsulated in bleach (1) dextrin can Photosensitized bleaching in soluble polymers: Aluminum sulfonated phthlocyanine, encapsulated in bleach (2) dextrin coagulant Brightener 1 in soluble polymers: 4,4′-5 bis(2-sulfostyrene Base) disodium biphenyl brightener 2: 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl)

Amino) 1,2-stilbene-2: disodium 2′-disulfonate HEDP: 1,1-hydroxyethane diphosphate PEGx: Polyethylene glycol, molecular weight x (typically 4,000) PEO: Polyepoxide Ethane, average molecular weight 50,000TEPAE: Tetraethylenepentamine ethoxylate PVI: Polyvinylpyridine N- Oxide polymer, average m.wt 50,000PVPVI: Copolymer of polyvinylpyrrolidone and vinylimidazole (average

m.wt 20,000)QEA: Bi((C2H5O)(C2H4O)n)(CH3)-N+-C6HI2-N+-(CH3)

Bis((C2H5O)-(C2H4O))n, where n=20 to 30 SRP1: Anion-terminated polyester SRP2: Short blocks of diethoxylated poly(1,2propylene terephthalate)

Polymer PEI: Polyethyleneimine with an average molecular weight of 1800 and an average degree of ethoxylation

For 7 ethyleneoxy residues/nitrogen polysiloxane: Polydimethylsiloxane foam control agent, polysiloxane-oxyalkylene co-foaming agent polymer as dispersant, said foam control agent and all of the dispersant

A 10:1 to 100:1 ratio of sunscreen: water-based monostyrene latex blend, manufactured by BASF

Aktiengesellschaft sells it under the tradename Lytton 621 Wax: Paraffin HMEO: Hexamethylenediaminetetrakis(ethylene oxide) 24 Example 1: Preparation of effervescent particles

A 2 kg batch of citric acid and sodium carbonate (composition: 64 wt% citric acid/36 wt% sodium carbonate) was mixed by mixing the following in a Hosokawa Mikron 'Nautamix' DBY-5R rotary screw mixer at a speed setting of 9 (maximum) Five minutes to prepare: 1280 g of anhydrous citric acid (available from Citrique Beige) (fine grade: 16/40), particle size 200-400 μm, and 720 g of anhydrous sodium carbonate (Light Soda Ash, available from Brunner Mond), which Pre-grind to a median particle size of 5 μm using a Hosokawa Mikron Air-Classifier Mill (ACM15). The mixture was then compacted in a Bepex Compaction Unit (rollers: 200mm diameter, 50mm width): the pre-mixed powder was poured into the feed hopper of the above-mentioned compaction rollers. The feed hopper has a vertical screw that feeds the powder to the roller. The force used to push the two rolls together is called the compaction force and was adjusted to 80 kN by adjusting the feed screw speed. The compacted material was collected as cracked and unbroken corrugated sheets, which were then ground in a Hosokawa Bepex F200 Flake Breaker at speed setting 1. The equipment consists of a roll mantle with a 1000 μm screen.

The material produced by the Flake breaker was then placed on a Vibrating Sieving device (Retsch model AST200) with a sieve aperture of 355 μm. The material retained on the screen was the desired finished granule (effervescent granule A in the table below) with a median particle size of 620 μm, while the powder was removed for recycling.

The procedure was repeated using the following mixtures of components in the amounts (respective amounts given in wt% based on the effervescent particle) indicated in Table 1 to make further effervescent particles B-E.

Table 1 effervescent particles B C D. E. citric acid 40 10 55 - maleic acid 20 30 - 35 tartaric acid - - - 15 Sodium carbonate 25 70 - 40 sodium bicarbonate 15 - 45 10

These effervescent particles were incorporated into detergent compositions as described in Examples 2 to 6. Example 2

The spray-dried granules, having the composition described in Example 3 below, were produced by forming an aqueous slurry followed by microgranulation in a spray drying tower, with 5 wt% TAED, 1 wt% suds suppressor as additional detergent ingredients , 7.5 wt% sodium carbonate and 2.5 wt% sodium sulfate were mixed in an Eirich mixer. An aqueous solution of PEG-4000 (35 wt% solids) was then sprayed onto the mixture and allowed to granulate for 5 minutes. The resulting product was sieved to collect particles between 300 and 1200 microns. Then 10 wt% sodium percarbonate, 0.5 wt% fragrance and 1 wt% enzyme (including a mixture of pellets containing amylase, cellulase, protease and lipase) were added in dry form and mixed. The mixture produced had an eRH of 59%. 10 wt% of effervescent granules of any of formulations A to E or a mixture of these are then added to the mixture in a Nautamix cone mixer and subsequently filled into detergent cartons. Example 3

The spray-dried granules are produced in a countercurrent spray drying tower with an inlet air temperature of 300 °C. Agglomerates and other mixtures (see Table 2) were mixed with the spray-dried granules in a batch tumbler mixer. The detergent base has an eRH of 38%. The effervescent particles A are then added and the product filled into detergent cartons. Other embodiments of detergent compositions according to the invention can be prepared by using effervescent particles B to E or mixtures of any of said particles A to E.

Table 2

Spray dried granules 50%

Spray-dried granule composition % weight of total feed

LAS 10.4

Tallow Alkyl Sulfate 1.6

EDDS 0.4

Brightener 15 0.1

Magnesium Sulfate 0.7

Sokalan CP5 2.5

HEDP 0.3

Sodium carbonate 8.4

Sodium sulfate 23.5

ZeoliteA 40.0

Other (water, spices, etc.) 12.07

100.0

Anionic Surfactant Agglomerates 10%

Agglomerate composition % weight of total feed

C45 alkyl ethoxylated sulfate (EO0.6) 29.1

Zeolite A 45.0

Sodium carbonate 15.1

Polyethylene glycol (MW4000) 1.3

Other (water, spices, etc.) 9.5

100.0

Percarbonate 10%

TAED 5%

Effervescent particles 10%

Minor component 15% Example 4

Example 3 was repeated except that the spray-dried granules were dried at a higher column inlet temperature of 350°C and some bound water was removed. In this case the detergent matrix eRH is 24%. Example 5

The detergent matrix of Example 3 was replicated, to which 5% of overdried zeolite was added in a Nautamix cone mixer. (The overdried zeolite is Zeolite A, most of its water of crystallization is removed by additional drying). The resulting detergent matrix had an eRH of 12%. 10% of Effervescent Particle B was then added to the matrix and the product was filled into detergent cartons. Another embodiment can be prepared by using a mixture of any of the effervescent particles B to E or any of the particles A to E. Example 6

The spray-dried granules, agglomerates and builder agglomerates described in Tables 3A and 3B below were first fed into a Lodige KM ^™ 600 mixer set at 660 kg with drum rotation at 100 RPM And knife speed at 3600RPM. The resulting mixture was fed to a fluidized bed dryer. Optionally, an aqueous solution of PEG-4000 (30% by weight solids) was sprayed onto the mixture in the first of three stages in the fluid bed dryer. The resulting product is sieved to collect particles in the range of about 600 to about 1100 μm. Powders are recycled to the LodigeKM, while large particles are ground and recycled to the fluid bed dryer. Then add the dry added detergent components and the spray components from the table below. The detergent matrix eRH is typically about 14%.

Table 3A

The following are compositions of the present invention. A B C D. E. f G h I spray dried granules LAS 10.0 10.0 15.0 5.0 8.0 10.0 - - - TAS - 1.0 - - - - MBAS - - 5.0 8.0 - - - C ₄₅ AS - - 1.0 1.0 2.0 - - - C ₄₅ AE ₃ S - - 1.0 - - - QAS 1.0 1.0 - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 - - - MgSO4 0.5 0.5 0.1 - - - - Sodium citrate - - - 3.0 5.0 - - - Sodium carbonate 10.0 7.0 15.0 10.0 10.0 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A 16.0 18.0 20.0 20.0 - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 11.0 - - 2.0 - - - PEG4000 - 2.0 - 1.0 - 1.0 - - - QEA 1.0 - - - 1.0 - - - - brightener 0.05 0.05 0.05 - 0.05 - - - - silicone oil 0.01 0.01 0.01 - - 0.01 - - - Agglomerates LAS - - - - 2.0 2.0 - MBAS - - - - - - 1.0 C ₄₅ AS - - - - 2.0 - - AE ₃ - - - - - 1.0 0.5 carbonate - - - 1.0 1.0 1.0 - Sodium citrate - - - - - - 5.0 CFAA - - - - citric acid - - - 4.0 - 1.0 1.0 QEA - - - 2.0 2.0 1.0 - SRP - - - 1.0 1.0 0.2 - Zeolite A - - - 15.0 26.0 15.0 16.0 Sodium silicate - - - - - - - PEG - - - - - - 4.0 - - builder agglomerates SKS-6 6.0 - - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry Add Granular Components Effervescent Particle A 8.0 10.0 12.0 2.0 4.0 Effervescent particles B 10.0 Effervescent Particles C 4.0 Effervescent particles D 8.0 Effervescent particles E 2.0 QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 1.5 - - - 2.5 - NOBS - 3.0 3.0 - - - - - 5.0 TAED 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (piece) 10.0 10.0 - - - - - 8.0 - Spray components brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 - dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - spices - - - 0.8 - 0.5 - 0.5 - dry addition components Citrate - - 20.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - - 18.0 5.0 Perborate - - - - 6.0 18.0 - - - photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.3 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 carbonate 0.0 10.0 - - - 5.0 8.0 10.0 5.0 Spices (encapsulated) 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6 Foam inhibitor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - citric acid - - - 6.0 6.0 - - - 5.0 Dyed carbonate (blue, green) 0.5 0.5 1.0 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - fill to 100%

Table IIIB

The following is the composition of the present invention A B C D. E. f G h I spray dried granules LAS 10.0 10.0 16.0 5.0 5.0 10.0 - - - TAS - 1.0 - - - - MBAS - - - 5.0 5.0 - - - C ₄₅ AS - - 1.0 2.0 2.0 - - - C ₄₅ AE ₃ S - - - 1.0 - - - QAS - - 1.0 1.0 - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.3 0.3 - - - MgSO4 0.5 0.4 0.1 - - - - Sodium citrate 10.0 12.0 17.0 3.0 5.0 - - - Sodium carbonate 15.0 8.0 15.0 10.0 - - - sodium sulfate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A - - - 2.0 - - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0 10.0 - - 2.0 - - - PEG4000 - 2.0 - 1.0 - 1.0 - - - QEA 1.0 - - - 1.0 - - - - brightener 0.05 0.05 0.05 - 0.05 - - - - silicone oil 0.01 0.01 0.01 - - 0.01 - - - Agglomerates LAS - - - - - - 2.0 2.0 - MBAS - - - - - - - - 1.0 C ₄₅ AS - - - - - - 2.0 - - AE ₃ - - - - - - - 1.0 0.5 carbonate - - - - 4.0 1.0 1.0 1.0 - Sodium citrate - - - - - - - - 5.0 CFAA - - - - - - - - citric acid - - - - - 4.0 - 1.0 1.0 QEA - - - - - 2.0 2.0 1.0 - SRP - - - - - 1.0 1.0 0.2 - Zeolite A - - - - - 15.0 26.0 15.0 16.0 Sodium silicate - - - - - - - - - PEG - - - - - - 4.0 - - builder agglomerates SKS-6 6.0 5.0 - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 Dry Add Granular Components Effervescent Particle A 8.0 4.0 4.0 - 2.0 2.0 4.0 Effervescent particles B 10.0 Effervescent particles D 8.0 QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 1.5 - - - 2.5 - NOBS - 3.0 3.0 - - - - - 5.0 TAED 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (piece) - - - - - - - 8.0 - Spray components brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 - dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - spices - - - 0.8 - 0.5 - 0.5 - dry addition components Citrate 4.0 - 3.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - - 18.0 5.0 Perborate - - - - 6.0 18.0 - - - photobleach 0.02 0.02 0.02 0.1 0.05 - 0.3 - 0.03 Enzymes (cellulase, amylase, protease, lipase) 1.5 0.3 0.5 0.5 0.8 2.0 0.5 0.16 0.2 carbonate - - - - - 5.0 8.0 10.0 5.0 Spices (encapsulated) 0.6 0.5 0.5 - 0.3 0.5 0.2 0.1 0.6 Foam inhibitor 1.0 0.6 0.3 - 0.10 0.5 1.0 0.3 1.2 soap 0.5 0.2 0.3 3.0 0.5 - - 0.3 - citric acid - - - 6.0 6.0 - - - 5.0 Dyed carbonate (blue, green) 0.5 0.5 - 2.0 - 0.5 0.5 0.5 1.0 SKS-6 - - - 4.0 - - - 6.0 - fill to 100%

Noise data were determined for the examples of the invention and it was found that with as little as 1 wt% effervescent particle A, based on the weight of the detergent composition, the noise level rose to about 49 dB, whereas for the application of 10 wt% of A, based on the weight of the detergent composition With effervescent particles, the noise level rises to a whopping 55dB.

Claims (20)

1. detergent composition, it comprises signal component, therefore generation signal when described detergent composition contacts with water.

2. the detergent composition of claim 1, wherein said signal is audible.

3. the detergent composition of claim 1 or claim 2, wherein said signal component comprises effervescent system.

4. the detergent composition of claim 3, wherein said effervescent system comprises the effervesce particle.

5. the detergent composition of any aforementioned claim, the noise level that wherein said sound signal produces be 45dB, 50dB at least preferably at least.

6. the detergent composition of any aforementioned claim, it is made up of effervesce particle and detergent base basically, it is characterized in that described detergent base has to be not more than 30% eRH.

7. the detergent composition of any aforementioned claim, it comprises effervesce particle and detergent base, total moisture content of wherein said effervesce particle is lower than 1wt% and moisture absorption is not more than 3%, when measuring during to moisture equilibrium at 60%RH with at 25 ℃.

8. the detergent composition of any aforementioned claim, wherein said detergent base comprises the component of at least a super-dry.

9. the detergent composition of claim 8, wherein said detergent base comprises the detergent base component, it comprises the preformed particle of tensio-active agent and the component that described detergent base component is a super-dry of comprising.

10. the detergent composition of claim 9, wherein said detergent base component comprises spray-dired particle.

11. the detergent composition of any aforementioned claim, it comprises that effervescent granule and tap density are lower than the low density detergent matrix component of 400g/l.

12. be used to wash the method for making goods dirty, it comprises that preparation comprises the detergent composition of signal component, described detergent composition is added in the entry, with the purified mechanically that begins to make goods dirty, it is characterized in that producing signal when adding detergent composition in the entry, it indicates when detergent composition is partly dissolved at least in water.

13. the method for claim 12, wherein purified mechanically is based on the existence of signal or end and begin.

14. the method for claim 13, wherein said signal continues for some time, so the end of signal represents the dissolving at least in part of described detergent composition, so chemical purification can begin.

15. any one method of claim 12 to 14, wherein said signal produces by effervescent system.

16. any one method of claim 12 to 15, wherein said signal is a sound signal.

17. the method for claim 16, the noise level that wherein said sound signal produces is 45dB at least, 50dB at least preferably.

18. be used to any one method of the claim 12 to 17 of doing washing.

19. the purposes of signal component in detergent composition, it produces signal when being added to washing water, and described detergent composition dissolved indication is provided.

20. the purposes of claim 19, wherein said signal is a sound signal.