CZ9903413A3 - Dry effervescent granules, granulated agent, process of their preparation, method of soaking clothes and use of the dry effervescent granules - Google Patents

Abstract

The present invention describes dry effervescent granules comprising an acid, a carbonate source, and optionally a binder where they are said acid, a carbonate source, and an optional binder in the sealant physical proximity. The solution also describes granulated compositions comprising effervescent material including acid a carbonate source having an effervescence index (E1) of at least 50. Granular compositions can be obtained by incorporation said previously produced dry effervescent granules of said granular compositions, particularly cleansing compositions resources. Improving sparkling is achieved when these are granular detergents dissolved in water to form washing / soaking solution, resulting in an increase dissolution / scattering properties and increased ability remove stains from dirty laundry.

Description

DRY SPARKLING GRANULES, GRANULATED PRODUCT, METHOD OF MANUFACTURING, METHOD OF Soaking of laundry and use of DRY SPARKLING GRANULES

TECHNICAL FIELD

The present invention is applicable to compositions that need to be dissolved in an aqueous medium quickly and easily. This technology can find application in a variety of industries, such as detergent compositions such as washing powders for washing machines, soaking detergents, dishwashing detergents or any other means for household, pharmaceutical, dental, food, and the like. More particularly, the present invention relates to granular fiber cleaning compositions.

BACKGROUND OF THE INVENTION

The problem associated with conventional granular formulations that are used by consumers when dissolved in water is their tendency to poorly dissolve. This tendency has been renewed in the light of the recent trend, for example in the detergent industry against the higher bulk density of the granular compositions and the granular detergents which contain a higher content of active ingredients. Granular detergents having a high bulk density ranging from 650 to 1100 kg / m ³ are attractive to consumers but not sufficiently soluble in aqueous media.

Other difficulties with cleaning agents are such that they are not readily washable from the dispenser drawers of the washing machine. Similar problems occur when such granular detergent compositions are used in dispensing devices in a washing machine drum.

It is known to use citric acid and bicarbonate in powder formulations to aid dissolution, e.g., pharmaceutical preparations. In order to ensure the horhogenic distribution of these effervescent materials in such formulations, it is necessary to use sodium bicarbonate and citric acid in the form of a fine powder. It is also necessary to incorporate a significant portion of these effervescent materials into the formulation to obtain the desired effect. Further, a major problem with such powder formulations is poor storage stability when exposed to moisture.

Thus, it is an object of the present invention to provide formulations with enhanced dissolution capability or dissolution properties when dissolved in an aqueous medium. Next destination • · · ···························

-. . . . The present invention is that the effective dissolution properties of the compositions of the present invention do not decrease or lose during storage.

It has now been found that these objectives can be achieved with a cleaning composition comprising an effervescent material consisting of an acid and a carbonate source having a certain effervescence index. Preferably, the effervescent material, or at least a portion thereof, is contained in the dry effervescent granule. In particular, it has been found that these objectives can be achieved by granular formulations obtained by a process comprising the first step of forming a dry effervescent granule containing an acid, carbonate or bicarbonate and optionally a binder, wherein the acid, carbonate or bicarbonate and binder are in close physical proximity thereafter incorporating the granule into the granular composition. Of course, it has been found that, for example, incorporation of such preformed dry effervescent granules, generally obtained by dry powder consolidation or pressure agglomeration, into compositions in accordance with the present invention provides an increase in dissolution and / or scattering capabilities for all active formulations present in the compositions and good storage stability due to the dissolution capacity. The compositions of the present invention have been found to provide increased effervescence, resulting in increased solubility or dispersion of the compositions when the compositions are in contact with water (i.e., under conditions of use) as compared to compositions containing the same amount of effervescent powder. homogeneously dispersed throughout the granular compositions, i.e., they have two separate granular particles.

Another problem associated with conventional cleaning agents is their tendency to not always satisfy the needs of the customer sufficiently in relation to the power delivered by the active ingredients present in said compositions.

In addition, when preparing bleach-containing cleaning compositions containing oxygen bleach, it is not only desirable to provide effective stain removal performance (e.g., stains that are bleachable), but it is important that such compositions be temperature stable at extended storage times prior to their normal use.

It has now been found that these problems are solved by the detergent compositions of the invention as described herein. It has further been found that, in preferred instances of the present invention, the presence of the preformed dry effervescent granules described herein in detergent compositions containing active detergents produces increased effervescence upon contact with water which results in increased solubility and / or dispersion of the composition and enhances removal performance. stains on the treated laundry as compared to the ability to remove stains under the same conditions with compositions containing the same substances in the same amount but having all the effervescent material uniformly distributed throughout the granular compositions, or with the same compositions containing no effervescent material. More specifically, it has been found that the ability to remove stains is even more enhanced despite the presence of dry preformed effervescent granules in the cleaning composition. This has also been found when the composition is briefly soaked, i.e., when dirty laundry is soaked in a soaking solution containing water and said composition, simultaneously or immediately after preparation (e.g., within 5 minutes and preferably within 1 minute after preparation), generally less. than after 30 minutes before removal from the soaking solution. Preferably, the enhancement of the stain removal capability associated with the detergent compositions of the present invention is even more remarkable at low use temperatures, typically below 30 ° C.

Preferably, an enhancement of the stain removal ability is observed on a number of different stains that contain resistant outdoor dirt, such as greasy stains (e.g., spaghetti sauce, bacon fat), enzyme stains (blood), bleachable stains (grass), or particulate soil ( mud, clay). Another advantage of the present invention is the ability to remove stains when soaking / washing laundry in the presence of the detergent described herein, an increased ability even in the presence of a relatively high level of water hardness ions.

It has now been found that the compositions of the invention and dry preformed effervescent granules are compatible with bleach and stable during storage.

SUMMARY OF THE INVENTION

The present invention provides a cleaning composition comprising an effervescent source, including an acid and a carbonate source, wherein the effervescent index is at least 10 as described herein. The present invention also comprises a dry effervescent granule comprising an acid, carbonate source, preferably carbonate / bicarbonate, and optionally a binder, wherein said acid, carbonate source and optionally a binder are in close physical proximity.

The present invention also includes a method of making the dry effervescent granules described herein, said method comprising the following steps:

- firstly, mixing the acid, carbonate source and optionally binder together to form a mixture,

- subjecting the mixture to a pressure agglomeration step as defined herein to obtain an agglomeration mixture,

and finally subjecting the agglomerated mixture to a granulation step.

The present invention also includes a composition obtained by a process comprising the first step of forming a dry effervescent granule comprising an acid, a carbonate source, preferably a carbonate / bicarbonate, and optionally a binder, wherein said acid, carbonate source and optionally

A · · · · ··· ·

The binder is in close physical proximity, the subsequent step comprising incorporating the granule into said composition. In a preferred case of the compositions, the granular or solid cleansing compositions are those containing at least a cleansing active ingredient, preferably at least an oxygen bleach or a mixture thereof.

The present invention further encompasses the use of a dry effervescent granule, described herein, in a cleaning composition, preferably solid or granular, containing at least one cleaning active ingredient, for enhancing stain removal capability. This can normally happen if the laundry is soaked for an effective time in a soaking solution containing water and an effective amount of said granular detergent composition before removing said laundry from said soaking solution.

The present invention further comprises the use of a dry effervescent granule, described herein, in a composition preferably solid or granulated, containing an oxygen bleach, preferably percarbonate and / or perborate, to increase the storage temperature stability of said composition.

Finally, the present invention also comprises a method of soaking laundry, wherein said laundry is soaked in a soaking solution containing water and an effective amount of the composition herein for an effective time thereafter removed from said soaking solution, and also comprising a method of washing laundry in a domestic washing machine. which is placed in the drum of the washing machine, or dispensed by the dispensing drawer of the washing machine, an effective amount of the cleaning composition described herein.

Dry effervescent granules and process for their production.

The present invention includes a dry effervescent granule comprising an acid, a carbonate source, preferably a carbonate or bicarbonate, and optionally a binder in which the acid, the carbonate source and optionally the binder are in close physical proximity and a method for producing the same.

By "dry" is meant that the granules are almost free of water, ie no water has been added or present other than as the moisture of the raw materials themselves. Generally, the water level is below 5% of the total weight of the granule, preferably below 3% and even more preferably below 1.5%.

For the purposes of the present invention, the term close physical proximity means that the effervescent materials, ie the acid and carbonate source, are in intimate contact with the effervescent granules and must not be separated by anything other than a binder if the binder is present in the dry effervescent granule. More preferably, at least a portion of the acid or carbonate is not separated by separate particles in the granular compositions.

The dry effervescent granules of the present invention comprise effervescent materials, i.e., an acid and carbonate source, in close physical contact, and are preferably obtained by solidification.

Or by pressure agglomeration of a dry powder. While all binding mechanisms can occur in a pressure agglomeration, the adhesion forces between the solid particles, i.e. between the acid, carbonate source and optionally the binder, if present, play a particularly important role. This is because pressure agglomeration, especially high pressure agglomeration, is essentially a dry process that creates new objects (ie, dry effervescent granules) from solid particles (ie, acid, carbonate source and optionally binder) under extreme forces that compact more or less defined bulk masses or volumes and create bonding mechanisms between the solid particles which ensure the cohesion of the new object, i.e., a high external applied force joins the solid particles tightly together.

Dry effervescent particles cause very high carbon dioxide evolution and thus increase dispersion and dissolution of the granular composition. The granular compositions of the present invention, as disclosed herein, comprise dry effervescent granules allowing dispensing and dissolving the granular compositions in water in a shorter time and using less effervescent particles / materials and ensuring faster and more efficient delivery of the cleaning compositions to the water.

Suitable acids which may be used herein include solid organic, mineral or inorganic acids, salts or derivatives thereof, or mixtures thereof. It may be preferred that the acids are mono-, di- or tri-protonic acids. Such acids include mono- or polycarboxylic acids, preferably citric acid, adipic acid, glutaric acid, 3-chetoglutaric acid, citric acid, tartaric acid, maleic acid, fumaric acid, malic acid, succinic acid, malonic acid. These acids are preferably used in acid form and their anhydride form, or a mixture thereof, may be used preferably. Derivatives also include acid esters. Surprisingly, it has been found that when using tartaric, maleic and especially malic acids as the acid in dry effervescent granules, these granules obtain increased physical and / or chemical stability over long storage periods. When citric acid is used, the amount used is preferably less than 20% in the dry effervescent granule of the present invention, in particular to facilitate production processes and provide suitable storage stability of the granules.

The acid is preferably present in dry effervescent granules of the present invention in an amount of from 0.1% to 99% of the total weight of the granule, more preferably from 3% to 75%, even more preferably from 5% to 60% and most preferably from 15% to 50%. %.

According to the present invention, 80% or more of the acid source preferably has a particle size in the range of 150 microns to 1200 microns, or up to 1000 or even 710 microns.

Another essential feature of the present invention is a carbonate source comprising carbonate, bicarbonate and percarbonate salts, especially bicarbonate or carbonate. Suitable carbonates ·························· As used herein, potassium, lithium, sodium and the like carbonates and bicarbonates, among which sodium and potassium carbonates are preferred, are used herein. Suitable bicarbonates used herein include alkali metal bicarbonate salts such as lithium, sodium, potassium, and the like, among which sodium and potassium bicarbonates are preferred. Bicarbonate is more preferred than carbonate because it has a higher efficiency per unit weight, ie the same amount of bicarbonate "gives" more carbon dioxide than carbonate. However, the choice of carbonate or bicarbonate or mixtures thereof for dry effervescent granules may depend on the pH required for the aqueous solution in which the dry effervescent granules are dissolved. For example, if a relatively high pH in an aqueous medium (e.g., above pH 9.5) is desired, it is preferred to use carbonate alone or a combination of carbonate and bicarbonate, wherein the amount of carbonate is higher than the amount of bicarbonate. Generally, the weight ratio between carbonate and bicarbonate is from 0.1 to 10, preferably from 1 to 5, most preferably from 1 to 2.

The carbonate source is preferably present in dry effervescent granules of the present invention in an amount of from 0.1% to 99% by weight, more preferably from 30% to 95%, more preferably from 45% to 85%, and most preferably from 50% to 80%. %.

In accordance with the present invention, 80% or more of the carbonate source has a preferred particle size in the range of 50 to 1200 microns, or even 150 to 1000 microns.

For optimal effervescence in aqueous solution, the weight ratio between acid and carbonate or bicarbonate in dry effervescent granules is from 0.1 to 10, preferably from 0.5 to 2.5, and most preferably from 1 to 2.

The average size of the dry effervescent granules of the present invention is preferably from 0.001 mm to 7 mm, more preferably less than 2 mm.

The average size as defined herein may be determined by sieving a sample of granules to a number of individual fractions (generally five fractions) using a series of sieves with different diameters of individual holes in the sieve. The average granule size can be calculated by plotting the weight of the sieving fractions against the diameter of the sieve holes. The average particle size is determined by determining the size of the screen through which 50% of the sample weight passes.

The bulk density of the dry effervescent granules of the present invention is preferably from 500 g / l to 1200 g / l, most preferably from 700 g / l to 1000 g / l.

The dry effervescent granules of the present invention may optionally contain a binder or a mixture thereof. Generally, dry effervescent granules contain up to 50% by weight of the total binder granules or mixtures thereof, preferably up to 35% and even more preferably up to 25%. Suitable binders that can be used herein are those known to those skilled in the art and include anionic surfactants such as C 6 to C ₂ alkyl or alkylarylsulfonates or sulfates, preferably C 8 to C ₂ alkyl alkyl benzene sulfonates, cellulose derivatives.

such as carboxymethylcellulose and homo- or copolymeric polycarboxylic acids or salts thereof, nonionic surfactants, more preferably C10 to C20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol and more preferably C15 to C20 primary alcohol ethoxylates containing from 20 to 100 moles of ethylene oxide per mole of alcohol . These tallow alcohols ethoxylated with 25 moles of ethylene oxide per mole of alcohol (TAE25) or 50 moles of ethylene oxide per mole of alcohol (TAE50) are preferred. Other preferred binders include polymeric materials such as polyvinylpyrrolidones with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average molecular weight of 600 to 10,000. Maleic anhydride copolymers with ethylene, methyl vinyl ether, methacrylic acid or acrylic acid are other examples of polymeric binders. Other binders further comprise C10 to C20 mono- and diglycerol ethers as well as C10 to C20 fatty acids. In the case of the present invention where a binder is desired, C8-C20 alkylbenzene sulfonates are particularly preferred.

In a preferred case, the granules of the present invention consist of an acid, a carbonate source and optionally a binder, wherein the acid, carbonate source and, optionally, the binder are in close physical proximity.

The present invention further comprises a method of making dry effervescent granules of the present invention comprising an acid, a carbonate source and optionally a binder, wherein the acid, carbonate source and optionally a binder are in close physical proximity. Preferably, the method comprises the steps of:

- first mixing the acid, carbonate source and optionally binder to form a mixture,

- then subjecting the mixture to an agglomeration step, preferably a pressure step, to form an agglomerate mixture,

and finally granulating the agglomeration mixture in a granulation step to form said granules. Because of this method, the raw materials for manufacture and optionally the binder, if present, are first mixed together without the addition of water or moisture that comes from the raw materials themselves, so as to obtain a dry, free-flowing powder mixture. Thereafter, the dry particulate powder composition comprising effervescent particles (i.e., acid and carbonate source) and optionally binder particles, if present, undergo a pressure agglomeration, i.e., a dry process where the dry particulate powder composition is exposed to high external forces that compress the particles tightly together, thus increasing the density of said particles and forming binding mechanisms between the solid effervescent particles and the binder, if present. In fact, pressure agglomeration is the result of aggregation mechanisms that are characterized by the presence of internal bonds between primary solid effervescent particles and a structure in which these effervescent particles are still identifiable and retain many of their properties, eg the ability to react together in the presence of water to form carbon dioxide.

The density increase associated with the preparation of the dry effervescent granules of the present invention obtained by pressure agglomeration is closely related to the applied pressure. Typically, the bulk density will be increased up to 200 g / l, preferably from 10 g / l to 150 g / l, starting from the density of the blend containing the effervescent raw material, ie, acid, carbonate source and optionally binder, before being subjected to pressure. agglomeration.

The agglomeration pressure can occur in various ways, which can be divided according to the amount of force used. The preferred method of use here is cylindrical pressing. In this method, after mixing the acid, bicarbonate or carbonate, and optionally the binder, the mixture is guided between two solid cylinders, where the said mixture is subjected to pressure such that it turns into solid chips / slices by rotating the cylinder. These are then granulated.

A common solid mill for use herein is, for example, Pharmapaktor L200 / 50P® commercially available from Hosokawa Bepex GmbH. The manufacturing differences during pressure agglomeration and compression are the distance between the rolls, the feed rate, the compression pressure and the rotation speed. A common dosing device is a dosing screw. The spacing between the rollers is generally from 0.5 cm to 10 cm, preferably from 3 to 7 cm, and most preferably from 4 to 6 cm. The compressive force is typically from 20 kN to 120 kN, preferably from 30 kN to 100 kN, and most preferably from 40 to 80 kN. Typically, the rotation speed is from 1 rpm to 180 rpm, preferably from 2 rpm to 50 rpm, and most preferably from 2 rpm to 35 rpm. Typically, the dosing rate is between 1 to 100 rpm, preferably from 5 to 70 rpm, and most preferably from 18 rpm to 50 rpm. The temperature at which the compression is performed is not significant, typically in the range of 0 to 40 ° C.

By "granulation step" is meant that the mixture, after undergoing the agglomeration step, is cut into granules of desired length and rounded until rounded or round granules according to the average size defined hereinbefore are obtained. In preferred cases, the first step is a granulation step, after rolling the solid chips / slices are ground. Grinding may conveniently be performed in Flake Crusher FC2000® commercially available from Hosokawa Bepex GmbH.

Depending on the final average size required for dry effervescent granules, the milled material may be further sieved. Such sieving of dry effervescent granules may be carried out, for example, in a commercially available Alpien Airjet Screen.

Detergent compositions

The present invention discloses in one instance a cleaning composition comprising an effervescent material consisting of an acid and a carbonate source, wherein the acid and carbonate source are

present together in the granule, or the acid and carbonate source are separately present in the composition, which is characterized by an efficacy index (E1) of at least 10 or even at least 15. The efficacy index (E1) is defined by:

E1 = (LxSx100) / MX (NCinter + NCintra) where L is the number of acidic groups of the acid having a pKa of less than or equal to 6, S is 3 ^ / ~ (water solubility in g / l at 25 ° C), M is molecular the weight of acid, NC Inter is the density of the contact points between the carbonate source and the acid separately present in the composition per mm ³ and the NC _intra is multiplied by (weight of the fraction of carbonate source in said granule) times 12 times.

NCinter and NCintra can be calculated according to the method shown in: T. Tanaka and N. Ouchiyama, Ind. Chem. Fundam., 1980, 19, 338-340.

NCinter is believed to represent the density of contact points between the carbonate source and the acid present in the same granule per mm.

The compositions of the invention provide increased, effective effervescence when the El value is at least 10. The granular compositions of the present invention, described herein, comprise dry effervescent granules allowing dispersion and dissolution of the granular composition in water in a shorter time and less total effervescent material particles. more efficient delivery of detergents for washing.

The compositions are preferably granular cleaning compositions. As used herein, the granular compositions comprise any composition which is in the form of granules, tablets, rollers, crisps, extrudates, etc.

The compositions of the invention preferably comprise a dry effervescent granule, as described herein, comprising an acid and a carbonate source or a portion thereof. It may be preferred that all the acid in the composition is contained in the dry effervescent granule. Alternatively, it may be preferred that the composition comprises a dry effervescent granule and a dry addition of acid and a dry addition of a carbonate source, preferably less than 10% by weight of the acid, preferably less than 8% or even less than 5% by weight.

Preferably, the composition is obtained by a method comprising the step of forming a dry effervescent granule comprising an acid and carbonate source and optionally a binder, wherein the acid, carbonate source and optionally binder are in intimate physical contact as disclosed herein, and then adding the granule to other cleaning components of the composition.

• · ·

The granular compositions of the present invention may be prepared with different bulk density, preferably from 500 to 1200 g / l, more preferably from 750 to 1050 g / l. These compositions can be made by a variety of methods well known in the art, including dry blending, spray drying, agglomeration and granulation, and combinations thereof.

Preferably, the dry effervescent granules comprise from 0.1% to 99% by weight of the total composition, preferably from 2% to 50%, the wetting agent content preferably from 5% to 40%, most preferably from 15% to 35% by weight, and automatic dishwashing or dishwashing composition, preferably from 3% to 25%, more preferably from 4% to 15% by weight.

Additional folders

The compositions of the present invention typically comprise at least one active ingredient in addition to said dry effervescent granules. In a preferred case, where the granular compositions of the present invention are granular cleaning compositions, they comprise at least the active cleaning component or a mixture thereof. Typically, the granular detergent composition comprises the active detergent component or mixture thereof in an amount of from 0.1% to 99% of the total weight of the composition, preferably from 1% to 80% and more preferably from 5% to 70% of the total weight. By "active cleansing component" is meant any ingredient known to those skilled in the art that provide a cleaning or bleaching benefit, including, for example, surfactants, bleaches, enzymes, polymers, brighteners, builders, bleach activators, surfactants, alkali metal silicate salts , chelating agents, fillers, soil suspending agents, scatterers, soil removal agents, photo activated bleaches such as zinc phthalocyanine sulfonate, dyes, dye transfer inhibitors, pigments, perfumes, soap suppressors, clay softening systems, cationic laundry softening agents and mixtures thereof. Depending on the final determination, a different mixture and the amount of individual components in the mixture are used.

In a preferred case of the present invention, the granular compositions comprise oxygen bleaches or mixtures thereof. Certainly oxygen bleaches provide a number of benefits such as bleach stains, deodorization as well as disinfection. The oxygen bleach in the granular compositions of the present invention may come from a variety of sources, such as hydrogen peroxide or any other hydrogen peroxide compound, or organic peroxyacids or mixtures thereof. By other hydrogen peroxide substances is meant those formed by binding hydrogen peroxide to another chemical, which may be, for example, an inorganic salt, urea or an organic carboxylate. Examples of other hydrogen peroxide materials include inorganic perhydrate salts, hydrogen peroxide compounds formed from organic carboxylates, urea, and compounds in which hydrogen peroxide is present in clathrates.

Examples of inorganic perhydrate salts are perborates, percarbonates, perfosphates, peroxymonopersulfates, and per silicate salts. Inorganic perhydrate salts are generally present in the form of alkali metal salts. The alkali metal salts of percarbonate, perborate or mixtures thereof are the preferred inorganic perhydrate salts used herein. A preferred alkali metal percarbonate salt is sodium percarbonate, which may be present in the carbonate source. A preferred perborate is sodium perborate in the form of a monohydrate or tetrahydrate, the chemical formula of which is NaBChFhCE and NaBCEIHCl2. Other suitable oxygen bleaches include persulfates, especially sodium persulfate K2S2O8 and sodium persulfate Na2S2O5.

Typically, the granular compositions of the present invention comprise an oxygen bleach or mixtures thereof up to 90% of the total weight of the composition, preferably from 2% to 45%, more preferably from 10% to 40%.

Surprisingly, it has been found that in an embodiment of the present invention wherein the granular compositions comprise at least some oxygen bleach as the active ingredient and dry effervescent granules, the thermal stability of the granular composition during long-term storage is increased.

Thus, in a broader context, the present invention also encompasses the use of such a dry effervescent granule as defined above in a granular composition comprising an oxygen bleach, preferably percarbonate or perborate, to increase the thermal stability of said composition during storage.

Bleach activators

Preferably, the granular compositions herein further comprise bleach activators or a mixture thereof up to 30% of the total weight of the composition. Examples of suitable compounds of this type are contained in British Patent GB 1 586 769 and GB 2 143 231. Preferred examples of such compounds are tetracetylethylenediamine, (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diperoxydodecanoic acid, as described, for example, in US Patent 4,818,425 and peroxyadipic acid nonylamide as described, for example, in US Patent 4,295,201 and n-nonanoyloxybenzenesulfonate (NOBS), and acetyltriethyl citrate (ATC), as disclosed in European Patent application 91870207, 7-phthalimidoperoxyhexanoic acid (PAP), fi N-nonanoyl-6-aminocaproic acid polyolsulfonate ester, an aliphatic diacyl peroxide (DAP) having the general formula RC (O) -OO- (O) C-R1, wherein R and R1 may be the same or different groups that are linear or branched aliphatic groups containing from 6 to 20 carbon atoms. Particularly preferred are N-acylcaprolactams selected from the group consisting of substituted or unsubstituted compounds such as benzoylcaprolactam, octanylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, formylcaprolactam, The granular compositions herein may comprise mixtures of said bleach activators.

Precursors of substituted alkylperoxyacid amides

The substituted alkyl peroxyacid amide precursors useful herein include compounds having the following general formula:

R ¹ —CNR ² or

R ¹ -N -CR ² -CL

R ⁵ O ⁰ where R ¹ is C 1 -C 14 alkyl, R ² is C 1 -C 14 alkylene and R ⁵ is H or C 1 -C 10 alkyl and L may be substantially any cleavable group group. Substituted bleach activator amide compounds of this type are disclosed in EP-A-0170386.

A highly preferred bleach activator is an amide-free caproyloxybenzenesulfonate, preferably in the form of the sodium salt (NACA-OBS).

Preferred bleach activator mixtures herein include n-nonanoylbenzene sulfonate, or amide-free caproyloxybenzene sulfonate together with a second bleach activator having the property of slow diacyl peroxide formation but which mainly provides peracid. Said second bleach activators may include teraacetylethylenediamine (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam and the like, or mixtures thereof. Bleach activator mixtures containing n-nonanoylbenzene sulfonate and said second bleach activators have been found to contribute to further partially enhancing dirt removal performance while at the same time having a good effect on diacylperoxide-sensitive impurity (e.g. beta-carotene) and peracid-sensitive impurity (eg body impurities).

The granular compositions herein may comprise NOBS or NACA-OBS in an amount of from 0% to 15% by weight of the composition, preferably from 1% to 10% and more preferably from 3% to 7% by weight of the composition, and said second bleach activator in an amount of 0% up to 15% of the total weight of the composition, preferably from 1% to 10% and more preferably from 3% to 7%.

Surfactants

The granular compositions of the present invention may contain surfactants or a mixture thereof. Such surfactants may be desirable for their contribution to providing effective stain removal performance. This includes a number of different stains, such as greasy stains, enzymatic stains, particulate contaminants, and the like. Such surfactants may be present in the compositions of the present invention in an amount of up to 50% of the total weight of the composition, preferably from 1% to 30% and most preferably from 5% to 20%. The surfactants used herein include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, and mixtures thereof.

Anionic surfactants

Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated for use herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidium and alkanolamine derived cations such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like. Exemplary surfactants are Cn to Cn alkylpolyethoxylated (1.0) sulfate, (C12-CnE (1.0) M), Cn to Cn alkylpolyethoxylated (2.25) sulfate, (CnCnE (2.25) M), Cn to Cn polyethoxylated (3.0) sulfate Cn-C And Cn to Cn alkylpolyethoxylated (4.0) sulfate (Cn-CnE (4.0) M), wherein M is either sodium or potassium.

Other anionic surfactants suitable for cleaning purposes may also be used herein. These surfactants may contain salts (e.g., sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soaps, C8 to C20 linear alkylbenzene sulfonates, C8 to C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the products pyrolysis of alkaline earth metal citrate, e.g., as disclosed in British patent specification no. 1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl ester sulfonates such as C14 to C ₆ methyl ester sulfonates, acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, alkyl phenol, alkyl phosphates, isethionates such as acyiisothionáty, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12 to C18 monoesters), sulfosuccinate diesters (particularly saturated and unsaturated C6 to C14 diesters), acyl sarcosinates, alkylpolysaccharide sulphates such as alkylpolyglucoside sulphates (nonionic non-sulphonated compounds will be described below), branched alkyl alkyl sulphoxides, (CH 2 CH 2 O) k CH 2 COO-M ⁺ , wherein R is C 8 to C 22 alkyl, k is an index in the range of 0 to 10 and M is a soluble salt-forming cation. Resin • · ·· · * ..........

acids and hydrogenated resin acids are also suitable, such as natural resin, hydrogenated natural resin and resin acids, and hydrogenated resin acids present or derived from tallow oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). Many such surfactants are also generally disclosed in U.S. Pat. No. 3929678, issued Dec. 30, 1975 to Laughlin et al. from paragraph 23, line 58 to paragraph 29, line 23 (reference herein in the references).

Other anionic surfactants suitable for use herein may include compounds of the formula R-SO3M, wherein R is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain containing from 6 to 40 carbon atoms and M is H or a cation. Preferably R is a substituted or unsubstituted, saturated or unsaturated, linear or branched alkyl group containing from 6 to 40 carbon atoms, preferably from 8 to 30, more preferably from 10 to 25 and most preferably from 12 to 18 carbon atoms. Preferably, M is a cation, which may be, for example, a metal cation (eg, sodium, potassium, lithium, carbon, magnesium, etc.) ammonium or substituted ammonium cations (eg, methyl, dimethyl, trimethylammonium, and quaternary ammonium cations, such as tetramethylammonium) and dimethylpiperidium, and cations derived from alkanolamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Suitable anionic sulfonates used herein are sodium paraffin sulfonates. They may be commercially available from Hoest under the name Hostapur® or Hostatat®.

Nonionic surfactants

Suitable nonionic surfactants for use herein are typically alkoxylated nonionic surfactants of the formula RO- (A) _n H, wherein R is a substituted or unsubstituted, saturated or unsaturated, linear or branched hydrocarbon chain containing from 6 to 40 carbon atoms, A is an alkoxy group having from 2 to 10 carbon atoms and wherein the index n is from 9 to 1000, or a mixture thereof.

Preferably R is a substituted or unsubstituted, saturated or unsaturated, linear or branched alkyl or aryl group containing from 6 to 40 carbon atoms, preferably from 8 to 25, more preferably from 12 to 20. Typical aryl groups contain C12 to C18 alkylbenzene groups . Preferably, the index n is from 9 to 100, more preferably from 10 to 80, and most preferably from 10 to 30. Preferably, the alkoxy group contains from 2 to 8 carbon atoms, more preferably from 2 to 5, most preferably propoxy or ethoxy.

Similarly suitable alkoxylated nonionic surfactants for use herein are Dobanol (R) 91-10 (R is a mixture of C9 to C11 alkyl chains, A is ethoxy, n is 10), Luthensol AT (R) or AO (R) surfactants (wherein R is a mixture of linear C 16 to C 18 alkyl) chains or unbranched C13 to C15, A is • · • ·

The ethoxy (n is 10, 18, 25, 50 or 80), or mixtures thereof. Dobanol® surfactants are commercially available from SHELL, while Luthensol® surfactants are available from BASF.

A suitable chemical process for preparing alkoxylated nonionic surfactants for use herein comprises condensing the corresponding alcohols with alkylene oxide in the desired ratio. Such methods are well known to those skilled in the art and have been widely described in the art.

Such highly alkoxylated nonionic surfactants are particularly suitable for use herein for their desirable enhancement of particulate stain removal performance. Of course, it is speculated that they form an impurity-suspending agent, i.e., they allow the suspension of particulate dirt and protect / prevent re-settling of the impurity.

Other suitable surfactants for use herein are sorbitan esters according to the formula CeHgCLíLúELOjxRiRsRs wherein x is an index from 0 to 40, Ri, _R2 are independently OH or (C _n H _{2n +)} COO, and R3 is (C "H _2n + ) COO group where n is an index from 11 to 17.

In preferred compositions herein, x is 0 or 20, and most preferred compositions herein include polyethoxylated (20) sorbitan tristearate, ie, C ₆ H 90 ₂ (C ₂ H ₄ O) ₂ o (C 17 H 35 COO) ₃ , or polyethoxylated (20) sorbitan monostearate, ie. C ₆ H 90 ₂ (C ₂ H ₄ O) ₂ o (OH) ₂ (C ₁₇ H ₃₅ COO) or sorbitan monostearate, ie C ₆ H ₉ O ₂ (OH) ₂ (C 17 H 35 COO), or sorbitan monopalmitate, ie C ₆ H ₉ O ₂ (OH) ₂ (C 15 H 31 COO); mixtures thereof. All these substances are commercially available under several trade names such as Glycosperse TS 20 from Lonza (polyethoxylated sorbitan tristearate), Glycosperse S 20 from Lonza (polyethoxylated sorbitan monostearate), Radiasurf 7145 from Fina (sorbitan monostearate), Radiasurf 7135 from Fopal (sorbitan sorbitan) MP from Azko (sorbitan monopalmitate). Furthermore, it has been found that the combination of ethoxylated sorbitan esters with nonethoxylated sorbitan esters provides a better effect than when each is separately.

A suitable example of an alkylaphodicarboxylic acid is Minarol ™ C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

The polyhydroxy fatty acid amides suitable for use herein have the structural formula R CONR Z, wherein R ¹ is H, a C 1 -C 4 hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy, or a mixture thereof, suitably C 1 -C 4 alkyl, more preferably C 1 -C 4 alkyl. C ₂ alkyl, most preferably Ci alkyl (i.e. methyl), and R ² is a C5-C31 hydrocarbyl, preferably linear alkyl or alkenyl chain C5 to C19, more preferably a straight alkyl or alkenyl chain C9 to C17 and most preferably a straight alkyl or alkenyl chain Cll- C17 or a mixture thereof and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon having at least 3 hydroxyls directly bonded to the chain or alkoxylated derivatives thereof (preferably ethoxylated or propoxylated). Z will preferably be derived from reducing sugars in reductive amination, more preferably Z will be glycityl.

Suitable fatty acid amides have the following structure: R ⁶ NOC (R ⁷ ) 2, wherein R ⁶ is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon atoms, and each R ⁷ is selected from hydrogen, C 1 to C 4 alkyl, C 1 to C 4 hydroxyalkyl, and - (C 2 H 4 O) _X H, wherein x is from 1 to 3. Suitable alkyl polysaccharides for use herein are described in U. S. Patent 4565647, Llenado, published Jan. 21, 1986, have a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide such as a polyglycoside, a hydrophilic group containing from 1.3 to 10 carbohydrate units.

Preferred alkyl glycosides have the formula

R ² O (C _n H _{2 n} O) t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof wherein the alkyl groups contain from 10 to 18, n is 2 or 3, t is from 0 to 10 and x is from 1.3 to 8. Glycosyl is suitably derived from glucose.

Suitable amine oxides include those compounds of formula R ³ (OR ⁴ ) _X N ° (R ⁵ ) 2 wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl, or mixtures thereof containing from 8 to 26 carbon atoms, R ⁴ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to 5, preferably from 0 to 3, and each R ⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3 or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. More preferably, C10 to C18 is alkyldimethylamine oxide and C10 to C18 is acylamidoalkyldimethylamine oxide.

Cationic surfactants

The cationic surfactants may contain surfactant components of the composition of the invention, suitably from 0.5% to 80% by weight of the component, preferably from 1% to 60%, preferably from 3% to 50% by weight of the component.

Suitably, the cationic surfactants are selected from the group consisting of cationic ester surfactants, cationic monoalkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants, and mixtures thereof.

Cationic mono-alkoxylated amine surfactants

Optionally, cationic monoalkoxylated amine surfactants for use herein have the formula:

R‘ / ApR *

2 ^ \ „3

X ·· · «· · · · · · · · · · · · · · · · · · · · ·

Π. ... Wherein R ¹ is an alkyl or alkenyl group containing from 6 to 18 carbon atoms, preferably from 6 to 16 carbon atoms, preferably from 6 to 11 carbon atoms, R ² and R ³ are each independently alkyl groups containing from one to three carbon atoms, preferably methyl, R ⁴ is selected from hydrogen (preferably), methyl and ethyl, X 1 is an anion such as chloride, bromide, methyl sulfate, sulfate, or similarly, generating electroneutrality, A is selected from C 1 to C 4 alkoxy, especially ethoxy (eg, -CH 2 CH 2 O-), propoxy, butoxy and mixtures thereof and is from 1 to 30, preferably 1 to 15, preferably 1 to 8.

Highly preferred cationic monoalkoxylated amine surfactants for use herein have the formula:

R ¹ ^ ^ / (CH ₂ CH ₂ O) i H ₅ / N ^+. x CH ₃ CH ₃ wherein R ¹ is Ce to hydrocarbyl and mixtures thereof, preferably Co-C14, especially to Cu alkyl, more preferably Cs to C10 alkyl, and X is any convenient anion to maintain the balance, preferably chloride or bromide. As noted, compounds of the foregoing type contain substances wherein the ethoxy (CH 2 CH 2 O) groups (EO) are replaced by butoxy, isopropoxy [CH (CH 3) CH 2 O] and [CH 2 CH (CH 3) O] groups (i-Pr) or n-propoxy units (Pr), or mixtures of EO or Pr or i-Pr groups.

Cationic bis-alkoxylated amine surfactants

The cationic bis-alkoxylated amine surfactants for use herein have the general formula:

ApR ³

X

A'qR ⁴ wherein R ¹ is an alkyl or alkylene group containing from 6 to 10 carbon atoms, preferably from 6 to 16 carbon atoms, more preferably from 6 to 11 carbon atoms and most preferably from 8 to 10 carbon atoms, R is an alkyl group containing one up to three carbon atoms, preferably methyl, R ³ and R ⁴ vary independently and are selected from hydrogen (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to establish elektroneutrality. A and A 'are independently of one another and each is selected from C 1 to C 4 alkoxy, in particular ethoxy, (eg, -CH 2 CH 2 O-), propoxy, butoxy and mixtures thereof, p is from 1 to 30, preferably from 1 to 4 and q has a value of from 1 to 30, preferably from 1 to 4, most preferably piq have a value of 1.

• ·

Highly preferred cationic bis-alkoxylated amine surfactants for use herein have the formula:

R ¹ ^ ^ 2 CH ₂ OH, ^{N +} \ ^X CH3 UH ₂ CH ₂ OH wherein R ¹ is C, to Cis hydrocarbyl and mixtures thereof, preferably Co, Cg, C10, C12, C14 alkyl and mixtures thereof, X is any convenient anion to form charge balance, better chloride. With reference to the general cationic bis-alkoxylated amines we have discussed earlier, hence, in the preferred compound R ¹ , it is derived from the (coconut) C 12 to C 14 fatty acid alkyl fraction, R ² is methyl and ApR ³ and A'qR ⁴ are any monoethoxy groups.

Other cationic bis-alkoxylated amine surfactants used herein include compounds of the general formula:

R ¹ - (CH ₂ CH ₂ O) pH ^{N +} 1 ^X R ² - (CH ₂ CH ₂ O) q H where R ¹ is a C 6 to C 18 hydrocarbon and mixtures thereof, preferably a C 6 to C 14, independently p is 1 to 3 and q is 1 R ³ is C 1 to C 3 alkyl, preferably methyl, and X is an anion, suitably chloride or bromide.

Other compounds of the above type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH (CH3) CH2O] and [CH2CH (CH3) O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO or Pr or i-Pr groups.

Surfactants may also include cationic ester surfactants. This is preferably a water-dispersed surfactant compound containing at least 1 ester bond (i.e., -COO-) and at least one cationic charged group. Suitable cationic ester surfactants including choline ester surfactants are described, for example, in U.S. Pat. U.S. Patents 4228042, 4239660 and 4260529.

Preferred cationic ester surfactants have the formula:

R.

^R 5 ^R 10 - (CH) _n O (X) _u - (CH ₂ ) _m - (Y) - (CH ₂ ), - NR ₃ where R 1 is C 5 to C ₃₁ linear or branched alkyl, alkenyl or alkaryl chain or MN ⁺ (R 6 R 7 R 8) (CH ₂ ) s, X and Y independently selected from the group consisting of COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO, wherein at least one X or Y is COO, φ · · ······························································· · · ·

OCO, OCOO, OCONH and NHCOO, R 2, R 3, R 4, R 6, R 7 and R 8 are independently selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, and C 1 -C 4 alkaryl groups and R 5 is independently H or a C 1 -C 3 alkyl group wherein the values of m, n, sat independently lie in the range of 0 to 20 and the values of a, u, v are independently either 0 or 1, provided that at least one u or v must be 1 and is the opposite anion.

Suitably, R 2, R 3 and R 4 are independently selected from CH 3 and -CH ₂ CH ₂ OH. More preferably, M is selected from the group consisting of halogen, methyl sulfate, sulfate and nitrate, more preferably methyl sulfate, chloride, bromide and iodide. Preferred water-dispersed cationic ester surfactants are choline esters having the structure:

O ch ₃

R 1 -CO-CH ₂ C ₁ -N-ClU ^M 'CH ₃ wherein R 1 is C 11 to C 19 linear or branched alkyl chain.

Particularly suitable cholinesters of this type include stearoylcholinester quaternized with methylammonium halide (R1 = C17 alkyl), palmitoylcholinester quaternized with methylammonium halide (R1 = C15 alkyl), myristoylcholinester quaternized with methylammonium halide (R1 = C13 alkyl), lauroylcholinester quaternized with methylammonium, methyoyl halide quaternized cocoylcholine ester (R 1 = C 11 to C 13 alkyl), methylammonium halol quaternized quaternized (R 1 = C 15 to C 13 alkyl), and mixtures thereof. In particular, given preferred choline esters can be prepared by direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, particularly in the presence of a solvent such as ethanol, propylene glycol or a suitable fatty alcohol ethoxylate, e.g., a C10 to C18 fatty alcohol ethoxylate with an ethoxylation degree of from 3 to 50 ethoxy. groups per mole of the desired cationic material formed. Choline esters can be prepared by direct esterification of a long fatty acid of the desired chain length together with 2-haloethanol in the presence of an acid catalyst. The reaction product is then quaternized with trimethylamine forming the desired cationic material.

Other suitable cationic ester surfactants have the structural formula below, wherein d can be from 0 to 20.

• · · · · · · · · · · · · · · · · · · · · · · · · · · · o

II ch ₃

Ri — OC— (ch ₂ ) —co-ch ₂ ch ₂ n-ch ₃ ^m ch ₃ ch ₃ oo ch ₃

I + II I ₊ II

M CH ₃ -N-CH ₂ -CH ₂ -O-C (CH ₂₎ c -O-CH ₂ -CH ₂ -N-CH ₃ m CH ₃ CH ₃

Amphoteric surfactants

Suitable amphoteric surfactants for use herein include amine oxide surfactants and alkylamphocarboxylic acids.

Suitable amine oxides include those compounds of formula R ³ (OR ⁴ ) _X N ° (R ⁵ ) 2 wherein R ³ is selected from alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl groups or mixtures thereof containing from 8 to 26 carbon atoms, R ⁴ is an alkylene or hydroxyalkyl group containing from 2 to 3 carbon atoms or mixtures thereof, x is from 0 to 5, preferably from 0 to 3, and each R ⁵ is an alkyl or hydroxyalkyl group containing from 1 to 3 or a polyethylene oxide group containing from 1 to 3 3 ethylene oxide groups. Preferred are C 10 -C 18 alkyldimethylamine oxide and C 10 -C 18 acylamidoalkyl dimethylamine oxide.

A suitable example of an alkylamphodicarboxylic acid is Miranol ™ C2M Conc. manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactants

Zwitterionic surfactants may also contain surfactant components of the composition of the invention or compositions comprising a particle of the 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 sultain surfactants are examples of zwitterionic surfactants used herein.

Suitable betaines are those compounds of formula R (R ') ² N ⁺ R2 COO' wherein R is a C 6 to C 6 hydrocarbyl group, each R ¹ is normally a C 1 to C 3 alkyl and R ² is a C 1 to C 5 hydrocarbyl group. to Ci? ammonium dimethylhexanoate and C10 to C18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. A betaine surfactant complex is also suitable for use herein.

9 9

9 9 9

9 9 9 · 9 9 9

Alkali metal silicate salts

The granular compositions herein may contain alkali metal silicate salts or mixtures thereof among optional preferred ingredients. The preferred alkali metal silicate salt for use herein is sodium silicate. In a preferred case, where the granular compositions contain an oxygen bleach and are normally intended to be soaked, it has been found that the decomposition of available oxygen that occurs in the soaking solutions before dissolving the granular compositions is reduced by the presence of at least 40 ppm sodium silicate in said soaking solutions.

Any type of alkali metal silicate salt, including the crystalline form, as well as the amorphous form of said alkali metal silicate salt or mixtures thereof can also be used herein.

Suitable crystalline forms of sodium silicate are crystalline layered silicate granules of the formula

NaMSi _x O 2 _{+ X} i. Y H ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, or mixtures thereof. Crystalline layered sodium silicates of this type are described in EP-A-164514 and methods for their preparation are described in DE-A-3417649 and DE-A-3742043. For purposes of the present invention, x in the above general formula has values of 2, 3 or 4, and more preferably 2. More preferably, M is sodium and y is 0, and preferred examples of this formula include a, b, g, and g of the Na 2 S 2 O 5 s. These materials are available from Hoechst AG FRG, respectively NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6. The most preferred material is d - Na 2 S 2 O 2 s, NaSKS-6. Crystalline layered silicates are incorporated into the wetting compositions herein either as dry solid mixtures or as solid components of agglomerates with other components.

Suitable amorphous forms of sodium silicate for use herein have the following general formula.

NaMSi _x O _2x + wherein M is sodium or hydrogen and x is a number from 1.9 to 4, or mixtures thereof. Preferred for use herein are the amorphous forms of Si 2 O 5 Na 2 O.

Suitable zeolites for use herein are aluminosilicates containing those according to the empirical formula: M _z (zA 102, y SiO ₂ ) wherein M is sodium, potassium, ammonia or substituted ammonia, z is from 0.5 to 2 and y is 1. This material has a capacity for the magnesium ion exchange of at least about 50 mg CaCCh ion hardness equivalents per gram of anhydrous aluminosilicate.

• * • · · · · · · · · · · · · · · · · · · ·

Preferred zeolites have the formula:

On _September (A102) z (Si0 _2), Yu. x H ₂ O where z and y are indices of at least 6, the molar ratio of z to y ranges from 1 to 0.5, x is the index from 15 to 264.

The materials used are commercially available. These aluminosilicates may have a crystalline or amorphous structure and may be natural or synthesized. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials used herein are available under the designations Zeolite A, Zeolite P (B) and Zeolite X. In a particularly preferred case, the crystalline aluminosilicate ion exchanger has the formula:

Nai ₂ (AlO ₂ ) i ₂ (SiO ₂ ) i ₂ .xH ₂ O where x is from 20 to 30, in particular 27. This material is known as Zeolite A. The aluminosilicate has a particle size in average of from 0.1 to 10 microns in diameter. .

Typically, the compositions herein may contain from 0.5% to 15% by weight of the total alkali metal silicate salt composition or mixtures thereof, preferably from 1% to 10%, and most preferably from 2% to 7%.

Building materials

The granular composition may also contain builders or mixtures thereof. All builders known in the art can be used herein. Suitable phosphate builders used herein include potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from 6 to 21, and orthophosphate. Other phosphorus builders are described in U.S. Pat. S. Patent 3159581, 3213030, 3422021, 3422137, 3400176 and 3400148, incorporated herein by reference. Suitable polycarboxylate builders for use herein include ether polycarboxylate compounds, including oxydisuccinate, as described in Berg, US 3128287, issued April 7, 1964, and Lamberti et al., US 3635830, issued January 18, 1972. See also "TMS / TDS" US Patent 4663071, Bush et al., Issued May 5, 1987. Suitable ether polycarboxylates also include cyclic, especially alicyclic compounds, such as those described in US Patents 3923679, 3835163, 4120874 and 4102903.

Other suitable builders are ether hydroxypolycarboxylates, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, a series of alkali metals, ammonium and substituted ammonium salts of polyacetic acids, e.g.

Ethylenediaminetetraacetic acid, nitrilotriacetic acid as well as melitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and their soluble salts.

Also suitable in the granular compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the like described in U.S. Pat. S. Patent 4566984, Bush, issued Jan. 28, 1986. Succinic acid builders used include C5 to C20 alkyls and alkenylsuccinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Particular examples of succinate builders are: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate and the like. Lauryl succinates are a preferred class of builders and are described in European Patent Application 86200690.5, November 5, 1986, 1986.

Other suitable polycarboxylate builders are described in U.S. Pat. S. 4,144,226, Crutchfield et al., Issued Mar. 13, 1979, and U.S. Pat. S. 3308067, Diehl, issued Mar. 7, 1967. See also Diehl, U.S. Patent 3723322.

Other suitable polycarboxylate builders for use herein are builders according to the formula:

R ¹ _Yp _ (- CH ₂ - CR ³ -) _ R ²

AND

CO ₂ M n where Y is a comonomer or comonomer mixture, R ¹ and R ² are bleaches and alkali-stable polymeric ends, R ³ is H, OH or C 1 -C 4 alkyl, M is H, alkali metal, alkaline earth metal, ammonium and substituted ammonium salts, p is from 0 to 2 and n is at least 10, or mixtures thereof.

Preferred polymers used herein fall into two categories. The first category belongs to the class of copolymeric polymers that have been formed from unsaturated polycarboxylic acids such as maleic, citraconic, itaconic, mesaconic and their salts as the first monomer and unsaturated monocarboxylic acids such as acrylic or alpha-C 1 -C 4 alkyl acrylic acid as the second monomer. Referring to Formula I hereinabove, the polymers belonging to said first group are those wherein p is not 0 and Y is selected from the acids enumerated above. Preferred polymers of this class are those of formula I above, wherein Y is maleic acid. Also, in preferred cases, R ³ and M are hydrogen and n is such that the polymers have a molecular weight of from 1000 to 400,000 atomic mass units.

····························

A second category of preferred polymers used herein belongs to the class of polymers in which, according to formula I above, p is R ³ is hydrogen or C 1 -C 4 alkyl. In preferred cases, n is such that the polymers have a molecular weight of from 1000 to 400,000 atomic mass units. In very preferred instances, R ³ and M are hydrogen.

The groups of the alkali-stable polymeric ends R ¹ and R ² in formula (I) above suitably comprise alkyl groups, oxyalkyl groups and alkylcarboxyl groups, and salts and esters thereof.

The above index n is the degree of polymerization of the polymer and can be determined from the average molecular weight of the polymer divided by the average molecular weight of the monomer. Thus, for a maleic-acrylic copolymer with an average molecular weight of 15,500 and containing 30 mol% of maleic acid derived units, n is 182 (i.e., 15,500 / (116 x 0.3 + 72 x 0.7)). Temperature controlled columns at 40 ° C versus sodium polystyrene sulfonate polymer standards, available from Polymer Laboratories Ltd., Shropshire, UK, polymer standards are 0.15M sodium dihydrogen phosphate and 0.02M tetramethylammonium hydroxide at pH 7.0 in water / acetonitrile 80 : 20.

All of the above-mentioned preferred polymers used herein are the first category wherein n is on average from 100 to 800, preferably from 120 to 400.

Preferred builders for use herein are maleic and acrylic acid polymers or maleic and acrylic acid copolymers.

Typically, the granular composition of the present invention comprises up to 50% by weight of the total builder composition or mixtures thereof, preferably from 0.1% to 20%, and most preferably from 0.5% to 11%.

Chelating agents

Preferably, the granular compositions herein further comprise chelating agents or mixtures thereof. Chelating agents are required here to help control the level of heavy metal ions in the wash / soak solutions, thus avoiding rapid decomposition of residual oxygen with the oxygen bleach. Suitable aminocarboxylate chelating agents which may be used herein include ethyldiaminetetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraamine hexaacetates and ethanediglycines, alkali metal salts, ammonium salts or mixtures thereof. Other suitable chelating agents include ethylenediamine-N, N'-disuccinic acid (EDDS) or alkali metal, alkaline earth, ammonium or substituted ammonium salts.

Particularly suitable EDDS compounds are the free acid and the sodium or magnesium salt or complex thereof. Other suitable chelating agents may also be organic phosphonates, including aminoalkylene poly (alkylene phosphonate), alkali metal ethane-1-hydroxydiphosphonates, nitrilotrimethylene phosphonates, ethylenediaminetetramethylene phosphonates, and diethylenetriaminepentamethylene phosphonates. These phosphonate compounds may be present either in acid form or in the form of their alkali metal salts. Suitably, the organic phosphonate compounds are present in the form of magnesium salts.

The granular compositions of the present invention may accordingly contain from 0% to 5% by weight of the total chelating agent composition, more preferably from 0% to 3%, most preferably from 0.05% to 2%.

Filler

The granular composition may further comprise a filler, such as an inorganic salt filler, e.g., sulfates. Typically, the composition of the present invention comprises up to 50% by weight of the total filler composition or mixture thereof, preferably from 0.1% to 20%, and most preferably from 0.5% to 10%.

Enzymes

The granular compositions herein also normally contain enzymes or a mixture thereof. Preferably, the compositions herein comprise a protease or mixtures thereof. Protease enzymes are generally present in preferred embodiments of the invention in an amount sufficient to provide an activity of from 0.005 to 0.2 Anson units (AU) per gram of composition. Proteolytic enzymes may be derived from animals, vegetables or, preferably, microorganisms. More preferred is a serine proteolytic enzyme of bacterial origin. Purified or unpurified forms of enzymes may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are defined as close structural enzyme variants. A particularly preferred proteolytic enzyme is a serine proteolytic enzyme derived from Bacillus, Bacillus subtilis or Bacillus licheniformis. Suitable common proteolytic enzymes are contained in Alcalase®, Esperase®, Durazym®, Savinase®, Maxatase®, Maxacal® and Maxapem® 15 (protein produced by Maxacal), Purafect®, and subtilisin BPN and BPN 'are also commercially available. Preferred proteolytic enzymes also include modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87303761.8, issued April 28, 1987 (particularly pages 17, 24, and 98), which is called "Protease B" and in European Patent Application 199,404, Venegas, published Oct. 29, 1986, which relates to a modified bacterial serine proteolytic enzyme, referred to herein.

"Protease A". More preferred is an enzyme, herein termed "Protease C", which is a triple variant of the Bacillus alkaline serine protease in which tyrosine is replaced at valine at position 104, serine is replaced by asparagine at position 123 and alanine is replaced by threonine at position 274. Protease C is disclosed in EP 90915958.4, corresponding to WO 91/06637, published May 16, 1991, which is incorporated herein by reference. Also included are genetically modified variants, particularly Protease C.

Also suitable for use herein is a protease designated as "Protease D", which is a carbonyl hydrolase variant with an amino acid sequence not yet found in nature, which is derived from a carbonyl hydrolase precursor by substituting a different amino acid for a variety of amino acid residues at said carbonyl hydrolase position. which are selected from the group consisting of +99, +101, +103, +107 and +123 in Bacillus amyloliquefaciens subtilisin, as described in co-pending patent application A. Baeck, CK Ghosh, PP Greycar, RR Bott and LJ Wilson, entitled "Protease-containing Cleaning Compositions" No. 08 / 136,797 (P & G Time 5040) and " Bleaching Compositions Comprising Protease Enzymes " 08/136626, incorporated herein by reference.

Some preferred proteolytic enzymes are selected from the group consisting of Savinase, Esperase ®, Maxacal ®, Purafect ®, BPN ', Protease A and Protease B, and mixtures thereof. Bacterial serine protease enzymes derived from Bacillus subtilis and / or Bacillus licheniformis are preferred. Savinase®, Alcalase®, Protease A and Protease B are particularly suitable.

Conventionally granulated compositions also contain amylase or mixtures thereof. The production of enzymes with increased stability, e.g., oxidative stability, is known. See. e.g., J. Biological Chem., Vol. 260, no. 11, June 1985, pp. 6518-6521. "Reference amylase" further refers to amylase outside the amylase component of the invention and against which the stability of any amylase of the invention can be measured.

The present invention thus utilizes amylases with increased stability to detergents, especially with increased oxidative stability. A suitable absolute stability of the reference point against which the amylases used in the invention show a measurable improvement is the stability of TERMAMYL® commonly used in 1993 available from Novo Nordisk A / S. This TERMAMYL® amylase is a 'reference amylase'. Amylases within the spirit and scope of the present invention share the amylase feature with an "enhanced stability" characterized by a minimally measurable improvement in one or more stability: oxidative stability, i.e. for hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10, thermal stability, i.e. for a normal wash temperature of 60 ° C or alkaline stability, i.e. at a pH of from 8 to 11, all measured against the above reference amylase.

• · • ·

Preferred amylases herein may demonstrate further improvements over much more demanding reference amylases, these reference amylases being demonstrated by any amylase precursors that are variants of the amylases of the invention. Such amylase precursors may be natural or genetic engineering products. Stability can be measured by any of the expert tests described in the art. See, for example, the references described in WO 94/02597, which is incorporated herein by reference.

In general, amylases with enhanced stability can be obtained from Novo Nordisk A / S or Genencor International.

Preferred amylases herein are generally obtained using site-directed mutagenesis of one or more amylases, particularly Bacillus-derived amylases, in particular Bacillus α-amylases, although one, two or all amylase strains are direct precursors.

As mentioned, the "enhanced oxidative stability" of amylases for use herein is preferred. Such amylases are described, without limitation, by the following:

a) Amylase according to WO / 94/02597 previously incorporated herein, Novo Nordisk A / S, published February 3, 1994, as further illustrated by a mutant in which alanine or threonine (especially threonine) methionine residue located at position 197 of aamylase is substituted Bacillus licheniformis, known as TERMAMYL or the homologous position of a variant of parental amylase-like, e.g. Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearotherrnophilus.

(b) Amylases with enhanced stability described by Genencor International in the article entitled "Oxidatively resistant alpha-Amylases" presented by C. Mitchinson at the 207th American Chemical Society Meeting, 13-17 March 1994. It is noted that bleaches in detergents intended for automatic dishwashing inactivates α-amylases but does not increase the oxidative stability of B. licheniformis amylases NCEB8061 manufactured by Genencor. Methionine (Met) was identified as the most suitable residue for modification. The methionine was substituted one at a time at positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, of particular importance being the M197L and the M197T with the M197T variant being the most stably expressed variants. Stability was measured on CASCADE® and SUNLIGHT®. Such enzymes are commercially available from Genencor under the tradename Plurafact Oxam.

c) Particularly preferred herein are amylase variants with added modification in direct parent form, available from Novo Nordisk A / S. These enzymes do not yet have a trade name, but are supplied by the supplier as QL37 + M197T. These enzymes are commonly available under the tradename SP 703 from Novo.

• · · ·

Any other amylases with increased oxidative stability, for example, derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases, may also be used.

Stain suspending agents

The granular compositions herein may also contain an impurity suspending agent or mixture thereof, typically in an amount of up to 20% by weight, preferably from 0.1% to 10%, preferably from 0.5% to 2%. Suitable soil suspending agents are ethoxylated diamines, ethoxylated polyamines, ethoxylated amine polymers as described in EP-A-112 593, incorporated herein by reference. A preferred soil suspending agent for use herein includes ethoxylated polyethylene amine having a molecular weight of from 140 to 310 prior to ethoxylation, ethoxylated 15-18 tetraethylenepentaamine, ethoxylated 15-18 polyethyleneamine, ethoxylated 15-18 ethylenediamine, ethoxylated polyethyleneimine molecular weight from 600 to 1800 prior to ethoxylation. mixtures thereof.

Soap suppressor system

The detergent compositions of the present invention, when formulated for use in washing machine compositions, preferably comprise a suds suppressor system, are present in an amount of from 0.01% to 15%, more preferably from 0.05% to 10%, and most preferably from 0, 1% to 5% by weight of the composition.

Suitable suds suppressor systems used herein may comprise substantially any known antifoam compound, including, for example, silicone antifoam compounds and 2alkylalkanol antifoam agents.

By antifoam compound is meant herein any compound or mixture of compounds that behaves in such a way that it suppresses foaming or suds formation caused by a detergent solution solution, particularly while stirring such a solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds, defined herein as any antifoam agent comprising a silicone component. Such antifoam silicone compounds also commonly contain silica gel. The term " silicone " as used herein and as generally used throughout the art includes a number of relatively high molecular weight polymers containing siloxane units and various types of hydrocarbon groups. Preferred silicone antifoam compounds are siloxanes, especially polydimethylsiloxanes with trimethylsilyl terminal block units.

• ·

Other suitable antifoam compounds are monocarboxylic fatty acids and soluble salts thereof. Such materials are described in U.S. Pat. No. 2954347, issued Sep. 27, 1960 to Wayne St.; John. The monocarboxylic fatty acids and their salts used as suds suppressors typically have a hydrocarbon chain of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanolammonium salts.

Other suitable antifoaming compounds are, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₄ to the ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di to tetraalkyldiamine chlorotriazines formed as products of the reaction of cyanuric chloride with two or three moles of a primary or secondary amine of 1 to 24 carbon atoms, propylene oxide, bisstearic acid amide and monostearyl alkali metal phosphates (e.g. sodium, potassium, lithium) and phosphate esters.

Preferred suds suppressor systems include:

(a) an antifoam, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination:

(i) a polydimethylsiloxane in an amount of from 50% to 90%, preferably from 75% to 95% by weight of a silicone antifoam; and (ii) silica gel in an amount of from 1% to 50%, preferably from 5% to 25% by weight of a silicone / silica gel. a compound wherein said silicone / silica gel antifoam compound is included in an amount of from 5% to 50%, preferably from 10% to 40% by weight

b) a dispersion compound, preferably containing a silicone glycol polymer having a polyoxylakylene content of 72% to 78% and an ethylene oxide to propylene oxide ratio of from 1: 0.9 to 1: 1.1, in an amount of from 0.5% to 10%, cleaved% to 10% by weight, a particularly preferred silicone glycol polymer of this type DCO544, commercially available from DOW Corning under the trade name DCO544,

c) an inert carrier liquid, preferably containing a C 16 to C 18 ethoxylated alcohol having an ethoxylation degree of from 5 to 50, preferably from 8 to 15, in an amount of from 5% to 80%, preferably from 10% to 70% by weight.

A very preferred suds suppressor system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier having a melting point in the range of 50 ° C to ° C, wherein the organic carrier comprises glycerol monoester and a C12 -C20 fatty acid. carbon. EP-0210721 discloses another preferred suds suppressor system wherein the organic carrier is a fatty acid or alcohol having a carbon chain of from 12 to 20 carbon atoms, or a mixture thereof with a melting point of from 45 ° C to 80 ° C.

Clay softening systems

The detergent composition of the present invention, conventionally intended for washing laundry in household washing machines, may comprise a clay softening system comprising clay mineral compounds and optionally a clay flocculating agent.

The clay mineral compound is a preferred smectic clay compound. These compounds are described in U.S. Pat. Patents 3862058, 3948790, 3954632 and 4062647. European Patents EP-A-299575 and EP-A-313146 on behalf of Procter & Gamble disclose suitable organic polymeric flocculating agents.

Polymeric dye transfer inhibiting agents

The detergent composition of the present invention, typically intended for washing laundry in household washing machines, may also contain from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of the polymeric dye transfer inhibiting agent.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein include units with the following structural formula:

P

I (I) A _x

AND

R where P is a polymerizable unit and A is

0 0 I I

NC, CO, C, -O-, -S-, -N-, x is 0 or 1

R are aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, wherein the nitrogen of the N-O group can be attacked or wherein the nitrogen of the N-O group is part of these groups.

• · ·

The following general structures may be an N-O group:

O = T (R 1) _x N- (R ₂ ) _y or = N- (R 1) _x (R ₃ ) z wherein R 1, R ₂ and R 3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, wherein x or y or z are 0 or 1 and wherein the nitrogen of the N-O group may be attached or wherein the nitrogen of the N-O group is part of these groups. The N-O group may be part of a polymerizable unit (P) or may be attached to a backbone polymer chain or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerizable unit include those polyamine N-oxides wherein R is selected from aliphatic, aromatic, heterocyclic or alicyclic groups. One class of said polyamine N-oxides comprises a group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group, e.g., pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are polyamine N-oxides wherein the N-O group is attached to the polymerizable unit. A preferred class of these polyamine N-oxides comprises a polyamine N-oxide of formula (I) wherein R is aliphatic, aromatic, heterocyclic or alicyclic, wherein the nitrogen of the N-O group is part of said R group. Examples of these classes are polyamine N-oxides wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole and derivatives thereof.

Polyamine N-oxides can be obtained at almost any degree of polymerization. The degree of polymerization is not critical provided the material is water-soluble and the color-suspending powder as desired. Typically, the average molecular weight is in the range of 500 to 1,000,000.

b) N-vinylpyrrolidone and N-vinylimidazole copolymers

Here, copolymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight in the range of 5,000 to 50,000 are suitable. Preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1 to 0.2.

c) Polyvinylpyrrolidone

Detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") with an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trade name PVP K-15. (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000), and PVP K-90 (average molecular weight 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polyvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2500 to 400,000.

(e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2500 to 400,000.

Optical brighteners

Optionally, the detergent compositions herein comprise from 0.005% to 5% by weight of a particular type of hydrophilic optical brightener.

The hydrophilic optical brighteners used in the present invention have the structural formula:

wherein 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-methylamine, morpholine, chlorine and amine, and M is a cation-forming salt such as sodium or potassium. When R1 is aniline in the above formula, R2 is N-2-bis-hydroxyethyl and M is a cation, e.g. sodium, is a brightener of 4,4'-bis [(4-aniline-6- (N-2-bishydroxyethyl)) -s-triazin-2-yl) amine] -2,2'-stilbenedisulfonic acid and the disodium salt. This particular type of brightener is commercially marketed under the trademark Tinopal-UNPA-GX,

Ciba-Geigy Corporation. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions herein.

When R1 is aniline in the above formula, R2 is N-2-hydroxyethyl-N-2-methylamine and M is a cation, e.g. sodium, the brightener is 4,4'-bis [(4-aniline-6-) disodium salt. (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amine] -2,2'-stilbenedisulfonic acid. This particular type of brightener is commercially marketed under the trademark Tinopal 5BM-GX, Ciba-Geigy Corporation. In the above formula, when R ₁ is aniline, R ₂ is morphilin and M is a cation, e.g. sodium, the brightener is 4,4'-bis [(4-anilino-6-morphilin-s-triazin-2-yl) acid (amine) -2,2'-stilbenedisulfonic acid. This particular type of brightener is commercially marketed under the trademark Tinopal ASM-GX, CibaGeigy Corporation.

Cationic laundry softening agents

A cationic laundry softening agent may also be included in the granular compositions of the present invention. Suitable cationic fabric softening agents include water-insoluble tertiary amines or long chain amides as described in GB-A-1 514 276 and EP-B-0 011 340. Cationic fabric softening agents are typically incorporated in amounts ranging from 0.5 % to 15% by weight, usually from 1% to 5% by weight.

Method of soaking clothes

The present invention includes a method of soaking laundry. In fact, the present invention comprises a method of soaking laundry wherein said laundry is immersed in a soaking solution comprising water and an effective amount of a granular composition as described hereinbefore for an effective period of time, then removed from said soaking solution.

As used herein, the term "laundry soaking method" refers to a method of allowing laundry to soak in a soaking solution containing water and a composition as described herein before for a time sufficient to clean said laundry. Compared to the normal washing method used in washing machines, the soaking method allows an extended contact time of the laundry and the soaking solution normally up to 24 hours. The soaking method may be performed independently of any method, such as a typical washing method or a first step before a second typical washing step, or a second step after a first typical washing step. In a preferred soaking process of the invention, the laundry is soaked in the soaking solution for a period of from 1 minute to 24 hours, more preferably from 10 minutes to 24 hours, and most preferably from 30 minutes to 18 hours, and most preferably from 1 hour to 6 hours. After the laundry has been soaked for a sufficient time in said soaking solution, it can be removed and rinsed in water. The laundry may also be laundered in a normal washing manner after it has been soaked, with or without rinsing in an intermediate soak step, and then laundered.

In the dipping process herein, the dipping composition described above is dissolved in an adequate amount of water to form a dipping solution. A suitable dosage is in the range of from 40 to 55 grams of wetting agent per 3.5 to 5 liters of water, up to 90-100 grams of wetting agent per 20 to 45 liters of water. Normally, one dose for concentrated soak (bucket / sink) is 40 to 55 grams per 3.5 to 5 liters of water. For washing machines, the dosage is 90 to 100 grams per 20 (Europe) to 45 (United States) liters of water. In order to soak the laundry, it is immersed in the soaking solution for a reasonable period of time. These are factors that affect the overall removal of stains caused by different mud / dirt patterns. These factors include extended soaking time. Of course, the longer the laundry is soaked, the better the result. Thus, the instructions for the perfect use of a commercially available soaking agent recommend that the soaking time is overnight, i.e. 8 hours to 24 hours. An advantage of the present invention is effective results obtained even for a short soaking time, typically less than 30 minutes. Other factors are the initial warm or near warm temperature. Of course, higher initial temperatures of the soaking solutions ensure greater success. Another advantage of the present invention is the effective result obtained even at a lower soaking temperature, normally below 30 ° C or even below 20 ° C.

This method is suitable for cleaning a variety of laundry, but it is suitable for soaking socks, which are mainly from mud or clay.

Method of washing clothes in household washing machines

The present invention comprises a method of washing laundry. In fact, the method of washing laundry in domestic washing machines, which comprises dispensing into an intermediate dispensing device that is placed in a washing machine drum or dispenser drawer, comprises an effective amount of a granular detergent composition containing dry effervescent granules as described herein.

Methods of washing laundry in a washing machine herein generally comprise treating the soiled laundry in an aqueous washing solution in a washing machine that is dissolved or dispersed in the solution with an effective amount of a detergent composition for washing machines in accordance with the invention. By an effective amount of a detergent composition is meant from 40 g to 300 g of product dissolved or dispersed in a wash solution of from 5 to 65 liters, such as conventional product dosing and washing solution volumes generally used in conventional washing machines.

In a preferred use, the dispensing device is used in a laundry process. The dispenser counts on the detergent product and is used to introduce the product directly into the drum.

washing machines before the start of the washing cycle. Its volume capacity should be such that it is able to accommodate a sufficient amount of the cleaning agent normally used in washing. The washing machine was filled with laundry detergent, which was in a dosing device placed in the drum of the washing machine. At the beginning of the wash cycle, water flows into the drum and the drum rotates periodically. The appearance of the dispensing device should be such as to allow the contents of the dry detergent composition, but then, during the wash cycle, to remove this product in response to the rotation of the drum and also as a result of its contact with the wash water.

To allow removal of the detergent composition during washing, the device may have a number of gaps through which the product may pass. Alternatively, the device may be made of a material which is permeable to water but impermeable to solid products and which allows the removal of insoluble products. Preferably, the detergent products will be quickly removed at the beginning of the wash cycle, thereby providing a transient localized high concentration of product in the drum of the washing machine during the wash cycle phase. Preferred dispensing devices are reusable and are constructed in such a way that the package can be used in both stages, drying and washing cycle. Particularly preferred dispensing devices for use with the composition of the invention have been described in the following patents: GB-B-2,157,717, GB-B-2,157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. In the article

J. Blanda, published in Manufacturing Chemist, November 19889, pages 41-46, also discloses a particularly preferred dispensing device for the use of granular laundry products, commonly known as "granules". Other preferred dispensing devices for use in the compositions of the invention are described in PCT Patent Application No. 5,940,549. WO94 / 11562. Particularly preferred dosing devices are described in European Patent Application Publication No. 0343069 and 0343070. Later applications disclose a device comprising a flexible pouch in the form of a cam that projects from a support ring precisely defining an aperture, the aperture being adapted to receive sufficiently product into the pouch for one wash wash cycle. A portion of the wash medium flows through the opening into the pouch, dissolves the product, and the solution then passes out through the opening into the wash medium. The support ring is provided with a cover device to prevent the outflow of wet and undissolved product, the device commonly comprising radially spaced walls extending from a central location in a radially circular configuration or similar structure in which the walls have a spiral shape. Alternatively, the dispensing device may be a flexible container, such as a bag or bag. The bag may have a fibrous structure coated with a protective material that is impermeable to water to prevent leakage of the contents as described in published European Patent Application No. 5,960,519. Alternatively, a water-insoluble synthetic polymeric material may be provided with a serrated cap or cap designed to break in an aqueous medium as described in European Patent Application No. 0018678. 0011500, 0011501

A suitable shape of the water-frangible closure comprises a water-soluble adhesive that is used to seal one edge of a bag made of a water-impermeable polymer film, such as polyethylene or polypropylene.

Packaging of granular compositions

Commercially available granular compositions may be packaged in any suitable packaging made of paper, cardboard, plastic and any plastic material.

Granular form

Granular compositions can be made by a variety of methods including dry mixing, extrusion, compression, and agglomeration of a variety of ingredients included in the detergent composition. The dry effervescent granules of the invention may be included in the cleaning compositions as a separate component of the composition or may be incorporated into or added to any of the components or compounds of the compositions.

The cleaning compositions take a variety of physical forms including granules, chips, extrudates, tablets or a piece of soap. Detergents are particularly so-called concentrated granular detergent compositions adapted to be dispensed by a dispensing container or dispensing device disposed in a washing machine drum into the washing machines together with the soiled laundry.

The intended particle size of the granular detergent base component comprising the foaming agent in accordance with the invention may be from 0.1 mm to 5 mm, but it would be preferable that no more than 5% of the particles be larger than 2.5 mm in diameter, or above 1.7 mm and not more than 5% of particles smaller than 0.15 mm in diameter.

The term particle size as defined herein is calculated by sieving a sample of the composition onto a plurality of fractions (typically 5 fractions) through Tyler screens. The weight of the fractions thus obtained is plotted against the aperture size of the sieves. The intended particle size is such that 50% of the sample weight passes through the orifice size.

The bulk density of the granular detergent composition containing the particulate components in accordance with the present invention is typically at least 300 g / l, preferably from 500 g / l or over 650 g / l to 1200 g / l, most preferably up to 850 g / l.

Test method for removing stains

The composition removes stains from soiled laundry, e.g. under soaking conditions in the following test method. The soaking solution is formed by dissolving, for example, 45 g of the soaking agent in 3.78 liters of water or 90 g of the soaking agent in 45 liters of water.

• · · · · · · · · · · · · · · ·

The laundry is then soaked in the resulting soaking solution for a period of 1 minute to typically 18 hours. Finally, the laundry is removed from the soaking solution, rinsed in water and washed in a conventional washing manner, manually or in a washing machine, with a conventional detergent, with or without re-use of the soaking solution, then the laundry is removed and dried.

For example, commonly soiled laundry for use in this test may be commercially available from EMC (Empirical Manufacturing Company) of Cincinnati, Ohio, USA, such as clay, grass, spaghetti juice, sauces, motor oil, barbecue sauces, blood on various surfaces: Cotton (CW120) and Cotton (PCW28).

The stain removed can be evaluated by comparing the site from the spot of the soiled laundry treated with the composition of the present invention to those of the citations, e.g. the same composition without these dry effervescent granules of the present invention. An optical gradient scale is used to determine the difference in graduations on the scale (psu), ranging from 0 to 4.

Temperature stability test method

To evaluate the thermal stability of the composition, a sample was placed in an oven where the temperature was set at 60 ° C. When the sample reaches 60 ° C, it is isolated in its adiabatic bell and the temperature is monitored for 2 hours. The heating rate is determined (SHR, average temperature increased over the first two hours). The lower the SHR, the more stable the composition.

Efficiency test method

The summity of a given granular composition can be measured by optical gradient. The composition of the present invention and the citation of the composition without dry effervescent granules, or the quotations wherein the effervescent materials are uniformly and separately distributed throughout the granular composition, are each separately dissolved in 5 liters of water at 35 ° C and the resulting formation of CO 2 is determined optically.

Test method of dissolution

The dissolution of the granular composition can be measured optically. The composition of the present invention and citations of the composition without dry effervescent granules or citations wherein the effervescent materials are uniformly and separately distributed throughout the granular composition are each separately dissolved in 2 liters of water at 5 ° C. Then the water is evaporated on a standard black cloth evaporator instead of a paper filter. The optical gradient measure can be used to determine the difference in scale (psu) scale, ranging from 0 to 4.

• • •

Test method of dosing

Dosing can be evaluated by a standard test used in washing machines by placing a given amount of the composition in the dispenser and water for a given time. The dry weight of the laundry detergent remaining in the dispenser is then measured in grams and the weight percent of the non-dosed detergent composition is calculated.

Bulk density test method

The bulk density of the granular composition and / or the dry effervescent granules of the present invention can be measured by a simple funnel and mug apparatus consisting of a conical funnel attached to the base and provided with a valve at its lower end to release the funnel contents into a cylindrical container. The funnel is 130 mm high and has an inner diameter of 130 mm and 40 mm at its upper and lower ends. It is fixed so that the lower end is 140 mm above the top shell of the base. The mug has a total height of 90 mm, an inner height of 87 mm and an inner diameter of 84 mm. Its volume is 500 ml. For measurement, the funnel is manually filled with powder, the valve is opened and the powder is poured into the cup. The filled mug is removed from the machine, the excess powder is removed by aligning the edge with, for example, a knife. The filled cup is then weighed and the value obtained for the powder weight is doubled to obtain a bulk density in g / l. If required, the measurement is repeated.

EXAMPLES OF EMBODIMENTS OF THE INVENTION

Example 1: Soaking agents.

The following soaking compositions are formed by mixing the listed ingredients in the indicated proportions:

Component 1 2 3 % w / w % w / w % w / w sodium percarbonate 22nd 22nd 22nd ethoxylated alcohol EO 25 2 - - ethoxylated alcohol EO 11 - 2 - ethoxylated alcohol EO 50 - - 2 non-ionic (LAS / AS / AES) 8 8 8 DTPA 0.2 0.2 0.2 TAED 8.3 5 5 dry sparkling granules sodium bicarbonate 40% sodium carbonate 16% malic acid 44% 20 May 10 10 minor and inert substances to 100 do.100 to 100

Folders 4 5 6 % w / w % w / w % w / w sorbitan monostearate (SMS) 2.5 - - sorbitan monostearate EO20 (SMS EO 20) - 3.0 - sorbitan tristearate EO 20 (STS EO 20) 0.5 - 3.0 citric acid 10 10 10 polyacrylate (Acusol 445 ND®) 11 11 11 sodium percarbonate 31 31 31 NOBS 6 6 6 TAED 5 5 5

♦ *

non-ionic (LAS / AS / AES) 7 7 7 alcohol EO 25 2 2 2 dry sparkling granules sodium bicarbonate 40% sodium carbonate 16% malic acid 40% citric acid 4% 20 May 20 May 20 May other inert and minor substances to 100 to 100 to 100

Folders 7 8 9 % w / w % w / w % w / w sodium percarbonate 22nd 22nd 22nd ethoxylated alcohol EO 25 2 - - non-ionic (LAS / AS / AES / NaPS) 10 10 10 enzymes (amylase, lipase, protease) 1.9 1.9 1.9 zeolites 6.0 4.0 2,0 polymers (polycarboxylate, carboxy methylcellulose) DTPA 0.2 0.2 0.2 TAED 8.0 8.0 8.0 NOBS 4.0 - - brightener 0.15 0.15 0.15 zinc phthalocyanide sulfonate 0.06 0.06 0.06 hydroxyethylidene diphosphonate 0.18 0.18 0.18 dry sparkling granules sodium bicarbonate 40% sodium carbonate 10% malic acid 44% LAS 6% 20 May 15 Dec 10 minor and inert substances to 100 to 100 to 100

TAED is tetracetyl ethylene

NOBS is n-nonanoyloxybenzene sulfonate NaPS is sodium paraffin sulfonate DTPA is diethylene triamine pentaacetic acid LAS is O 2 alkylbenzene sulfonate

Folders 10 11 12 % w / w % w / w % w / w sodium percarbonate 45 40 35 non-ionic (LAS / AS / AES / NaPS) 8 8 8 DTPA 0.2 0.2 0.2 TAED 8.3 8.3 8.3 brightener 0.15 0.15 0.15 zinc phthalocyanide sulfonate 0.06 0.06 0.06 enzymes (amylase, lipase, protease) 1.9 1.9 1.9 dry sparkling granules sodium bicarbonate 40% sodium carbonate 16% malic acid 44% 20 May 15 Dec 10 minor and inert substances to 100 to 100 to 100

The soaking solutions are formed by diluting each time 45 g of the above compositions in 3.5 to 5 liters of water. 0.5 to 2 kg of laundry are then always immersed in the soaking solution. The soaking time of the soaking solution containing the soaking agents 1 to 12 is normally from 1 minute to 24 hours.

Finally, the laundry is removed from the soaking solution, rinsed in water and washed in a conventional washing manner, manually or in a washing machine with a conventional detergent, with or without re-use of the soaking solution, then allowing the laundry to dry. With these compositions, excellent stain removal capabilities have been achieved, including oily or enzyme-bleached stains, and the like.

An example of a process for producing dry effervescent granules according to the present invention.

• 9 • 9

• * • 9 9 9 9 9 · ·

9 * 9

The following process can be conducted to form a dry effervescent granule comprising 40% by weight of the total bicarbonate granule, 40% by weight of malic acid, 16% by weight of carbonate, and 4% by weight of citric acid. In a first step, the respective components are mixed together in given proportions. Then, the obtained mixture is incorporated into the Pharmapactor L200 / 50P® commercially available from Hosokawa Bepex GmbH. The distance between the disks is approximately 5 cm, the compressive force used during the compression step is about 60 kN, the yaw rate is about 15 rpm, and the dispensing device is about 15 rpm. In the Pharmapaktor L200 / 50P® mixture, the mixture is compressed between the press rolls to form solid chips / slices. This solid chip / leaf is then milled to 1.2 mm in Flake Crusher FC200®. Bar-head is mounted on Flake Crusher FC200®. The temperature is around 25 ° C. The resulting granules are then in accordance with the present invention incorporated into the granular formulation (eg, compositions 4-6 above).

Example 2: Detergents for washing laundry in washing machines. Component abbreviations have the following meanings in detergent products:

LAS linear C12 alkylbenzene sulfonate sodium TAS sodium tallow alkyl sulphate C45AS C14 to C15 linear sodium sodium sulphate MES α-sulfomethyl ester of C 18 fatty acid C _xy E _of S C _x to ciy branched alkyl sulfate condensed with z moles of ethylene MBAS _x , _y medium branched sodium alkyl sulphate with an average number of carbon atoms x, where the average number of carbons is y contained in (a) branched units c ₄₈ sas C14 to C18 secondary sodium alcohol sulphate SADE _X S C14 to _C22 sodium alkyl disulfate according to the formula 2- (R) .C4H7l, 4- (SO4-) ₂ , where R = C10OCis condensed with from a mole of ethylene oxide QASI R ₂ .N ⁺ _(CH3) 2 (C2H4OH) with _R2 = 50% -60% C _9, 40% to 50% Cn QAS II R ¹ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) ₂ with R 1 = C 12 to C 14 soap linear sodium alkyl carbonate derived from an 80/20 tallow mixture and coconut oil TFAAI C12 to C14 alkyl N-methylglucamide TFAAII C 16 to C 18 alkyl N-methylglucamide

• 9 • * • · · · · · · · · · ·

TPKFA STPP Zeolite AI

Zeolite AII NaSKS-6 citric acid I citric acid II malic acid maleic acid tartaric acid carbonate I carbonate II bicarbonate silicate sodium sulfate citrate

MA / AA

CMC protease alkalase cellulase amylase

C12 to C14 fatty acids with reduced ends anhydrous sodium tripolyphosphate sodium aluminosilicate aqueous according to the formula Nai2 (AlO ₂ SiO2) i2-27H ₂ O with a primary particle size in the range of 0.1 to 10 microns overdried Zeolite AI crystalline layered silicate of formula 5- Anhydrous citric acid citric acid monohydrate anhydrous malic acid anhydrous maleic acid anhydrous aspartic acid anhydrous sodium carbonate with an average particle size of 200 pm to 900 pm anhydrous sodium carbonate with an average particle size of 100 pm to 200 pm anhydrous sodium bicarbonate with an average particle size of 400 pm to 1200 pm amorphous sodium silicate (SiO ₂ : Na2O, ratio 2) anhydrous sodium sulphate tri-sodium citrate dihydrate with an activity of 86.4% with an average particle size of 425 pm to 850 pm maleic acid / acrylic acid copolymer 1: 4, average molecular weight 70,000 sodium carboxymethylcellulose proteolytic enzyme with activity 4 KNPU / g sold by NOVO Industries A / S under the trade name Savinase proteolytic enzyme with activity 3 AU / g sold by NOVO Industries A / S cellulose enzyme with activity of 1000 CEVU / g sold by NOVO Industries A / S under the trade name Carezym amylolytic enzyme with an activity of 60 KNU / g sold by NOVO Industries A / S under the trade name Termamyl 60T • · · lipase endolase

PB4

PB1 percarbonate

NAC-OBS

NOBS

DPDA

PAP

NAPAA

NACA

TAED

DTPMP Photoactivated Brightener I Brightener II

HEDP

PVNO

PVPVI

QEA

CFP 1

SRP 2 silicone antifoam lipolytic enzyme with an activity of 100 kLU / g sold by NOVO

Industries A / S under the trade name Lipolase endoglunas enzyme of 3000 CEVU / g marketed

NOVO Industries A / S sodium perborate tetrahydrate of formula NaBO2.3H2O.H2O2 anhydrous sodium perborate of formula NaBO2.H2O2 sodium percarbonate according to the formula 2Na2CO3.3H2O2 (nonanamidocaproyl) oxybenzenesulphonate in the form of sodium salt 6-nonylamino-6-oxocaproic acid tetraacetylethylenediamine diethylenetriaminpenta (methylenephosphonate), sold by Monsanto under the trade name Dequest 2060 thickened sulfonated zinc or aluminum phthalocyanine 4,4'-bis (2-sulfostyryl) biphenyl disodium 4,4'-bis (4- anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2: 2'-disulfonate

1.1 -hydroxyethandifosfonová acid, polyvinylpyridine N-oxide, copolymer of polyvinylpyrrolidone and vinyl imidazole bis ((C 2 H ₅ O) (C 2 H ₄ O) _n) (CH3) -N ⁺ -C 6 H 2 N ⁺ (CH ₃₎ bis ((C 2 H ₅ O) - (C2H4O) n, wherein n is from 20 to 30 oxyethyleneoxy and terephthaloyl backbone esters terminated with a sulfobenzoyl cap of a polymer of diethoxylated poly (1,2-propylene terephthalate) polydimethylsiloxane foam controller with siloxanoxyalkylene copolymer as dispersant 10 as dispersant : 1 to 100: 1 • ·

........

•. . · · · •. ·· * ···: · · ·

..........

In the following examples, all concentrations are expressed in% by weight of the composition. The following high density granular laundry detergent compositions A to F for a particular use according to European washing machine conditions were prepared in accordance with the invention.

AND (B) C D E F LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 C46AS 1.0 2,0 2.5 - 3.0 4.0 C68AS 3.0 2,0 5.0 7.0 · 1.0 0.5 QASI - - 0.8 - - 0.8 Zeolite A 18.1 18.1 16.1 18.1 18.1 18.1 Zeolite MAP - 4.0 3.5 - - - carbonate I 12.0 12.0 11.5 25.5 25.0 25.0 silicate 1.4 1.4 1.4 3.0 3.0 3.0 MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.0 1.5 - 1.5 Mn catalyst - 0.03 0.07 - - - DTMPM 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.2 0.2 0.3 0.3 EDDS - - 0.4 0.2 - - QEA 1 1.0 0.8 0.7 1,2 - 0.5 protease 0.26 0.26 0.26 0.26 0.26 0.26 amylase o, i o, i 0.4 0.3 o, i o, i lipase 0.05 0.6 0.7 o, i · 0.07 o, i photoactivated bleach (ppm) 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm 15 ppm brightener 1 0.09 0.09 0.09 0.09 0.09 0.09

<1 ·

perfume 0.3 0.3 0.3 0.3 0.3 0.3 dry sparkling granules malic acid 44%, sodium bicarbonate 40%, sodium carbonate II10%, LAS 6% 10 10 15 Dec 15 Dec 20 May 20 May silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5 minor / inert substances up to 100%

The following granular laundry detergent compositions G to I have been prepared for a particular use according to European washing machine conditions in accordance with the invention.

G H AND LAS 5.25 5.61 4.76 TAS 1,25 1.86 1.57 C45AS - 2.24 3.89 C25E3S - 0.76 1.18 C45E7 3.25 - 5.0 C25E3 - 5.5 - QAS 0.8 2,0 2.0. Zeolite A - 19.5 19.5 Zeolite MAP 2,0 - - NaSK-6 / citric acid (79:21) - 10.6 10.6 carbonate I 4.7 19.3 18.6 silicate 6.8 - - MA / AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 percarbonate 5.0 - 12.7 TAED 0.5 3.1 -

• ·

Mn catalyst 0.04 - - DTPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 QEA 1 0.9 1,2 - protease 0.26 0.85 0.85 lipase 0.15 0.25 0.15 cellulase 0.28 0.28 0.28 PVP 0.9 1.3 0.8 photoactivated bleach (PPm) 15 ppm 27 ppm 27 ppm brightener 1 0.08 0.19 0.19 brightener 2 - 0.04 0.04 perfume 0.3 0.3 0.3 · dry sparkling granules malic acid 40%, citric acid 6%, sodium bicarbonate 40%, sodium carbonate 14% 10 15 Dec 5 silicone antifoam 0.5 2.4 2.4 minor / inert substances up to 100%

Further, high-density and bleach-containing detergent compositions in accordance with the present invention are:

J TO L You blown powder Zeolite A 5.0 5.0 5.0 sodium sulfate o, o 5.0 0.0 LAS - 5.0 3.0 C45AS 3.0 2,0 4.0

QAS II - - 1.5 DTMPM 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2,0 2,0 dry effervescent granules (maleic acid 30%, sodium bicarbonate 40%, sodium carbonate 114%, PEG) 20.0 5.0 Dry additives: dry effervescent granules (maleic acid 30%, sodium bicarbonate 40%, sodium carbonate II 14%, PEG 16%) 5.0 dry sparkling granules (tartaric acid 30%, sodium bicarbonate 40%, sodium carbonate I 14%, TAE50 16%) 5.0 Sprayed (for particles) thickened perfume 0.3 0.3 0.3 C25E3 - - 2,0 Dry additives QEA - - 0.5 citrate 3.0 - 2,0 bicarbonate - 3.0 - carbonate 8.0 10.0 5.0 NAC OBS 6.0 - - Mn catalyst - - 0.3 NOBS - 2,0 - PB1 or percarbonate 14.0 7.0 -

polyethylene oxide of M _w 5 000 000 - - 0.2 bentonite clay - - 10.0 citric acid II - - 1.5 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 antifoam 5.0 5.0 5.0 Dry additives sodium sulfate 0.0 3.0 o, o balance (humidity and various) 100 ALIGN! 100 ALIGN! 100 ALIGN! density (g / l) 850 850 850

The following are cleaning compositions of the present invention:

M N dry effervescent granules (maleic acid 30%, sodium bicarbonate 40%, sodium carbonate I 14%, PEG) 10.0 dry effervescent granules (malic acid 40%, sodium bicarbonate 40%, sodium carbonate II 20%) 4.0 Sprayed to dry sparkling particles C25E3 1.0 4.0 perfume 0.5 0.5 Dry additives HEDP 0.5 0.3 SKS6 13.0 10.0

• ·

citrate / citric acid - 2,0 malic acid 2,0 - NAC OBS 4.1 - TAED 0.8 - percarbonate 20.0 5.0 SRPI 0.3 0.3 protease 1.4 1.4 lipase 0.4 0.4 cellulase 0.6 0.6 amylase 0.6 0.6 QEA 1.0 - silicone antifoam 5.0 5.0 brightener I 0.2 0.2 brightener II 0.2 - Density (g / 1) 850 850

Further, the high density cleaning compositions of the present invention are:

O P R Agglomerates C45AS 11.0 14.0 5.0 QASI 1,8 2.2 Zeolite A 15.0 6.0 15.0 AE5 5.0 TFAA II 5.0 MA / AA 4.0 2,0 2,0 CMC 0.5 0.5 0.5 DTPMP 0.4 0.4 0.4

dry effervescent granules (malic acid 20%, sodium bicarbonate 20%, sodium carbonate II20%, TAE50 10%, TFAA II 30%) 3.0 7.0 Sprayed on C25E3 1.0 4.0 4.0 C25E7 5.0 - - perfume 0.5 0.5 0.5 Dry additives HEDP 0.5 0.3 0.3 SKS6 13.0 10.0 10.0 citrate - 1.0 1.0 citric acid II 2,0 - - NAC OBS 4.1 6.2 6.2 TAED 0.8 1.0 1.0 percarbonate 20.0 20.0 20.0 SRPI 0.3 0.3 0.3 protease 1.4 1.4 1,4 ¹ lipase 0.4 0.4 0.4 cellulase 0.6 0.6 0.6 amylase 0.6 0.6 0.6 QEA 1.0 - - silicone antifoam 5.0 5.0 50 brightener I 0.2 0.2 0.2 brightener II 0.2 - - dry sparkling granules 2,0 10.0 > (maleic acid 30%, sodium bicarbonate 30%, sodium carbonate I 10%) Density (g / 1) 850 850 850

γ / '3½½

Claims (21)

PATENT CLAIMS A dry effervescent granule, characterized in that it comprises an acid, a carbonate source, in particular a carbonate or bicarbonate, and optionally a binder, wherein said acid, carbonate source and optionally a binder are in close physical proximity. Granules according to claim 1, characterized in that they have an average size of from 0.001 to 7 mm, preferably less than 2 mm. Granules according to any one of the preceding claims, characterized in that they have a density of from 500 g / l to 1200 g / l, more preferably from 700 g / l to 1100 g / l. Granules according to any one of the preceding claims, characterized in that it contains from 0.1% to 99% by weight of the total acid granule or mixture thereof, preferably from 3% to 75%, more preferably from 5% to 60% and most preferably from 15% up to 50% provided that the citric acid is present in an amount that is below 20% by weight of the total granule. Granules according to any one of the preceding claims, characterized in that the acid is a mono or polycarboxylic acid or a mixture thereof, preferably citric acid, adipic acid, glutaric acid, 3-chetoglutaric acid, citric acid, tartaric, maleic, fumaric, malic, succinic or malonic. acid form, their salts (mono-, di-, tri- salts), their anhydrous or hydrated form. Granules according to any one of the preceding claims, characterized in that it contains from 0.1% to 99% by weight of the total granulate of carbonate or bicarbonate, preferably from 30% to 95%, more preferably from 45% to 85% and most preferably from 50% to 85%. 80%. Granules according to any one of the preceding claims, characterized in that it contains up to 50% by weight of the total binder granules or a mixture thereof, preferably up to 35% and more preferably up to 20%. Granules according to any one of the preceding claims, characterized in that the binder is selected from the group consisting of cellulose derivatives, carboxymethylcellulose and homo- and copolymeric polycarboxylic acids and their salts, C 6 to C 20 alkyl and alkylarylsulphonates and sulphates, C 10 to C 20 alcohol ethoxylates containing from 5 to 100 moles of ethylene oxide per mole of alcohol, polyvinylpyrrolidones of an average molecular weight of 12,000 to 700,000, polyethylene glycols of an average molecular weight of 600 to 10,000, copolymers of maleic anhydride and ethylene, methyl vinyl ether, methacrylic and acrylic acids, C 10 to C 20 mono and diglycerol ethers, C 10 to C 20 fatty acids and mixtures thereof, and preferably C 8 to C 20 alkylbenzene sulfonates. A process for producing a dry effervescent granule according to any one of claims 1 to 8, characterized in that said process comprises the following steps: - first mixing the acid, carbonate source and optionally the binder to form a mixture, - the mixture is then subjected to an agglomeration step, preferably a pressure agglomeration step, to form a mixture of agglomerates, and finally granulating the agglomeration mixture in a granulation step. Method according to claim 9, characterized in that the specific bulk density of the dry effervescent granule which has undergone said pressure agglomeration step is increased up to 200 g / l, preferably from 10 g / l to 150 g / l, as compared to the bulk density of the resulting mixture comprising said acid and bicarbonate or carbonate and optionally a binder prior to said pressure agglomeration. Method according to claims 9 and 10, characterized in that said pressure agglomeration is cylindrical pressing, wherein the resulting mixture is pressed between press rolls under pressure, wherein the obtained solid mixture (chips / slices) is then granulated to form dry effervescent granules and optionally sifted. 12. A granular composition comprising an effervescent material consisting of an acid and a carbonate source, wherein the acid and carbonate source are present in the granule or the acid and carbonate source are present in the composition separately, characterized in that the effervescence index (E1) is at least 10, the effervescence index is defined by the formula E1 = (LXSX 100) / MX (NCinter + N Cintra) where L is the acid group number of the acid by pK a less than or equal to 6, S is (acid solubility in water in g / l, at 25 ° C), M is the acid molecular weight , NCinter is the density of the contact points between the carbonate source and the acid present separately in the composition per mm ³ , and NCintra is (the weight of the acid fraction in said granule) x (the weight of the carbonate source fraction in said granule) x 12. • · · · · · A granular composition according to claim 12, wherein the granule comprises a dry effervescent granule according to any one of claims 1 to 8. Granular composition according to claim 12 or 13, characterized in that the granule comprises a dry effervescent granule and additional cleaning ingredients obtained by a process comprising first a step of forming a dry effervescent granule according to any of the preceding claims 1, then adding the granule to the additional cleaning ingredients. . A granular composition according to any one of claims 12 to 14, characterized in that it contains from 0.1% to 99% by weight of the total composition of dry effervescent granules, preferably from 2% to 50%, more preferably from 3% to 25% and most preferably from 4% to 15%. A granular composition according to claims 12 to 15, characterized in that it contains an oxygen bleach, preferably an alkali metal or perborate percarbonate salt, up to 80% by weight of the total composition, preferably from 2% to 45% and most preferably from 10% to 40%; preferably a bleach activator up to 30% by weight of the total composition. A granular composition according to claims 12 to 16, characterized in that it comprises at least a surfactant or a mixture thereof up to 50% by weight of the total composition, preferably from 1% to 30%, more preferably from 5 to 20%, preferably containing nonionic surfactants. A granular composition according to claims 12 to 18, characterized in that it comprises a dry effervescent particle and an additional dry acid, preferably citric or malic acid, or a dry addition of a carbonate source. A granular composition according to claims 12 to 19, in the form of an extrudate or a tablet. A method of soaking laundry wherein said laundry is immersed in a soaking solution comprising water and an effective amount of a granular detergent composition according to any one of the preceding claims 12 to 19 for an effective time, then removed from said soaking solution. γί / Use of a dry effervescent granule according to any one of the preceding claims 1 to 8 in a granular composition comprising an oxygen bleach, preferably percarbonate or perborate, to increase the thermal stability of said composition during storage.