CN1354780A - Effervescence component - Google Patents

Abstract

The present invention relates to an effervescence composition comprising an acid source and a carbon dioxide source, wherein at least 85 % of said acid source has a particle size from 0.1 to 150 microns, preferably from 0.5 to 100 microns. The carbon dioxide source is preferably also of a small particle size. The effervescence composition is in particular useful in solid detergent compositions. The effervescence component is preferably in the form of a granule comprising at least part of the acid source and the at least part of the carbon dioxide source. The effervescence component can also be coated by a coating comprising an alkoxylated alcohol having an alkoxylation degree of at least 20.

Description

effervescent component

                      

The present invention is applicable to a variety of compositions requiring dissolution in aqueous media in an easy and rapid manner. The present technology can be used in various fields such as laundry detergent compositions, soaking detergent compositions, dishwashing detergent compositions or any other compositions for household use, pharmaceutical preparations, dentifrices, food, etc. More particularly, the present invention relates to granular detergent compositions for fabric cleaning.

Background of the invention

One problem with conventional granular compositions used by consumers, usually after dilution with water, is their poor dissolution or poor dispensability. This trend is exacerbated by current trends such as the detergent industry towards higher bulk density granular compositions and granular detergent compositions with higher levels of active ingredients. Granular detergent compositions having a high bulk density of 650 to 1100 kg/ ^m3 are attractive to consumers but do not dissolve satisfactorily into aqueous media.

Another difficulty with detergent compositions is that they are not easily rinsed from the ingredient drawer of the washing machine. Similar problems arise when using these granular detergent compositions in the dispensing equipment of washing machine drums.

It is well known to use citric acid and carbonates in powder compositions to improve the dissolution of eg pharmaceutical preparations and detergents by effervescent means.

A possible problem with these compositions containing granular acids and carbonates is poor storage stability when they are exposed to moisture, resulting in reduced effervescence. Therefore, it is suggested in eg EP534525-A to use large particle size citric acid which is said to be stable when exposed to moisture.

However, the present inventors have now surprisingly found that very small particle size acid materials provide improved effervescence. Surprisingly they found that, contrary to what the prior art suggests, smaller particle size acids can be used in various compositions without causing stability problems in effervescent systems, while providing more efficient and rapid effervescence. They found that the addition of a very small particle size acid source not only resulted in improved partitioning/dissolution (compared to larger particle size acids), but also improved and faster foaming, which can be very beneficial for certain applications . A further improved effervescence performance and more efficient dispensing and/or dissolution and/or foaming is obtained when the carbon dioxide source also has a small particle size.

It may be highly preferred that the acid and carbon dioxide source are in intimate mixture, preferably in the form of dry effervescent granules. This not only further improves the stability of the effervescent system, but also increases the effervescence efficiency, thus resulting in the lesser amount of acid source being required for the desired effervescence, dispensing/dissolving and/or foaming. In addition, the inventors have found that effervescent granules having a larger particle size advantageously result in more stable and better effervescent granules.

The present inventors have surprisingly found that when using a smaller particle size acid source, stronger and more uniform particles can be obtained, thereby improving effervescent performance. Additionally, when compressed effervescent granules are desired, the compression pressure can be reduced when using a smaller particle size acid source and optionally a smaller particle size carbon dioxide source. These particles dissolve faster and thus provide improved effervescence. Furthermore, or alternatively, when the particles are prepared by agglomeration, it has been found to be advantageous to use smaller particle size acids, especially when binders are used to form agglomerates, which have been found to be incompatible with the use of larger particle size materials. The performance characteristics of the effervescent agglomerates are less affected by the binder than when a smaller acid source is incorporated.

In addition, the present inventors have discovered that when a coating comprising a specific alkoxylated alcohol is present on the effervescent component, or one or more components thereof, it not only enhances the Stability in humidity and surprisingly increased high volume long duration foam generation.

The increased high-volume, long-duration suds generation obtained by the coated effervescent component also has the additional advantage of giving the user a clear signal that the detergent composition containing the coated effervescent component has dissolved And cleaning the soiled article is now or is about to begin. It is especially suitable for hand wash applications: it may be optimal to introduce soiled articles into the wash cycle until the detergent composition has dissolved.

The alkoxylated alcohols selected above may also act as suds suppressors in later stages of the wash cycle, such as in the rinse, and thus have a dual role in the wash cycle. Specific alkoxylated alcohols used in this dual fashion have a favorable impact on formulation space allowing more room for other optional detergent ingredients as it helps to avoid Two separate detergent composition ingredients are necessary.

Summary of the invention

The present invention provides an effervescent component comprising an acid source and a carbon dioxide source, wherein at least 75% of said acid source has a particle size of 0.1-150 microns, more preferably 0.5-100 microns.

In one embodiment, it is highly preferred that the carbon dioxide source has a volume median particle size of 5-375 microns, whereby preferably at least 60% have a particle size of 1-425 microns, or more preferably 10-250 A volume median particle size in microns, whereby preferably at least 60% have a particle size in the range from 1 to 375 microns. In a preferred embodiment, the carbon dioxide source has a particle size similar to that of the acid source, preferably such that at least 60% or even 75% of the carbon dioxide source has a particle size of 1-150 microns, more preferably 1-100 microns.

In a highly preferred embodiment, the source of acid and the source of carbon dioxide are present in intimate admixture with each other, preferably in granules.

The present inventors also provide a method for preparing such particles, the method comprising the following steps:

- mixing an acid source and a carbon dioxide source and optionally a binder to form a mixture,

- Subsequent subjecting said mixture to a granulation step, preferably this step comprises a compression and/or agglomeration step to form a compressed and/or agglomerated mixture.

Preferably the acid source is a particulate material which is first ground to obtain the acid source of the invention before being mixed with the carbon dioxide source. Carbon dioxide sources can also be obtained by grinding larger particle size materials.

The invention also includes compositions comprising an effervescent component. In a preferred embodiment, the composition is a solid or non-aqueous detergent composition, including laundry, pretreatment and dishwashing compositions, preferably a solid composition in the form of granules, tablets or bars.

Additionally, the present invention also encompasses detergent compositions comprising a coated effervescent component, wherein said coating comprises an alkoxylated alcohol having a degree of alkoxylation of at least 20.

The present invention describes in detail the acid source

Acid sources suitable for use herein are capable of providing solid organic, mineral or inorganic acids and are preferably present in the form of their acids, salts or derivatives or mixtures thereof. Derivatives specifically include esters of acids.

Organic acids are especially preferred. It may be preferred that the acid is a mono-, di- or tri-protic acid. These preferred acids include monocarboxylic or polycarboxylic acids, preferably citric acid, adipic acid, glutaric acid, 3 cetoglutaric acid, citramalic acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, Malonate. These acids are preferably used in their acid form, and may preferably be used in the form of their anhydrides, or a mixture thereof. Preferred acid sources are malic anhydride and maleic anhydride. Other preferred acids include sulfonic acids such as toluenesulfonic acid.

Surprisingly, it has now been found that improved physical and/or chemical stability over prolonged storage periods is obtained by using citric, tartaric, maleic and/or malic acid. In addition, these materials, especially tartaric acid, were found to have improved dissolution, resulting in improved effervescent properties.

The acid source and preferably the acid itself is a particulate compound at least 75%, preferably at least 85% or even at least 90% or even at least 95% or even at least 99% by volume of a particle size of 0.1-150 microns and more preferably 0.5-100 microns, and it may even be preferred that at least 65% or even at least 75% or even at least 85% of the particles are 1.0-75 microns or even 1.0-55 microns or even 1.0-25 microns.

The particle size of the following acid source and carbon dioxide source can be measured by any method known in the art, especially by laser scattering or deftraction technology, such as using Malvem 2600 or Sympatec Helos laser scattering instrument (or defractometer).

It may be preferred here that the acid source has a volume median particle size of 1-120 microns or even 5-75 microns or even 5-55 microns or even 5-30 microns.

The volume median particle size of the acid source and carbon dioxide source can be determined by any method known in the art, specifically using the mentioned laser light scattering instrument (programmed to provide the volume median particle size).

Preferably, the acid source herein is obtained by grinding or milling a crude acid source material having a larger particle size than the acid source, just prior to adding the effervescent component. That said, it has been found that handling of the fine particle size acid source here after storage can be problematic, so it may be advantageous to store the acid source in a coarser form and grind this material prior to use. carbon dioxide source

Another important feature of the invention is the source of carbon dioxide. As used herein, a carbon dioxide source includes any material that reacts with an acid source to provide carbon dioxide when in contact with water. The source especially comprises carbonates, bicarbonates and percarbonates or mixtures thereof, especially bicarbonates and/or carbonates. Carbonates suitable for use herein include carbonates and bicarbonates of potassium, lithium, sodium, etc., of which sodium carbonate and potassium carbonate are preferred. Bicarbonates suitable for use herein include bicarbonates of any alkali metal such as lithium, sodium, potassium, etc., among which sodium bicarbonate and potassium bicarbonate are preferred. It may be preferred to use bicarbonate in combination with or instead of carbonate because of its greater effective weight. However, the carbonate or bicarbonate salts or mixtures thereof in the dry effervescent granules can be selected according to the desired pH of the aqueous medium in which the dry effervescent granules are dissolved. For example, when the aqueous medium requires a higher pH (such as greater than pH 9.5), it may be preferable to use carbonate alone or use a combination of carbonate and bicarbonate, wherein the content of carbonate is higher than the content of bicarbonate , usually the weight ratio of carbonate to bicarbonate is 0.1 to 10, more preferably 1-5 and most preferably 1-2.

The carbon dioxide source preferably has a volume median particle size of 5-375 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume has a particle size of 1-425 microns. More preferably the carbon dioxide source has a volume median particle size of 10-250, whereby preferably at least 60%, or even at least 70% or even at least 80% or even at least 90% by volume has a particle size of 1-375 microns or even preferably a volume median particle size of 10-200 microns, whereby preferably at least 60%, preferably at least 70% or even at least 80% or even at least 90% by volume have a particle size of 1-250 microns.

In a preferred embodiment, the carbon dioxide source has a particle size similar to the acid source, preferably such that at least 60% or even 75% of the carbon dioxide source has a particle size of 1-150 microns, whereby it is preferred that the source has a particle size of 1-150 microns. A volume median particle size of 120 microns, but more preferably at least 60% or even 75% of the source has a particle size of 1-100 microns with a volume median particle size of 5-75, or more preferably at least 60% or even 75 % of the source has a particle size of 1.0-75 microns or even 1.0-55 microns or even 1.0-25 microns.

It may be preferred that the carbon dioxide source of the desired particle size is obtained by milling a material of larger particle size, optionally followed by selection of the material of the desired particle size by any suitable method. Compact effervescent mixture/effervescent granule and method for its production

The acid source and the carbon dioxide source, or at least a part thereof, are preferably present in an intimate mixture with each other, which in the context of the present invention means that the acid source and the carbon dioxide source are homogeneously mixed. Thus, in a highly preferred embodiment, at least part of the acid source and at least part of the carbon dioxide source are not separate separate particles. It is highly preferred that said acid source and carbon dioxide source are present in an effervescent granule, preferably a dry effervescent granule.

The acid is preferably present in the intimate mixture or effervescent granule at a level of 0.1% to 99%, preferably 3-75%, more preferably 5%-60%, most preferably 15-50% by weight of the total granule.

The carbon dioxide source is preferably present in the intimate mixture or effervescent granule at a level of 0.1% to 99%, preferably 30-95%, more preferably 45%-85%, most preferably 50-80% of the total weight.

"Dry" should be understood to mean that the particles are substantially anhydrous, ie no added water or moisture other than the raw material itself is present. Typically the water content is less than 5%, preferably less than 3%, more preferably less than 1.5% by weight of the total intimate mixture or granules.

It may be preferred that drying agents are present in the intimate mixture or effervescent granules, such as overdried inorganic or organic salts, anhydrous salts, especially overdried silicates and aluminosilicates, anhydrous silicates and/or Sulfates.

For optimal effervescence in aqueous media, the weight ratio of acid source to carbon dioxide source in the intimate mixture or effervescent granules is preferably from 0.1 to 10, preferably from 0.5 to 2.5, more preferably from 1-2.

Preferably the effervescent granules are obtained by a process comprising a granulation step, preferably a dry powder compression or pressure agglomeration step. While all bonding mechanisms are possible in pressure agglomeration, the bonding forces between the solid particles, ie acid, carbon dioxide source and optional binder (if present) play an important role. This is because pressure agglomeration, especially high pressure agglomeration, is an important process for forming new entities (i.e. dry effervescent granules) from solid particles (i.e. acid, bicarbonate, carbonate source and optional binder). A drying method that provides strength to a new entity by applying an external force to more or less increase the mass or volume of the defined bulk and create a bonding mechanism between the solid particles, that is, apply a large external force to separate the solid particles tightly bound together. The inventors have surprisingly found that in the present invention, reducing the pressure may be sufficient to form stable particles doped with a smaller particle size acid source, preferably together with a smaller particle size carbon dioxide source as defined above.

The effervescent granules may have any particle size, the preferred particle size being dependent on the application and composition of the granule.

In a preferred embodiment, the effervescent granules have a weight average particle size of 500 microns to 1500 microns, whereby preferably at least 70% or even at least 80% by weight of the granules have a particle size of 350-2000 microns. diameter, or even have a weight-average particle diameter of 650-1180 microns, whereby preferably at least 70% or even 80% (by weight) of the particles have a particle diameter of 500-1500 microns, or even have a weight of 710-1000 microns Average particle size, whereby preferably at least 70% or even 80% by weight of the particles have a particle size of 600-1180 microns. It has been found that effervescent particles having these particle size parameters (including an acid source as defined herein) not only provide improved dispersion/dissolution, but can also provide improved foaming (including faster foaming and/or improved lather).

In another preferred embodiment, the effervescent particles preferably have a weight average particle size of 200-500 microns, whereby preferably at least 70% of the particles have a particle size of 100-710 microns, or even 250-500 microns. A weight average particle size of 450 microns, whereby preferably at least 70% of the particles have a particle size of 150-650 microns. It has been found that effervescent particles having these particle size parameters, including an acid source as defined herein, can provide better dispensing and / or dissolve.

The weight average particle size of the effervescent granules herein and hereafter detergent granules can be determined by any method known in the art, in particular by passing a sample of the granular acid-related material herein through meshes having different diameters or pore sizes. The weight (weight Fraction). The average particle size for each fraction can be calculated, taking into account the weight percent of each fraction, and then the weight average particle size for the material can be calculated (eg, plotted as weight fraction versus sieve aperture).

The intimate mixture or effervescent granules may optionally include a binder or a mixture of binders. Any binder material known in the art may be used. For example, highly suitable materials have melting points above 40°C, but preferably below 200°C or 100°C. In general, binders suitable for use herein are known to those skilled in the art and include anionic surfactants such as C ₆ -C ₂₀ alkyl or alkylaryl sulfonates or sulfates, preferably C ₈ -C ₂₀ Alkylbenzenesulfonates, fatty acids, cellulose derivatives such as homopolymers or copolymers of carboxymethylcellulose and polycarboxylic acids or their salts, nonionic surfactants, preferably C ₁₀ -C ₂₀ fatty alcohols Oxylates (containing 5-100 moles of ethylene oxide per mole of alcohol), more preferably _C15 - _C20 primary fatty alcohol ethoxylates (containing 20-100 moles of ethylene oxide per mole of alcohol). Of these materials, tallow alcohol ethoxylate containing 25 moles of ethylene oxide per mole of alcohol (TAE25) or tallow alcohol ethoxylate containing 50 moles of ethylene oxide per mole of alcohol (TAE50) is preferred . Other preferred binders include, for example, polyvinylpyrrolidone with an average molecular weight of 12,000 to 700,000 and polyethylene glycol with an average molecular 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 also include C ₁₀ -C ₂₀ mono- and diglyceryl ethers and C ₁₀ -C ₂₀ fatty acids.

It may be preferred that the effervescent granules contain a coating agent, which may be selected from any coating agent known in the art. Preferred film coating agents are materials that can be used for melt-form particles that are solid at ambient conditions, such as polymeric materials, nonionic surfactants. These materials can also be used as adhesives as described herein. Coating agents that can be used for particles in the form of solutions in aqueous solutions or in organic solvents, including organic and inorganic acids or salts, may also be preferred. Alternatively, the particles may be coated by sprinkling particulate material onto the particles, such as the desiccants described herein.

It may also be preferred that the intimate mixture or granule includes other components, such as detergent actives when used in detergent compositions. Preferred are surfactants (which may also act as binders and/or film coating agents), bleach components (especially bleach actives or precursors), catalysts or perhydrogenated salts, perfumes, brighteners, builders, enzyme.

Typically they contain up to 70%, preferably up to 50%, more preferably up to 35% of one or more binders and/or other actives by weight of the total granule or mixture.

The present invention also includes a process for preparing an effervescent granule of the present invention comprising an acid source, a carbon dioxide source and an optional binder, wherein the acid source, carbon dioxide source and optional binder are in close contact with each other. in the mixture. This method preferably comprises the following steps:

- first obtaining an acid source having a particle size as defined herein, preferably by grinding a commercially available acid source material of larger particle size,

- mixing the acid source thus obtained, preferably an acid source and a carbon dioxide source obtained by grinding a commercially available acid source material of larger particle size, and optionally a binder and/or other components to form a mixture,

- The mixture is subsequently sent to a granulation step, preferably comprising extrusion, spheronisation, more preferably compression or agglomeration steps.

Optionally, other components such as film coating agents, which are discussed in more detail below, may be added to the resulting granules.

By "granulation step" is meant the preparation of the resulting mixture into granules of the desired size as previously defined.

The preferred method used here is roller compaction. In this method, the acid source and carbon dioxide source and optional binder and other components are mixed and forced between two compression rollers, which apply pressure on the mixture so that the rollers Rotation of the mixture converts the mixture into compressed flakes/blocks. This compressed tablet/chunk is subsequently granulated. One way of doing this is by grinding the blocks/flakes or granulating the agglomerated mixture by conventional methods. Grinding can generally be performed using a Flake Crusher FC 200 ^(R) available from Hosokawa Bepex GmbH. Depending on the desired final particle size of the effervescent granules, the milled material can be further sieved. Screening of such dry effervescent granules can be performed, for example, using a commercially available Alpine Airjet Screen ^(R) .

According to this method, the effervescent raw material and optional binder (if present) are preferably mixed with each other without adding water and/or moisture (other than that from the raw material itself) so as to obtain a dry free Flowable powder mixture. This dry free-flowing powder mixture containing effervescent particles (i.e. the acid source and carbon dioxide source) and optionally binder particles (if present) is then subjected to a granulation step, preferably including a pressure agglomeration step , a dry process in which this free-flowing powder mixture is subjected to high external forces to tightly bind the particles together, thereby densifying the bulky mass of the particles and separating them between solid effervescent particles and viscous particles. Adhesive mechanism is created between the mixture (if present).

A typical roller compressor used here is eg Pharmapaktor L200/ ^50P® from Hosokawa Bepex GmbH. Process variables in the pressure agglomeration step by roll compression are roll spacing, feed rate, compression pressure and roll speed. A typical feeding device is a feeding screw. The roller spacing is usually 0.5-10 cm, preferably 3-7 cm, more preferably 4-6 cm. The extrusion force is typically 20kN-120kN, preferably 30kN-100kN, more preferably 40kN-80kN, although lower pressures are possible and may be preferred for use in the present invention using a fine particle size acid source. Typically the roll speed is from 1 rpm to 180 rpm, preferably from 2 rpm to 50 rpm and more preferably from 2 rpm to 35 rpm. Usually the feed rate is from 1 rpm to 100 rpm, preferably from 5 rpm to 70 rpm, more preferably from 8 rpm to 50 rpm. The temperature at which the compression is carried out is not critical and is usually 0-40°C.

It may be preferred that the granules are prepared in dry air with a humidity below 35%. Application of effervescent components

It may be preferred that the effervescent component is coated by any film coating agent or mixture thereof known in the art. Preferably the coating includes a surfactant and any other optional detergent components. Typically the surfactant comprises at least 20%, preferably greater than 75%, more preferably greater than 95% and even more preferably 100% by weight of the coating.

The surfactant may be any surfactant known in the art, preferably an alkoxylated alcohol, more preferably an alkoxylated alcohol having an average degree of alkoxylation of at least 20, more preferably at least 40, even more preferably 50-80. Alcohols. The alkoxylated alcohol typically has a melting point of at least 40°C, preferably at least 50°C, more preferably from 60°C to 70°C. Preferred alkoxy groups are ethoxy groups.

The alkoxylated alcohols are derived from alkoxylated alcohols comprising hydrocarbon radicals having preferably 12-18 carbon atoms, preferably hydrocarbon chains having a length of 12-18 carbon atoms. The hydrocarbon chain may be straight or branched and includes all derivative forms obtainable in any conformation of 12-18 carbon atoms.

The coating is applied to the effervescent component by any method known in the art, preferably by spraying the coating in a melt containing the alkoxylated alcohol onto the effervescent component. This involves melting the coating containing the alkoxylated alcohol typically at a temperature of at least 40°C, preferably at least 50°C, more preferably 60°C to 70°C. The spraying method can be any method known in the art, preferably by spraying the coating into a rotary mixer containing the core material by means of a hot melt spray gun, or by countercurrent spraying of a fluidized bed or wurster type cocurrent coating machines, both of which spray the coating onto a fluidized bed containing an effervescent component.

The effervescent composition obtainable by the method described above comprises a coating on the surface, preferably in such a way that said coating covers said effervescent composition, although said coating may also partly cover said effervescent composition point. The coating may also fully or partially cover any component of the effervescent component, ie the acid source and/or carbon dioxide source.

The coating is preferably contacted with the effervescent component by any method known in the art. Typically in order to form an intimate mixture, it is preferred that the coating partially or completely encloses the effervescent component in such a manner. The coating is 0.5%-25%, preferably 2%-10%, of the total weight of the effervescent component.

The coated effervescent component may be obtained by any method involving mixing the various components, which may be part of a compression or tableting process, extrusion and agglomeration. Preferably the coated effervescent component is produced by mixing a melt of one component with the other, wherein solid particles are formed simultaneously or subsequently, preferably by subsequent solidification of said melt, preferably by lowering the processing temperature form solid particles. When more than one component is to be doped to the coated effervescent component, it is preferred to mix the melt with a premix of the various components which is mixed with the melt Pre-mixed beforehand to obtain an intimate mixture of the various components prior to addition to the melt. The various components mentioned above are a particular alkoxylated alcohol, acid source, carbon dioxide source, any other optional detergent component or any combination thereof.

The effervescent component, together with any optional detergent components, may form part of a detergent composition for automatic and/or hand wash applications.

Specifically, coated effervescent components comprising certain alkoxylated alcohols can be used to generate suds during the dispensing phase of the wash cycle and can also act as suds suppressors during the later phases of the wash cycle. The latter phase of the wash cycle is at least 5 minutes after the dispensing phase. detergent composition

In a preferred embodiment, the effervescent components or effervescent granules herein are included when dispensing and dissolving in water (especially in a shorter period of time and/or in cold water and/or at lower total levels) is required. Effervescent Granules/Materials in the composition below).

The effervescent component is preferably present at a level such that the acid source is present at a level of from 0.5% to 40%, more preferably from 1% to 30% or even from 2% to 25% or even from 4% to 20% by weight of the detergent component. % (by weight); and such that the carbon dioxide source is preferably present at a level of 1% to 60% by weight of the detergent composition, more preferably 2% to 50% or even 4% to 35% or even 6% to 30% (weight ).

The effervescent components herein are particularly incorporated into cleaning compositions such as laundry detergent compositions and pretreatment compositions, hard surface cleaning compositions and dishwashing compositions. Especially non-aqueous liquid compositions and solid compositions, especially granular compositions, tablets, extrudates and bars are contemplated here.

The composition may contain the acid source and the carbon dioxide source as separate particulate components. The composition preferably contains the effervescent component in the form of effervescent granules. It may be preferred that all acids in the composition are included in the dry effervescent granules. Alternatively, it may be preferred that the composition comprises effervescent granules and dry added acid and/or dry added carbon dioxide source.

In a preferred embodiment, the solid detergent compositions herein comprise detergent base granules, at least a portion of which comprise at least one effervescent component (preferably in granular form). The detergent base particles then preferably have a weight average particle size of from 350 microns to 4 mm, more preferably from 500 microns to 2.5 mm or even from 710 microns to 2 mm.

Preferably the effervescent component of the present invention is present in detergent granules comprising components which may cause dispensing or dissolution problems or require faster dissolution, such as surfactants, especially non-ionic surfactants and or Anionic surfactants and detergent actives such as bleach activators and mixtures of surfactants with builders (especially aluminosilicate builders and anionic surfactants).

Such detergent base granules may be prepared by any method and may comprise any detergent ingredients. It may be preferred that the detergent base granules are prepared by mixing different detergent granules containing a mixture of different detergent components, preferably by agglomeration, spray drying or extrusion granulation, followed by optional addition of a binder Compression, agglomeration, spheroidization or pelletization or extrusion. It may therefore be preferred to mix the effervescent granules herein and other granular detergent ingredients with a binder, followed by a granulation step such as agglomeration, spheronization or pelletization.

It has been found that improved sudsing detergent compositions are obtained when the effervescent component of the present invention is present in particles of larger particle size. Thus, the present invention provides a method for improving sudsing of detergent compositions by incorporating an effervescent component of the present invention, including effervescent components described herein in granular form, into detergent granules, said detergent particles have a weight average particle size of from 500 microns to 1500 microns, whereby preferably at least 70% of said particles have a particle size of from 350 to 2000 microns, or even have a weight average particle size of from 650 microns to 1180 microns, It is thus preferred that at least 70% of the particles have a particle size of 500-1500 microns.

It has also been found that when the effervescent component of the present invention is present in particles of smaller particle size, the resulting detergent compositions have more efficient distribution and/or dissolution. Thus, the present invention provides a method for improving the dispensing and/or dissolution of detergent compositions by incorporating an effervescent component according to any one of claims 1 to 13 in detergent granules, said washing The agent particles have a weight average particle size of 200 microns to 500 microns, whereby preferably at least 70% of said particles have a particle size of 100 to 710 microns, or even have a weight average particle size of 250 microns to 450 microns, thereby preferably At least 70% of the particles have a particle size of 150-650 microns.

The granular composition of the present invention can be prepared with different bulk densities, preferably 300-1200 g/l, preferably 500-1100 g/l. These compositions can be prepared by various methods known in the art, including dry blending, spray drying, agglomeration and granulation, and combinations thereof.

In a preferred embodiment, the composition comprises from 0.1% to 99%, preferably from 2% to 50%, or even from 3% to 25%, of the effervescent component or granules by weight of the total composition.

In a preferred embodiment, it is preferred that the composition comprises particles of which at least 60%, more preferably at least 80% by weight, have a weight average particle size of 600 microns to 1400 microns, preferably 700 microns to 1100 microns or even 750-1000 microns. It may be preferred that the composition comprises less than 20%, or even less than 10%, or even less than 5% by weight of various particulate components having a particle size of less than 300 microns, or even less than 425 microns, or even less than 600 microns; it may also be preferred The composition comprises less than 20%, or even less than 10%, or even less than 5% (by weight of the composition) of various particulate components having a particle size greater than 1700 microns, or even greater than 1400 microns, or even greater than 1180 microns.

The composition may be prepared by any method known in the art, including agglomeration and/or spray drying, whereby certain components may be mixed or sprayed on as described herein. Compositions may preferably be prepared by mixing all or part of the granules, including those prepared by agglomeration or spray drying and even effervescent compositions herein, and subsequently adding a binder and mixing or agglomerating said granules and Binder to form preferably agglomerated detergent particles. They can be of the desired particle size or they can be sieved to obtain particles of the desired size.

The compositions of the present invention may also contain other detergent ingredients. The exact nature of these other ingredients and the level of their incorporation will depend on the physical form of the composition or component, and the exact nature of the laundering operation in which it is employed.

When present in the detergent composition, it may also be preferred that only less than 25% by weight of the detergent composition of the admixed hydratable inorganic salt is present, thus present in the form of separate particles, or even present in the total composition. Less than 25% by weight of the detergent composition of hydratable inorganic salts. It may be preferred that inorganic peroxygen bleaches are present, whereby percarbonates are preferably present.

In a preferred embodiment, it may be preferred that the detergent compositions herein contain one or more anionic surfactants and aluminosilicate builders, whereby preferably only small amounts of aluminosilicate builders and Anionic surfactants in an intimate mixture, i.e. the total amount of anionic surfactants is less than 50% or even less than 30% and the total amount of aluminosilicates is less than 50% or even less than 30%; it may even be preferred that substantially Free of anionic surfactants and aluminosilicate builders. Accordingly, it may be preferred that the composition contains at least two separate particles comprising anionic surfactant or aluminosilicate. "Intimate mixture" means, for the purposes of the present invention, that two or more component compositions are substantially uniformly divided within a component or particle. That is, it has been found that the solubility and/or dispensability of the composition is thereby improved.

In another embodiment of the present invention, it may be preferred that the composition contains only low levels, such as less than 10% or even less than 5% by weight of the composition, of aluminosilicate builders, whereby it is preferred that the composition contains a high solubility builders such as sodium citrate or citric acid, carbonates and/or crystalline layered silicates.

It may also be preferred that the composition contains as a builder system or as part of a builder system an agglomerate comprising from 0.5% to 80% by weight of a crystalline layered silicate (preferably NaSKS-6) and 10 %-70% by weight of surfactants (preferably anionic surfactants), whereby less than 10% of free water by weight of the agglomerates can be preferred, more preferably 30%-60% by weight of crystalline layered silicon salt and 20%-50% (weight) of anionic surfactants.

The effervescent component of the present invention may contain one or more other detergent components as described herein, and the detergent compositions herein preferably contain one or more components selected from the group consisting of surfactants

The components of the compositions according to the invention and herein preferably contain one or more surfactants selected from the group consisting of anionic, nonionic, cationic, amphoteric, amphoteric and zwitterionic surfactants and mixtures thereof.

A general list of these types and materials of anionic, nonionic, amphoteric and zwitterionic surfactants is given in U.S.P. 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Other examples are given in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). Suitable cationic surfactants are listed in U.S.P. 4,259,217, issued March 31, 1981 to Murphy. When present, amphoteric, amphoteric and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants. anionic surfactant

The components according to the invention and/or the detergent compositions herein preferably contain further anionic surfactants. Essentially any anionic surfactant useful for detersive purposes can be included in the detergent composition. These may include various salts of anionic sulfuric, sulfonic, carboxylic and sarcosine surfactants (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts). Anionic sulfate and sulfonate surfactants are preferred.

Preferably the anionic surfactant is present at a level of from 0.1% to 60%, more preferably from 1 to 40%, most preferably from 5% to 30% by weight.

Highly preferred surfactants include sulfonate and sulfate surfactants, preferably linear or branched chain alkylbenzene sulfonates and alkyl ethoxylated sulfates as described herein, preferably with the cationic Surfactant binding.

Other anionic surfactants include isethionates such as acetyl isethionates, N-acyl taurates, methyl taurates of fatty acid amides, alkyl succinates and sulfosuccinates , monoesters of sulfosuccinic acid (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinic acid (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosine Also suitable are acid salts, resin acids, and hydrogenated resin acids, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow. Anionic Sulfate Surfactant

Anionic sulfate surfactants suitable for use herein include linear and branched primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkylphenol oxide ethylene 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 polyglucosides Sulfates (non-ionic, non-sulfate compounds as described herein).

Preferably the alkyl sulfate surfactant is 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 Salt.

Preferably the alkyl ethoxy sulphate surfactants are selected from C ₁₀ -C ₁₈ alkyl sulphates (ethoxylated with 0.5-20 moles of ethylene oxide per molecule). More preferably the alkyl ethoxy sulfate surfactant is C ₁₁ -C ₁₈ , most preferably C ₁₁ -C ₁₅ alkyl sulfate (0.5-7, preferably 1-5 moles of ethylene oxide per molecule ethoxylation).

A particularly preferred aspect of the present invention employs mixtures of the preferred alkyl sulfate and/or sulfonate and alkyl ethoxy sulfate surfactants. These mixtures are disclosed in PCT Patent Application No. WO 93/18124. Anionic Sulfonate Surfactant

Anionic sulfonate surfactants suitable herein include C ₅ -C ₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ Olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates and mixtures thereof. Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ('alkyl carboxyls'), especially as herein Certain secondary soaps mentioned above.

Suitable alkyl ethoxy carboxylates include those compounds of formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ^- M ⁺ , wherein R is C ₆ -C ₁₈ alkyl, x is 0-10, E The oxide distribution is such that the amount of material where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having RO-(CHR ₁ -CHR ₂ -O)-R ₃ where R is C ₆ -C ₁₈ alkyl and x is 1 -25, R ₁ and R ₂ are selected from hydrogen, methyl acid group, succinic acid group, carboxysuccinic acid group and mixtures thereof, R ₃ is selected from hydrogen, substitution with 1-8 carbon atoms or Unsubstituted hydrocarbons and mixtures thereof.

Suitable soap surfactants include secondary soap surfactants comprising a carboxyl unit attached to a secondary carbon. Preferred secondary soap surfactants for use herein are water soluble materials selected from 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, Water-soluble salts of 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid.

Certain soaps can also be included in the suds suppressor. Alkali metal sarcosinate surfactant

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 a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Preferred examples are the sodium salt forms of myristyl and oleoyl methyl sarcosine. Alkoxylated Nonionic Surfactants

Essentially any alkoxylated nonionic surfactant is suitable for use herein. Ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants may be selected from nonionic condensates of alkylphenols, 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. Nonionic Alkoxylated Alcohol Surfactants

Condensation products of aliphatic alcohols with 1 to 25 moles of alkylene oxides, especially ethylene oxide and/or propylene oxide, are suitable here. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains 6 to 22 carbon atoms. Particular preference is given to condensation products of alcohols having alkyl groups of 8 to 20 carbon atoms with 2 to 10 moles of ethylene oxide per mole of alcohol. Nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides useful herein have the formula ^R2CONR1Z where ^{R1 is} H, _C1 - _{C4hydrocarbyl} , 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or Its mixture, preferably C ₁ -C ₄ alkyl, more preferably C ₁ -C ₂ alkyl, most preferably C ₁ alkyl (ie methyl); R ² is C ₅ -C ₃₁ hydrocarbon group, preferably straight chain C ₅ - C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof; A polyhydroxyhydrocarbyl group in which three hydroxyl groups are directly linked in a linear hydrocarbyl chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Nonionic Fatty Acid Amide Surfactant

Suitable fatty acid amide surfactants include those having the formula R ⁶ CON(R ⁷ ) ₂ wherein R ⁶ is an alkyl group containing 7-21, preferably 9-17 carbon atoms, each R ⁷ being selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and -(C ₂ H ₄ O) _x H, where x is 1-3. Nonionic Alkyl Polysaccharide Surfactant

Alkylpolysaccharides suitable for use herein are disclosed in U.S. Patent 4,565,647, issued January 21, 1986 to Llenado, which have hydrophobic groups of 6-30 carbon atoms and hydrophilic groups containing 1.3-10 sugar units. Polysaccharides with sexual groups such as polyglucosides.

Preferred alkyl polyglycosides have the formula R ² O(C _n H _2n O) _t (glycosyl) _x , wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof , wherein the alkyl group contains 10-18 carbon atoms; n is 2 or 3; t is 0-10, and x is 1.3-8. The glycosyl is preferably derived from glucose. amphoteric surfactant

Amphoteric surfactants suitable for use herein include amine oxide surfactants and alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R ³ (OR ⁴ ) _x NO(R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, amidopropyl and Alkylphenyl group or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; R ⁵ is each containing 1 -3 alkyl or hydroxyalkyl groups, or polyethylene oxide groups containing 1-3 oxirane groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ amidoalkyldimethylamine oxides.

A suitable example of an alkyl amphocarboxylic acid is Miranol ^™ C2M Conc manufactured by Miranol, Inc., Dayton, NJ. zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly 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. Betaine and sultaine surfactants are examples of zwitterionic surfactants useful herein.

Suitable betaines are compounds having the formula R(R') ₂ N ⁺ R ^{2 COO-} , where R is C ₆ -C ₁₈ hydrocarbyl, R ¹ is each typically C ₁ -C ₃ alkyl, R ² is C ₁ -C ₅ Hydrocarbyl. Preferred betaines are C _12-18 dimethylammonium hexanoate and C _10-18 amidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfaces are also suitable here. cationic surfactant

Cationic surfactants suitable for use herein include quaternary ammonium surfactants. Preferred quaternary ammonium surfactants are mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants in which the remaining N positions are replaced by methyl, hydroxyethyl or hydroxypropyl base substitution. Also preferred are monoalkoxylated and bisalkoxylated amine surfactants.

Another class of suitable cationic surfactants which may be used in the detergent compositions or components thereof herein are cationic ester surfactants. The cationic ester surfactant is a (preferably water-dispersible) compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in US Pat. Nos. 4,228,042, 4,239,660 and 4,260,529.

In a preferred aspect, the ester bond and the cationically charged group are separated from each other in the surfactant molecule by a spacer comprising at least 3 atoms (i.e. a chain length of three atoms), preferably 3-8 atoms. , more preferably 3-5 atoms, most preferably 3 atoms chain composition. The atoms forming the spacer are selected from carbon, nitrogen and oxygen atoms and any combination thereof, provided that any nitrogen and oxygen atoms in the chain are bonded only to carbons in the chain. Spacers with bonds such as -OO- (ie peroxide), -NN- and -NO- are thus excluded, but spacers with bonds such as -CH ₂ -O-CH ₂ - and -CH ₂ -NH-CH ₂ - Bond spacer. In a preferred aspect, the spacer chain comprises only carbon atoms, most preferably the chain is a hydrocarbyl chain. Cationic mono-alkoxylated amine surfactants

式中R¹为含有约6至约18个碳原子，优选6至约16个碳原子，最优选约6至约14个碳原子的烷基或链烯基部分；R²和R³各自独立地为含有1至约3个碳原子的烷基，优选甲基，最优选R²和R³均为甲基；R⁴选自氢(优选)、甲基和乙基；X^-为阴离子如氯负离子、溴负离子、甲基硫酸根、硫酸根等从而提供电中性；A为烷氧基，尤其乙氧基、丙氧基或丁氧基；p为0至约30，优选2至约15，最优选2至约8。Highly preferred cationic mono-alkoxylated amine surfactants herein preferably have the following general formula I,

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, most preferably from about 6 to about 14 carbon atoms; R ^and R ^are each independently is an alkyl group containing 1 to about 3 carbon atoms, preferably methyl, most preferably ^{both R2} and ^R3 are methyl; ^R4 is selected from hydrogen (preferred), methyl and ethyl; X ^- is an anion such as Chloride, bromide, methylsulfate, sulfate, etc. to provide electrical neutrality; A is an alkoxy group, especially ethoxy, propoxy or butoxy; p is 0 to about 30, preferably 2 to about 15, most preferably 2 to about 8.

Preferably the ApR group in formula I has p=1 and is a hydroxyalkyl group with no more than 6 carbon atoms, whereby the -OH group is separated from ^the nitrogen atom of the quaternary ammonium by no more than 3 carbon atoms. Especially preferred ^ApR4 _{groups are -CH2CH2OH} , _-CH2CH2CH2OH , -CH2CH( _CH3 )OH and -CH( _{CH3 ) CH2OH} , especially preferably _{-CH2CH2OH .} Preferably the ^R1 group is a straight chain alkyl group. Straight-chain R ¹ groups having 8-14 carbon atoms are preferred.

Another highly preferred class of cationic mono-alkoxylated amine surfactants for use herein has the formula In the formula, ^R is a C ₁₀ -C ₁₈ hydrocarbon group and combinations thereof, especially a C ₁₀ -C ₁₄ alkyl group, preferably a C ₁₀ -C ₁₂ alkyl group, and X is any convenient anion to provide charge balance, preferably a chloride anion or a bromide anion .

It should be noted that compounds of the preceding type include those in which the ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH Compounds substituted by (CH ₃ )O] units (i-Pr) or n-propoxy units (Pr), or combinations of EO and/or Pr and/or i-Pr units.

Preferred levels of cationic mono-alkoxylated amine surfactants are from 0.1% to 20%, more preferably from 0.2% to 7%, most preferably from 0.3% to 3.0% by weight. Cationic bis-alkoxylated amine surfactants

Preferred cationic bis-alkoxylated amine surfactants have the general formula II, In the formula R ¹ is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably from 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R ² is an alkyl or alkenyl moiety containing 1-3 Alkyl of carbon atoms, preferably methyl; ^R3 and ^R4 can vary independently and be selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride anion, bromide anion, methylsulfate, sulfuric acid roots, etc., sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and combinations thereof; p is 1 to About 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

式中R¹为C₁₀-C₁₈烃基及其组合，优选C₁₀、C₁₂、C₁₄烷基及其组合。X为任意方便的阴离子从而提供电荷平衡，优选氯负离子。参照上述阳离子双烷氧基化胺的结构通式，由于在优选化合物中，R¹衍生自(椰油)C₁₂-C₁₄烷基部分脂肪酸，因此R²为甲基，ApR³和A’qR⁴各自为单乙氧基。Highly preferred cationic bisalkoxylated amine surfactants for use herein have the formula,

In the formula, R ¹ is a C ₁₀ -C ₁₈ hydrocarbon group and combinations thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl groups and combinations thereof. X is any convenient anion to provide charge balance, preferably a chloride anion. With reference to the general structural formula of the above-mentioned cationic bis-alkoxylated amines, since in the preferred compounds ^R is derived from (coco) C ₁₂ -C ₁₄ alkyl partial fatty acid, ^R is methyl, ApR ³ and A' qR ⁴ are each monoethoxy.

式中R¹为C₁₀-C₁₈烃基，优选C₁₀-C₁₄烷基，独立的p为1至约3，q为1至约3，R²为C₁-C₃烷基，优选甲基，X为阴离子，尤其氯负离子或溴负离子。Other cationic bisalkoxylated amine surfactants useful herein include compounds having the formula,

In the formula, R ¹ is C ₁₀ -C ₁₈ hydrocarbon group, preferably C ₁₀ -C ₁₄ alkyl group, independently p is 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl group, preferably methyl base, X is an anion, especially a chloride anion or a bromide anion.

Other compounds of the foregoing type include those in which the ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ ) O] unit (i-Pr) or n-propoxy (Pr), or a compound replaced by a combination of EO and/or Pr and/or i-Pr units. bleach activator

The components of the invention and/or the detergent compositions herein 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 as defined herein and at least one hydrophilic peroxyacid bleach precursor as defined herein. body. The organic peroxyacid is then generated by in situ reaction of the precursor with a source of hydrogen peroxide.

Bleach activators may also alternatively, or additionally, comprise preformed peroxyacid bleaches.

Preferably the bleach activator is present in the component or particulate component of the compositions herein. It may preferably be present as separate, mixed particles. Alternatively, a bleach activator or part thereof may be present in the base detergent particle.

Preferably at least one bleach activator, preferably a peroxyacid bleach precursor, is present in a particulate component having a weight average particle size of from 600 microns to 1400 microns, preferably from 700 microns to 1100 microns. More preferably all activators are present in one or more particulate components having a particular weight average particle size.

Thus, it may be preferred that at least 80%, preferably at least 90% or even at least 95% or even substantially 100% of the component or components comprising said bleach activator have a particle size of from 300 microns to 1700 microns, preferably 425 microns to 1400 microns.

Hydrophobic peroxyacid bleach precursors preferably comprise compounds having oxy-benzenesulfonate groups, preferably NOBS, DOBS, LOBS and/or NACA-OBS as described herein.

Hydrophilic peroxyacid bleach precursors preferably comprise TAED as described herein. Peroxyacid Bleach Precursors

式中L为离去基团，X基本上可以为任意官能团，这样在过水解中生成的过氧酸的结构为

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to form peroxyacids. Usually peroxyacid bleach precursors can be expressed as

In the formula, L is a leaving group, and X can be any functional group substantially, so the structure of the peroxyacid generated in perhydrolysis is

For purposes of the present invention, hydrophobic peroxyacid bleach precursors yield peroxyacids of the above formula wherein X is a group containing at least 6 carbon atoms and hydrophilic peroxyacid bleach precursors yield peroxyacids of the above formula Acid bleaches wherein X is a group containing 1 to 5 carbon atoms.

The preferred level of incorporation of peroxyacid bleach precursor compounds is from 0.5% to 30% by weight, more preferably from 1% to 15% by weight, most preferably from 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 and there can be a wide choice of precursor types. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials of these types are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. leaving group

The leaving group (hereinafter denoted by the L group) must be sufficiently reactive for the perhydrolysis reaction to take place within an optimal time period (eg wash cycle). However, if L is too active, the activator will be difficult to use stably in bleaching compositions.

Preferred L groups are selected from: and mixtures thereof, wherein R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1-8 carbon atoms, and R ⁴ is H or R ³ . Y is H or a solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substantially substituted with any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkyl ammonium group.

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 - SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , where R ³ is an alkyl chain containing 1-4 carbon atoms, M is a cation that provides solubility for bleach activators, and X is a cation that provides solubility for bleach activators anion. 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. Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids in perhydrolysis. Preferred precursors of this type provide peracetic acid in the perhydrolysis reaction.

Preferred alkyl percarboxylic acid precursor compounds of the imide type include N,N,N ¹ ,N ¹ tetraacetylalkylenediamines wherein the alkylene group contains 1 to 6 carbon atoms, especially the alkylene group Those compounds containing 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED) is especially preferred for use 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 Precursors

式中R¹为具有约1至约14个碳原子的芳基或烷芳基，R²为含有约1至14个碳原子的亚烷基、亚芳基和烷基亚芳基，R⁵为H或含有1-10个碳原子的烷基、芳基或烷芳基，L基本上可为任何离去基团。R¹优选含有约6至12个碳原子。R²优选含有约4至8个碳原子。R¹可以为直链或支链烷基、取代芳基或包含支链、取代基或两者的烷基芳基，并且可以来自合成源和天然源(包括如牛脂)。类似结构的变体也适合R²。R²可包括烷基、芳基，其中所述R²也可包括卤素、氮、硫和其它典型的取代基或有机化合物。R⁵优选为H或甲基。R¹和R⁵总的不应含有多于18个碳原子数。这种类型的酰胺取代的漂白活化剂化合物描述于EP-A-0170386。可以优选R¹和R⁵与氮和碳原子一起形成环结构。Amide-substituted alkyl peroxyacid precursor compounds useful herein include those compounds having the general formula:

In the formula, R ^is an aryl or alkaryl group having about 1 to about 14 carbon atoms, ^R is an alkylene, arylene and alkylarylene group having about 1 to 14 carbon atoms, and R ^is is H or an alkyl, aryl or alkaryl group containing 1-10 carbon atoms, and L can be essentially any leaving group. ^R1 preferably contains about 6 to 12 carbon atoms. ^R2 preferably contains about 4 to 8 carbon atoms. ^R can be straight or branched chain alkyl, substituted aryl, or alkylaryl containing branching, substituents, or both, and can be derived from synthetic and natural sources including, for example, tallow. Variants of similar structures are also suitable for R ² . R ² may include alkyl, aryl, wherein said R ² may also include halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. ^R1 and ^R5 together should not contain 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-hexanoyl)oxybenzenesulfonate, (6-decylamido- Hexanoyl)oxybenzenesulfonates, highly preferably (6-nonamidocaproyl)oxybenzenesulfonate and mixtures thereof (described in EP-A-0170386). Precursor of perbenzoic acid

Perbenzoic acid precursor compounds provide perbenzoic acid in perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, sorbitol, glucose, and benzoylation products of all sugars with benzoylating reagents, and acyl Those compounds of the imine type include N-benzoylsuccinimide, tetrabenzoylethylenediamine, and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamate. cationic peroxyacid precursor

Cationic peroxyacid precursor compounds generate cationic peroxyacids in perhydrolysis.

Cationic peroxyacid precursors are typically formed by substituting a positively charged functional group such as an ammonium or alkylammonium group, preferably an ethylammonium or methylammonium group, for the peroxyacid moiety of a suitable peroxyacid precursor compound. Cationic peroxyacid precursors are usually present in solid detergent compositions in the form of a salt with a suitable anion such as an anion halide.

Such a cationic substituted peroxyacid precursor compound may be perbenzoic acid or a substituted derivative thereof, a precursor compound (as previously described). Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor (as described hereinafter).

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852;

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 for N-acylated caprolactams include trialkylammoniummethylenebenzoylcaprolactams and trialkylammoniummethylenealkylcaprolactams. Benzoxazine (benzoxazin) organic peroxyacid precursor

式中R¹为H、烷基、烷芳基、芳基或芳烷基。预形成的有机过氧酸Precursor compounds of the benzoxazine class disclosed in eg EP-A-332,294 and EP-A-482,807 are also suitable, especially those compounds of the formula,

In the formula, R ¹ is H, alkyl, alkaryl, aryl or aralkyl. preformed organic peroxyacids

Components of detergent compositions according to the invention and/or herein may contain (in addition to or as a substitute for organic peroxyacid bleach precursor compounds) pre-formed organic peroxyacids, typically at levels of 1%- 15% by weight, more preferably 1%-10% by weight.

式中R¹为具有1-14个碳原子的烷基、芳基或烷芳基，R²为含有1-14个碳原子的亚烷基、亚芳基和烷亚芳基，R⁵为H或含有1-10个碳原子的烷基、芳基或烷芳基。这类酰胺取代的有机过氧酸化合物描述于EP-A-0170386。A preferred class of organic peroxyacid compounds are amide substituted compounds having the general formula,

In the formula, ^R is an alkyl, aryl or alkaryl group with 1-14 carbon atoms, ^R is an alkylene, arylene and alkarylene group with 1-14 carbon atoms, and R ^is H or an alkyl, aryl or alkaryl group containing 1-10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperazelaic acid, mono- and diperbasyl acid and N-phthalamidoperoxycaproic acid are also suitable here. perhydrogen source

Inorganic perhydrate salts are the preferred source of peroxide. These salts are preferably present at a level of 0.01% to 50% by weight of the composition or component, more preferably 0.5% to 30% by weight.

Inorganic perhydrate salts include perborates, percarbonates, perphosphates, persulfates and persilicates. Inorganic perhydrate salts are generally alkali metal salts. Inorganic perhydrate salts can be included as unprotected crystalline solid forms. For certain perhydrate salts, however, preferred implementations of these granular compositions employ a coated form of the material, which provides better storage stability of the perhydrate salt in the granular product. Suitable 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 _a preferred perhydrate salt and _may exist _as the monohydrate _of the norninal formula _NaBO2H2O2 or the _tetrahydrate of _{NaBO2H2O2.3H2O} .

Alkali metal percarbonates, especially sodium percarbonate, are the preferred perhydrates herein. Sodium percarbonate _is an addition compound corresponding to _{2Na2CO3.3H2O2} and _is commercially available as a crystalline solid _.

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the detergent compositions herein. dye

A preferred component of the compositions herein are dyes and dye particles or speckles which are sensitive to bleaching. The dye used herein may be a dye or an aqueous or non-aqueous solution of the dye. It may be preferred that the dye is an aqueous solution comprising a dye at any level to achieve suitable staining of the detergent particles or spots, preferably such that the dye solution is obtained at a level of up to 2% by weight of the dye particle herein, or more preferably Up to 0.5% by weight. The dyes may also be mixed with non-aqueous carrier materials such as non-aqueous liquid materials including nonionic surfactants.

The dye optionally also includes other components such as organic binding materials, which may also be non-aqueous liquids.

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 V), Ultra Marine blue (trade name), E133-food blue 2 (brilliant blue FCF), E140-natural green 3 (chlorophyll and chlorophyllin), E141 and Pigmentgreen 7 (chlorinated copper phthalocyanine). Preferred dyes may be Monastral Blue BV paste (trade name) and/or Pigmasol Green (trade name).

Dyed detergent granules or effervescent components preferably contain up to 10% or more preferably up to 2% or even up to 1% by weight of colored granules or components. spices

Another preferred component of the present invention or composition herein is a perfume or perfume composition. Any fragrance composition can be used herein. The flavors may also be encapsulated.

Preferred perfumes contain at least one low molecular weight volatile component such as a component having a molecular weight of 150-450 or preferably 350.

Preferably the perfume component includes oxygen-containing functional groups. Preferred functional groups are aldehyde, ketone, alcohol or ether functional groups or combinations thereof. Heavy metal ion chelating agent

The components of the detergent compositions according to the invention and/or herein preferably contain, as an optional ingredient, a heavy metal ion sequestrant. A heavy metal ion sequestrant here refers to a component that acts as a heavy metal ion sequestrant. These components may also have calcium and magnesium chelating capacity, but preferably they are selective for binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are typically present at 0.005% to 10%, preferably 0.1% to 5%, more preferably 0.25% to 7.5%, most preferably 0.3% to 2%, by weight of the composition or component.

Heavy metal ion sequestrants useful herein include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilopropylene phosphonates.

Among the above compounds, preferred heavy metal ion chelating agents are diethylene triamine penta (methylene phosphonate), ethylenediamine tri (methylene phosphonate), hexamethylene diamine tetra (methylene phosphonate) salt) and hydroxy-ethylene 1,1-diphosphonate, 1,1-hydroxyhexanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other suitable heavy metal ion sequestrants for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropanedi Amine disuccinic acid or any salt thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid (described in EP-A-317,542 and EP-A-399,133). The iminodiacetic acid-N-2-hydroxypropylsulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropylsulfonic acid chelating agents described in EP-A-516,102 are also suitable herein. β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodibutylene, described in EP-A-509,382 Acid sequestrants are also suitable.

EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,331 describes suitable chelating agents 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. Glycinamide-N,N'-disuccinic acid (GADS), Ethylenediamine-N-N'-diglutaric acid (EDDG), and 2-hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) is 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 salts or substituted ammonium salts, or mixtures thereof.

In particular, chelating agents containing amino or amine groups may be sensitive to bleach and are suitable for use in the compositions of the present invention. enzyme

Another highly preferred class of ingredients for use in the components 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, pectinases, lactases and peroxidase. Suitable enzymes are discussed in US Patent Nos. 3,519,570 and 3,533,139.

Preferred commercial proteases include those sold under the trade names Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), the proteases sold under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades, the proteases sold by Genencor Proteases sold International and those sold under the tradenames Opticlean and Optimase by Solvay Enzymes. Proteases that can be added to the compositions of the invention can be added to the compositions of the invention at levels of 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include alpha-amylases such as those obtained from a particular strain of Bacillus licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercial amylases include those sold under the tradename Rapidase by Gist-Brocades, 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.

Amylases may be added to the compositions of the present invention at levels of active enzyme ranging from 0.0001% to 2% by weight.

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, eg produced by strains Humicola sp, Thermomyces sp. or Pseudomonas sp. Lipases from chemically or genetically modified mutants of these strains are also suitable for use here. Preferably the lipase is derived from Pseudomonas pseudoalcaligenes as described in granted European patent EP-B-0218272.

Another preferred lipase here is obtained by cloning the gene from Humicola lanuginosa and expressing it in Aspergillus oryza (host) (described in European Patent Application EP-A-0258 068) from Novo Industri A/S, Bagsvaerd , Denmark is commercially available under the tradename Lipolase. This lipase is also described in US Patent 4,810,414, issued March 7,1989 to Huge-Jensen et al. Fluorescent whitening agent

The components or compositions herein also preferably contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners (as described above).

式中R₁选自苯胺基、N-2-双-羟乙基和NH-2-羟乙基；R₂选自N-2-双-羟乙基、N-2-羟乙基-N-甲基氨基、吗啉基、氯和氨基；M为成盐阳离子如钠或钾。Hydrophilic optical brighteners suitable herein include those compounds having the formula,

In the formula, R ₁ is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N - methylamino, morpholino, chlorine and amino; M is a salt-forming cation such as sodium or potassium.

In the above formula, when R ₁ is an anilino group, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino -6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and disodium salt. This particular brightener is sold under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-CBS-X and Tinopal-UNPA-GX are preferred hydrophilic optical brighteners for detergent compositions herein.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the whitening agent is 4,4'-bis[ (4-anilino-6-(N-2-bis-hydroxyethyl-N-methylamino)-s-triazin-2-yl)-amino]2,2'-stilbene disulfonic acid disodium salt . This particular brightener is sold under the tradename Tinopal-5BM-GX by Ciba-Geigy Corporation.

In the above formula, when _R1 is anilino, _R2 is morpholino and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino -s-triazin-2-yl)amino]2,2'-stilbene disulfonic acid sodium salt. Such specific brighteners are sold under the tradenames Tinopal-DMS-X and Tinopal AMS-GX by Ciba-Geigy Corporation. photobleach

Photobleaches are a preferred component of the compositions or components herein. Preferred photobleaches herein include compounds having a porphine or porphyrin structure.

Porphine and porphyrin are used synonymously in the literature, but conventional porphine represents the simplest porphyrin without substitution; where porphyrin is a subclass of porphine. References to porphines in this application shall include porphyrins.

The porphin 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 Zn.

It may be preferred that the photobleaching compound or component is substituted with a substituent selected from the group consisting of alkyl groups such as methyl, ethyl, propyl, tert-butyl and aromatic ring systems such as pyridyl, pyridyl-N-oxide compounds, phenyl, naphthyl and anthracenyl moieties.

Photobleaching compounds or components may have solubilizing groups as substituents. Alternatively, or in addition, the photobleach may contain a polymeric component capable of solubilizing the photobleaching compound, such as PVP, PVNP, PVI or copolymers or mixtures thereof.

Highly preferred photobleaching compounds are compounds having a phthalocyanine structure, preferably with metal elements or cations as described above.

Metallophthalocyanines and their derivatives have the structures shown in Figure 1 and/or Figure 2, where the positions of atoms on the phthalocyanine structure are coded using conventional methods.

The phthalocyanine can be substituted at one or more positions of 1-4, 6, 8-11, 13, 15-18, 20, 22-25, 27 atoms in the phthalocyanine structure. water soluble builder compound

The components or compositions herein preferably contain a water-soluble builder compound, which is typically present in the detergent composition in an amount of 1% to 80% by weight, preferably 10% to 60% by weight, most preferably 15% by weight. %-40% by weight.

The detergent compositions of the present invention preferably include phosphate-containing builder materials. Preferably it is present at a level of 0.5% to 60%, more preferably 5% to 50%, more preferably 8% to 40%.

Phosphate-containing builder materials preferably comprise tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylic acids or their salts (wherein the polycarboxylic acids contain at least two carboxyl groups), borate and any mixture of the foregoing.

The carboxylate or polycarboxylate builder can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of price and performance.

Suitable carboxylate salts containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxyl groups include water-soluble polycarboxylates of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, hydroxymalonic acid, and fumaric acid salts and ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups or their acids specifically include the water soluble citrate, aconitrate and citrate and succinate derivatives such as carboxymethyl as described in British Patent No. 1,379,241 Oxysuccinates, lactoxysuccinates described in British Patent No. 1,389,732 and aminosuccinates described in Dutch Patent Application 7205873 and oxygen polycarboxylate materials as described in British Patent No. 1,387,447 of 2-oxa-1,1,3-propane tricarboxylate. The most preferred polycarboxylic acid containing three carboxy groups is citric acid, preferably present at a level of from 0.1% to 15%, more preferably from 0.5% to 8% by weight.

Polycarboxylates containing four carboxyl groups include oxydisuccinates, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3- Propane tetracarboxylate 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 US Patent No. 3,936,448 and the sulfonated pyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more preferably citrates.

Parent acids of monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof and their salts such as citric acid or citrate/citric acid mixtures are also contemplated for use in the builder component.

Borate builders and builders containing borate-forming materials which can form borate under detergent storage or wash conditions are suitable water-soluble builders for use herein.

Suitable examples of water-soluble phosphate builders are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, having a degree of polymerization of about 6 to 21 Sodium polymetaphosphate/sodium polyphosphate and phytate. Partially soluble or insoluble builder compounds

Components according to the present invention or compositions herein may contain partially dissolved or insoluble builder compounds, which are generally present in detergent compositions at levels of 0.5% to 60% by weight, preferably 5% to 50% ( weight), most preferably 8%-40% (weight).

Prime examples of water-insoluble builders include sodium aluminosilicates. As noted above, in one embodiment of the invention it may be preferred that only minor amounts of aluminosilicate builder be present.

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

The aluminosilicate zeolites may be natural materials, but are preferably synthetic materials. Synthetic crystalline aluminosilicate ion exchange materials are available commercially under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O where x is 20-30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ].276H ₂ O.

Another preferred aluminosilicate zeolite is zeolite MAP builder. Zeolite MAP may be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal aluminosilicate of zeolite P type, with a silicon-aluminum ratio not greater than 1.33, preferably in the range of 0.9-1.33, and more preferably in the range of 0.9-1.2.

Of particular interest are zeolites MAP having a silica-to-alumina ratio of not greater than 1.15, more particularly not greater than 1.07.

In a preferred aspect, the zeolite MAP detergent builder has a particle size (expressed as median particle size _d50 ) of from 1.0 to 10.0 microns, more preferably from 2.0 to 7.0 microns, most preferably from 2.5 to 5.0 microns.

The d ₅₀ value indicates that 50% by weight of the particles have a diameter smaller than this value. Said particle size can be determined in particular by conventional analytical techniques described here, such as microscopic determination with a scanning electron microscope or by a laser particle size analyzer. Other methods of establishing _d50 values are disclosed in EP384070A. organic polymer

Organic polymers are a preferred further component here and are preferably present as components of any particulate components where they can serve to bind the particulate components to each other. Organic polymer herein means essentially any polymeric organic compound commonly used as a dispersant, anti-redeposition agent or soil-suspension agent in detergent compositions, including any of the high molecular weight compounds described herein as clay flocculants. Organic polymers, including quaternised ethoxylated (poly)amine clay-soil release/anti-redeposition agents according to the present invention.

Organic polymers are typically incorporated into the detergent compositions of the present invention at a level of from 0.01% to 30%, preferably from 0.1% to 15%, most preferably from 0.5% to 10%, by weight of the composition or component.

Examples of organic polymers include water-soluble organic homo- or co-polymeric polycarboxylic acids or their salts, wherein the polycarboxylic acids include 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 these salts are polyacrylates having a MWt of 1000-5000 and their copolymers with maleic anhydride, these copolymers having a molecular weight of 2000-100,000, especially 40,000-80,000.

Polyamino compounds are suitable for use herein and include those derived from aspartic acid as disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomers selected from the group consisting of maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000-10,000 are also suitable for use herein.

Other organic polymers suitable for incorporation into the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Other suitable organic polymers are polyethylene glycols, especially those having a molecular weight of 1000-10000, more preferably 2000-8000, most preferably about 4000.

Highly preferred polymeric components herein are cotton and non-cotton soil release polymers according to Scheibel et al. US Patent 4,968,451 and Gosselink et al. US Patent 5,415,807, especially US Patent Application No. 60/051517.

Another class of organic compounds of the preferred clay dispersants/anti-redeposition agents for use herein may be ethoxylated cationic monoamines and diamines of the formula, In the formula, X is a non-ionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl esters or ether groups and combinations thereof, a is 0-20, preferably 0-4 (such as ethylene, propylene group, hexamethylene), b is 1 or 0; for cationic monoamines (b=0), n is at least 16, usually in the range of 20-35; for cationic diamines (b=1), n is at least about 12 and typically ranges from about 12 to about 42.

Other dispersants/redeposition agents useful herein are described in EP-B-011965 and US Patents 4,659,802 and 4,664,848. Antifoam system

When formulating machine wash compositions, the components and detergent compositions herein may contain a suds suppressing system present at a level of from 0.01% to 15%, preferably from 0.02% to 10%, and most preferably from 0.02% to 10% by weight of the composition or component. Preferably 0.05%-3%.

Foam suppressing systems suitable for use herein may consist essentially of any known antifoam compound including, for example, silicone antifoams and 2-alkyl alcanol antifoam compounds.

By antifoam compound is meant herein any compound or mixture of compounds which can be used, for example, to suppress foam arising from a solution of a detergent composition, especially when the solution is agitated.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds including a silicone component defined herein as optional antifoam compounds. These silicone antifoam compounds usually also contain a silica component. The term "silicone" as used herein and commonly used in the industry includes various higher molecular weight polymers containing siloxane units and hydrocarbyl groups of different types. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes having trimethylsilyl end-block units.

Other suitable antifoam compounds include monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The hydrocarbon chains of the monocarboxylic fatty acids and their salts used as suds suppressors generally have 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium, as well as ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (such as fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated aminotriazines Such as three to six alkyl melamines or two to four alkyl diamine triazine chlorides, which are cyanuric chloride and two or three moles of primary or secondary amines containing 1-24 carbon atoms, propylene oxide, dihard Fatty acid amides and monostearyl dialkali metal (eg sodium, potassium, lithium) phosphates and esters.

Preferred suds suppressor systems include:

(a) antifoam compounds, preferably silicone antifoam compounds, most preferably silicone antifoam compounds, comprising combinations of,

(i) Dimethicone at a level of 50% to 99%, preferably 75% to 95%, by weight of the silicone antifoam compound; and

(ii) silica at a level of 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound;

Wherein the silicon dioxide/silicone antifoaming compound is added at a level of 5%-50%, preferably 10%-40% by weight;

(b) a dispersant compound, most preferably comprising a rake copolymer of silicone diol, with an amount of polyoxyalkylene of 72-78% and a ratio of ethylene oxide to propylene oxide of 1: 0.9 to 1:1.1 at a level of 0.5-10%, preferably 1%-10% by weight; an especially preferred type of silicone diol rake copolymer of this type is DCO544, available from DOW Corning under the name DCO544 commodity;

(c) an inert carrier fluid compound, most preferably containing a _C16 - _C18 ethoxylated alcohol with a degree of ethoxylation of 5-50, preferably 8-15, at a level of 5%-80%, preferably 10%- 70% (by weight);

A highly preferred particulate antifoam system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50°C to 85°C, wherein the organic carrier material comprises glycerol and has 12-20 carbon Atomic fatty acid monoesters, or mixtures thereof, have a melting point of 45°C to 80°C.

Other highly preferred suds suppressing systems include polydimethylsiloxanes or silicone blends such as polydimethylsiloxanes, aluminosilicates and polycarboxylic acid polymers such as copolymers of laic and acrylic acid. polymeric dye transfer inhibitor

The components and/or compositions herein may also comprise from 0.01% to 10%, preferably from 0.05% to 0.5%, by weight, of a polymeric dye transfer inhibiting agent.

The polymeric dye transfer inhibitors are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof whereby these polymers can be cross-linked joint polymer. polymeric soil release agent

Polymeric soil release agents (hereinafter "SRA") may optionally be used in the components or compositions of the present invention. If used, typically 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0% by weight of SRA is included.

Preferred SRAs typically have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fibers and remains adhered to them throughout the wash and rinse cycle, Thereby acting as an anchor for the hydrophilic portion. This makes soils treated with SRA easier to remove in subsequent wash cycles.

Preferred SRAs include oligomeric terephthalates, typically prepared by at least one transesterification/oligomerization reaction, usually using a metal catalyst such as titanium(IV) alkoxide. These esters can be prepared using other monomers capable of incorporating the ester structure at one, two, three, four or more positions, without, of course, forming a tightly cross-linked overall structure.

Suitable SRAs include the sulfonation products of substantially linear ester oligomers with terephthaloyl and oxyalkyleneoxy repeating units in the oligoester backbone and allyl derivatives of sulfonium covalently attached to the backbone. Ol capping moieties (as described in US Patent 4,968,451 issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink). These ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate in a secondary transesterification/oligomerization procedure reacting an ester ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters in U.S. 4,711,730 issued December 8, 1987 to Gosselink et al. ) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG") transesterification/oligomerization of those produced. Other examples of SRAs include: partially or fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6- Sodium dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomers such as DMT, methyl (Me)-capped Block oligomers produced from PEG and EG and/or PG, or DMT, EG and/or PG, methyl-terminated PEG and sodium dimethyl-5-sulfoisophthalate; and 31 October 1989 Anions in U.S. 4,877,896 issued to Maldonado, Gosselink et al., especially sulfoaroyl-terminated terephthalates, which are typical SRAs used in laundry and fabric conditioning products. An ester composition prepared from monosodium benzoate, PG and DMT, optionally but preferably further comprising added PEG (such as PEG 3400).

SRA also includes: Simple block copolymers of ethylene or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see May 25, 1976 US 3,959,230 issued to Hays on July 8 and US 3,893,929 issued to Basadur on July 8, 1975; Cellulose derivatives such as hydroxyether cellulose polymers from Dow available as METHOCEL; C ₁ -C ₄ alkyl fibers and C ₄ hydroxyalkyl cellulose, see US 4,000,093, issued December 28, 1976 to Nicol et al; and methyl cellulose ethers, wherein the average degree of substitution (methyl) per anhydroglucose unit is about 1.6 to about 2.3, with a solution viscosity of about 80 to about 120 centipoise as measured at 20°C for a 2% aqueous solution. These materials are available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers produced by Shin-etsu Kagaku Kogyo KK.

Other types of SRAs include: (I) nonionic terephthalates attached to polymeric ester structures using diisocyanate coupling agents, see U.S. 4,201,824 to Violland et al. and U.S. 4,240,918 to Lagasse et al.; and (II) SRAs with carboxylate end groups were prepared by adding trimellitic anhydride to known SRAs to convert the capped hydroxyl groups to trimellitate esters. With proper selection of the catalyst, the trimellitic anhydride forms linkages to the polymer ends through the ester of the isolated carboxylic acid of the trimellitic anhydride rather than by opening the anhydride linkage. Nonionic or anionic SRAs can be used as starting materials, provided they have hydroxyl end groups that can be esterified. See U.S. 4,525,524 to Tung et al. Other types include: (III) urethane-linked anionic terephthalate-based SRA variants, see U.S. 4,201,824 to Violland et al. other optional components

Other optional components suitable for inclusion in the compositions of the present invention include colorants and filler salts, with 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. It may also be preferred to mix with carbonates, small amounts (such as less than about 20% (by weight)) of neutralizing agents, buffers, phase regulators (phase regulators), hydrotropes, enzyme stabilizers, polyacids, foam regulators , sunscreens, antioxidants, bactericides, and dyes (such as those described in US Patent 4,285,841 issued to Barrat et al. in 1981, incorporated herein by reference). Chlorine Bleach

The detergent compositions may contain, as an additional ingredient, chlorine-based bleaches. But since 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 are suitable.

Alternatively, the detergent composition can be formulated to be chlorine-based bleach compatible, thereby ensuring that chlorine-based bleach can be added to the detergent composition by the user at the beginning or during the wash cycle.

Chlorine-based bleaches can form hypochlorite in aqueous solutions. The chemical expression for the hypochlorite ion is OCl ⁻ .

These bleaching agents that form hypochlorite in aqueous solution include alkali and alkaline earth metal hypochlorites, addition products of hypochlorites, chloramines, imine chlorides, N-(-2-trichloroethanol) formazan Amides and chlorimides. Specific examples of such compounds include sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, dichloroisocyanuric acid Sodium, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, dichloramine T , Chloramine B and Dichloramine B. Preferred bleaches 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 above hypochlorite-generating bleaches are available in solid or concentrated form and are dissolved in water in preparing the compositions of the present invention. Some of the above materials are available as aqueous solutions. laundry method

Machine laundering herein generally involves treating soiled garments in a washing machine with an aqueous wash solution in which is dissolved and dispersed an effective amount of the machine detergent composition of the present invention. An effective amount of the detergent composition means that 10 grams to 300 grams of product is dissolved or dispersed in 5 to 65 liters of wash solution, which effective amount is a typical dosage of product and wash solution usually used in conventional machine laundry volume. Preferred washing machines may be so called low-fill machines.

In a preferred use aspect, the composition is formulated for hard surface cleaning or hand washing. In another preferred aspect the detergent composition is a pretreatment or soaking composition for pretreating or soaking fabrics containing stains and stains. Abbreviations used in the examples of effervescent components and detergent compositions LAS sodium linear _C11-13 alkylbenzenesulfonate LAS(I) potassium linear or branched _C11-13 alkylbenzenesulfonate TAS cattle Sodium oil alkyl sulfate C _xy AS C _1x -C _1y sodium alkyl sulfate C ₄₆ SAS C ₁₄ -C ₁₆ secondary (2,3) sodium alkyl sulfate C _xy E _z S C _1x -C _1y sodium alkyl sulfate with z Condensation of Moles of Ethylene Oxide C _xy E _z C _1x -C _1y Condensation of Major Linear Primary Alcohols with Average z Moles of Ethylene Oxide QAS R ² .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ² =C ₁₂ -C ₁₄ QAS1 R ² .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ² =C ₈ -C ₁₁ APA C ₈ -C ₁₀ Amidopropyl dimethylamine soap derivative Linear alkanes from an 80/20 blend of tallow and coconut fatty acids

Sodium Carboxylate STS Sodium Toluene Sulfonate CFAA C ₁₂ -C ₁₄ (Coco) Alkyl N-Methyl Glucamide TFAA C ₁₆ -C ₁₈ Alkyl N-Methyl Glucamide TPKFA C ₁₂ -C ₁₄ Top Cut Fatty Acid STPP Anhydrous Sodium Tripolyphosphate TSPP Tetrasodium Pyrophosphate Zeolite A Hydrated Sodium Aluminosilicate of Formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O Particle Size

0.1-10 microns (expressed weight based on anhydrous ₎ NaSKS-6 crystalline layered silicate of formula d- _Na2Si2O5 Citric acid I Anhydrous citric acid, 80% of _the particle size is 40 microns-70 micron, volume

Median particle size 55 microns Citric acid II Citric acid anhydrous or monohydrate, 80% particle size 15 microns - 40 microns

m, volume median particle size 25 microns malic acid anhydrous malic acid, 80% particle size 50 microns to 100 microns, volume

   Maleic acid with a product median particle size of 75 microns Anhydrous maleic acid, 80% of the particle size ranges from 5 microns to 30 microns, volume

    Median particle size is 15 microns Tartaric acid Anhydrous tartaric acid, 80% of the particle size is 25 microns to 75 microns, volume

Product median particle size of 50 microns Carbonate I Anhydrous sodium carbonate, 80% by volume

                                                                                                                                   

75 microns with a volume median particle size of 55 microns Bicarbonate II Anhydrous sodium bicarbonate with 80% of the particles by volume at 100 microns

m to 200 microns with a volume median particle size of 150 microns bicarbonate I anhydrous sodium bicarbonate with 80% (volume) of the particles having a particle size of 15 microns

to 40 microns with a volume median particle size of 25 microns Silicate Amorphous sodium silicate (SiO ₂ : _{Na 2} O = 2.0:1) sulfate anhydrous sodium sulfate magnesium sulfate anhydrous magnesium sulfate citrate dihydrate lemon Trisodium acid, 86.4% activity, particle size distribution 425

Micron - 850 micron MA/AA 1:4 maleic/acrylic acid copolymer with an average molecular weight of about 70,000 MA/AA(1) 4:6 maleic/acrylic acid copolymer with an average molecular weight of about 10,000AA Average molecular weight Sodium polyacrylate polymer CMC of 4,500 Sodium carboxymethyl cellulose cellulose ether Methyl cellulose ether with a degree of polymerization of 650 was purchased from Shin Etsu

                                                                                  

Industries A/S sells Protease I under the tradename Savinase Proteolytic enzyme with 4% by weight active enzyme, described in WO

95/10591, sold by Genencor Int. Inc. Alcalase Proteolytic enzyme with 5.3% by weight active enzyme, sold by NOVO

                                                                                                                                         

NOVO Industries A/S sells amylase under the tradename Carezyme Starch hydrolase with 1.6% by weight of active enzyme, supplied by NOVO

                                                                                                                               

Industries A/S sells lipase(1) lipohydrolase with 2.0% by weight of active enzyme under the tradename Lipolase, supplied by NOVO

Endoglucanase Endoglucanase with 1.5% by weight of active enzyme sold by Industries A/S under the tradename Lipolase Ultra, supplied by NOVO

Industrial A/S sells PB4 pellets containing sodium perborate tetrahydrate of the formula NaBO ₂ .3H ₂ O

Particles, the weight average particle size of the particles is 950 microns, 85% of the particles

Particle size of 850 microns to 950 microns PB1 Contains particles of anhydrous sodium perborate bleach of the standard formula NaBO ₂ .H ₂ O ₂

Granules, the weight-average particle diameter of said particles is 800 microns, and 85% of the particles

The particle size is 750 μm to 950 μm percarbonate Contains particles of sodium percarbonate of the standard formula 2Na ₂ CO ₃ .3H ₂ O ₂ , the

       Particles have a weight-average particle size of 850 microns, with 5% or less of the particles smaller than

600 microns, 2% or less of particles greater than 1180 microns NOBS Contains nonanoyloxybenzenesulfonate in sodium salt form, weight average particle size

                                           Years of 750 microns - 900 microns NAC-OBS  Containing (6-nonamidohexanoyl) oxybenzenesulfonate particles, granules

The weight-average particle diameter of the particles is 825 microns-875 microns. TAED I contains tetraacetylethylenediamine particles, and the weight-average particle diameter of the particles is

700 microns to 1000 microns TAED II Tetraacetylethylenediamine, particle size 150 microns to 600 microns DTPA Diethylene triamine pentaacetic acid DTPMP Diethylene triamine penta(methylene phosphonate) Monsanto with

Dequest 2060 is sold under the trade name Photoactivator Sulfonated Zinc Phthalocyanine Encapsulated in Bleach (1) Dextrin Soluble Polymer Photoactivator Sulfonated Phthalocyanine Encapsulated in Bleach (2) Dextrin Soluble Polymer Aluminum cyanine brightener 1 4,4'-bis(2-sulfostyrene)biphenyl disodium brightener 2 4,4'-bis(4-anilino-6-morpholino-1.3.5 -Triazin-2-yl)amino)stilbene-

2: Disodium 2'-disulfonate EDDS Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in sodium salt form HEDP 1,1-Hydroxyethane diphosphonic acid PEG _x Polyethylene glycol, molecular weight x (typically 4,000) PEO Polyethylene oxide, average molecular weight 50,000 TEPAE Tetraethylenepentamine ethoxylate PVI Polyvinyl imidosole, average molecular weight 20,000 PVP Polyvinylpyrrolidone Polymer with an average molecular weight of 60,000 PVNO Polyvinylpyridine N-oxide polymer with an average molecular weight of

50,000 PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole, average score

Quantity is 20,000QEA bis((C ₂ H ₅ O)(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ )

Bis((C ₂ H ₅ O)(C ₂ H ₄ O)) _n where n is 20-30 SRP1 Anion-terminated polyester SRP2 Diethoxylated poly(1,2-trimethylene terephthalate) short block Duan Ju

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

  7 ethylene oxide residues per nitrogen Silicone defoamer Silicone-oxyalkylene copolymer as dispersant Dimethicone

Alkane foam control agent, the ratio of the foam control agent to the dispersant

is a 10:1-100:1 sunscreen agent water-based monostyrene latex blend, manufactured by BASF

Aktiengesellschaft sells wax under the trade name Lytron 621 Paraffin Effervescent Granules Any of the effervescent granules I-XII

The following effervescent granules I-XII are granules according to the invention (percentage of components calculated by weight of the effervescent granule). The granules can be prepared by mixing the components and agglomerating the components or by compressing the mixed components, the latter being the preferred method of making granules I, IV and VIII. particles I II III IV V VI VII VIII IX x XI XII Citric acid I 60 35 20 20 Citric acid II 40 20 30 30 Malate I 50 20 40 Malic acid II 30 Tartaric acid 50 maleic acid 30 Carbonate I 40 20 40 30 30 20 Carbonate II 20 30 30 35 30 20 Bicarbonate I 20 Bicarbonate II 30 20 20 LAS 10 20 20 Nonionic* 30 20 30 AS 10 20 TAED 20 5 Desiccant# 2 5 10 NACOBS 20 NOBS 20 CMC 5 5 Percarbonate 10 brightener 3 PEG4000 10 5 10

# (overdried or anhydrous salt/zeolite or overdried zeolite)

*Nonionic ethoxylated alcohol surfactant with an average degree of ethoxylation of 3-9 and an alcohol alkyl chain with 12-18 carbon atoms.

Example 1

All levels in the following examples are by weight of the composition,

Table I

The following compositions 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 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 0.5 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 - - - 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 - - - Effervescent Granules I, III, IV or VIII 10 7.0 - - - - - - - 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 - - - 6.0 3.0 - 7.0 10.0 LAS 4.0 5.0 - - 5.0 3.0 - 10.0 12.0 dry added granules components effervescent granules - 4.0 10.0 4.0 25 8.0 12.0 2.0 4.0 QEA - - - 0.2 0.5 - - - - NACAOBS 3.0 - - 4.5 - - - 2.5 - NOBS 1.0 3.0 3.0 - - - - - 5.0 TAED I 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (flaky) 10.0 10.0 - - - - - 8.0 - Citric acid II - - - spray drying brightener 0.2 0.2 0.3 0.1 0.2 0.1 - 0.6 0.3 dye - - - 0.3 0.05 0.1 - - - AE7 - - - - - 0.5 - 0.7 - spices 1.0 0.5 1.1 0.8 0.3 0.5 0.3 0.5 - dry addition Citrate - - 20.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - 24.0 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) - 0.5 0.5 - 0.3 - 0.2 - - Foam suppressor 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 (I or crude product) - - - 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 II

The following compositions are compositions of the present invention. A B C D. E. f G h I spray dried granules LAS or LAS(I) 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 - - - Effervescent Granules I, III, IV, VII or VIII 5 12 - - - - - - - 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 - - TAED II 3.0 1.5 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 added granular components effervescent granules - 10.0 4.0 5 15 8.0 2.0 20 4.0 NACAOBS 3.0 - - 1.5 - - - 5.5 - NOBS/LOBS/DOBS - 3.0 3.0 - - - - - 5.0 TAED I 2.5 - - 1.5 2.5 6.5 - 1.5 - MBAS - - - 8.0 - - 8.0 - 4.0 LAS (flaky) - - - - - - - 8.0 - spray drying 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 0.8 0.5 1.0 dry additive QEA - - - 0.2 0.5 - - - - Citrate 4.0 - 3.0 4.0 - 5.0 15.0 - 5.0 Percarbonate 15.0 3.0 6.0 10.0 - - 12.0 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 II - - - - - 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 suppressor 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 II - - - - - - - 5.0 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%

Table III

The following are high density and bleach-containing detergent formulations according to the invention. A B C blown powder Zeolite A - - 15.0 sodium sulfate 0.0 5.0 0.0 LAS 3.0 - 3.0 C45AS 3.0 2.0 4.0 QAS - - 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Effervescent Granules I or VIII 7.0 - - TAED - - 3.0 Agglomerates Effervescent granules I, III, VIII or IX 7.0 - 7.0 QAS 1.0 - - LAS - 11.0 7.0 TAS 2.0 2.0 1.0 Silicate 3.0 - 4.0 Zeolite A 8.0 8.0 8.0 carbonate 8.0 8.0 4.0 Agglomerates NaSKS-6(I) or (II) 15.0 12.0 5.0 LAS 8.0 7.0 4.0 AS 5.0 - - spray spices 0.3 0.3 0.3 C ₂₅ E ₃ 2.0 - 2.0 brightener 0.1 0.4 photobleach 0.03 0.05 - dry additive - - - QEA 1.0 0.5 0.5 Citric acid I 5.0 - 2.0 Bicarbonate I - 3.0 - Carbonate II 8.0 15.0 10.0 NAC OBS 6.0 - 5.0 manganese catalyst - - 0.3 TAED I - 3.0 - NOBS - 2.0 - Percarbonate 14.0 7.0 10.0 Polyethylene oxide, molecular weight 5,000,000 - - 0.2 Bentonite - - 10.0 effervescent granules - 5.5 7.5 protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 dry additive sodium sulfate 0.0 3.0 0.0 Balance (moisture and impurities) 100.0 100.0 100.0 Density (g/L) 850 850 850 Example 2 Coating the Effervescent Component

Tallow alcohol ethylene oxide condensate (TAE), which is condensed tallow alcohol with 50-80 moles of ethylene oxide (TAE 50/80), is melted at 70°C. 4.750 kg of the effervescent component (64% citric acid compressed with 36% sodium carbonate) was placed in a tumbler mixer (Eirich) and the mixer was started but not rotated. This will stimulate slow mixing of "aerated particles". 250 grams of molten TAE 50/80 was placed in a heating vessel (outer water jacket ~80°C) connected to a Devilbliss spray gun with atomizing air at 80°C. This results in a TAE 50/80 of 5% by weight overall. Turn on the drum mixer to rotate and spray the molten TAE 50/80 onto the moving effervescent component, thereby adhering to the surface of the effervescent component in this way, effectively coating said effervescent component. Once all of the molten TAE 50/80 is sprayed onto the effervescent components, the tumbler mixer is allowed to rotate until the TAE 50/80 hardens on the effervescent surface (i.e. until solidified). The TAE 50/80 coated effervescent fraction was then sieved at 1180 microns to remove any agglomerated particles. This is particle XIII of the described example.

Claims (20)

1. effervescence component that comprises acid source and carbon dioxide source, at least 75% particle diameter of wherein said acid source is the 0.1-150 micron, preferred 0.5-100 micron.

2. according to the effervescence component of claim 1, the volume medium of wherein said carbon dioxide source is the 5-375 micron, preferred at least 60% particle diameter is the 1-425 micron thus, perhaps even the volume medium of preferred 10-250 micron, preferred at least 60% particle diameter is the 1-375 micron thus, perhaps even have a volume medium of 1-120 micron, preferred at least 60% particle diameter is the 1-150 micron thus.

3. according to each component of aforementioned claim, wherein said acid source comprises sulfonic acid or monobasic or polycarboxylic acid or its mixture, citric acid, hexanodioic acid, pentanedioic acid, 3 cetoglutaric acid, citromalic acid, tartrate, toxilic acid, fumaric acid, oxysuccinic acid, Succinic Acid and/or the propanedioic acid and/or the toluenesulphonic acids of preferred anhydrous and/or hydrated form, optimization citric acid, oxysuccinic acid, toxilic acid or tartrate or its mixture.

4. according to the component of claim 1, described thus effervescence component, or one or more described acid sources or carbon dioxide source are contained the coating of average extent of alkoxylation by at least 20 alcohol alcoxylates and are coated with.

5. according to each component of aforementioned claim, described thus carbon dioxide source comprises yellow soda ash or sodium bicarbonate or its mixture.

6. according to each effervescence component of aforementioned claim, described acid source and described carbon dioxide source are present among the intimate mixture each other together.

7. according to the effervescence component of claim 6, wherein said acid source and described carbon dioxide source are present in the particle, preferred described particulate weight average particle diameter is 500 microns to 1500 microns, the particle diameter of preferred described particulate at least 70% is 350 to 2000 microns thus, perhaps even have 650 microns to 1180 microns weight average particle diameter, the particle diameter of preferred described particulate at least 70% is 500 to 1500 microns thus.

8. according to the effervescent granule of claim 6, it is in 200 microns to 500 microns the particle that wherein said acid source and described carbon dioxide source are present in weight average particle diameter, the particle diameter of preferred described particulate at least 70% is the 100-710 micron thus, perhaps even have 250 microns to 450 microns weight average particle diameter, the particle diameter of preferred described particulate at least 70% is the 150-650 micron thus.

9. according to each particle in claim 7 or 8, it comprises and accounts for total particle weight 30%-95%, preferred 45%-85%, the most preferably carbon dioxide source of 50%-80% and 3%-75%, preferred 5%-60% or the more preferably acid source of 15%-50%.

10. according to each particle among the claim 7-9, it comprises 50% one or more tackiness agents, the detergent active that is at most total particle weight, preferred surfactant and/or SYNTHETIC OPTICAL WHITNER or its mixture.

11. according to the particle of claim 10, wherein said tackiness agent is selected from derivatived cellulose; The homopolymer of carboxymethyl cellulose and polycarboxylic acid and multipolymer and their salt; C ₆-C ₂₀Alkyl and alkylaryl sulphonate and vitriol; The C of every mol of alcohol 5-100 moles of ethylene oxide ₁₀-C ₂₀Fatty alcohol ethoxylate; Lipid acid; Molecular-weight average is 12000 to 700000 Polyvinylpyrolidone (PVP); Molecular-weight average is 600 to 10000 polyoxyethylene glycol; Maleic anhydride and ethene, methylvinylether, methacrylic acid or acrylic acid multipolymer; C ₁₀-C ₂₀List and two glyceryl ethers; C ₁₀-C ₂₀Lipid acid and composition thereof and preferred C ₈-C ₂₀Alkylbenzene sulfonate.

12. one kind prepares according to each particulate method among the claim 7-11, wherein said method may further comprise the steps:

-grinding thick acid source to obtain a kind of acid source, its particle diameter of at least 75 is the 0.1-150 micron, preferred 0.5-100 micron,

-mix described thick acid source and described carbon dioxide source and optional tackiness agent and/or other actives forming mixture,

-subsequently described mixture is implemented granulation step, preferred described granulation step comprises compression step and/or agglomeration step.

13. according to the method for claim 11 or 12, wherein said granulation step comprises the roll compaction step, wherein the gained mixture is forced between the compressing roller of sending under the pressure, after this compressing mixt granulation that obtains is become effervescent granule and optional sieving.

14. a detergent composition that comprises effervescence component is characterized in that described effervescence component is contained the coating of average extent of alkoxylation by at least 20 alcohol alcoxylates and is coated with.

15. according to the detergent composition of claim 14, it comprises the effervescence component that obtains coating by the method that may further comprise the steps:

(a) form the fused alcohol alcoxylates;

(b) described fused alcohol alcoxylates is contacted with effervescence component.

16. according to the detergent composition of claim 14 or 15, the level that exists of described coating is the 0.5%-25% of described effervescence component weight thus.

17. detergent composition, be preferably the form of on-aqueous liquid, particulate composition, tablet or medicated roll, it comprises according to each effervescence component of aforementioned claim, the preferred levels of described effervescence component is the 2%-50% of described detergent composition weight, more preferably 3%-25% most preferably is 4%-15%.

18. granular detergent composition according to claim 17, the wherein at least a effervescence component that is preferably particle form is included in the particle of at least a washing composition basis, the preferred weight average particle diameter of described base particle is 350 microns to 4 millimeters, more preferably 500 microns to 2.5 millimeters or even be 710 microns to 2 millimeters.

19. by in detergent particles, adding according to each effervescence component among the claim 1-12 so that the blistered method of improving detergent composition to be provided, the weight average particle diameter of described detergent particles is 500 microns to 1500 microns, the particle diameter of preferred described particulate at least 70% is 350 to 2000 microns thus, perhaps even have 650 microns to 1180 microns weight average particle diameter, the particle diameter of preferred described particulate at least 70% is the 500-1500 micron thus.

20. by in detergent particles, adding according to each effervescence component among the claim 1-11 so that distribution and/or the dissolved method of improving detergent composition to be provided, the weight average particle diameter of described detergent particles is 200 microns to 500 microns, the particle diameter of preferred described particulate at least 70% is the 100-710 micron thus, perhaps even have 250 microns to 450 microns weight average particle diameter, the particle diameter of preferred described particulate at least 70% is the 150-650 micron thus.