CN1322236A - Detergent compositions - Google Patents

Abstract

The present invention discloses a solid detergent composition comprising 8% to 60% by weight of a surfactant system and having a Grand Compatibility Index of at least 0.5, preferably at least 0.6. The use of these detergent compositions for cleaning soils in a washing method is also disclosed.

Description

detergent composition

technical field

The present invention relates to detergent compositions, especially laundry detergent compositions.

Background of the invention

All detergents for laundry applications contain surfactants and builders. In general, most detergents comprise a base powder prepared by spray drying or granulating builder and surfactant components, eg by agglomeration or extrusion. Base powders are usually also treated with post-treatment steps such as dry addition of other granular detergent ingredients, spraying with other liquid ingredients such as surfactants, especially non-ionic surfactants and/or post-coating powders with fine solid particulate materials Steps to reduce the caking and cohesiveness of the prepared solid detergent.

Environmental pressures have led to the need to produce detergents that are as effective as possible. The tendency to use lower amounts of more dense detergent compositions, such as detergent compositions with densities above 600g/l or 650g/l or above 700g/l or even higher, highlights the need to ensure that all detergents Components have to perform well in the wash.

However, solid detergents tend to form clumps or gels upon contact with water. The clumps of gelled material then sink into the washing machine sump where they are not disturbed mechanically or by their usage in the washing machine, the solid detergents are not dissolved and as a result the product is released from the feed compartment of the washing machine or from the feeder And/or poor feeding in the case of the washing machine itself. The application of all detergent ingredients is thus poor. It is generally preferred that the compositions contain no phosphorus-containing builder materials.

The present inventors have carried out careful research on these properties of detergents, and found that there are many factors affecting these properties, and they are interrelated in a complex manner. Inorganic compounds in detergent formulations through their effects on the ionic strength of , can affect the phase chemistry of surfactants; certain surfactant phases can trap inorganic species in the phase that contribute to hydrate formation; microdomains that facilitate the formation of the surfactant phase. Further complicating the situation is the fact that many inorganic hydrate and surfactant phases are affected by detergent concentration in the water, by water hardness and by water temperature. The prior art therefore does not quantitatively describe this complication and suggest a way to provide detergent compositions which avoid this problem. The present inventors have now surprisingly found that a sufficient understanding of these complex interrelated factors has enabled them to provide detergent compositions which avoid the problems described above. New detergent compositions with a defined Grand Compatibility Index are thus provided.

Thus, new detergent compositions are obtained which provide good wash performance and achieve good detergent dosing in the wash and reduced localized high bleach concentrations, using a minimum amount of detergent. Fabric damage.

Summary of the invention

According to the present invention there is provided a solid detergent composition comprising 8% to 60% by weight of a surfactant system and having a minimum Grand Compatibility Index of 0.5, preferably 0.6, more preferably 0.7 or even 0.8 or 0.9.

The Grand Compatibility Index (Compatibility Index) is a function of the Compatibility Index and the Secondary Compatibility Index.

Compatibility index can be determined by the following method:

1 liter of deionized water was placed in a tergitometer (ErwekaDT6-R hereinafter referred to as 'Sotax' device) (USP 711 dissolution standard). The hardness is adjusted to 100 ppm equivalent CaCO ₃ using a suitable calcium soluble form such as calcium chloride. The Sotax was fitted with a plexiglass lid to suppress evaporation, the temperature was calibrated to 5°C, and the stirrer (stirring paddle) was fixed at 200 rpm. The impeller has two blades fixed on the central axis, which are directly opposite each other, so that the two blades together make the diameter of the impeller 75 mm. The stirring paddle is located at the center of the Sotax equipment, and the distance between the bottom of the stirring paddle and the bottom of the detergency tester is 25 mm. The total height of the paddle blades is 19 mm. A wire basket was provided with side walls and bottom made of 20 mesh (850μ) stainless steel wire, 25 mm in diameter and 41 mm in height. The wire basket is filled with detergent product, the surface of the detergent product is smoothed and the top of the wire basket is closed with an impermeable lid. The amount of the sample was determined gravimetrically from the difference in weight. The wire basket was then suspended in a fixed position midway between the central axis of the Sotax and the side walls at a height such that the bottom of the wire basket was 7mm above the upper surface of the paddle.

After 12 minutes, the assembled wire baskets were removed from the Sotax apparatus and the residue was transferred to a sealed container.

The entire residue in the sealed container was analyzed for moles of any carbonate, sulfate, borate, and phosphate in hydrated and non-hydrated forms. This is done using some standard techniques known to those skilled in the art of detergent analysis. It will be appreciated that this analysis is performed immediately so that the salts do not change their hydration state prior to analysis.

The water retained in the Sotex equipment was also completely analyzed. First filter through a 0.45 micron filter and analyze for moles of carbonate, sulfate, borate and phosphate ions. It will be appreciated that filtration should be performed immediately to avoid the formation of insoluble salts from soluble salts in solution. The filtered solution should be analyzed for moles of any carbonates, sulfates, borates and phosphates in solution. Any carbonates, sulfates, borates, and phosphates that precipitated out of solution after filtration were also analyzed and added to the amount they were present in solution.

Compatibility index was calculated according to the following formula:

Residue index = (I _s +I _<8h +O _o ^* (I _o -I _>8h )/I _o )/(I _o +O _o ) where: I _s = the above-mentioned inorganic substances (carbonic acid) measured in aqueous solution salt, sulphate, borate and phosphate) ions; I _{< 8h} = the number of moles of the above-mentioned inorganic hydrate salts containing less than 8 moles of water of hydration per mole determined in the residue of the wire basket; I _{> 8h} = number of moles of the above-mentioned inorganic hydrate salt containing more than 8 moles _of water of hydration per mole determined in the residue of the wire basket; Number of moles; O _o = number of moles of anionic, nonionic, cationic and semi-polar surfactants (as described below) placed in the wire basket at the beginning of the experiment.

The secondary compatibility index is determined by the following method:

Using the same equipment, 800ml of deionized water was added to the Sotax apparatus and the temperature was allowed to equilibrate to 20°C with a stirrer at a speed of 200rpm. The hardness is adjusted to 100 ppm equivalent CaCO ₃ using a suitable and soluble form of calcium such as calcium chloride. Then 2 g of the product were added to the water and stirred for 20 minutes at a stirrer speed of 200 rpm. After 20 minutes, the aqueous detergent sample was filtered through a 0.45 micron filter. The solid collected on the filter was analyzed using the same procedure as described in the Compatibility Index Determination, except that the sample was kept at 20°C instead of 5°C. Similarly, this aqueous solution was analyzed using the same procedure as described in Compatibility Index Determination.

Calculate the secondary compatibility index according to the following formula:

Secondary residual index = (I _s +I _<1/2h +O _o ^* (I _o -I _>1/2h )/I _o )/(I _o +O _o ) where: I _s = measured in aqueous solution The total number of moles of ions _of the above-mentioned inorganic substances (carbonate, borate, sulfate and phosphate); I _{> 1/2h} = the number of moles of the above-mentioned inorganic hydrate salts measured in the filter cake per mole containing more than 1/2 mole of water of hydration; I _o = put into Sotax at the beginning of the experiment Number of moles of the above inorganic salts; O _o = number of moles of anionic, nonionic, cationic and semi-polar surfactants (as described on pages 13-25) placed in Sotax at the beginning of the experiment.

Using the Compatibility Index and Secondary Compatibility Index calculated above, the Grand Compatibility Index is defined as follows:

Grand Compatibility Index = Compatibility Index * Secondary Compatibility Index

The new detergent formulations according to the invention have a well matched and compatible surfactant system and inorganic system which give a Grand Compatibility Index of at least 0.5, preferably at least 0.6, more preferably at least 0.7, or even at least 0.8 or at least 0.9.

The detergent compositions of the present invention preferably comprise no more than 3% by weight inorganic phosphate, more preferably no more than 1% by weight phosphate and most preferably no more than 0.5% by weight phosphate. Preferably the compositions of the present invention comprise no more than 5% by weight inorganic borate, more preferably no more than 2% by weight inorganic borate, most preferably no more than 0.5% by weight inorganic borate. Preferably, the detergent compositions of the present invention contain less than 10% by weight of inorganic chloride salt, more preferably less than 5%, or even less than 2%, or 0.5% by weight of inorganic chloride salt. Preferred compositions comprise at least 5% by weight of sodium or potassium carbonate, sodium or potassium bicarbonate or sodium or potassium sesquicarbonate or mixtures thereof.

Sesquicarbonate and/or bicarbonate is preferably present in the composition in an amount of at least 5% by weight, most preferably at least 10% by weight. Builder system

Detergent compositions comprise a builder system which may be provided by one builder or a mixture of more than one builder. Water-soluble and/or water-insoluble builders can be used. The builder system generally comprises from 1% to 90% by weight of the detergent composition, preferably from 20% to 80% by weight. Water-soluble or partially water-soluble builders

The builder system in the compositions of the present invention preferably comprises water-soluble and/or partially water-soluble builder compounds, typically at levels of from 1% to 80% by weight, preferably at levels up to 50% by weight, or up to 40% or even 35% by weight. %. Preferably the level of water-soluble builders is at least 3% or 8%, but preferably they are present at from 6% to 25% by weight.

The detergent compositions herein may contain phosphorus-containing builder materials such as tetrasodium pyrophosphate or more preferably anhydrous sodium tripolyphosphate. Phosphate builders may be present at levels from 0.5% to 60%, or from 5% to 50%, or even from 8% to 40% by weight. However, crystalline layered silicates are also suitable partially water-soluble builders. Preferred crystalline layered silicates according to the invention have the general formula:

NaMSi _x O _2x+1 .yH ₂ O wherein M is sodium or hydrogen, x is a value from 1.9-4, and y is a value from 0-20. Such crystalline layered sodium silicates are disclosed in EP-A-0164514 and processes for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. For the purposes of the present invention, x in the above general formula is 2, 3 or 4, preferably 2. M is preferably H, K or Na or a mixture thereof, preferably Na. The most preferred material is α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ or δ-Na ₂ Si ₂ O ₅ or mixtures thereof, preferably at least 75%-Na ₂ Si ₂ O ₅ , for example from NaSKS-6 available from Clariant. Crystalline layered silicate materials, in particular of formula _{Na2Si2O5 ,} may optionally contain other elements such as B, P, S, obtained for example by the method _described in EP578986-B.

Partially water-soluble builders are preferably present at levels up to 40%, more preferably up to 35%. When present, it is preferred that the compositions herein comprise from 10% to 40%, more preferably from 12% to 35% or even from 15% to 25% by weight of the composition, of partially water-soluble builders.

Water-soluble builders include organic carboxylic acids and their salts. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or co-polymeric polycarboxylates or salts thereof, wherein the polycarboxylic acids are separated from each other by not more than two carbon atoms at least two carboxyl groups of , and mixtures of any of the foregoing.

Carboxylate or polycarboxylate builders can be monomeric or oligomeric, although monomeric polycarboxylates are generally preferred for reasons of cost and performance. In addition to these water-soluble builders, polymeric polycarboxylates including homopolymers and copolymers of maleic acid and acrylic acid and their salts can also be included.

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include those of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, glyoxylic acid, tartaric acid, tartronic acid, malic acid, and fumaric acid Water-soluble salts, as well as ether carboxylates and sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, inter alia, the water-soluble citrates, aconitates and citraconates, and succinate derivatives such as carboxymethoxysuccinates as described in British Patent 1,379,241, Lactyloxysuccinates described in British Patent 1389732, aminosuccinates described in Dutch Patent 7205873, and oxypolycarboxylate materials such as 2-oxa-1,1, described in British Patent 1,387,447, 3-Propane tricarboxylate.

Polycarboxylates containing four carboxyl groups include oxydisuccinates described in British Patent 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylate. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patents 1,398,421 and 1,398,422 and US Patent No. 3,936,448, and the sulfonated pyrolyzed citrates described in British Patent 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, more particularly citrates. Mixtures of the parent acids of monomeric or oligomeric polycarboxylate chelating agents or their salts are also contemplated as useful builder ingredients, for example citric acid or citrate/citric acid mixtures.

Most preferred may be acetic acid, citric acid, malic acid and fumaric acid, or their salts or mixtures thereof. Preference is given to mixtures of their salt and acid forms.

Water-soluble builders are preferably present at levels up to 40%, more preferably up to 35%. When present, it is preferred that the compositions herein comprise from 10% to 40%, more preferably from 12% to 35% or even from 15% to 25%, by weight, of water-soluble builders.

Preferably the level of polymeric or oligomeric polycarboxylate is less than 5%, preferably less than 3% or even less than 2% or even 0% by weight of the composition.

Borate builders and builders containing borate-forming materials which are capable of generating borate under detergent storage or wash conditions are water-soluble builders useful herein.

Other suitable water-soluble builder materials are polymeric polycarboxylic acids or polycarboxylates, including water-soluble homo- or co-polymeric polycarboxylic acids, or salts thereof, wherein the polycarboxylic acids are separated from each other by not more than two carbon atoms. separated by at least two carboxyl groups. Polymers of the latter type are disclosed in GB-A-1596756. Examples of such salts are polyacrylates with a MWt of 1000-50000, preferably 10000 or even 7000, and copolymers of (poly)acrylates and maleic acid or maleic anhydride, such copolymers preferably having a molecular weight of 2000-100000 , especially 40000-80000.

In a preferred embodiment of the invention, water-soluble or partially insoluble builders, especially crystalline layered silicates, when present, are present at least in part in intimate admixture with surfactants, preferably anionic surfactants, For example at least 50% by weight.

It has also been found that when a highly water-soluble carboxylate or carboxylic acid-containing compound is present in an intimate mixture of the same one or more surfactants and optionally other components, the dissolution rate of the intimate mixture and the surfactant and other The dissolution rate of the components is increased. Thus, a comprehensive and rapid release of surfactants and other components can be achieved.

Thus, a preferred granular component in detergent compositions of the present invention may comprise preferably 25% to 75% by weight of the component, more preferably 35% to 68% by weight, even more preferably 45% to 62% by weight An intimate mixture of crystalline layered silicate or water-soluble builder and 25% to 75%, more preferably 32% to 62%, more preferably 38% to 48%, by weight of the composition, of anionic surfactant.

Such particulate components preferably contain less than 10% by weight free water, preferably less than 5% or even less than 3% or even less than 2% by weight. The free water described here can be measured by the following method: put 5 grams of granule components into a Petri dish, place the Petri dish in a convection oven at 50° C. for 2 hours, then measure Weight loss due to evaporation.

The anionic surfactant preferably comprises from 50% to 100% by weight, preferably 60% or even 75% to 100%, of a sulfonate anionic surfactant as described below, preferably an alkylbenzene sulfonate surfactant. Preferably up to 50% by weight or more of anionic surfactant is incorporated into such particulate components, based on the total amount of anionic surfactant in the detergent composition.

Preferably such particulate components are present in the detergent composition at a level of from 0.5% to 60% by weight, preferably from 3% to 50%, more preferably from 5% to 45%, even more preferably at least 7% by weight.

Preferably, the weight ratio of crystalline layered silicate and/or one or more water-soluble builders to anionic surfactant in the intimate mixture is from 4:5 to 7:3, more preferably from 1:1 to 2 :1, most preferably 5:4-3:2.

This component may also contain other ingredients, for example 0-25% by weight of the particulate component, generally not more than 20% or even 15% by weight. The exact nature of these other ingredients and the amount incorporated therein will depend upon the application of the component or composition and the physical form of the component or composition. Preferably the granular composition comprises less than 15% or less than 10% or even 5% by weight of nonionic ethoxylated alcohol surfactant particles, preferably less than 15% or even less than 10% or even less than 5% of any Nonionic surfactant.

Preferably the particulate composition comprises less than 10% by weight, preferably less than 5% by weight of aluminosilicate material. If some aluminosilicate material is present, it is preferred that the particulate composition is powdered with the aluminosilicate material.

The particulate component may contain polymeric binder material, but preferably as little binder material as possible is used. Preferably the intimate mixture comprises less than 25%, preferably less than 10%, more preferably less than 5% by weight, most preferably 0% by weight ethylene oxide polymer.

The particulate component preferably has a weight average particle size of at least 50 microns, preferably 150 microns to 1500 microns, or more preferably 80% by weight of the particles have a particle size greater than 300 microns (80% by weight on a mesh 48 Tyler sieve) and less than 10% by weight of the particles have a particle size greater than 1180 microns or even 710 microns (on a mesh 24 Taylor sieve).

Preferably, the granular component has a density of from 380 g/liter to 1500 g/liter, or more preferably from 500 g/liter to 1200 g/liter, more preferably from 550 g/liter to 900 g/liter.

The granular component may be present in the detergent compositions herein as a separate particle, or it may be further mixed with other detergent ingredients, including further agglomeration, moulding, tableting or extrusion.

The intimate mixture or granule component can be prepared by any known method for preparing such detergent granules, such as agglomeration, spray drying, rolling and/or extrusion or combinations of these process steps. This process may optionally be followed by a drying step or a powdering step and/or a spraying step. The prepared granules are then preferably mixed with other detergent ingredients.

The crystalline layered silicates and/or highly water-soluble builders can also be polymerized with other materials, including one or more water-soluble builders as described herein, or polymeric compounds such as acrylic acid and/or maleic acid compounds, inorganic acids or salts including carbonates and sulfates, or small amounts of other silicate materials including amorphous silicates, metasilicates and aluminosilicates in intimate mixtures.

Preferably some or even all of the water-soluble builder, especially monomeric or oligomeric (poly)carboxylic acids or salts thereof, is in the form of individual particles, whereby preferably the mean particle size of the builder material is below 150 microns, or Even below 100 microns. When necessary, a portion of the water-soluble or partially water-soluble builder is preferably used as a release agent to reduce caking of the product.

In particular, when a small amount of insoluble builder is present in the composition, the polycarboxylate polymer such as maleic anhydride or maleic acid polymer and its copolymer with (poly)acrylic acid and its salts in the composition The content may be from 0.5% to 15%, preferably from 1% to 12%, even from 2% to 8% by weight. Thus, it is preferred that the water-insoluble builder and polymer are not present in intimate admixture with another material.

The inventors have also found that when a polymeric polycarboxylate is present, it is preferred that the polymer is contained in an intimate admixture with other detergent ingredients, preferably in a spray-dried granule which is prepared by first adding the carbonate Mix with the polymer, then add and mix the other ingredients intimately. insoluble builder

The compositions herein may contain insoluble builder compounds. In general, they will be present in an amount of not more than 30% by weight, preferably not more than 25% by weight, based on the total detergent composition.

Examples of substantially water insoluble builders include sodium aluminosilicates.

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

Aluminosilicate zeolites may be natural products, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are commercially available as Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na ₁₂ [AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ].xH ₂ O where x is 20-30, especially 27. Zeolite X has the formula: Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]·276H ₂ O.

Another preferred aluminosilicate zeolite is the zeolite MAP builder. Zeolite MAP is described in EP384070A (Unilever). It is defined as an alkali metal aluminosilicate of zeolite P type having a silicon to aluminum ratio not greater than 1.33, preferably 0.9-1.33, more preferably 0.9-1.2. Of particular interest are zeolites MAP having a silicon to aluminum ratio not greater than 1.15, more specifically not greater than 1.07.

In preferred cases, the particle size of the zeolite MAP detergent builder, expressed as d ₅₀ , is 1.0-10.0 μm, more preferably 2.0-7.0 μm, most preferably 2.5-5.0 μm. The d ₅₀ value means that 50% by weight of the particles have a diameter smaller than this value. Specifically, the particle size can be determined by conventional analytical techniques, such as microscopic measurement using a scanning electron microscope or measurement with a laser particle size analyzer. Other methods of determining _d50 values are described in EP 384070A.

It has been found that water-insoluble builders, especially aluminosilicates, contribute to the problem of poor overall application of detergent composition ingredients. Therefore, they are generally incorporated in detergent compositions at low levels, or require special processing, to maximize the effectiveness of all detergent ingredients in detergent compositions.

Thus, in one embodiment of the invention, the aluminosilicate builder is preferably present at less than 9% by weight, preferably less than 6% or 4% by weight. It is even preferred that water-insoluble builders are substantially absent. Preferably, the detergent composition contains low levels of amorphous silicate, eg less than 5% by weight of the composition of amorphous sodium silicate, most preferably less than 2% by weight.

In preferred cases, the detergent composition preferably comprises a builder system comprising less than 30%, or even less than 20% or even less than 10% by weight of water-insoluble builder, whereby in preferred embodiments In, the balance of the builder system is a water-soluble builder and/or a partially water-soluble builder.

When present, aluminosilicates may be included in detergent agglomerates, extrudates or blown powder components containing other detergent ingredients such as surfactants. Even preferably substantially no aluminosilicate is present as a separate (dry added) particle component.

Also, preferably less than 3%, or even less than 1.5%, or even less than 0.8% by weight of amorphous silicate is present. When present, the amorphous silicate is preferably contained in detergent agglomerates, extrudates or blown powder components containing other detergent ingredients such as surfactants. Preferably, substantially no amorphous silicate is present as a separate particle component.

As stated, the detergent compositions of the present invention preferably comprise at least one granular component comprising an intimate admixture of one or more water-soluble or partially water-soluble builders and one or more surfactants. Preferably, at least two such particulate components are present in the detergent composition.

In another embodiment of the present invention, if desired, insoluble builders, especially aluminosilicates, are incorporated, e.g., in an amount of 5% by weight or more, wherein the composition further comprises an anionic surfactant, e.g., in an amount of 5 % by weight or more, the detergent composition is preferably such that at least two (n) detergent components (i), anionic surfactants and aluminosilicate builders are present in the composition in admixture (M) is 0-0.7, where

M=∑ _i ⁿ =1√(σ _i .ζ _i ) and σ is the fraction of the anionic surfactant contained in component (i) in the composition; ζ is the silicon aluminum contained in component (i) Salts account for the fraction of the composition.

In order to achieve particularly good detergent dosing, M is preferably from 0 to 0.6, or even from 0 to 0.5.

In this embodiment of the invention, the detergent compositions of the present invention comprise at least two multi-ingredient components (i.e. no more than 95% by weight of a single ingredient in each component) comprising anionic surfactants or silica-alumina Acid salts or mixtures thereof, whereby if a mixture of aluminosilicates and surfactants is present in one or more components, the M of the mixture defined by the above formula is lower than 0.7. Thus, each component comprises part or all of the aluminosilicate, all or part of the anionic surfactant or a mixture thereof, provided that M is 0-0.7.

The components comprise in total at least 5% by weight of the composition of aluminosilicate builder and at least 5% by weight of the composition of anionic surfactant. Preferably, this component comprises at least 7%, or more preferably at least 10% or even 15%, by weight of the composition, of aluminosilicate. Depending on the exact formulation and conditions of use of the composition, the compositions of the invention may comprise even higher amounts of aluminosilicate, for example more than 20% or even more than 25%, and still provide improved detergent performance in the wash. material.

Preferably at least 7% by weight of the composition or more preferably at least 10% or even at least 12% by weight of the anionic surfactant is present in this component. Depending on the exact formulation of the composition and the conditions of use, it is preferred that the anionic surfactant is present in an amount of 18% or more by weight of the composition.

This composition is prepared as described above: by any granulation method such as agglomeration, co-extrusion, spray drying or extrusion. foaming system

Any sudsing system known in the art can be used in the detergent compositions of the present invention. A preferred effervescent system for incorporation into the particles of the present invention comprises an acid source capable of reacting with an alkali source in the presence of water to produce a gas.

Where the foaming system comprises two or more reactants, preferably they are provided in intimate admixture as the foaming system. Most preferably the foaming composition comprises an intimate mixture of substantially anhydrous stabilizer and acid and base reactants.

The acid source component can be any organic, mineral or inorganic acid, or derivatives or mixtures thereof. Preferably the acid source component comprises an organic acid. The acid source is preferably substantially anhydrous or non-hygroscopic, and the acid is preferably water soluble. Preferably the acid source is overdried. Suitable acid source components include citric acid, malic acid, maleic acid, fumaric acid, aspartic acid, glutaric acid, tartaric acid, succinic or adipic acid, monosodium phosphate, boric acid or derivatives thereof. Citric acid, maleic acid or malic acid are particularly preferred.

Most preferably, the acid source provides acidic compounds having an average particle size of from about 75 microns to 1180 microns, more preferably from 150 microns to 710 microns, as calculated by sieving a sample of the acid source on a series of Taylor sieves.

As noted above, the sudsing system preferably comprises a source of alkalinity, however, for the purposes of the present invention it is to be understood that the source of alkalinity may be part of the sudsing particle or may be part of the cleaning composition comprising the particle, or may be present in the wash solution In , the particles or cleaning composition are added to a washing solution.

Any source of alkalinity capable of reacting with an acid source to produce a gas, which may be any gas known in the art, including nitrogen, oxygen and carbon dioxide gas, may be present in the particle. Preferred may be perhydrate bleaches, including perborate and silicate materials. The source of alkalinity is preferably substantially anhydrous or non-hygroscopic. Preferably the source of alkalinity is overdried.

Preferably this gas is carbon dioxide and the source of alkalinity is therefore preferably a carbonate source, which may be any carbonate source known in the art. In a preferred embodiment, the carbonate source is carbonate. Examples of preferred carbonates are alkaline earth and alkali metal carbonates, including sodium or potassium carbonate, sodium or potassium bicarbonate, and sodium or potassium sesquicarbonate and any mixtures thereof, ultrafine calcium carbonate such as disclosed in 1973 In German patent application 2321001 published on November 15. Alkali metal percarbonates are also suitable carbonate sources, which may be present in combination with one or more other carbonate sources.

Carbonates and bicarbonates preferably have an amorphous structure. Carbonates and/or bicarbonates can be coated with coating materials. Preferably the carbonate and bicarbonate particles may have an average particle size of 75 microns or preferably 150 μm or larger, more preferably 250 μm or larger, preferably 500 μm or larger. Preferably the carbonate is such that a sample of the carbonate or bicarbonate has less than 20% by weight of particles having a particle size of less than 500 [mu]m, calculated by sieving a sample of the carbonate or bicarbonate over a series of Taylor sieves. Alternatively or in addition to the carbonates mentioned above, a sample of carbonate or bicarbonate is sieved on a series of Taylor sieves, preferably with less than 60% or even 25% of particles having a particle size below 150 μm and particles having a particle size greater than 1.18 mm There are less than 5% particles, more preferably less than 20% particles having a particle size greater than 212 μm.

The molar ratio of acid source to alkali source present in the particle is preferably 50:1-1:50, more preferably 20:1-1:20, more preferably 10:1-1:10, more preferably 5:1-1 :3, more preferably 3:1-1:2, more preferably 2:1-1:2. stabilizer

Preferred stabilizers are substantially anhydrous stabilizers. Stabilizers may comprise one or more components. Preferred stabilizers include compounds that are at least partially water soluble. Preferably, the stabilizer is solid under normal storage conditions, e.g. the component preferably has a melting point above 30°C, more preferably above 45°C or even more preferably above 50°C, preferably the stabilizer is such that it readily melts above 80°C A melt is formed.

Preferably, the stabilizer comprises one or more components selected from alkoxylated alcohols, including polyethylene glycol and/or polypropylene glycol, and alkoxylated alcohol amides, including ethanolamides, alkoxylated ethanolamides, alkanes Oxylated fatty acid amides or ethanol amides and certain nonionic surfactants, including (polyhydroxy) fatty acid amides, alkoxylated alcohol surfactants and certain alkyl polyglycoside surfactants, and any mixtures of these compounds , as described in this article.

Preferably, one or more components included in the stabilizer are detergent active which can contribute to the cleaning performance of the granule or cleaning compositions comprising the granule. A highly preferred substantially anhydrous component of the stabilizer suitable for the granules of the present invention is one or more nonionic surfactants selected from nonionic alkoxylated surfactants, including alkoxylated alcohols Surfactants, polyhydroxy fatty acid amide surfactants, fatty acid amide surfactants, alkoxylated fatty acid amides, fatty acid alkyl esters, and alkyl polyglycoside surfactants, and mixtures thereof, are described below.

In a highly preferred aspect of the invention, the stabilizer comprises polyhydroxy fatty acid amides and/or polyethylene glycol, and/or alkoxylated fatty acid amides and/or fatty alcohols with 1 to 15, or more preferably 11 moles of alkylene oxide Mixtures of condensation products of , as described in more detail below in the description of suitable surfactants. When present, the ratio of polyhydroxy fatty acid amide to fatty alcohol condensation product is preferably 20:1 to 1:20, more preferably 10:1 to 1:10, more preferably 8:1 to 1:8, more preferably 6:1 - 1:6, most preferably 2:1-1:3. When present, the ratio of polyhydroxy fatty acid amides to polyethylene glycol is preferably from 20:1 to 1:8, more preferably from 15:1 to 1:3, more preferably from 12:1 to 1:1, more preferably 10:1 -1:1. When present, the ratio of polyhydroxy fatty acid amides to alkoxylated fatty acid amides is preferably from 20:1 to 1:20, more preferably from 15:1 to 1:10, more preferably from 10:1 to 1:10. Surfactants suitable for use in detergent compositions

The detergent compositions of the present invention may contain one or more surfactants selected from the group consisting of anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants or nonionic surfactants such as Active agents, and mixtures thereof.

A general list of these surfactants is given in US 3,929,678, issued December 30, 1975 to Laughlin and Heuring. Additional examples are given in "Surface Active Agents and Detergents" (Vol. I and II, Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in US Patent 4,259,217, Murphy, issued March 31,1981. Some examples are given below. anionic surfactant

Any anionic surfactant can be incorporated in the compositions of the present invention. The anionic surfactants herein preferably comprise at least one sulfate surfactant and/or sulfonate surfactant or mixtures thereof. Preferred anionic surfactants include alkyl sulfonate surfactants alone or optionally in combination with fatty acids or soap salts thereof. Additionally, it is preferred that the composition comprises only alkyl sulphate surfactants, but here preferably at least one mid-chain branched alkyl surfactant is present or at least two alkyl surfactants are present.

Depending on the exact formulation of the composition and its use, it is preferred that the composition according to the invention comprises a granular component as described above, preferably in the form of flakes of an alkyl sulfate or sulfonate surfactant, preferably an alkyl benzene sulfonate, It is contained in a concentration of 85%-95% in granules or cakes, the balance being sulphate and water, which are mixed with other detergent components or ingredients.

Other possible anionic surfactants include isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurates, alkyl succinates, and alkyl sulfonates Succinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₄ di esters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow.

Depending on the exact formulation of the composition and its use, it is preferred that the compositions of the present invention comprise a component comprising a high level of alkyl sulfate or sulfonate surfactant or a mixture thereof in intimate admixture with sulfate and water, Alkylbenzenesulfonates are preferred. For example such a composition comprises 85%-95% of an anionic sulfate or sulfonate surfactant and 15%-5% sulfate and water. This component may be in the form of flakes which may be mixed with other ingredients of the detergent compositions of the present invention or added dry thereto. Anionic Sulfonate Surfactant

Anionic sulfonate surfactants according to the present invention include C ₅ -C ₂₀ linear or branched alkylbenzene sulfonates, alkyl ester sulfonates, C ₆ -C ₂₂ primary or secondary alkane sulfonates, C ₆ - _C24 olefinic sulfonates, sulfonated polycarboxylic acids and any mixtures thereof.

Highly preferred are C12-C16 linear alkylbenzene sulfonates. Preferred salts are sodium and potassium salts.

Sulfonated alkyl ester surfactants are also suitable for the present invention, preferably those having the formula:

R ¹ -CH(SO ₃ M)-(A) _x -C(O)-OR ² wherein R ¹ is C ₆ -C ₂₂ hydrocarbon group, R ² is C ₁ -C ₆ alkyl, A is C ₆ -C ₂₂ Alkylene, alkenylene, x is 0 or 1, M is a cation. The counterion M is preferably sodium, potassium or ammonium.

The sulfonated alkyl ester surfactant is preferably an alpha-sulfoalkyl ester of the above formula whereby x is zero. Preferably, R ¹ is an alkyl or alkenyl group having 10-22 carbon atoms, preferably 16 carbon atoms, and x is preferably 0. ^R2 is preferably ethyl or more preferably methyl.

Preferably ^R1 of the ester is derived from an unsaturated fatty acid preferably having 1, 2 or 3 double bonds. It is also preferred that ^R1 of the ester is derived from a naturally occurring fatty acid, preferably palmitic acid or stearic acid or mixtures thereof. Anionic Alkyl Sulfate Surfactant

Anionic sulfate surfactants of the present invention include linear and branched primary and secondary alkyl sulfates and disulfates, alkyl ethoxy sulfates having an average ethoxylation value of 3 or less, fatty Oleoyl Glyceryl Sulfate, Alkyl Phenoxyethylene Sulfate, C ₅ -C ₁₇ Acyl-N-(C ₁ -C ₄ Alkyl) and -N-(C ₁ -C ₂ Hydroxyalkyl) Glucosamine Sulfates, and sulfates of alkyl polysaccharides.

The primary alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably C ₁₁ -C ₁₅ linear or branched chain alkyl sulfates, or more preferably C ₁₂ - _C14 linear alkyl sulfate.

Preferred secondary alkyl sulfate surfactants have the formula:

R ³ -CH(SO ₄ M)-R ⁴ wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, R ⁴ is a hydrocarbon group, and M is a cation.

The alkyl ethoxy sulfate surfactants are preferably selected from C ₁₀ -C ₁₈ alkyl sulfates ethoxylated with 0.5 to 3 moles of ethylene oxide per mole. More preferably, the alkyl ethoxy sulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkane ethoxylated with 0.5-3, preferably 1-3 moles per mole of ethylene oxide. base sulfate.

A particularly preferred aspect of the invention is the use of mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Preferred salts are sodium and potassium salts. Mid-chain branched anionic surfactants

这些表面活性剂具有直链伯烷基硫酸盐链骨架(即包括硫酸化的碳原子的最长碳直链)，其优选包含12-19个碳原子并且它们支化的伯烷基部分优选包含总共至少14个碳原子，优选不超过20个碳原子。在包含多于一种这些硫酸盐表面活性剂的表面活性剂体系中，支化的伯烷基部分的平均总碳原子数优选大于14.5-约17.5。因此，该表面活性剂体系优选包含至少一种支化的伯烷基硫酸盐表面活性剂化合物，其具有不少于12个碳原子或不多于19个碳原子的最长碳直链，和包括支链的碳原子总数必须至少为14，另外，对于支化伯烷基部分，平均总碳原子数为大于14.5-约17.5。Preferred mid-chain branched primary alkyl sulfate surfactants for use herein have the formula:

These surfactants have a backbone of linear primary alkyl sulfate chains (i.e. the longest straight chain of carbons including the sulfated carbon atoms) which preferably contain 12-19 carbon atoms and their branched primary alkyl moieties preferably contain A total of at least 14 carbon atoms, preferably no more than 20 carbon atoms. In surfactant systems comprising more than one of these sulfate surfactants, the average total number of carbon atoms in the branched primary alkyl moieties is preferably greater than 14.5 to about 17.5. Accordingly, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having the longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and The total number of carbon atoms including branching must be at least 14, additionally, for branched primary alkyl moieties, the average total number of carbon atoms is from greater than 14.5 to about 17.5.

R, ^R and ^R are each independently selected from hydrogen and C ₁ -C ₃ alkyl (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, and most preferably methyl), with the proviso that R , R ¹ and R ² are not both hydrogen. Additionally, when z is 1, at least R or ^R1 is not hydrogen.

M is hydrogen or a salt-forming cation, depending on the method of synthesis.

w is an integer of 0-13; x is an integer of 0-13; y is an integer of 0-13; z is an integer of at least 1; and w+x+y+z is an integer of 8-14.

Preferred mid-chain branched primary alkyl sulfate surfactants are primary alkyl sulfate surfactants of 16 total carbons with 1, 2 or 3 of 13 carbons and a total of 3 carbon atoms in their backbone. branching units (ie R, R ¹ and/or R ² ), (thereby the total number of carbon atoms is at least 16). Preferred branching units may be one propyl branching unit or three methyl branching units.

Another preferred surfactant is a branched primary alkyl sulfate having the formula: wherein the total number of carbon atoms including branching is from 15 to 18, and when more than one of these sulfates are present, the average total number of carbon atoms in the branched primary alkyl portion having the above formula is greater than 14.5 to about 17.5; R ¹ and R ² are each independently hydrogen or C ₁ -C ₃ alkyl; M is a water-soluble cation; x is 0-11; y is 0-11; z is at least 2; and x+y+z is 9 -13; with the proviso that ^R1 and ^R2 are not both hydrogen. double anionic surfactant

其中R是具有链长C₁-C₂₈，优选C₃-C₂₄、最优选C₈-C₂₀的任选被取代的烷基、链烯基、芳基、烷芳基、醚、酯、胺或酰胺基团，或氢；A和B独立地选自链长为C₁-C₂₈，优选C₁-C₅，最优选C₁或C₂的亚烷基、亚链烯基、(聚)亚烷氧基、羟亚烷基、芳基亚烷基或酰氨基亚烷基，或共价键，优选A和B总共含有至少2个碳原子；A、B和R总共含有4至约31个碳原子；X和Y是选自羧酸根，优选硫酸根和磺酸根的阴离子基团；z是0或优选是1；和M是阳离子部分，优选是取代的或未取代的铵离子、或碱金属或碱土金属离子。Dianionic surfactants are also useful anionic surfactants herein, especially those having the formula:

wherein R is optionally substituted alkyl _{, alkenyl , aryl} , _alkaryl , _ether , ester, Amine or amide group, or hydrogen; A and B are independently selected from chain lengths of C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ or C ₂ alkylene, alkenylene, ( Poly)alkyleneoxy, hydroxyalkylene, arylalkylene or amidoalkylene, or covalent bond, preferably A and B together contain at least 2 carbon atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from carboxylate, preferably sulfate and sulfonate; z is 0 or preferably 1; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion , or alkali metal or alkaline earth metal ions.

The most preferred dianionic surfactants have the formula above, wherein R is an alkyl group having a chain length of _C10 - _C18 , A and B are independently _C1 or _C2 , X and Y are both sulfate, and M is potassium , ammonium or sodium ions.

Preferred dianionic surfactants of the present invention include:

(a) 3 disulfate compounds, preferably 1,3 C7-C23 (i.e. the total number of carbon atoms in the molecule) linear or branched chain alkyl or alkenyl disulfates, more preferably they have the formula: wherein R is a straight or branched chain alkyl or alkenyl group having a chain length of from about _C4 to about _C20 ;

(b) 1,4 disulfate compounds, preferably 1,4 C8-C22 linear or branched chain alkyl or alkenyl disulfates, more preferably having the following formula: wherein R is a straight or branched chain alkyl or alkenyl group having a chain length of about _C4 to about _C18 ; preferably R is selected from the group consisting of octyl, nonyl, decyl, dodecyl, tetradecyl, decadecyl Hexaalkyl, octadecyl, and mixtures thereof; and

其中R是具有链长约C₄-约C₁₈的直链或支链烷基或链烯基。(c) 1,5 disulfate compound, preferably 1,5 C9-C23 linear or branched chain alkyl or alkenyl disulfate, more preferably it has the following formula:

wherein R is a straight or branched chain alkyl or alkenyl group having a chain length of from about _C4 to about _C18 .

Preferably the dianionic surfactants of the present invention are alkoxylated dianionic surfactants.

The alkoxylated dianionic surfactants of the present invention comprise a structural backbone of at least 5 carbon atoms to which two anionic substituents are spatially separated by at least three carbon atoms. At least one of the anionic substituents is a sulfate or sulfonate group attached to an alkoxy group. The structural backbone may comprise, for example, any of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine, and amide groups. Preferred alkoxy moieties are ethoxy, propoxy and mixtures thereof.

The structural backbone preferably comprises 5-32, preferably 7-28, most preferably 12-24 atoms. Preferably the structural backbone comprises only carbon-containing groups, more preferably only hydrocarbyl groups. Most preferably the structural backbone contains only straight or branched chain alkyl groups.

The structural backbone is preferably branched. Preferably, the branched chain accounts for at least 10% by weight of the structural backbone, and the length of the branched chain is preferably 1-5 atoms, more preferably 1-3, most preferably 1-2 atoms (excluding sulfate or sulfonate groups attached to the branched chain). ).

Preferred alkoxylated dianionic surfactants have the formula: wherein R is _optionally substituted alkyl, _alkenyl , _{aryl , alkaryl ,} ether, ester, Amine or amide groups, or hydrogen; A and B are independently selected from optionally substituted alkyl and alkenes having a chain length C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ or C ₂ group, or a covalent bond; EO/PO is an alkoxy moiety selected from ethoxy, propoxy and mixed ethoxy/propoxy groups, wherein n and m independently range from about 0 to about 10 range, at least m or n is at least 1; A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from sulfate and sulfonate , with the proviso that at least one of X or Y is sulfate; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion.

The most preferred alkoxylated dianionic surfactants have the above formula, wherein R is an alkyl group having a chain length of _C10 to _C18 , A and B are independently _C1 or _C2 , n and m are both 1, Both X and Y are sulfate radicals, and M is potassium, ammonium or sodium ion.

Preferred alkoxylated dianionic surfactants of the invention include: ethoxylated and/or propoxylated disulfate compounds, preferably C10-C24 linear or branched chain alkyl or alkenyl ethoxylated and/or propoxylated disulfates, more preferably of the formula: wherein R is a straight or branched chain alkyl or alkenyl group with a chain length of about _C6 to about _C18 ; EO/PO is an alkoxy moiety selected from ethoxy, propoxy and mixed ethoxy/ Propoxy group; wherein n and m are independently in the range of about 0 to about 10 (preferably about 0 to about 5), at least m or n is 1. Anionic Carboxylate Surfactants

Suitable anionic carboxylate surfactants include alkyl ethoxy carboxylates, alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxylate" soaps), especially as described herein Certain secondary soaps.

Suitable alkyl ethoxy carboxylates include those having the formula RO(CH ₂ CH ₂ O) _x CH ₂ COO ⁻ M ⁺ , wherein R is C ₆ -C ₁₈ alkyl, x is 0-10, and The distribution of the ethoxylates is such that the amount of species where x is 0 is less than 20% by weight and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those of the formula RO-(CHR ₁ -CHR ₂ -O)-R ₃ wherein R is an alkyl group of C ₆ -C ₁₈ mats and x is 1-25, R _{and R} are selected from hydrogen, formyl, succinic, hydroxysuccinic and mixtures thereof, _R is selected from hydrogen, substituted or unsubstituted hydrocarbon groups having 1-8 carbon atoms, or its mixture.

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

Certain soaps can also be added as suds suppressors. Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are alkali metal sarcosinates of the formula R-CON(R ¹ )CH ₂ COOM, wherein R is C ₅ -C ₁₇ -straight chain or branched chain alkyl or alkenyl, R ¹ is a C ₁ -C ₄ alkyl group, and M is an alkali metal ion. Preferred examples are myristyl and oleoyl methyl sarcosinates in the sodium salt form. Nonionic Alkoxylated Surfactants

When nonionic surfactants are present, it is preferred that the components of the compositions of the present invention do not contain nonionic alkoxylated alcohol surfactants which are sprayed on. It has been found that this improves dosing of the composition into the wash water and reduces product caking. Preferably the composition comprises a nonionic surfactant which is solid below 30°C or even 40°C, preferably in intimate admixture with the other components.

Essentially any alkoxylated nonionic surfactant can also be included in the detergent compositions herein. Ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants may be selected from nonionic alkylphenol condensates, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylated/propoxylated condensates with propylene glycol, and nonionic ethoxylated condensation products with propylene oxide/ethylenediamine adducts.

Highly preferred are nonionic alkoxylated alcohol surfactants which are fatty alcohols with 1-75 moles of alkylene oxide, especially about 50 or 1-15 moles, preferably to 11 moles, in particular ethylene oxide and/or or the condensation product of propylene oxide, which is a highly preferred nonionic surfactant for inclusion in the anhydrous component of the granules of the invention. The alkyl chain of the fatty alcohol may be straight or branched, primary or secondary, and generally contains 6-22 carbon atoms. Particular preference is given to condensation products of alkyl groups having 8 to 20 carbon atoms with 2 to 9 moles, in particular 3 or 5 moles, of ethylene oxide per mole of alcohol. Nonionic Polyhydroxy Fatty Acid Amide Surfactant

Polyhydroxy fatty acid amides are highly preferred nonionic surfactants for ^use herein, especially those having the formula: ^R2CONR1Z , where ^R1 is H, _C1-18 , preferably _C1 - _C4 hydrocarbyl , 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or mixtures thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl ( i.e. methyl); R ² is C ₅ -C ₃₁ hydrocarbon group, preferably straight chain C ₅ -C ₁₉ or C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl Z is a straight-chain C ₁₁ -C ₁₇ alkyl or alkenyl group, or a mixture thereof; Z is a polyhydroxyl hydrocarbon group having a straight-chain hydrocarbon group directly attached to at least 3 hydroxyl groups, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Highly preferred nonionic polyhydroxy fatty acid amide surfactants for use herein are _C12 - _C14 , _C15 - _C17 and/or _C16 - _C18 alkyl N-methyl glucamides.

In particular the condensation of C ₁₂ -C ₁₈ alkyl N-methyl glucamides and alcohols having alkyl groups having 8-20 carbon atoms with 2-9 moles, especially 3 or 5 moles, of ethylene oxide per mole product.

Polyhydroxy fatty acid amides can be prepared by any suitable method. A particularly preferred method is described in detail in WO9206984. Nonionic Fatty Acid Amide Surfactant

Fatty acid amide surfactants or alkoxylated fatty acid amides include those having the formula: R ⁶ CON(R ⁷ )(R ⁸ ), wherein R ⁶ is a carbon atom containing 7-21, preferably 9-17 or even 11 -Alkyl of 13 carbon atoms, R ⁷ and R ⁸ are each independently selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and -(C ₂ H ₄ O) _x H, wherein x is 1-11, preferably 1-7, more preferably 1-5, whereby preferably ^R7 and ^R8 are different, one having x being 1 or 2 and one having x being 3-11 or preferably 5. Nonionic fatty acid alkyl ester surfactant

Fatty acid alkyl esters include those having the formula R ⁹ COO(R ¹⁰ ), wherein R ⁹ is an alkyl group containing 7-21, preferably 9-17 carbon atoms or even 11-13 carbon atoms, and R ¹⁰ is C ₁₀ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, or -(C ₂ H ₄ O) _x H, wherein x is 1-11, preferably 1-7, more preferably 1-5, thus preferably R ¹⁰ is methyl or ethyl. Nonionic Alkyl Polysaccharide Surfactant

Alkyl polysaccharides may also be included in the anhydrous material of the particles of the present invention, such as those disclosed in US 4,565,647 to Llenado, issued January 21, 1986, which have hydrophobic groups containing 6-30 carbon atoms and contain 1.3 - Hydrophilic groups of polysaccharides of 10 sugar units, such as polyglycosides.

Preferred alkylpolyglycosides have the formula: ^R2O ( _CnH2nO ) _t ( _glycosyl ) _x wherein ^R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and other The mixture, wherein the alkyl group contains 10-18 carbon atoms; n is 2 or 3; t is 0-10; x is 1.3-8. The glycosyl is preferably derived from glucose. cationic surfactant

Another preferred component of the composition of the present invention is a cationic surfactant, preferably in an amount of 0.1%-60%, more preferably 0.4%-20%, most preferably 0.5%-5% by weight of the composition .

When present, the ratio of anionic surfactant to cationic surfactant is preferably from 25:1 to 1:3, more preferably from 15:1 to 1:1, most preferably from 10:1 to 1:1. The ratio of cationic surfactant to stabilizer is preferably 1:30-20:1, more preferably 1:20-10:1.

Preferably the cationic surfactant is selected from cationic ester surfactants, cationic monoalkoxylated amine surfactants, cationic dialkoxylated amine surfactants and mixtures thereof. Cationic Monoalkoxylated Amine Surfactants

其中R¹是含有约6-约18个碳原子，优选6-约16个碳原子，最优选约6-约11个碳原子的烷基或链烯基；R²和R³各独立地是含有1-约3个碳原子的烷基，优选甲基；R⁴选自氢(优选的)、甲基和乙基，X-是提供电中性的阴离子，例如氯、溴、甲基硫酸根、硫酸根等。A选自C₁-C₄烷氧基，特别是乙氧基(即-CH₂CH₂O-)、丙氧基、丁氧基和其混合物；p是1-约30，优选1-约15，最优选1-约8。Optional cationic monoalkoxylated amine surfactants useful herein have the general formula:

Wherein ^R is an alkyl or alkenyl group containing about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably about 6 to about 11 carbon atoms; R ^{and R} are each independently An alkyl group containing 1 to about 3 carbon atoms, preferably methyl; R ^is selected from hydrogen (preferred), methyl and ethyl, and X- is an anion that provides electrical neutrality, such as chlorine, bromine, methylsulfuric acid root, sulphate, etc. A is selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixtures thereof; p is 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.

Highly preferred cationic monoalkoxylated amine surfactants for use herein have the formula: wherein R ¹ is C ₆ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₆ -C ₁₄ , especially C ₆ -C ₁₁ alkyl, preferably C ₈ and C ₁₀ alkyl, and X is any suitable charge balance Anion, preferably chlorine or bromine.

As noted, compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy, isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH( Those replaced by CH ₃ O] units (i-Pr) or n-propoxyl units (Pr) or mixtures of EO and/or Pr and/or i-Pr units. Cationic dialkoxylated amine surfactants

其中R¹是含有约6-约18个碳原子，优选6-约16个碳原子，更优选6-约11，最优选约8-约10个碳原子的烷基或链烯基部分；R²是含有1-3个碳原子的烷基，优选甲基；R³和R⁴可独立地变化，它们选自氢(优选的)、甲基和乙基；X^-是足以提供电中性的阴离子，例如氯、溴、甲基硫酸根、硫酸根等。A和A’可独立地变化，各选自C₁-C₄烷氧基，特别是乙氧基(即-CH₂CH₂O-)、丙氧基、丁氧基和它们的混合物；p是1-约30，优选1-约4，q是1-约30，优选1-约4，最优选p和q都是1。The cationic dialkoxylated amine surfactants useful in the present invention have the general formula:

wherein ^R is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably from 6 to about 16 carbon atoms, more preferably from 6 to about 11, most preferably from about 8 to about 10 carbon atoms; R ² is an alkyl group containing 1-3 carbon atoms, preferably methyl; ^R3 and ^R4 can vary independently, they are selected from hydrogen (preferred), methyl and ethyl; ^X- is sufficient to provide electrical neutrality Anions such as chlorine, bromine, methylsulfate, sulfate, etc. A and A' can vary independently, each selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixtures thereof; p is 1 to about 30, preferably 1 to about 4, q is 1 to about 30, preferably 1 to about 4, most preferably both p and q are 1.

Highly preferred cationic dialkoxylated amine surfactants for use herein have the formula: wherein R ¹ is C ₆ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, and X is any suitable anion providing charge balance, preferably chlorine. With regard to the general structure of the above cationic dialkoxylated amines, in preferred compounds ^R1 is derived from a fatty acid of the (coco) _C12 - _C14 alkyl moiety, ^R2 is methyl, ^ApR3 and A' pR ⁴ are both monoethoxy.

Other cationic dialkoxylated amine surfactants suitable for use herein include compounds of the formula: wherein R ¹ is C ₆ -C ₁₈ hydrocarbyl, preferably C ₆ -C ₁₄ alkyl, p is independently 1 to about 3, q is 1 to about 3, R ² is C ₁ -C ₃ alkyl, preferably methyl , X is an anion, especially chlorine or bromine.

Other compounds of the above type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O] units (i-Pr) or n-propoxy units (Pr) or mixtures of EO and/or Pr and/or i-Pr units replace those. Amphoteric surfactants

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

Suitable amine oxides include those compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ³ is selected from the group consisting of alkyl, hydroxyalkyl, acylamidopropyl and Alkylphenyl, or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing 2-3 carbon atoms, or a mixture thereof; x is 0-5, preferably 0-3; each R ⁵ is a Alkyl or hydroxyalkyl groups with 1-3 carbon atoms, or polyoxyethylene groups with 1-3 oxyethylene groups. Preference is given to C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₁₀ -C ₁₈ acylamidoalkyldimethylamine oxides.

An example of a suitable alkyl amphodicarboxylic acid is Miranol(TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ. zwitterionic surfactant

Zwitterionic surfactants may also be incorporated into the particles of the invention or compositions containing the particles 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 sultaine surfactants are exemplary of zwitterionic surfactants useful in the present invention.

Suitable betaines are those compounds having the formula: R(R') ₂ N ⁺ R ^{2 COO-} , wherein R is C ₆ -C ₁₈ hydrocarbyl, each R ¹ is usually C ₁ -C ₃ alkyl, R ² It is a C ₁ -C ₅ hydrocarbon group. Preferred betaines are C ₁₂ -C ₁₈ dimethylammonium hexanoate and C ₁₀ -C ₁₈ acylamidopropane (or ethane) dimethyl (or diethyl) betaine. Complex betaine surfactants are also suitable for use in the present invention. other detergent ingredients

The detergent compositions of the present invention may contain other detersive actives or ingredients known in the art. The exact nature of these other ingredients and their incorporation will depend upon the physical form of the composition and the exact nature of the laundering operation for which it is used.

Other preferred ingredients include perfumes, brighteners or dyes or mixtures thereof which may be sprayed onto the particular components of the invention.

The compositions of the present invention preferably contain one or more other detergent ingredients selected from the group consisting of surfactants, bleaches, builders, chelating agents, (other) sources of alkalinity, organic polymeric compounds, enzymes, brighteners, pH Foaming agent, lime soap dispersant, soil suspending agent and anti-redeposition agent and corrosion inhibitor. Heavy metal ion chelating agent

Heavy metal ion sequestrants are also other components suitable for use in the present invention. The so-called heavy metal ion chelating agent herein refers to components that play the role of chelating heavy metal ions. These components may also have calcium and magnesium chelating capacity, but preferably they exhibit selectivity for binding heavy metal ions such as iron, manganese and copper.

The content of the heavy metal ion chelating agent is generally 0.005-10% by weight of the composition of the present invention, preferably 0.1%-5%, more preferably 0.25-7.5%, most preferably 0.3-2%.

Suitable heavy metal ion sequestrants for use in the present invention include organic phosphonates such as aminoalkylene poly(alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilotrimethylenephosphine salt.

Among the above substances, diethylenetriaminepenta(methylenephosphonate), ethylenediaminetris(methylenephosphonate), hexamethylenediaminetetrakis(methylenephosphonate) and hydroxyl - Ethylene 1,1-diphosphonate, 1,1-hydroxyethanediphosphonic acid and 1,1-hydroxyethane dimethylenephosphonic acid.

Other heavy metal ion sequestrants suitable for use in the present invention include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid, ethylenediaminediglutaric acid, 2-hydroxypropylene Diamine disuccinic acid or any salt thereof.

Other heavy metal ion sequestrants suitable for use in the present invention are iminodiacetic acid derivatives, such as 2-hydroxyethyldiacetic acid or glyceryl iminodiacetic acid, as described in EP-A-317,542 and EP-A-399,133. Iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid chelating agent described in EP-A-5126,102 Also applicable to the present invention. β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodiacetic acid described in EP-A-509,382 Succinic acid chelating agents are also suitable.

EP-A-476,257 describes suitable amino-based chelating agents. EP-A-510,311 describes suitable chelating agents derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyliminodiacetic acid sequestrant. Also suitable are dipicolinic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. Glycineamide-N,N'-disuccinic acid (GADS), Ethylenediamine-N,N'-diglutaric acid (EDDC) and 2-hydroxypropylenediamine-N,N'-disuccinic acid (HPDDS) is also suitable.

Particularly preferred are diethylenetriaminepentaacetic acid, ethylenediamine-N,N'-disuccinic acid (EDDS) and 1,1-hydroxyethanediphosphonic acid or their alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. perhydrate bleach

Preferably the detergent compositions of the present invention comprise a peroxygen bleach, preferably a source of hydrogen peroxide and a bleach precursor or activator. Since the present invention improves product release into the wash, it increases bleach efficacy and reduces fabric damage caused by bleach present in the detergent.

A preferred source of hydrogen peroxide is a perhydrate bleach, such as a metal perborate, more preferably a metal percarbonate, especially the sodium salt. Perborate may be monohydrate or tetrahydrate. Sodium percarbonate _has a chemical formula corresponding to _{2Na2CO3-3H2O2} and is commercially available as _a crystalline _solid .

In particular percarbonate is preferably coated. Suitable coating agents are known in the art and include silicates, magnesium salts and carbonates.

Potassium peroxymonopersulfate, its sodium salt, is another optional inorganic perhydrate salt for use in the detergent compositions herein. Organic Peroxyacid Bleach System

The compositions of the invention preferably feature an organic peroxyacid bleach system. In a preferred embodiment, the bleach system comprises a source of hydrogen peroxide and an organic peroxyacid bleach precursor compound. Organic peroxyacids can be produced by in situ reaction of precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches, such as the perborate bleaches described herein. In another preferred embodiment, preformed organic peroxyacids are added directly to the composition. Compositions comprising a mixture of a hydrogen peroxide source and an organic peroxyacid precursor mixed with a preformed organic peroxyacid are also contemplated. Peroxyacid Bleach Precursors

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Typically, peroxyacid bleach precursors are represented by the formula: Wherein, L is a leaving group, and X is basically any functional group, so that the peroxyacid structure produced during perhydrolysis is:

Peroxyacid bleach precursor compounds are preferably present at levels of from 0.5% to 20%, more preferably from 1% to 15%, most preferably from 1.5% to 10% by weight of the detergent composition.

Suitable peroxyacid bleach precursor compounds generally contain one or more N- or O-acyl groups and such precursors may be selected from a wide variety of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A-0170386. leaving group

The leaving group, hereinafter referred to as the L group, must be sufficiently reactive for the perhydrolysis reaction to occur during an optimal period of time, such as a wash cycle. However, if L is too reactive, the activator will be difficult to use stably in bleaching compositions.

其中，R¹为包含1-14个碳原子的烷基、芳基或烷芳基，R³为包含1-8个碳原子的烷基链，R⁴为H或R³，Y为H或增溶基团。R¹、R³和R⁴中任一种可基本上被任何官能团取代，包括例如烷基、羟基、烷氧基、卤素、氨基、亚硝酰基、酰氨基和铵或烷基铵基团。Preferred L groups are selected from the following groups or mixtures thereof:

Wherein, R ¹ is an alkyl, aryl or alkaryl group containing 1-14 carbon atoms, R ³ is an alkyl chain containing 1-8 carbon atoms, R ⁴ is H or R ³ , Y is H or Solubilizing group. Any of R ¹ , R ³ and R ⁴ may be substituted with essentially any functional group including, for example, alkyl, hydroxyl, alkoxy, halogen, amino, nitrosyl, amido, and ammonium or alkylammonium groups.

Preferred solubilizing groups are -SO ₃ ^- M ⁺ , -CO ₂ ^- M ⁺ , -SO ₄ ^- M ⁺ , -N ⁺ (R ³ ) ₄ X ^- and O<--N(R ³ ) ₃ , Most preferred are -SO ₃ ^{-M +} and -CO ₂ ^{-M +} , wherein R ³ is an alkyl group containing 1 to 4 carbon atoms, M is a cation that provides solubility to the bleach activator, and X is a cation that provides solubility to the bleach activator. Provides solubility anions. Preferably M is an alkali metal, ammonium or substituted ammonium cation, most preferably sodium and potassium, and X is a halide, hydroxide, methylsulfate or acetate anion. Alkyl percarboxylic acid bleach precursor

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid upon perhydrolysis.

Preferred imide-type alkyl percarboxylic acid precursor compounds include N,N,N ¹ ,N ¹ -tetraacetylated alkylenediamines, wherein the alkylene group contains 1 to 6 carbon atoms, Especially those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Particular preference is given to tetraacetylethylenediamine (TAED). TAED is preferably absent from the agglomerated particles of the present invention, but is preferably present in detergent compositions comprising the particles.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS), sodium nonanoyloxybenzenesulfonate (NOBS), acetoxybenzene Sodium Sulfonate (ABS) and Pentaacetyl Glucose. Amide Substituted Alkyl Peroxyacid Precursors

其中，R¹为具有1-14个碳原子的烷基，R²为具有1-14个碳原子的亚烷基，R⁵为H或包含1-10个碳原子的烷基，L基本上可以是任何离去基团。该类型的酰胺取代的漂白活化剂化合物在EP-A-0170386中有述。过苯甲酸前体 Amide substituted alkyl peroxyacid precursor compounds are suitable for use in the present invention and include compounds of the general formula:

Wherein, R ^is an alkyl group with 1-14 carbon atoms, ^R is an alkylene group with 1-14 carbon atoms, R is ^H or an alkyl group with 1-10 carbon atoms, and L is basically Can be any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. Precursor of perbenzoic acid

Perbenzoic acid precursor compounds provide perbenzoic acid upon perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzenesulfonates, and benzoylating sorbitol, glucose, and all sugars with benzoylating reagents. The products, those of the imide type, include N-benzoylsuccinimide, tetrabenzoylethylenediamine, and N-benzoyl-substituted ureas. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoylpyroglutamate. Preformed Organic Peroxyacids

The detergent compositions of the present invention may comprise, in addition to or alternatively, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 to 15 percent by weight of the composition of the present invention. %, more preferably 1-10%.

其中，R¹为具有1-14个碳原子的烷基、芳基或烷芳基，R²为具有1-14个碳原子的亚烷基、亚芳基和烷亚芳基，R⁵为H或具有1-10个碳原子的烷基、芳基或烷芳基。这种类型的酰胺取代的有机过氧酸化合物公开于EP-A-0170386中。A preferred class of organic peroxyacid compounds are amide substituted compounds having the general formula:

Wherein, R ¹ is an alkyl group, aryl group or alkaryl group with 1-14 carbon atoms, R ² is an alkylene group, arylene group and alkarylene group with 1-14 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are disclosed in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecandioic acid. Mono- and diperazelaic acid, mono- or dipertridecanedioic acid and N-naphthoylaminoperoxycaproic acid are also suitable for the present invention. enzyme

Another preferred component for use in the present invention is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, fruit enzymes conventionally added to detergent compositions. Gelase, Lactase and Peroxidase. Suitable enzymes are discussed in US3519570 and US3533139. organic polymer compound

Organic polymeric compounds are preferred additional components of the compositions of the present invention.

By organic polymeric compound is meant herein substantially any organic polymeric compound commonly used as a binder, dispersant, anti-redeposition agent and soil suspension agent in detergent compositions, including those described herein as clay flocculants Any high molecular weight organic polymeric compound, including quaternary ethoxylated (poly)amine clay-based detergents/anti-redeposition agents.

The organic polymeric compound is generally incorporated in the detergent compositions herein at a level of from 0.01 to 30%, preferably from 0.1 to 15%, more preferably from 0.5 to 10%, by weight of the composition.

Examples of organic polymeric compounds include water-soluble organic homo- or co-polymeric polycarboxylic acids or salts thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight (MWt) 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 2000-100,000, especially 40,000-80,000.

Polyamine compounds are useful herein and include those derived from aspartic acid, such as those described in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers comprising monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000-10,000, are also suitable for use in the present invention.

Other organic polymeric compounds suitable for incorporation into the detergent compositions of the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

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

Highly preferred polymeric components of the present invention are cotton and non-cotton soil release agent polymers according to Scheibel et al. US Patent No. 4,968,451 and Gosselink et al.

其中X为非离子基团，选自H、C₁-C₄烷基或羟基烷基酯或醚基团，和其混合物，a为0-20，优选0-4(如亚乙基、亚丙基、六亚甲基)，b为1或0；对于阳离子单胺(b＝0)，n至少为16，一般范围为20-35；对于阳离子二胺(b＝1)，n至少约12，一般范围为约12-约42。Another organic compound useful in the present invention, which is a preferred clay dispersant/anti-redeposition agent, can be a cationic ethoxylated monoamine and diamine having the formula:

Wherein X is a nonionic group selected from H, C ₁ -C ₄ alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is 0-20, preferably 0-4 (such as ethylene, ethylene propyl, hexamethylene), b is 1 or 0; for cationic monoamines (b=0), n is at least 16, generally in the range of 20-35; for cationic diamines (b=1), n is at least about 12, generally in the range of about 12 to about 42.

Other dispersants/anti-redeposition agents useful in the present invention are described in EP-B-011965, US4659802 and US4664848. Antifoam system

When the detergent composition of the present invention is formulated as a composition for machine washing, it may contain a suds suppressing system, by weight of the composition, in an amount of 0.01-15%, preferably 0.02-10%, more preferably 0.05- 3%.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound including, for example, silicone antifoam compounds and 2-alkyl alkanol antifoam compounds.

By antifoam compound is meant any compound or mixture thereof which acts, for example, to inhibit foaming or foaming of a solution of a detergent composition, especially when the solution is agitated.

Particularly preferred antifoam compounds for use in the present invention are silicone antifoam compounds, which are defined herein as any antifoam compound that includes a silicone component. Such silicone antifoam compounds typically also contain a silica component. The term "polysiloxane" as used herein and commonly used in the industry includes various relatively high molecular weight polymers containing siloxane units and various types of hydrocarbyl groups. Preferred silicone antifoam compounds are silicones, especially polydimethylsiloxanes having trimethylsilyl endcapping units.

Other suitable antifoam compounds include monobasic fatty carboxylic acids and soluble salts thereof. These substances are described in US 2954347, issued September 27, 1960 to Wayne St. John. The monohydric fatty carboxylic acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10-24 carbon atoms, preferably 12-18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty acid esters (such as fatty acid triglycerides), monohydric alcohol fatty acid esters, aliphatic C ₁₈ -C ₄₀ ketones (such as stearyl ketone), N-alkylated amino Triazines, such as tri to hexaalkylmelamines or di to tetraalkyl diamine chlorotriazines, which are cyanuric chloride and 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms, propylene oxide , distearyl amide and monostearyl phosphate dialkali metal (such as sodium, potassium, lithium) salts and phosphate reaction products.

A preferred suds suppressing system comprises: (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound comprising the following composition:

(i) polydimethylsiloxane, its content accounts for 50-99% by weight of polysiloxane antifoam compound, preferably 75-95%; And

(ii) silicon dioxide, its content accounts for 1-50% by weight of polysiloxane/polysiloxane antifoam compound, preferably 5-25%; The amount is 5%-50%, preferably 10%-40% by weight; (b) a dispersant compound, most preferably comprising polysiloxane diol rake copolymer (rakecopolymer), its polyoxyalkylene content is 72 -78%, the ratio of oxyethylene to oxypropylene is 1:0.9-1:1.1, its content is 0.5-10%, preferably 1-10% by weight; particularly preferred polysiloxane glycol rake copolymers of this type is DCO544, commercially available under the tradename DCO544 from DOW Corning; (c) an inert carrier compound, most preferably comprising a _C16 - _C18 ethoxylated alcohol having a degree of ethoxylation of 5-50, Preferably 8-15, its content is 5-80%, preferably 10-70% by weight.

Particularly preferred granular antifoam systems are disclosed in EP-A-0210731, which contain a polysiloxane antifoam compound and an organic carrier substance having a melting point of 50-85° C., wherein the organic carrier substance comprises glycerol Monoesters with a fatty acid having a carbon chain of 12-20 carbon atoms. EP-A-0210721 discloses other preferred granular suds suppressor systems in which the organic carrier substance is a fatty acid or alcohol having a carbon chain of 12-20 carbon atoms, or a mixture thereof, with a melting point of 45-80°C.

Other highly preferred suds suppressing systems include polydimethylsiloxane or polysiloxane blends such as polydimethylsiloxane, aluminosilicates and polycarboxylic acid polymers such as copolymers of lactic acid (laic) and acrylic acid things. polymeric dye transfer inhibitor

The compositions of the invention may also comprise from 0.01 to 10%, preferably from 0.05 to 0.5%, by weight of a polymeric dye transfer inhibiting agent.

The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or mixtures thereof, whereby these polymers may be cross-linked polymer. Fluorescent whitening agent

The compositions of the present invention also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners known in the art. polymeric soil release agent

Polymeric soil release agents, hereinafter abbreviated "SRA", may optionally be used in the compositions of the present invention. If used, SRA's generally comprise from 0.01% to 10.0% by weight of the composition, typically from 0.1% to 5% by weight, preferably from 0.2% to 3.0% by weight.

Preferred SRA's generally have a hydrophilic portion that hydrophilizes the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic portion that deposits on the hydrophobic fiber and remains attached to it throughout the wash and rinse cycle, thus acting as the hydrophilic portion of fixtures. This can make stains subsequently created by the SRA treatment easier to remove in subsequent washes.

Preferred SRA's include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization reaction, usually over a metal catalyst such as titanium(IV) alkoxide. The esters can be prepared using other monomers that can incorporate ester structures through one, two, three, four or more positions, without, of course, forming a dense fully cross-linked structure.

Suitable SRA's include sulfonation products of substantially linear ester oligomers containing a terephthaloyl oligoester backbone with oxyalkylene oxygen repeat units and allyl derivatives covalently attached to the backbone. Sulfonated terminal moieties are described, for example, in US Patent No. 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. The ester oligomer can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with dimethyl terephthalate in a two-step transesterification/oligomerization step ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters, e.g. ) methyl ether, DMT, PG, and poly(ethylene glycol) ("PEG") transesterification/oligomerization products. Other examples of SRA's include partially and fully anionically terminated oligoesters such as those derived from ethylene glycol ("EG"), PG, DMT and 3,6- Oligomers of sodium dioxa-8-hydroxyoctane sulfonate; non-ionic end-capped block polyester oligomers in U.S. Patent No. 4,702,857, Gosselink, issued October 27, 1987, such as DMT, methyl (Me)-capped PEG and EG and/or PG, or a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl-5-sulfoisophthalate and anions in U.S. Patent No. 4,877,896 issued October 31, 1989 to Maldonado, Gosselink et al., especially sulfoaroyl-terminated terephthalates, which are typically found in both laundry and fabric conditioning products. An example of useful SRA's is an ester composition prepared from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally, but preferably also containing added PEG, eg, PEG3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyoxyethylene or polyoxypropylene terephthalate, see Hays, May 25, 1976 U.S. Patent No. 3,959,230 and U.S. Patent No. 3,893,929 of Basadur on July 8, 1975; cellulose derivatives such as hydroxyether cellulose polymers available from Dow by METHOCEL; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkane cellulose, see U.S. Patent No. 4,000,093 to Nicol et al., December 28, 1976; and methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit of from about 1.6 to about 2.3, according to A 2% aqueous solution has a solution viscosity of about 80 to about 120 centipoise measured at 20°C. Such substances are commercially available as METOLOSE SM100 and METOLOSE SM200, which are trade names of methyl cellulose ethers produced by Shin-etsu Kagaku Kogyo KK.

Another class of SRA's includes: (I) nonionic terephthalate esters linked to polyester structures using diisocyanate coupling agents, see U.S. Pat. Nos. 4,201,824 to Violland et al. and U.S. Pat. SRA's having carboxylate end groups prepared by adding trimellitic anhydride to known SRA's to convert the terminal hydroxyl groups to trimellitate esters. With proper choice of catalyst, trimellitic anhydride forms linkages to the terminal groups of the polymer through the isolated carboxylate of trimellitic anhydride rather than by opening the anhydride linkage. Both nonionic and anionic SRA's can be used as starting materials as long as they have hydroxyl end groups that can be esterified, see US Patent No. 4,525,524 to Tung et al. Other types include: (III) Anionic terephthalate-based SRA's linked to urethanes, see US Patent No. 4,201,824 to Violland et al. other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the present invention include perfumes, speckles, pigments or dyes, filler salts, sodium sulfate being the preferred filler salt. Additionally, minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffers, phase regulators, hydrotropes, enzyme stabilizers, polyacids, foam regulators, opacifiers, antioxidants, bactericides, and dyes may be included. , such as those described in US Patent No. 4,285,841 to Barrat et al., issued August 25, 1981 (which is incorporated herein by reference). Highly preferred are encapsulated fragrances, preferably comprising starch encapsulates.

In the compositions of the present invention, when the dye and/or perfume is sprayed onto another component, it is preferred that the component does not include the nonionic alkoxylated alcohol surfactant sprayed on. form of composition

The compositions of the present invention can be prepared by a variety of methods, including mixing components, including dry blending of the various compounds contained in detergent components, compaction such as agglomeration, extrusion, tableting, or spray drying, Or a mixture of these techniques, whereby the composition of the invention can also be prepared by, for example, compression molding, including extrusion and agglomeration, or spray drying.

The compositions of the present invention may take various solid physical forms including, for example, tablets, flakes, lozenges and bars, preferably the composition is in the form of granules or flakes.

The compositions of the present invention may also be used in or in combination with bleach additive compositions, for example those comprising chlorine bleach.

The composition preferably has a density greater than 350 g/l, more preferably greater than 450 g/l, or even greater than 570 g/l.

The following are some examples of detergent compositions according to the invention. Abbreviations used in the examples

In the detergent composition of the following example, the abbreviated component symbols have the following meanings: LAS: linear C _11-13 sodium alkylbenzene sulfonate LAS (I): containing linear C _11-13 alkylbenzene sulfonic acid Flakes of sodium (90%) and sodium sulfate and moisture LAS(II): Potassium linear C _11-13 alkylbenzene sulfonate MES: α-sulfonated C ₁₈ fatty acid methyl ester TAS: Sodium tallow alkyl sulfate C _xy AS : C _1X -C _1Y sodium alkyl sulfate C46SAS : C ₁₄ -C ₁₆ secondary (2,3) alkyl sodium C _xy E _z S : C _1X -C _1y condensed with Z moles of ethylene oxide Sodium Alkyl Sulfate C _XY E _Z : Predominantly linear C _1X -C _1y primary alcohols condensed with average Z moles of ethylene oxide QAS : R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄ QAS1 : R ² N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₈ -C ₁₁ SADS : Formula 2-(R)C ₄ H ₇ -1, 4-(SO ₄ -) ₂ sodium C ₁₄ -C ₂₂ alkyl disulfate, where R = C ₁₀

-C ₁₈ SADE2S : Sodium C ₁₄ -C ₂₂ alkyl disulfate of the formula 2-(R)C ₄ H ₇ -1,4-(SO ₄ -) ₂ , where R=C ₁₀

-C ₁₈ , condensed z moles of ethylene oxide APA: C ₈ -C ₁₀ amidopropyl dimethylamine soap: sodium linear alkyl carboxylate, STS obtained from 80/20 mixture of tallow and coconut fatty acids: Sodium tosylate CFAA: C ₁₂ -C ₁₄ (coconut oil) alkyl N-methyl glucamide TFAA: C ₁₆ -C ₁₈ alkyl N-methyl glucamide TPKFA: C ₁₆ -C ₁₈ topped Fraction fatty acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ .27H ₂ O, primary particle size is

0.1-10 microns (weight expressed on anhydrous basis) NaSKS-6(I): a crystalline phyllosilicate of formula δ-Na ₂ Si ₂ O ₅ with a weight-average particle size of 18 microns, up to

At least 90% by weight of a particle size below 65.6 microns NaSKS-6(II): crystalline phyllosilicates of _the formula δ- _Na2Si2O5 having _a weight-average particle size of 18 microns to

Less than 90% by weight of particle size below 42.1 microns Citric acid: Anhydrous citrate Borate: Sodium borate Carbonate: Particle size 200-900 microns Anhydrous sodium carbonate bicarbonate: Particle size distribution 400-1200 microns Anhydrous Sodium Bicarbonate Silicate: Amorphous Sodium Silicate (SiO ₂ : Na ₂ O Ratio = 2.0:1) Sulfate: Anhydrous Sodium Sulfate Magnesium Sulfate: Anhydrous Magnesium Sulfate Citrate: Trisodium Citrate Dihydrate, active 86.4%, particle size distribution in 425-850 microns

MMA/AA : 1:4 maleic acid/acrylic acid copolymer, average molecular weight about 70000MA/AA(1): 4:6 maleic acid/acrylic acid copolymer, average molecular weight about 10000AA : sodium polyacrylate polymer with average molecular weight 4500 CMC: sodium carboxymethyl cellulose cellulose ether: methyl cellulose ether with a degree of polymerization of 650, purchased from Shin Etsu Chemicals

Protease: protein water sold under the tradename Savinase by Novo Industries A/S

Hydrolytic enzyme with 3.3% by weight active enzyme Protease I: proteolytic enzyme described in WO95/10591 with 4% by weight active enzyme,

Sold by Genencor Int. Inc. Alcalase: a proteolytic enzyme sold by Novo Industries A/S with 5.3% by weight

Amount of active enzyme Cellulase: cellulose sold under the trade name Carezyme by Novo Industries A/S

Enzyme with 0.23% by weight active enzyme Amylase: sold under the tradename Termamyl 120T by Novo Industries A/S

Amylase with 1.6% by weight activity Enzyme Amylase II: the amylase disclosed in PCT/US9703635 Lipase: a lipolytic enzyme sold under the tradename Lipolase by Novo Industries A/S,

With 2.0% by weight active enzyme lipase (1): sold by Novo Industries A/S under the tradename Lipolase Ultra

Lipolytic enzyme with 2.0% by weight activity Enzyme Endolase: Endoglucanase, marketed by Novo Industries A/S, with 1.5

% weight activity Enzyme PB4: _Sodium perborate _tetrahydrate of _standard formula _{NaBO2.3H2OH2O2} PB1: _Anhydrous sodium _perborate bleach of standard formula _NaBO2.H2O2 Sodium percarbonate: Standard formula 2Na ₂ CO ₃ 3H ₂ O ₂ sodium percarbonate DOBS: decanoyloxybenzenesulfonate, sodium salt form DPDA: diperoxydodecanedioic acid NOBS: nonanoyloxybenzenesulfonate, sodium salt form NACA-OBS: (6-nonanoylhexanoyl)oxybenzenesulfonate LOBS: dodecanoyloxybenzenesulfonate in sodium salt form DOBS: decanoyloxybenzenesulfonate in sodium salt form DOBA: decane Acyloxybenzoic acid TAED: Tetraacetylethylenediamine DTPA: Diethylenetriaminepentaacetic acid DTPMP: Diethylenetriaminepenta(methylene phosphoric acid), sold by Monsanto under the trade name Dequest

2060 Sales EDDS : Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer, sodium salt form Photosensitized bleaching agent: Sulfonated phthalein encapsulated in or carried by a soluble polymer Zinc cyanine or encapsulated in soluble

sulfonated aluminum phthalocyanine brightener 1 : 4,4'-bis(2-sulfostyrene)biphenyl disodium brightener 2 : 4,4'-bis( 4-phenylamino-6-morpholino-1,3,5-triazin-2-yl)amino)stilbene-

2: Disodium 2'-disulfonate HEDP: Hydroxyethane 1,1-diphosphonic acid PEGx: Polyethylene glycol, molecular weight x (generally 4000) PEO: Polyoxyethylene, average molecular weight 50000 TEPAE: Ethoxylated Tetraethylenepentamine PVI: polyvinylimidazole, average molecular weight 20000PVP: polyvinylpyrrolidone polymer, average molecular weight 60000PVNO: polyvinylpyridine N-oxide polymer, average molecular weight 50000PVPVI: polyvinylpyrrolidone and vinyl Copolymer of imidazole, average molecular weight 20000QEA: bis((C ₂ H ₅ O)-(C ₂ H ₄ O) _n )(CH ₃ )-N ⁺ -C ₆ H ₁₂ -N ⁺ -(CH ₃ ) bis( (C ₂ H ₅ O)-(C ₂ H ₄ O)) _n , where n=20-30 SRP1 : anion-terminated polyester SRP2 : diethoxylated poly(1,2-propylene phthalate) Short block copolymer PEI: polyethyleneimine, average molecular weight 1800, average ethoxylation per nitrogen atom

   Polysiloxane defoamer with 7 oxyethylene residues: polydimethylsiloxane foam control agent copolymerized with polysiloxane-oxyalkylene as dispersant

A mixture of substances, the weight ratio of the foam control agent to the dispersant is 10:1-

                                                                                                                                 

Wax sold under the tradename Lytron 621: Paraffin Example 1

Preparation of detergent compositions comprising blown powders, agglomerates comprising crystalline layered silicates and anionic surfactants, effervescent granules and dry blended bleach activator granules, sodium percarbonate, sodium citrate and Foam suppressor.

Each granulate is prepared and dry mixed for at least 4 minutes with gentle mixing, eg in a Nautamixer. Preparation of blown powder

The composition of the final blown powder is as follows: Components in blown powder % linear alkylbenzene sulfonate (LAS) 24 (average carbon chain length 11.8) acrylic acid/maleic acid copolymer 5 polyethylene glycol ( MW=4000) 2 sodium sulfate 15 sodium carbonate 23 sodium citrate 23 water 8

Blown powders were prepared by standard spray drying methods. Mix the above components with water to form a slurry. The aqueous slurry is prepared in a batch or continuous process. In this case, a batch mixer or "blender" was used in which the various detergent ingredients were dissolved in water, or slurried with water, resulting in a 35% water slurry. The water content may range from about 20% to about 60% by weight, preferably from about 30% to about 40% by weight water. In this example, the order of addition of the components to water to make an aqueous slurry was as listed above in the final composition of the blown powder. The aqueous slurry is then pumped at high pressure through atomizing nozzles into a spray drying tower where excess water is removed to produce a flowable powder product (blown powder). Sift a fine powder through a sieve. Preparation of Crystalline Layered Silicate/Anionic Surfactant Particles

Agglomerates comprising 70% SKS6 and 30% LAS were prepared using conventional agglomeration methods. Preparation of effervescent granules

Granules were prepared with the following composition: Component Component % Malic Acid 44 Sodium Bicarbonate 40 Sodium Carbonate 16

Granules were prepared by roller compaction. The raw materials in the proportions shown above were fed into a Pharmapaktor L200/50P roller press under a pressure of 80 kN, which was fixed with a concave smooth roller, and the roller was provided with 0.3 mm axial grooves. The resulting flakes were then compacted using a flake crusher FC200 with a mesh size selected to produce the desired particle size. The product is sieved to remove fines. The detergent compositions of the present invention are prepared by mixing these three components with the other dry additive components listed below in the proportions given below. Component % in detergent composition spray dried 60 bleach activator 4 sodium percarbonate 2 sodium citrate 5 sodium sesquicarbonate (Na ₃ H(CO ₃ ) ₂ .2H ₂ O) 9 SKS6/LAS granules 10 pH Foaming agent particles (95% PEG, 5% polysiloxane) 0.3 Foaming particles 9.7 Example 2

Additional examples of detergent compositions according to the present invention are given in Formulations AD in the table below which also illustrate the method of making the examples. A B C D. blown powder LAS II (KLAS) 5.0 5.0 - - LAS - - 5.0 8.0 TAS - - - - MBAS - - - - C 45 AS - - - - C 45 AE 3 S - 1.0 - 1.0 QAS - - DTPA, HEDP and/or EDDS 0.8 0.7 0.8 1.0 MgSO4 - - - - Sodium citrate 10.0 12.0 - - Sodium carbonate 10.0 9.0 5.0 10.0 sodium sulfate - - 1.0 3.0 Sodium silicate 1.6R - - - - Zeolite A - - 16.0 18.0 SKS-6 - - - - MA/AA or AA 1.0 2.0 1.0 2.0 PEG4000 - 1.0 - 1.0 QEA 1.0 - 1.0 - brightener 0.05 0.05 0 05 0.05 Silicone oil 0.01 0.01 0 01 0.01 Agglomerates SKS-6 6.0 5.0 6.0 6.0 LAS 4.0 5.0 4.0 3.0 dry added granular components Maleic acid/carbonate/carbonate/hydrogen salt (40:20:40) 8.0 10.0 8.0 10.0 QEA - - - - NACAOBS 3.0 - 3.0 - NOBS - 3.0 - 3.0 TAED 2.5 - 2.5 - MBAS - - - - LAS(I) 10.0 8.0 10.0 5.0 sodium sesquicarbonate 10.0 5.0 - 10.0 sodium bicarbonate - - 9.0 - spray on brightener 0.2 0.2 0.2 0.2 Dye - - - - C24AE5 - - - - spices - - - - dry addition Citrate 4.0 - - 4.0 Percarbonate 15.0 3.0 15.0 3.0 Perborate - - - - photobleach 0.02 0.02 0.02 0.02 Enzymes (cellulase, amylase, protease, lipase) 1.5 0.3 1.3 0.3 carbonate - - 0.0 5.0 Spices (encapsulated) 0.6 0.5 0.6 0.5 Foam suppressor 1.0 0.6 1.0 0.6 soap 0.5 0.2 0.5 - citric acid - - - - Dyed Carbonate (Blue, Green) 0.5 0.5 0.5 0.5 SKS-6 - - - - Filler added to 100%

Claims (8)

CLAIMS 1. A solid detergent composition comprising 8% to 60% by weight of a surfactant system and having a Grand Compatibility Index of at least 0.5. 2. A detergent composition according to claim 1 having a Grand Compatibility Index of at least 0.6. 3. A detergent composition according to claim 2 having a Grand Compatibility Index of at least 0.8. 4. A detergent composition according to any preceding claim comprising less than 3% by weight of inorganic phosphate. 5. A detergent composition according to any preceding claim comprising less than 5% by weight of inorganic borate. 6. A detergent composition according to any preceding claim comprising less than 10% by weight of an inorganic chloride salt. 7. A detergent composition according to any preceding claim comprising an enzyme. 8. Use of a detergent composition according to any preceding claim for cleaning soils in a washing process.