WO2001068794A1 - Detergent compositions - Google Patents

Abstract

The present invention relates to a solid detergent composition comprising a thickening agent, wherein the detergent composition when present in a solution of water at a concentration of 180g/litre, has a viscosity of from 24mPas to 3000mPas when measured at a shear rate of 20.2s-1, a temperature of 20 °C and 1 atmospheric pressure. Said detergent composition is applicable to laundering processes, especially hand-wash-applications. Said detergent composition may be used in combination with a hand-held container to clean soiled laundry.

Description

DETERGENT COMPOSITIONS

Technical Field

This invention relates to the laundering of soiled articles. It is particularly applicable to hand- ash applications and for use in combination with a hand-held container.

Background Of The Invention

For many years the laundry hand-wash industry has been moving towards solid detergent compositions which, when dissolved in a solution of water, have a low viscosity (e.g. below 15mPas), since low viscosity improves the dispensing of solid detergent composition, when dissolved in a solution of water, during the washing process.

To improve the cleaning performance of hand- wash detergent compositions, in particular during the hand-washing of severely soiled articles, the Applicant (Assignee) developed hand-held containers for use in combination with these solid detergent compositions, as described in WO98/16438 and WO98/16622. These hand-held containers improve the cleaning performance of solid detergent compositions by providing dispensing and frictional means to aid the cleaning process of severely soiled articles.

However, the inventors have now found that the detergent rest-time on residual stains is not long enough to provide optimum cleaning results, thus the cleaning performance of these solid detergent compositions when used with a hand-held container, is still not satisfactory.

The inventors also found that to get satisfactory cleaning performance, the consumer must use a large quantity of the composition. However, this method of laundering is very inefficient and results in an extremely high consumption of the detergent product. The inventors have found that by adding a thickening agent to a solid detergent composition, the said detergent composition can be used with a hand-held container at a much lower concentration and achieve good cleanmg results. The presence of a thickening agent in a solid detergent composition for use in combination with a hand-held container, is a highly efficient washing process which results in a much lower consumption of product than was previously achieved. When a thickening agent- comprising solid detergent composition is in solution, the thickening agent increases the viscosity of the said solution such that an optimum viscosity is achieved at a much lower detergent concentration, in particular because the viscous composition stays on the stains or soils long enough to provide good cleaning. Thus negating the need to use a high detergent concentration to achieve this optimum viscosity.

In addition, the dispensing performance of a thickening agent-comprising solid detergent composition when in solution, from a hand-held container, is surprisingly improved. This is due to the increased viscosity of the said solution in the hand-held container, which remains in the hand-held container and does not spill when the consumer uses the said hand-held container to apply frictional means to a severely soiled article.

Thus, the aim of the present invention is to provide a solid detergent composition which can be used at low concentrations in combination with a hand-held container, but where the viscosity is such that the detergent rest time on residual stains is long enough to achieve good cleaning results, hence improving the efficiency of the washing process by lowering the consumption level of the detergent product during the laundering process.

Summary Of The Invention

In accordance with a first embodiment of the invention, a solid detergent composition is provided, which comprises;

(a) at least one surfactant, and a building agent or chelating agent, and optionally a bleaching agent, an enzyme, a perfume, an effervescence agent, or combination thereof; and (b) a thickening agent; wherein the detergent composition when present in a solution of water at a concentration of 180g/litre, has a viscosity of from 24mPas to 3000mPas when measured at a shear rate of 20.2s^"1, a temperature of 20°C and 1 atmospheric pressure.

In accordance with a second embodiment of the invention, a hand-held container is provided, which comprises a mixing volume, frictional means and dispensing means, where the mixing volume contains the said detergent composition of the first embodiment of the invention.

In accordance with a third embodiment of the invention, a process for laundering a soiled article is provided, which uses the said detergent composition of the first embodiment of the invention.

In accordance with a fourth embodiment of the invention, a use of a thickening agent is provided, where the thickening agent is used in the said detergent composition of the first embodiment of the invention.

Detailed Description Of The Invention

Thickening agent

The solid detergent composition of the invention comprises at least one organic thickening agent, and may also preferably comprise at least one organic thickening agent and at least one inorganic thickening agent. Preferably the detergent composition of the invention comprises one organic thickening agent, of the molecular weight and viscosity described hereinafter.

The thickening agent increases the viscosity of the solid detergent composition of the invention when dissolved in water. This is described hereinafter. Thus, any organic (and optionally inorganic thickening agent) may be used, provided the viscosity as claimed and described is obtained.

When the thickening agent is a combination of an organic thickening agent with an inorganic thickening agent, the weight ratio of organic thickening agent to inorganic thickening agent is preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50, even more preferably from 10:1 to 1:10, most preferably from 2:1 to 1:2.

Typically, the organic thickening agent is present in the detergent composition of the invention at a level of from 0.01% by weight to 15% by weight, preferably from 0.5% by weight to 15% by weight, more preferably from 1% by weight to 10% by weight, most preferably from 2% by weight to 10% by weight.

Preferred organic thickening agents are gums selected from the group consisting of karaya gum, tragacanth gum, guar gum, locust bean gum, alginates, carragean, xanthan gum, or a combination thereof. Preferably the said gum has a weight average molecular weight of at least lOOkDa, preferably at least 200kDa, more preferably at least 500kDa, even more preferably at least 750kDa, most preferably at least lOOOkDa.

Other preferred organic thickening agents are starches. The said starches are natural or synthetically modified polymers of amylose and amylopectin

Other preferred organic thickening agents are high weight average molecular weight modified celluloses, having a weight average molecular weight of at least 200kDa, preferably at least 300kDa, more preferably at least 500kDa, even more preferably at least 750kDa, most preferably at least lOOOkDa. The weight average molecular weight ratio of the said high molecular weight modified celluloses to other modified celluloses having weight average molecular weights of less than the said high weight average molecular weight modified celluloses, if present, is preferably greater than 1:1, preferably greater than 1.5:1, more preferably greater than 2:1, even more preferably greater than 5:1, most preferably greater than 10: 1.

Preferred modified celluloses and derivatives thereof are selected from the group consisting of carboxy methyl cellulose, hydroxyethyl cellulose HEC, hydrophobically modified HEC, hydroxypropyl cellulose HPC, hydroxypropylmethyl cellulose, hydroxybutylmethyl cellulose.

Other preferred organic thickening agents are synthetic homo-polymers, co-polymers, ter- polymers, or a combination thereof, of acrylic acid , maleic acid, asparic acid, or vinyl ester, and having a weight average molecular weight of at least 200kDa, preferably at least 300kDa, more preferably at least 500kDa, even more preferably at least 750kDa, most preferably at least lOOOkDa.

Preferably, the said polymer is hydrophobically modified. Preferably the said polymer is a cross-linked polyacrylate. Preferred cross-linked polyacrylates are selected from the group consisting of acrylic acid polymer cross-linked with alkyl ethers of pentaerythrol or sucrose, vinyl ester acrylate cross-polymer, Cιo-C₃₀ alkyl acrylate cross-polymer, polymer of acrylic acid covalently bound with hydrophobic groups, acrylonitrogen co-polymer, steareth 20 methacrylate co-polymer

Other preferred organic thickening agents are polyethylene glycols, having a weight average molecular weight of at least lOOkDa, preferably at least 200kDa, more preferably at least 500kDa, even more preferably at least 750kDa most preferably at least lOOOkDa.

Most preferred organic thickening agents are selected from the group consisting of high molecular weight carboxymethyl cellulose derivatives, xanthan gum, cross-linked polyacrylates, or a combination thereof.

Especially preferred organic thickening agents are selected from the group consisting of a carboxymethyl cellulose having a weight average molecular weight of 250000 and a degree of substitution of from 0.7 to 1.3, a carboxymethyl cellulose having a weight average molecular weight of 700000 and a degree of substitution of from 0.7 to 1.3, a hydroxyl propyl di-starch phosphate having a weight average molecular weight of at least 800000, or combination thereof.

Especially preferred organic thickening agents are Xanthan gums.

Preferred inorganic thickening agents are clays selected from the group consisting of smectite clay, hectorite clay, bentonite clay or a combination thereof.

Preferably, thickening agents have an average molecular weight viscosity of at least

20mPas, preferably at least 25mPas, more preferably at least 50mPas, even more preferably at least lOOmPas, even more preferably at least 150mPas, even more preferably at least 300mPas, even more preferably at least 500mPas, when measured by the following method: The average molecular weight viscosity can for example be determined as follows. The viscosity of a solution of 1% by weight/ thickening agent volume (e.g. 3g thickening agent in 300ml aqueous solution) in a solution of 5% by weight/volume NaOH in de- ionised water (e.g 15g NaOH in 300ml de-ionised water) was measured at a temperature of 20°C and at 1 atmospheric pressure using a Brookfield viscometer.

Depending on viscosity, a spindle (e.g. either spindle 1, 2, 3 or four of a Brookfield viscometer) and a spindle speed (e.g. either 12rpm, 30rpm or 60rpm) is selected so that the viscosity of said solution of thickening agent can be measured. The skilled person will select a spindle and spindle speed combination recommended by the manufacturer of the Brookfield viscometer to measure the viscosity of the thickening agent solution.

For example, in general the skilled person will select spindle 1 and a spindle speed of 60rpm to measure the viscosity of a solution having a viscosity of from ImPas to lOOmPas. If the viscosity of said thickening agent solution cannot be measured using spindle 1 and a spindle speed of 60rpm, then the skilled person will select a spindle and spindle speed combination recommended by the manufacturer of the Brookfield viscometer to enable the measurement of a more viscous solution, until the viscosity of the thickening agent solution can be measured.

Typically the skilled person will selected the following spindle and spindle speeds when using a Brookfield viscometer to measure the following viscosity ranges; spindle one and a spindle speed of 60rpm to measure the viscosity of a solution with a viscosity of from ImPas to lOOmPas; spindle two and a spindle speed of 60rpm to measure the viscosity of a solution with a viscosity of from lOOmPas to 500mPas; spindle three and a spindle speed of 60rpm to measure the viscosity of a solution with a viscosity of from 500mPas to 2000mPas; spindle three and a spindle speed of 30rpm to measure the viscosity of a solution with a viscosity of from 2000mPas to 4000mPas; spindle four and a spindle speed of 30rpm to measure the viscosity of a solution with a viscosity of from 4000mPas to 20000mPas; and spindle four and a spindle speed of 12rpm to measure the viscosity of a solution with a viscosity of 20000mPas or more.

The exact level of the inorganic thickening agent in the detergent composition will depend on its average molecular weight and/or viscosity. Typically, this is a level of from 0.01% by weight to 15% by weight, preferably from 0.1% by weight to 10% by weight, more preferably from 0.5% by weight to 10%o by weight.

Especially preferred is a detergent composition comprising (by weight) from 1% to 10%), preferably from 2% to 7%, more preferably from 2% to 5%, even more preferably from 2.5%) to 3.5%) by weight a carboxymethyl cellulose having a weight average molecular weight of 250000 and a degree of substitution of from 0.7 to 1.3.

Another especially preferred feature is a detergent composition comprising (by weight) from 0.5% to 10%, preferably from 0.5%) to 7%, more preferably from 0.5% to 5%, even more preferably from 1%> to 3%> a carboxymethyl cellulose having a weight average molecular weight of 700000 and a degree of substitution of from 0.7 to 1.3.

The said thickening agent may be added to the detergent composition by any process known in the art. Preferably the thickening agent is added to the detergent composition by dry mixing, or is present in a spray-dried or agglomerated particle, most preferably in a spray dried particle.

The said thickening agent is used in solid detergent compositions to provide improved stain removal during hand-washing processes. In addition, the thickening agent is used in a solid hand-wash detergent composition to obtain a viscosity of from 24mPas to 3000mPas, preferably from 24mPas to 2000mPas, more preferably from 30mPas to lOOOmPas, even more preferably from 40mPas to 800mPas, most preferable from 50mPas to 500mPas, when present in solution at a concentration of 180g/litre at a temperature of 20°C. Detergent composition

The detergent composition of the invention is in any solid form. This could be in the form of a tablet, a granular detergent composition or a combination thereof.

The said granular detergent composition of the invention can take a variety of physical forms including granular, flakes or extrudate.

The detergent composition of the invention has a bulk density of from 300g/litre to 1 OOOg/litre, preferably from 400g/litre to 850g/litre.

The solid detergent composition of the invention has a viscosity of from 24mPas to 3000mPas, preferably from 24mPas to 2000mPas, more preferably from 30mPas to lOOOmPas, even more preferably from 70mPas to 800mPas, most preferable from 200mPas to 500mPas, when present in solution at a concentration of 180g/ litre in water at a temperature of 20°C, and measured at a shear rate of 20.2s^"1 and at 1 atmospheric pressure.

The solid detergent composition of the invention is preferably a hand-wash detergent composition, and preferably comprises from 0.005%> to 0.5% by weight a suds suppressing silicone. Typical suds suppressing silicones for use in the invention, are described hereinbefore.

The solid detergent composition of the invention preferably comprises from 0.1% to 10%> by weight TAED, from 0.1% to 20%) by weight sodium perborate, form 0.1% to 20% by weight sodium percarbonate, or a combination thereof.

The detergent composition of the invention can be made by a variety of methods, including dry-mixing, extruding, compacting and agglomerating of the various compounds comprised in the detergent composition. Viscosity

The detergent composition of the invention has a viscosity of from 24mPas to 3000mPas, preferably from 24mPas to 2000mPas, more preferably from 30mPas to lOOOmPas, even more preferably from 40mPas to 800mPas, most preferable from 50mPas to 500mPas, when present in solution at a concentration of 180g/litre at a temperature of 20°C, as measured by the following method:

45g solid detergent composition is added to 250ml water and stirred for 5 minutes on a magnetic stirrer plate at a temperature of 20°C to obtain a wash solution. The viscosity of the said wash solution is measured at a shear rate of 20.2s^"1, a temperature of 20°C and at 1 atmospheric pressure.

The detergent composition of the invention can be contacted to water to obtain a wash solution. The said wash solution can be contacted to a soiled article, wherein said wash solution has then preferably a viscosity of from ImPas to 5000mPas, preferably ImPas to 3000mPas, more preferably ImPas to lOOOmPas, most preferably ImPas to όOOmPas, at the time of contact to the soiled article, which can be measured with the above method.

Additional detergent ingredients

The detergent composition typically comprises additional detergent ingredients. These detergent ingredients are described hereinafter. The detergent composition comprises a surfactant, and most preferably a building agent and/or a chelating agent. Any of the following surfactants or combinations thereof may be useful.

Detersive surfactants

Nonionic alkoxylated surfactant Essentially any alkoxylated nonionic surfactants can also be comprised by the composition of the invention. The ethoxylated and propoxylated nonionic surfactants are preferred. Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Highly preferred are nonionic alkoxylated alcohol surfactants, being the condensation products of aliphatic alcohols with from 1 to 75 moles of alkylene oxide, in particular about 50 or from 1 to 15 moles, preferably to 11 moles, particularly ethylene oxide and/or propylene oxide, are highly preferred nonionic surfactant comprised in the anhydrous component of the particles of the invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and 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 surfactant comprised by the composition of the invention , in particular those having the structural formula

R^CONRIZ wherein : Rl is H, Cι_ιg, preferably C1-C4 hydrocarbyl, 2-hydroxy ethyl,

2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably C\ alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 or C7-C19 alkyl or alkenyl, more preferably straight-chain C9-C17 alkyl or alkenyl, most preferably straight-chain C^-

C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive animation reaction; more preferably Z is a glycityl.

A highly preferred nonionic polyhydroxy fatty acid amide surfactant for use herein is a C12-C14 , a C15-C17 and/or Cjg-Cig alkyl N-methyl glucamide.

It may be particularly preferred that the composition of the invention comprises a mixture of a Ci2"Cl8 alkyl N-methyl glucamide and condensation products of an alcohol having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 9 moles and in particular 3 or 5 moles, of ethylene oxide per mole of alcohol.

The polyhydroxy fatty acid amide can be prepared by any suitable process. One particularly preferred process is described in detail in WO 9206984. A product comprising about 95% by weight polyhydroxy fatty acid amide, low levels of undesired impurities such as fatty acid esters and cyclic amides, and which is molten typically above about 80°C, can be made by this process.

Nonionic fatty acid amide surfactant

Fatty acid amide surfactants or alkoxylated fatty acid amides can also be comprised by the composition of the invention. They include those having the formula: R^CON(R^) (R° ) wherein R° is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and R^ and R8 _{are eac}h individually selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and -(C2H4θ)_xH, where x is in the range of from 1 to 11, preferably 1 to 7, more preferably form 1-5, whereby it may be preferred that R? is different to R⁸> ^one having x being 1 or 2, one having x being from 3 to 11 or preferably 5.

Nonionic alkyl esters of fatty acid surfactant Alkyl esters of fatty acids can also be comprised in any material of the invention. They include those having the formula: R9COO(R10) wherein R9 is an alkyl group containing from 7 to 21, preferably from 9 to 17 carbon or even 11 to 13 carbon atoms and T ® is a C1-C4 alkyl, C1-C4 hydroxyalkyl, or -(C2H4θ)_xH, where x is in the range of from 1 to 11, preferably 1 to 1, more preferably form 1-5, whereby it may be preferred that R^ *^{s a} methyl or ethyl group.

Nonionic alkylpolysaccharide surfactant

Alkylpolysaccharides can also be comprised by the composition of the invention, such as those disclosed in US Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R2θ(C_nH_2nO)t(glycosyl)_x

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

Polyethylene/propylene glycols

The composition of the invention may comprise polyethylene and/or propylene glycol, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Anionic surfactant The detergent composition of the invention, preferably comprises one or more anionic surfactants. Any anionic surfactant useful for detersive purposes is suitable. Examples include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamme salts) of the anionic sulphate, sulphonate, carboxylate and sarcosinate surfactants. Anionic sulphate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated

diesters of sulfosuccinate (especially saturated and unsaturated C^-C₁₄ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic sulphate surfactant

Anionic sulphate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulphates, alkyl ethoxysulphates, fatty oleoyl glycerol sulphates, alkyl phenol ethylene oxide ether sulphates, the C5-C17 acyl-N-(Cι -C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine sulphates, and sulphates of alkylpolysaccharides such as the sulphates of alkylpolyglucoside (the nonionic non-sulphated compounds being described herein).

Alkyl sulphate surfactants are preferably selected from the linear and branched primary C9-C22 alkyl sulphates, more preferably the C 1-C15 branched chain alkyl sulphates and the C12- 14 linear chain alkyl sulphates. Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the (- 10"Cl8 alkyl sulphates which have been ethoxylated with from 0.5 to 50 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C\ \-

Ci g, most preferably Ci \-C\ζ alkyl sulphate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

Anionic sulphonate surfactant

Anionic sulphonate surfactants suitable for use herein include the salts of C5-C20 linear or branched alkylbenzene sulphonates, alkyl ester sulphonates, in particular methyl ester sulphonates, Cg-C22 primary or secondary alkane sulphonates, C -C24 olefin sulphonates, sulphonated polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphonates, and any mixtures thereof.

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x

CH2C00"M⁺ wherein R is a Cg to C^g alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHRj-CHR2-O)χ-R3 wherein R is a Cg to C g alkyl group, x is from 1 to 25, Rj and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof. Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l-undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressers.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (R!) CH2 COOM, wherein R is a C5-C1 linear or branched alkyl or alkenyl group, R is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Cationic surfactant

Another preferred surfactant of the detergent composition of the invention, is a cationic surfactant, which may preferably be present at a level of from 0.1% to 60% by weight of the composition or particle, more preferably from 0.4% to 20%>, most preferably from 0.5% to 5% by weight of the composition.

When present, the ratio of the anionic surfactant to the cationic surfactant is preferably from 35:1 to 1:3, more preferably from 15:1 to 1:1. most preferably from 10:1 to 1:1.

Preferably the cationic surfactant is selected from the group consisting of cationic ester surfactants, cationic mono-alkoxylated amine surfactants, cationic bis-alkoxylated amine surfactants and mixtures thereof. Cationic mono-alkoxylated amine surfactants

Preferred cationic mono-alkoxylated amine surfactant for use herein, has the general formula:

wherein R! is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms; R^ and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulphate, sulphate, or the like, to provide electrical neutrality; A is selected from C1 -C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about 8.

Highly preferred cationic mono-alkoxylated amine surfactants for use herein are of the formula:

wherein R! is Cβ-Ci hydrocarbyl and mixtures thereof, preferably C6-C14, especially Cβ-Ci 1 alkyl, preferably Cg and C\Q alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide. As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy, isopropoxy [CH(CH3)CH2θ] and

[CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Cationic bis-alkoxylated amine surfactant

The cationic bis-alkoxylated amine surfactant for use herein, has the general formula:

wherein R! is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R^ and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X" is an anion such as chloride, bromide, methylsulphate, sulphate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof; p is from 1 to about

30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

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

wherein R is Cg-Cjg hydrocarbyl and mixtures thereof, preferably C5, Cg, Cιo_> C12,

C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. With reference to the general cationic bis-alkoxylated amine structure noted above, since in a preferred compound R! is derived from (coconut) C12-

C14 alkyl fraction fatty acids, R^ is methyl and ApR^ and A'q .4 are each monoethoxy.

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

wherein R is C6-Cι g hydrocarbyl, preferably C6-C14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R^ is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing type include those wherein the ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids. Suitable amine oxides include those compounds having the formula R3(OR4)_XNO(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are Ci ()-Ci alkyl dimethylamine oxide, and Ci Q_i acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants can also be comprised by the composition 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 zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N⁺R2C00~ wherein R is a C -Ci hydrocarbyl group, each R! is typically C1-C3 alkyl, and R^ is a C1-C5 hydrocarbyl group. Preferred betaines are Ci2-l dimethyl-ammonio hexanoate and the lO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Water-soluble building agent The detergent composition of the invention preferably comprises at least a water-soluble building agent, typically present at a level of from 0%> to 36% by weight, preferably from 1% to 35% by weight, more preferably from 10% to 35%, even more preferably from 12% to 30% by weight of the composition or particle. Preferably, the water-soluble builder compound is an alkali or earth alkali metal salt of phosphate present at the level described above.

Other typical water-soluble building agents include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.

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

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 the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa- 1,1, 3 -propane tricarboxylates described in British Patent No. 1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in

British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1, 2, 3 -propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in US Patent No. 3,936,448, and the sulphonated pyrolysed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21, and salts of phytic acid.

Partially soluble or insoluble building agent

The detergent composition of the invention may contain a partially soluble or insoluble building agent.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na_z[(AlO2)_z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22%> water in bound form. The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula:

Na i2 [AlO₂) i2 (SiO2)i2]. xH₂O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Nagg [(Alθ2)86(Siθ2)i06]- 276 H₂O.

Preferred crystalline layered silicates for use herein have the general formula:

NaMSi_xO_2x+l.yH₂O

wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na2Si2θ5, available from Hoechst AG as NaSKS-6.

Bleach Activator

The components in accord with the present invention and/ or the detergent compositions herein preferably comprises a bleach activator, preferably comprising an organic peroxyacid bleach precursor. It may be preferred that the composition comprises at least two peroxy acid bleach precursors, preferably at least one hydrophobic peroxyacid bleach precursor and at least one hydrophilic peroxy acid bleach precursor, as defined herein. The production of the organic peroxyacid occurs then by an in situ reaction of the precursor with a source of hydrogen peroxide. The bleach activator may alternatively, or in addition comprise a preformed peroxy acid bleach.

It is preferred that the bleach activator is present in a particulate component in the component or compositions herein. It may be preferred that the is present as a separate, admixed particle. Alternatively, the bleach activator or part thereof can be present in the base detergent particle.

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

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

The hydrophobic peroxy acid bleach precursor preferably comprises a compound having a oxy-benzene sulphonate group, preferably NOBS, DOBS, LOBS and/ orNACA-OBS, as described herein.

The hydrophilic peroxy acid bleach precursor preferably comprises TAED, as described herein.

Organic peroxyacid bleaching system

The detergent composition of the invention preferably comprises an organic peroxyacid precursor. The production of the organic peroxyacid may occur by an in situ reaction of such a precursor with the percarbonate source. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as:

O X-C-L

where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is:

O

II

X-C-OOH

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O- acyl groups, which precursors can be selected from a wide range 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 groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

R³ Y

I I

-O-CH=C— CH=CH₂ -O-CH=C-CH=CH₂

-O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R 3 is an alkyl chain containing from 1 to 8 carbon atoms, R 4 is H or R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.

The preferred solubilizing groups are -SO₃ ^"M⁺, -CO₂ ^"M⁺, -SO₄ ^"M⁺, -N⁺(R³)₄X^" and

3 - + - + 3

0<— N(R )o and most preferably -SO, M and -CO- M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulphate or acetate anion.

Alkyl percarboxylic acid bleach precursors

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

Typical alkyl percarboxylic precursor compounds of the imide type include the N-

,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. The TAED is preferably not present in the agglomerated particle of the present invention, but preferably present in the detergent composition, comprising the particle.

Other alkyl percarboxylic acid precursors include sodium 3,5,5-tri-methyl hexanoyloxybenzene sulphonate (iso-NOBS), sodium nonanoyloxybenzene sulphonate (NOBS), sodium acetoxybenzene sulphonate (ABS) and pentaacetyl glucose. The detergent composition preferably comprises 0.1% to 2%, preferably 0.1% to 1.5%, more preferably 0.2% to 1.0%, even more preferably 0.2% to 0.6%, by weight TAED.

The detergent composition preferably comprises 00.1% to 4%, preferably 0.3% to 3%, more preferably 0.5% to 2%, even more preferably 0.6% to 1.3%, by weight NOBS.

The detergent composition can also comprise a combination of NOBS and TAED, present at the levels described hereinbefore.

Amide substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

R¹ — C — N — R² — C L R¹ — N — C — R² — C — L

O R ,5^Ό O or R 5° O O

wherein R! is an alkyl group with from 1 to 14 carbon atoms, R-2 is an alkylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulphonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic Peroxyacid Precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

wherein R, is H, alkyl, alkaryl, aryl, or arylalkyl.

Pre-formed organic peroxyacid

The organic peroxyacid bleaching system may contain a pre-formed organic peroxyacid.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R¹ C — N — R² C — OOH R¹ N — C — R² C — OOH

O R⁵ O or R⁵ O O

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

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N- phthaloylaminoperoxicaproic acid are also suitable herein.

Peroxide Source

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

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilise a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBU2H2θ2 or the tefrahydrate NaBθ2H2θ2-3H2θ.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Chelating agents or heavy metal ion sequestrant

The detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, preferably comprise as an optional detergent ingredient, a chelating agent or heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.05% to 2%, preferably from 0.1%> to 1.5%, more preferably from 0.25% to 1.2% and most preferably from 0.5%) to 1% by weight of the composition.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy bisphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1,1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof. Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropy 1-3 -sulfonic acid sequestrants described in EP-A-516, 102 are also suitable herein. The β-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-N-monoacetic acid and iminodisuccinic acid sequestrants described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane- 1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'-disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.

Enzyme

Another preferred optional detergent ingredient useful in the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, is one or more additional enzymes.

Preferred additional enzymatic materials include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.

Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist- Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001% to 4% active enzyme by weight of the composition.

Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl and BAN by Novo Industries A/S. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001% to 2% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001%) to 10% by weight of the particle, preferably 0.001% to 3% by weight of the composition, most preferably from 0.001%) to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in US Patent 4,810,414, Huge- ensen et al, issued March 7, 1989.

Organic polymeric compound Organic polymeric compounds other than any polymeric thickening agents of the invention described hereinbefore, are preferred additional detergent ingredients of the detergent composition of the invention, or any detergent component comprised by the detergent composition of the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. For example, useful additional polymers are polymers acting as dispersants, and anti-re-deposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 %> to 50%> by weight of the particle, preferably from 0.5%) to 25%», most preferably from 1%> to 15%> by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include low molecular weight (as defined above in the paragraphs of the thickening agents) cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Another organic compound, which is a preferred clay dispersant/ anti-re-deposition agent, for use herein, can be the ethoxylated cationic monoamines and diamines of the formula:

wherein X is a nonionic group selected from the group consisting of H, -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof, a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 1 or 0; for cationic monoamines (b=0), n is at least 16, with a typical range of from 20 to 35; for cationic diamines (b=l), n is at least about 12 with a typical range of from about 12 to about 42.

Other dispersants/ anti-re-deposition agents for use herein are described in EP-B-011965 and US 4,659,802 and US 4,664,848.

Suds suppressing system

The detergent composition preferably comprises a suds suppresser at a level less than 10%, preferably 0.001%> to 10%>, preferably from 0.01% to 8%, most preferably from 0.05% to 5%, by weight of the composition Preferably the suds suppresser is either a soap, paraffin, wax, or any combination thereof. If the suds suppresser is a suds suppressing silicone, then the detergent composition preferably comprises from 0.005%) to 0.5% by weight a suds suppressing silicone. Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxane units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units. Preferably the composition comprises from 0.005%) to 0.5%> by weight suds suppressing silicone.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppresser typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the 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 esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic (- 18"C40 ketones (e.g. stearone) N-alkylated amino triazines such as tri- to hexa- alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monosteaiyl di-alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises:

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

(i) polydimethyl siloxane, at a level of from 50%> to 99%, preferably 75%o to 95%> by weight of the silicone antifoam compound; and

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

wherein said silica/silicone antifoam compound is incorporated at a level of less than 5%, preferably 0.01%) to 5%, more preferably 0.05%> to 4%, even more preferably 0.1% to 3%, by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of less than 5%, preferably 0.01%) to 5%, more preferably 0.05%> to 4%>, even more preferably 0.1% to 3%>, by weight; a particularly preferred silicone glycol rake copolymer of this type is DCO544, commercially available from DOW Corning under the tradename DCO544;

(c) an inert carrier fluid compound, most preferably comprising a Ci g-Ci g ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of less than 5%, preferably 0.01% to 5%, more preferably 0.05%> to 4%, even more preferably 0.1 % to 3 %, by weight; A highly preferred particulate suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85°C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A-0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point offrom 45°C to 80°C.

Polymeric dye transfer inhibiting agents

The detergent composition of the invention may also comprise from 0.01%> to 10 %>, preferably from 0.05% to 0.5%> by weight of polymeric dye transfer inhibiting agents.

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

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :

(I) Ax

R

wherein P is a polymerisable unit, and O O O

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

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures :

O

(R₁)x

wherein Rl, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water- solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b Copolymers ofN-vinylpyrrolidone and N-vinylimidazole

Suitable herein are co-polymers of N-vinylimidazole and N-vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c Polvvinylpyrrolidone

The detergent composition of the invention may also utilise polvvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Co-operation include Sokalan HP 165 and Sokalan HP 12.

d Polyvinyloxazolidone The detergent composition of the invention may also utilise polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e Polyvinylimidazole

The detergent composition of the invention may also utilise polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical Brightener

The detergent composition of the invention may also optionally comprise from 0.005% to 5%> by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein R\ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, Rj is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-

2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba- Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above foπnula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and

M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, Ri is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-mo hilino-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Cationic fabric softening agents

Cationic fabric softening agents can also be incorporated into the detergent composition of the invention or in compositions containing the detergent component in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.

Cationic fabric softening agents are typically incorporated at total levels of from 0.5% to 15%) by weight, normally from 1% to 5% by weight.

Other optional ingredients

Other optional detergent ingredients suitable for inclusion in the compositions or detergent component of the invention include highly preferably perfumes, colours and filler salts, with sodium sulphate being a preferred filler salt. Hand-held container

In a particular embodiment of the invention, a hand-held container, comprising a mixing volume, frictional means and dispensing means, where the mixing volume contains a detergent composition of the invention, is provided. Preferred hand-held containers are those described in patent application EP-931870 and co-pending application number EP- 99870166.8.

By a hand-held container, it is meant that it is suitable to be held by hand. The hand-held container may be used in hand-washing applications or in automatic machine-washing applications. Preferably, the hand-held container is used in hand-washing applications or in a pre-treatment step of automatic machine- washing applications.

The hand-held container of the invention comprises a mixing volume. The mixing volume is a volume where two or more components, for example, a solid detergent composition of the present invention as the first component and water as the second component, are mixed to form a mixture. By mixed, it is meant contacted to each other. If the first component is a solid, e.g. a solid detergent composition of the invention, and the second component is a liquid, e.g. water, then preferably, the components are mixed in such a manner as to form a mixture, wherein the solid component is dissolved in the liquid component. The mixing volume is the volume in which the mixture is found.

The mixing volume may be partially or completely full of the mixture, the remainder being filled with air for example. Partial filling of the mixing volume allows the remainder to be filled with air, thus aiding the mixing of the two or more components, for example by shaking. This could be encouraged, for example, by means of a dosing line.

Preferably, the mixing volume is formed from a hollow body, although other forms of mixing volume may be used, such as a puff having at least one internal pocket and at least one surrounding extension, wherein both the pocket and the surrounding extension form the mixing volume. The mixing volume may not have a homogeneous structure, for example, the mixing volume may be formed from a hollow body with a part defining a plurality of inter-linked channels or cavities such as a sponge medium or plastic medium or a combination thereof. The mixing volume may also be formed from more than one chamber, the chambers being inter-linked with one another. The mixing volume may be formed from a net-like structure.

The hand-held container of the invention comprises frictional means. By frictional means it is meant a means of allowing active mechanical treatment of the surface of a soiled article in combination with the applied mixture. For example, scrubbing, rubbing or wiping. Frictional means improves the cleaning efficiency while avoiding damage to the treated surface. Such frictional means may include a net like structure, the net is typically made from relatively abrasive woven fibres.

The hand-held container of the invention comprises dispensing means. By dispensing means it is meant a means of applying the mixture to the surface of a soiled article, or to a solution or liquid to form a washing solution, the said washing solution is then contacted to the surface of a soiled article.

The hand-held container of the invention must have a structure that remains stable at high temperatures up to 90°C or 100°C. The hand-held container must not incur temperature damage during a washing process at these high temperatures. By temperature damage it is meant combustion, melting leading to a deformity in shape or any other such damage caused by high temperatures.

Preferably, a detergent composition of the invention is contacted to water to obtain a wash solution in the mixing volume of the hand-held container. Preferably, the said wash solution is applied to the surface of a soiled article by the dispensing means of the handheld container. Preferably, the said wash solution has a viscosity of from ImPas to 3000mPas, preferably ImPas to lOOOmPas, more preferably 50mPas to 500mPas, most preferably 50mPas to 200mPas, at the time of contact to the soiled article. Active mechanical treatment of the surface of the soiled article is achieved by the frictional means of the hand-held container.

Laundry washing method

Laundering process

It is preferred such that effective cleaning is obtained by contacting the detergent composition of the invention to water to form a washing solution, wherein the detergent composition is at a concentration of from lg/litre to 360g/litre, preferably from 5g/litre to 300g/litre, more preferably from lOg/litre to 280g/litre, even more preferably from 50g/litre to 165g/litre, most preferably from 140g/litre to 220g/litre at the time of contact to a soiled article.

Preferably the said washing solution is comprised by a hand-held container, although the detergent composition of the invention can be comprised by a hand-held container when in solid form.

During the laundering process, a detergent composition according to the invention is contacted to the soiled article, preferably using a hand-held container, typical hand-held containers are described herein. The detergent composition of the invention can be contacted directly to water to obtain a wash solution. The soiled article can be contacted to the wash solution, the wash solution has a viscosity of from ImPas to 5000mPas, preferably ImPas to 3000mPas, more preferably ImPas to lOOOmPas, most preferably ImPas to 600mPas, at the time of contact to the soiled article.

The detergent composition of the invention can be contacted directly to the soiled article, this step may be a pre-treatment step in the washing process, preferably the detergent composition of the invention is applied to a soiled article using a hand-held container. The detergent composition of the invention is contacted to the soiled article at least once, the contact can occur at any stage of the washing process. The detergent composition of the invention can be contacted to water at any stage of the washing process. The soiled article can be contacted to water at any stage of the washing process, either before, after or at the same time as the detergent composition of the invention is contacted to the soiled article. Preferably, the detergent composition is contacted to water, preferably the said contact occurs in the hand-held container, more preferably the said contact occurs in the mixing volume of the hand-held container, to form a wash solution. The said wash solution is contacted to a soiled article, preferably using the hand-held container, more preferably using the dispensing means of the said hand-held container. Even more preferably, the detergent composition of the invention is used in the active mechanical treatment of the surface of the soiled article using the frictional means hand-held container, for example, scrubbing, rubbing or wiping.

Preferably, the detergent composition of the invention is the only detergent composition used in the laundering process. Although one or more other detergent compositions can be used in combination with the detergent composition of the invention during the laundering process, such that detergent composition of the invention is used as a pre- treatment, main-treatment, post-treatment or a combination thereof during such a laundering process.

Examples

Abbreviations used in examples

In the detergent compositions, the abbreviated component identifications have the following meaning:

Abbreviation Description

Thickening agent(l): Carboxymethyl cellulose having a weight average molecular weight of from 200000 to 300000 and a degree of substitution of from 0.7 to 1.3. Thickening agent(2): Carboxymethyl cellulose having a weight average molecular weight of 650000 to 750000 and a degree of substitution of from 0.7 to 1.3

Thickening agent(3): Hydroxyl propyl di-starch phosphate having a weight average molecular weight of at least 750000 Thickening agent(4): Cross-linked polyacrylate having a weight average molecular weight of at least 200000 APA: C8 - CIO amido propyl dimethyl amine

C46SAS: Sodium C14 - C16 secondary (2,3) alkyl sulfate

CFAA: C12-C14 (coco) alkyl N-methyl glucamide

CxyAS: Sodium Clx - Cly alkyl sulfate

CxyEz: C lx-C ly predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide

CxyEzS: Sodium Clx-Cly alkyl sulfate condensed with z moles of ethylene oxide

LAS(l) Sodium linear Cl 1-13 alkyl benzene sulfonate

LAS(2) Potassium linear or branched Cl 1-13 alkyl benzene sulfonate QAS(l) R2.N+(CH3)2(C2H4OH) with R2 = C12 - C14

QAS(2) R2.N+(CH3)2(C2H4OH) with R2 = C8 - C 11 STS: Sodium toluene sulphonate TAS: Sodium tallow alkyl sulfate TFAA: C16-C18 alkyl N-methyl glucamide TPKFA: C12-C14 topped whole cut fatty acids Bicarbonate(l): Anydrous sodium bicarbonate having 80% by volume of particles with a particle size from 15 microns to 40 microns, having a volume median particle size of 25 microns

Bicarbonate(2): Anhydrous sodium bicarbonate having 80% by volume of particles with a particle size from 100 microns to 200 microns with a volume median particle size of 150 microns

Carbonate(l): Anydrous sodium carbonate having 80% by volume of particles with a particle size from 50 microns to 150 microns with a volume median particle size of 100 microns

Carbonate(2): Anydrous sodium carbonate having 80% by volume of particles with a particle size from 35 microns to 75 microns, having a volume median particle size of 55 microns

Citrate: Tri-sodium citrate dihydrate of activity 86.4%) with a particle size distribution between 425μm and 850μm

Silicate: Amorphous sodium silicate (SiO2:Na2O = 2.0:1) Sulfate: Anhydrous sodium sulfate

Citric acid(l): Anhydrous citric acid, 80% having a particle size of from 40 microns to 70 microns, and having a volume median particle size of 55 microns

Citric acid(2): Anhydrous or monohydrate citric acid, 80% having a particle size of from 15 microns to 40 microns, having a volume average particle size of 25 microns

Maleic acid: Anhydrous maleic acid, 80% having a particle size of from 5 microns to 30 microns, having a volume median particle size of 15 microns Malic acid: Anhydrous malic acid, 80%> having a particle size of from 50 microns to 100 microns, having a volume median particle size of

75 microns

NaSKS-6: Crystalline layered silicate of formula d- Na2Si2O5 STPP: Anhydrous sodium tripolyphosphate

Tartaric acid: Anhydrous tartaric acid, 80% having a particle size of from 25 microns to 75 microns, having a volume median particle size of 50 microns

TSPP: Tetrasodium pyrophosphate Zeolite A: Hydrated sodium aluminosilicate of formula

Nal2(AlO2SiO2)12.27H2O having a primary particle size in the range from 0.1 to 10 micrometers (weight expressed on an anhydrous basis)

DTPA: Diethylene triamine pentaacetic acid DTPMP: Diethylene triamine penta (methylene phosphonate), marketed by

Monsanto under the Tradename Dequest 2060

EDDS: Ethylenediamine-N,N'-disuccinic acid, (S,S) isomer in the form of its sodium salt.

HEDP: 1,1-hydroxyethane diphosphonic acid Mg sulfate: Anhydrous magnesium sulfate PB1: Particle containing anhydrous sodium perborate bleach of nominal formula NaBO2.H 202, the particles having a weight average particle size of 800 microns, 85%_> particles having a particle size of from 750 microns to 950 microns PB4: Particle containing sodium perborate tefrahydrate of nominal formula NaBO2.3H2 O, the particles having a weight average particle size of 950 microns, 85%» particles having a particle size of from 850 microns to 950 microns

Percarbonate: Particle containing sodium percarbonate of nominal formula

2Na₂CO₃.3H₂O₂. NAC-OBS: Particle comprising (6-nonamidocaproyl) oxybenzene sulfonate, the particles having a weight average particle size of from 825 microns to 875 microns

NOBS: Particle comprising nonanoyloxybenzene sulfonate in the form of the sodium salt, the particles having a weight average particle size of 750 microns to 900 microns

TAED(l): Particle containing tefraacetylethylenediamme, the particles having a weight average particle size of from 700 microns to 1000 microns

TAED(2): Tetraacetylethylenediamine of a particle size from 150 microns to

600 microns

Photo Bleach(l): Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer

Photo Bleach(2): Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer

Brightener(l): Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener(2): Disodium 4,4'-bis(4-anilino-6-morpholino-l .3.5-triazin-2- yl)amino) stilbene-2:2'-disulfonate

PVI: Polyvinyl imidosole, with an average molecular weight of 20,000 PVP: Polyvinylpyrolidone polymer, with an average molecular weight of

60,000

PVNO: Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000

PVP VI: Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000

AA: Sodium polyacrylate polymer of average molecular weight 4,500

CMC: Sodium carboxymethyl cellulose

Cellulose ether: Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals

MA/AA(1): Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000 MA/AA(2): Copolymer of 4:6 maleic/acrylic acid, average molecular weight about 10,000

PEGx: Polyethylene glycol, with a molecular weight of x, where x = from

1000 to 10000

PEO: Polyethylene oxide with an average molecular weight of from

10000 to 60000

PEI(l): Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen

PEI(2): propoxylated/ethoxylated polyethylene imine

QEA(l): bis((C2H5O)(C2H4O)n)(CH3) -N+-C6H12-N+-(CH3) bis((C2H5O)-(C2H4 O))n, wherein n = from 20 to 30

QEA(2): Sulphonated ((C₂H₅O)(C₂H₄O)„)CH₃-N⁺-C₆H₁₂-N⁺-

CH₃((C₂H₄O)_n(C₂H₅O)) where n= from 20 to 30

QEA(3): ((C₂H₅O)(C₂H₄O)_n)CH₃-N⁺-C₆H₁₂-N⁺-CH₃((C₂H₄O)_n(C₂H₅O)) where n= from 20 to 30

QEA(4): ((C₂H₅O)(C₂H₄O)_n)CH₃-N⁺-C₃H₆OC₄H₈-OC₃H₆-N⁺-

CH₃((C₂H₄O)_n(C₂H₅O)) where n= from 15 to 25

SRP(l): Anionically end capped poly esters

SRP(2): Diethoxylated poly (1, 2 propylene terephtalate) short block polymer

Alcalase: Proteolytic enzyme, having 5.3% by weight of active enzyme, sold by NOVO Industries A/S

Amylase: Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T

Cellulase: Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme

Endolase: Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S Lipase(l): Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipase(2): Lipolytic enzyme, having 2.0%> by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Protease(l): Proteolytic enzyme, having 3.3%> by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Protease(2): Proteolytic enzyme, having 4%> by weight of active enzyme, as described in WO 95/10591, sold by Genencor Int. Inc. Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1 Soap: Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids

Example I

The following compositions are in accordance with the invention.

Example II The following compositions are in accordance with the invention.

Example III

The following compositions are in accordance with the invention.

Claims

WHAT IS CLAIMED IS:

1. A solid detergent composition comprising;

(a) at least one surfactant, and optionally a building agent chelating agent, bleaching agent, enzyme, perfume, effervescence agent, or combination thereof; and

(b) a thickening agent; wherein the detergent composition when present in a solution of water at a concentration of 180g/litre, has a viscosity of from 24mPas to 3000mPas when measured at a shear rate of 20.2s^"1, a temperature of 20°C and 1 atmospheric pressure.

2. A detergent composition according to claim 1, whereby the said thickening agent is an organic thickening agent or a combination of an organic thickening agent and an inorganic thickening agent.

3. A detergent composition according to claim 1 or 2, whereby the thickening agent is selected from the group consisting of a cross-linked polyacrylate, a high molecular weight carboxymethyl cellulose derivative, a xanthan gum, or a combination thereof.

4. A detergent composition according to any preceding claim, whereby the detergent composition is a hand-wash detergent composition and comprises from 0.005% to 0.5% by weight a suds suppressing silicone.

5. A detergent composition according to any preceding claim, whereby the detergent composition comprises by weight from 0.1 % to 10%> TAED, from 0.1 % to 20%> sodium perborate, from 0.1 % to 20% sodium percarbonate, or a combination thereof.

6. A process for laundering a soiled article comprising the steps,

(a) contacting a detergent composition according to any of claims 1-5 to water to obtain a wash solution; and (b) contacting the said wash solution to a soiled article; wherein the wash solution has a viscosity ImPas to 5000mPas at the time of contact to the soiled article.

7. A hand-held container comprising:

(a) a mixing volume; and

(b) friction means; and

(c) dispensing means; where the mixing volume contains a detergent composition according to any of claims 1- 8.

8. A process for laundering a soiled article, whereby the soiled article is contacted to a hand-held container according to claim 7 in such a manner as to dispense a detergent composition according to any of claims 1-5 onto the said soiled article.

9. Use of a thickening agent in a solid detergent composition to provide improved stain removal during hand- washing processes, or pre-treatment washing processes.

10. Use of a thickening agent in a solid detergent composition, such that when the said solid detergent composition is present in a solution of water at a concentration of 180g/litre, a viscosity of from 24mPas to 3000mPas is obtained when measured at shear rate of 20.2s^"1, a temperature of 20°C and 1 atmospheric pressure.