WO2021180546A1

WO2021180546A1 - Low foaming solid cleaning composition

Info

Publication number: WO2021180546A1
Application number: PCT/EP2021/055349
Authority: WO
Inventors: Seetharam Padmanabhan Nurani; Yogita Ajay PINGLE; Pradeep SALUNKHE; Archana Sinha; Nitya SRIVASTAVA; Neetu Verma
Original assignee: Unilever Ip Holdings B.V.; Unilever Global Ip Limited; Conopco, Inc., D/B/A Unilever
Priority date: 2020-03-11
Filing date: 2021-03-03
Publication date: 2021-09-16
Also published as: EP4118172B1; CN115279877A; BR112022018106A2; EP4118172A1

Abstract

The present invention is in the field of solid cleaning composition having good cleaning characteristics in the main wash, yet significant foam reduction during rinse. It is an object of the invention to provide total foam reduction during the first rinse. It has been found that this object is achieved in cleaning processes by a solid cleaning composition comprising specific anionic surfactant, water soluble alkyl carboxylate salt of C₈ to C₁₈ fatty acid and a nonionic surfactant and where the solid cleaning composition has a carbonate builder.

Description

LOW FOAMING SOLID CLEANING COMPOSITION

Field of the invention The present invention relates to a laundry cleaning composition; in particular a solid detergent composition having low or no foaming in the main wash, and which shows significant reduction in water consumption during rinsing. Background of the invention

Water is becoming a more and more scarcely available commodity, especially in developing countries, where it is not unusual that people must walk long distances to arrive at a water source. As a result of which, there is an increasing need to save water.

One way of saving water is to reuse the water and another way is to reduce the amount of water being used.

Washing processes, including laundry, dishwashing and other household cleaning processes, consumes large amounts of water throughout the world. These are daily chores in which the use of water and a detergent cannot be avoided.

Foam is a significant consumer cue and acts as the primary reason by which a consumer perceives that a composition is having a cleaning effect. Unfortunately, while good foam is easy to generate, it also needs to be removed from the substrate after cleaning. So, there is a balance to be struck between generating a good foam and then removing it.

Laundry formulations such as rinse aids have been used to help reduce the foam carried by the laundered fabric into the rinse water. Rinse aids reduces the amount of water used during rinsing. However, the use of rinse aids adds an extra step and the consume needs to use an additional product in the washing process. In today’s fast paced world consumers look for a single composition which provides cleaning benefits and at the same time reducing water consumption. This need is particularly felt by consumers who dwell in regions where there is acute shortage of water.

However, it remains a challenge to provide a cleaning composition which gives low or no foaming without compromising on the cleaning performance. The main reason behind this is that conventional cleaning composition use LAS for providing good stain removal benefits. LAS is an anionic detersive surfactant and has been conventionally used for achieving desired cleaning performance, but LAS also generates copious foam upon agitation in the washing step. Following the washing step, it is common for an appreciable amount of surfactant to remain in the fabric fibers and on the fabric surface. This may be referred to as "carry-over". As a result, significant amounts of foaming occur in the rinse step. This carry over typically persists over multiple rinses and typically consumes 2 or 3 rinse buckets of clean water to satisfactorily remove the foam, soapy feel, or turbidity in the rinse liquor.

Thus, there is a need for a cleaning composition that reduces and preferably eliminates foam without adversely affecting the cleaning performance.

Some solutions towards addressing this problem of foaming at the rinse stage, is by incorporating rinse triggered antifoams which act on the foam and suppresses it at the rinse stage. However, such rinse triggered antifoam add to the amounts of chemicals incorporated in the composition and such compositions must be formulated carefully to avoid the antifoam being released during cleaning stage. Further the antifoams are generally expensive and provide no other performance benefit to the composition other than foam suppression. Therefore, it is desirable that their presence is minimised.

Other compositions such as those disclosed in WO 93/18128 (Unilever) provide a low foaming liquid cleaning composition which shows a reduced tendency to form a stable foam. The liquid cleaning composition includes a hydrophobic oil, a first surfactant to form a sparingly soluble calcium salt in aqueous solutions and a second surfactant which is foaming and different from the first surfactant.

In spite of the efforts made in the past towards providing detergent composition for laundering fabrics which is low foaming and requires lesser number of rinsing steps, there is still a need for a solid cleaning composition which provides good cleaning performance and reduced or no foaming.

It is thus an object of the present invention to provide a solid cleaning composition which does not foam or produces low foam at the rinse stage and has superior cleaning properties.

It is yet another object of the present invention to provide a solid cleaning composition which requires less than 3 rinses, preferably only one rinse.

It is yet another object of the present invention to provide a solid cleaning composition which enhances stability of enzymes.

It is yet another object of the present invention to provide a solid cleaning composition which delivers improved stain removal.

It is yet another object of the present invention to provide a solid cleaning composition which provides improved bleachable, oily, enzymatic or particulate soil removal.

Summary of the invention

It has been found that a combination of specific anionic surfactants and a nonionic surfactant in a carbonate built solid cleaning composition exhibits good cleaning performance and the foam produced during the washing step is effectively and completely removed from the laundered fabrics in less than 3 rinses, preferably in the first rinse. More particularly, the improved solid cleaning composition including specific anionic surfactants, nonionic surfactant and an alkaline builder salt, which suppresses formation of foam in the wash liquor even when a minor proportion of an antifoam is included.

It has been found that the inventive solid cleaning composition having specific anionic surfactants and a nonionic surfactant generate less foam than the existing detergent composition in water with varying degree of hardness. The cleaning composition of the present invention permits the consumer to use higher levels of detergent and still requiring less than 3 rinse, preferably a single rinse step to obtain complete removal of the foam, soapy feel and dirt in the rinse water. It was found that aqueous solutions of the cleaning composition herein generate very low degree of foam under conditions of vigorous and/or continuous agitation. It has been surprisingly found that detergent composition exhibits detergency performance at least equivalent to that of a full LAS-containing detergent composition.

The terms “fabric”, “clothes” and “fabric article”, as interchangeably used herein, are intended to mean any article that is customarily cleaned in a conventional laundry process. As such the term refers non-specifically to any type of flexible material consisting of a network of natural or artificial fibers, including natural, artificial, and synthetic fibers, such as, but not limited to, cotton, linen, wool, polyester, nylon, silk, acrylic, and the like, as well as various blends and combinations. It encompasses articles of clothing, linen, drapery, and clothing accessories. The term also encompasses other items made in whole or in part of fabric, such as tote bags, furniture covers, tarpaulins and the like.

As used herein the term “low foaming” herein means that a foam height or a foam volume for the solid cleaning composition according to the present invention which is less than the foam height or foam volume which is achieved in comparable composition containing LAS anionic surfactant. It also includes a decrease in the duration of visible foam in a washing process cleaning soiled articles compared to a composition containing LAS anionic surfactant.

In a first aspect, there is provided a solid cleaning composition, comprising: i) an anionic non-soap surfactant selected from primary alkyl sulfate surfactant, alkyl ester fatty acid sulphonate surfactant or mixtures thereof; ii) a water-soluble alkyl carboxylate salt of Cs to Cis fatty acid; iii) a nonionic surfactant; iv) 0 wt.% to 0.5 wt.% linear alkylbenzene sulfonate surfactant; and, v) a carbonate builder.

These and other aspects, features and advantages of the invention will be apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims.

Detailed description of the invention

According to a first aspect of the present invention disclosed is a solid cleaning composition having an anionic non-soap surfactant selected from a primary alkyl sulfate surfactant, alkyl ester fatty acid sulphonate or mixtures thereof, a water-soluble alkyl carboxylate salt of Cs to Cis fatty acid, a nonionic surfactant, 0 wt.% to 0.5 wt.% linear alkylbenzene sulfonate surfactant and a carbonate builder.

Primary alkyl sulfate surfactant The solid cleaning composition according to the present invention includes a primary alkyl sulfate surfactant. In the present invention the term “primary alkyl sulfate surfactant” refers to both the acid form and the neutralized salt form.

Preferably the primary alkyl sulfate surfactant according to the present invention has the general formula: ROSChlvr, wherein:

R is typically a linear Cs to C24 alkyl group, which is straight chain; and, M is a water-solubilizing cation.

Preferably R is a Cs to Cis alkyl, C₁₀ to C₁₅ alkyl, still preferably C₁₀ to CM alkyl and most preferably from C₁₂ to CM alkyl. R may preferably be a hydroxyalkyl having a C₁₀ to C₁₈ alkyl component, more preferably CM to Cis_, still preferably a C₁₂ to C₁₅ alkyl component. Preferably the primary alkyl sulfate surfactant has Cs to Cis alkyl chain, still preferably Cs to Cis alkyl chain and most preferably Cs to CM alkyl chain. Typically, for laundry applications alkyl chains of C12 to Cis, especially CM to Cis are preferred for lower wash temperatures (e.g., below about 50°C) and Cis to Cis alkyl chains are preferred for higher wash temperatures (e.g., above about 50°C).

In the general formula for primary alkyl sulfate surfactant, M is preferably hydrogen or an alkali metal cation selected from sodium, potassium or lithium, more preferably M is sodium. M may also be preferably selected from lithium, calcium, and magnesium, ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.

The primary alkyl sulfate surfactant may exist in an acid form, or the acid form may be neutralized to form a surfactant salt, preferably a water-soluble salt form. Typical agents for neutralization include metal counterion bases, such as hydroxides, e.g., NaOH or KOH. Further suitable agents for neutralizing anionic surfactants in their acid forms include alkaline earth metal, alkali metal, ammonium, ammonia, amines, or alkanolamines (e.g., mono-, di-, and tri ethanolamine). Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art; suitable alkanolamines include 2- amino-l-propanol, 1- 10 aminopropanol, monoisopropanolamine, or 1-amino-3- propanol. Amine neutralization may be done to a full or partial extent, e.g., part of the anionic surfactant mix may be neutralized with sodium or potassium and part of the anionic surfactant mix may be neutralized with amines or alkanolamines. The solid cleaning composition according to the present invention comprises from 1 wt.% to 45 wt.% by weight of primary alkyl sulfate surfactant. Preferably the solid cleaning composition comprises at least 2 wt.%, at least 4 wt.%, at least 5 wt.%, still preferably at least 6 wt.%, still preferably at least 8 wt.%, most preferably at least 10 wt.% of the primary alkyl sulfate surfactant, but typically not more than 40 wt.%, still preferably not more than 35 wt.%, most preferably not more than 25 wt.% primary alkyl sulfate surfactant based on the weight of the solid cleaning composition. More preferably the solid cleaning composition includes from 1 wt.% to 10 wt.%, 2 wt.% to 8 wt.%, still preferably 2 wt.% to 6 wt.%, most preferably from 2 wt.% to 4 wt.% by weight of primary alkyl sulfate surfactant.

Alkyl ester fatty acid sulphonate surfactant

The cleaning composition according to the present invention includes an alkyl ester fatty acid sulphonate surfactant.

Preferably the alkyl ester fatty acid sulphonate surfactant has a general formula

wherein Ak = predominantly linear C_M to Cis alkyl chain.

Preferably the alkyl ester fatty acid sulphonate surfactant is methyl ester fatty acid sulphonate surfactant. More preferably it is a sodium Cie to Cie methyl ester sulphonate surfactant (MES). MES surfactant preferably has a purity of 80 to 90% and an average molecular weight of sodium salt of from 370 to 390 g/mol. Preferably the alkyl ester fatty acid sulphonate surfactant is sodium neutralized but may be neutralized with other traditional salts such as potassium and the like. Moreover, the MES may also be neutralized in whole or in part, by divalent ions, example magnesium. The solid cleaning composition according to the present invention comprises from 4 wt% to 45 wt% by weight of alkyl ester fatty acid sulphonate surfactant. Preferably the solid cleaning composition comprises at least 5 wt%, still preferably at least 6 wt%, still preferably at least 8 wt%, most preferably at least 10 wt% of the alkyl ester fatty acid sulphonate surfactant, but typically not more than 40 wt%, still preferably not more than 35 wt%, most preferably not more than 25 wt% alkyl ester fatty acid sulphonate surfactant based on the weight of the solid cleaning composition. More preferably the solid cleaning composition includes from 4 wt% to 10 wt%, preferably 4 wt.% to 8 wt.% and most preferably from 4 wt.% to 6 wt.% by weight of alkyl ester fatty acid sulphonate surfactant. It is highly preferred that the anionic non-soap surfactant according to the present invention is predominantly an alkyl ester fatty acid sulphonate surfactant, most preferably all of the anionic non-soap surfactant according to the present invention is composed of an alkyl ester fatty acid sulphonate surfactant. Water soluble alkyl carboxylate salt of Ce to Cie fatty acid

The cleaning composition according to the present invention includes a water-soluble alkyl carboxylate salt of Cs to Cis fatty acid.

Water soluble alkyl carboxylate salt of Cs to Cis fatty acid also known as “soaps”. As described herein, the term soap refers to carboxylate salts of fatty acids. Preferably the water-soluble alkyl carboxylate salt of the Cs to Cis fatty acid includes alkali metal soaps such as the sodium, potassium, ammonium, and alkyl ammonium salts of higher fatty acids containing from about 8 to about 18 carbon atoms, and preferably from about 8 to about 16 carbon atoms. More preferably from 8 to 14 carbon atoms. The fatty acid may preferably be saturated or an unsaturated fatty acid. More preferably saturated.

The alkyl carboxylate salt of fatty acid (soap) content of the composition of the invention may comprise of a single alkyl carboxylate salt of fatty acid (soap compound) or a mixture of alkyl carboxylate salt of fatty acid (soap compounds). In some cases, a single fatty acid carboxylate is used. The counter ion may be a single counter ion or mixture of counter ions. Suitable counter ions are known in the art and include potassium and sodium ions as well as organic amine based counter ions such as those based on triethanolamine. The fatty acid carboxylate may be unsaturated or saturated. For example, the fatty acid may comprise one or more double bond. Preferably, the soap is more than 50 wt.% monounsaturated. The fatty acid may be a Cio to C30 compound, for example a C15 to C25 compound. A suitable fatty acid present in the water-soluble alkyl carboxylate salt is lauric acid. In these cases, the soap is more than 50 wt.% a carboxylate salt of lauric acid. For example, it may be the potassium salt. In other words, the soap may be more than 50 wt.% potassium laurate. In some cases, the soap is more than 75 wt.% a carboxylate salt of lauric acid, for example more 90 wt.% or even more than 95 wt.%.

The cleaning composition according to the present invention comprises from 1 wt.% to 45 wt.% of water-soluble alkyl carboxylate salt of C12 to C18 fatty acid. Preferably the cleaning composition comprises at least 3 wt.% , still preferably at least 5 wt.% , still preferably at least 8 wt.%, most preferably at least 10 wt.% of the water soluble alkyl carboxylate salt of C12 to C18 fatty acid, but typically not more than 40 wt.% , still preferably not more than 35 wt.% , most preferably not more than 25 wt.% water soluble alkyl carboxylate salt of C12 to C18 fatty acid based on the weight of the cleaning composition. It is highly preferred that the composition of the present invention includes from 1 wt.% to 10 wt.% of water-soluble alkyl carboxylate salt of C12 to C18 fatty acid. Nonionic surfactant

The cleaning composition according to the present invention includes a nonionic surfactant.

Suitable nonionic surfactant includes the condensation products of aliphatic alcohols having from 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 10 to 18 carbon atoms, preferably from 10 to 15 carbon atoms with from 2 to 18 moles, preferably 2 to 10 15, more preferably 5-12 of ethylene oxide per mole of alcohol. Highly preferred nonionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5 to 12 of ethylene oxide per mole of alcohol.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N- dimethylamine oxide and N-tallow alcohol-N, N-dihydroxymethylamine oxide, and of the fatty acid alkanolamide type may also be suitable.

A further class of preferred nonionic surfactants, which may be used either as sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Low-foaming nonionic surfactants are preferred. These includes but are not limited to nonionic surfactants from the group of alkoxylated alcohols. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol residue may be linear or preferably methyl-branched in position 2 or may contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms, for example from oleyl alcohol, and on average 2 to 8 mol of EO per mol of alcohol are preferred. The preferred ethoxylated alcohols include for example C12 to C_M alcohols with 3 EO to 4 EO, Cg to C12 alcohol with 7 EO, C13 to C15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12 to C_M alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12 to CM alcohol with 3 EO and C12 to C19 alcohol with 5 EO. The stated degrees of ethoxylation are statistical averages which for a specific product may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants fatty alcohols with more than 12 EO (ethylene oxide groups) may also be used. Examples of these are sources having narrow range of predominantly Cie to Cie fatty alcohol with 14 EO, 25 EO, 30 EO, 40 EO or 80 EO. Preferred Cie to Cie fatty alcohols with more than 12 EO have from 60 to 100 EO, and more preferably from 70 to 90 EO. Particularly preferred Cie to Cie fatty alcohols with more than 12 EO are Cie to Cie fatty alcohols with 80 EO.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO nonionic surfactants, are likewise particularly preferentially used.

The nonionic surfactant preferably comprises propylene oxide units in its molecule. Such PO units preferably constitute up to 25 wt.%, more preferably up to 20 wt.% and even more preferably up to 15 wt.% of the entire molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally comprise polyoxyethylene/polyoxypropylene block copolymer units. The alcohol or alkylphenol moiety of such nonionic surfactant molecules here preferably constitutes more than 30 wt.%, more preferably more than 50 wt.% and even more preferably more than 70 wt.% of the entire molar mass of such nonionic surfactants. Preferred cleaning compositions are characterized in that they contain ethoxylated and propoxylated nonionic surfactants, in which the propylene oxide units constitute in each molecule up to 25 wt.%, more preferably up to 20 wt.% and even more preferably up to 15 wt.% of the entire molar mass of the nonionic surfactant. Preferably the nonionic surfactant is an alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally complex surfactants such as polyoxypropylene/ polyoxyethylene/ polyoxypropylene ((PO/EO/PO) surfactants). Such (PO/EO/PO) nonionic surfactants are furthermore distinguished by good foam control. Further nonionic surfactants with melting points above room temperature which are particularly preferably to be used contain 40 to 70% of a polyoxypropylene/ polyoxyethylene/ polyoxypropylene block polymer blend, which contains 75 wt.% of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 wt.% of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 mol of ethylene oxide and 99 mol of propylene oxide per mol of trimethylolpropane.

Nonionic surfactants which have proved to be particularly preferred for the purposes of the present invention are low-foaming nonionic surfactants which comprise alternating ethylene oxide and alkylene oxide units. Among these, surfactants with EO-AO-EO-AO blocks are in turn preferred, with in each case one to ten EO or AO groups being attached to one another before being followed by a block of the respective other groups. Preferred nonionic surfactants are those of the general formula

In which R¹ denotes a straight-chain or branched, saturated or mono- or polyunsaturated Ob to C24 alkyl or alkenyl residue; each group R² or R³is mutually independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2 and the indices w, x, y, z mutually independently denote integers from 1 to 6.

The preferred nonionic surfactants of the above formula may be produced by known methods from the corresponding alcohols R¹-OH and ethylene or alkylene oxide. Residue R¹ in the above formula may vary depending on the origin of the alcohol.

Depending on the source used, residue R¹ comprises an even number of carbon atoms and is generally unbranched, preference being given to linear residues from alcohols with 12 to 18 C atoms, for example alcohols formed from source having C12 to C_M, alcohols formed from source having Cie to C18, source having a narrow range of alcohol with predominantly Cie to Cie carbon atoms, or oleyl alcohol. Alcohols obtainable from synthetic sources are for example Guerbet alcohols or residues methyl-branched in position 2 or linear and methyl-branched residues in a mixture as are conventionally present in oxo alcohol residues. Irrespective of the nature of the alcohol used for producing nonionic surfactants contained in the preparations, preferred nonionic surfactants are those in which R¹ the above formula denotes an allyl residue with 6 to 24, more preferably with 8 to 20, even more preferably with 9 to 15 and still even more preferably with 9 to 11 carbon atoms.

Apart from propylene oxide, butylene oxide may in particular be considered as the alkylene oxide unit which alternates with the ethylene oxide unit in preferred nonionic surfactants.

However, further alkylene oxides, in which R² or R³is mutually independently selected from -CH2CH2-CH₃, -CH(CH₃) are also suitable. Nonionic surfactant of the above formula which are preferably used are those in which the R² or R³ denotes a residue - CH_3, w and x mutually independently denote values of 3 or 4 and y and z mutually independently denotes values of 1 or 2.

Preferred nonionic surfactants are those which comprise a Cg to C15 alkyl residue with 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Nonionic surfactants of the general formula R¹-CH(0H)CH₂0-(A0)_w-(A'0)_x-(A"0)_y- (A"'0)_z-R², in which R¹ or R² mutually independently denote a straight-chain or branched, saturated or mono- or polyunsaturated C₂ to C₄₀ alkyl or alkenyl residue; A, A', A" and A'" mutually independently denote a residue from the group -CH₂CH₂, - CH2CH2-CH2, -CH₂-H(CH₃), -CH2-CH2-CH2-CH2, -CH₂-CH(CH₃)-CH₂-, -CH₂-CH(CH₂- CH₃); and w, x, y and z denote values between 0.5 and 90, with x, y and/or z possibly also being 0, are preferred according to the invention.

In particular, preferred end group-terminated poly(oxyalkylated) nonionic surfactants are those which, according to the formula R¹0[CH2CH20]_XCH2CH(0H)R², in addition to a residue R¹, which denotes linear or branched, saturated or unsaturated aliphatic or aromatic hydrocarbon residues with 2 to 30 carbon atoms, preferably with 4 to 22 carbon atoms, furthermore comprise a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residue R² with 1 to 30 carbon atoms, x denoting values between 1 and 90, preferably values between 30 and 80 and in particular values between 30 and 60.

Particularly preferred nonionic surfactants are those of the formula R [CH₂CH(CH₃)0]_x[CH₂CH₂0]_yCH₂CH(0H)R², in which R¹ denotes a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof. R² denotes a linear or branched hydrocarbon residue with 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y denotes a value of at least 15.

Particularly preferred end group-terminated poly(oxyalkylated) nonionic surfactants are furthermore those of the formula R [CH₂CH20]x[CH2CH(R³)0]_yCH₂CH(0H)R², in which R¹ and R² mutually independently denote a linear or branched, saturated or mono- or polyunsaturated hydrocarbon residue with 2 to 26 carbon atoms, R³ is mutually independently selected from -CH3, -CH2CH3, -CH2CH2-CH3, -CH(CH3)2 but preferably denotes -CH₃, and x and y mutually independently denote values between 1 and 32, with nonionic surfactants with R³ = -CH₃ and values of x from 15 to 32 and y of 0.5 and 1.5 being very particularly preferred. Further usable nonionic surfactants are the end group-terminated poly(oxyalkylated) nonionic surfactants of the formula R¹0[CH₂CH(R³)0]x[CH₂]_kCH(0H)[CH₂]_j0R², in which R¹ and R² denote linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R³ denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x denotes values between 1 and 30, k and j denote values between 1 and 12, preferably between 1 and 5. If the value of x is ³ 2, each R³ in the above formula

R [CH₂CH(R³)0]_x[CH₂]_kCH(0H)[CH₂]_j0R² may be different. R¹ and R² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms, residues with 8 to 18 C atoms being particularly preferred. H, -CH3 or-CH₂CH3 are particularly preferred for the residue R³. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15. As described above, each R³ in the above formula may be different if x ³ 2. In this manner, it is possible to vary the alkylene oxide unit in the square brackets. For example, if x denotes 3, the residue R³ may be selected in order to form ethylene oxide (R³= H) or propylene oxide (R³ = CH₃) units, which may be attached to one another in any sequence, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO),

(PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected here by way of example and may perfectly well be larger, the range of variation increasing as the value of x rises and for example comprising a large number of (EO) groups combined with a small number of (PO) groups or vice versa.

Particularly preferred end group-terminated poly(oxyalkylated) alcohols of the above- stated formula have values of k=1 and j=1, such that the above formula simplifies to R [CH₂CH(R³)0]_XCH₂CH(0H)CH₂0R². In the latter-stated formula, R¹, R² and R³ are defined as above and x denotes numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the residues R¹ and R² comprise 9 to 14 C atoms, R³ denotes H and x assumes values from 6 to 15.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the above-stated nonionic surfactants are statistical averages which, for a specific product, may be an integer or a fractional number. Due to production methods, commercial products of the stated formulae do not in the main consist of an individual representative, but instead of mixtures, whereby not only the C-chain lengths but also the degrees of ethoxylation or degrees of alkoxylation may be averages and consequently fractional numbers.

Another preferred nonionic surfactant are according to the formula:

wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein n is from 0 to 3 and m is from 15 to 40, and even more preferably wherein n is 0 and m is from 18 to 25. Such nonionic surfactants are commercially available, e.g. under the tradename Dehypon WET (Supplier: BASF) and Genapol EC50 (Supplier Clariant). Another preferred nonionic surfactant is according to the formula:

wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein n is from 0 to 3 and m is from 15 to 40, and even more preferably wherein n is 0 and m is from 18 to 25;

Yet another preferred nonionic surfactant(s) is according to the formula:

wherein n is from 0 to 5 and m from 10 to 50, more preferably wherein n is from 0 to 3 and m is from 15 to 40, and even more preferably wherein n is 0 and m is from 18 to 25.

Preferably the cleaning composition includes a C12 to Cisalkoxylated alcohol, comprising 3 to 9 alkylene oxide units per molecule, preferably 3 to 7 alkylene oxide units per molecule. A preferred nonionic surfactant is Laundrocilin ex. Clariant having a nonionic surfactant with 7 EO group. The composition has 50 wt.% to 55 wt.% nonionic, 35 wt.% to 40 wt.% silicates and a coating having 5 wt.% to 10 wt.% sodium carbonate. The cleaning composition according to the present invention comprises from 1 wt.% to 45 wt.% of nonionic surfactant, more preferably the composition includes 1 wt.% to 25 wt.% and still more preferably from 1 wt.% to 5 wt.% nonionic surfactant. Preferably the cleaning composition comprises at least 2 wt.%, still preferably at least 4wt.%, still preferably at least 6 wt.%, most preferably at least 10 wt.% of the nonionic surfactant, but typically not more than 40 wt.% , still preferably not more than 35 wt.%, most preferably not more than 25 wt.% of nonionic surfactant based on the weight of the cleaning composition. Most preferably the cleaning composition includes from 1wt.% to 3 wt.% nonionic surfactant.

The solid cleaning composition according to the present invention preferably includes from 1 wt.% to 25 wt.% surfactant which surfactant includes anionic non-soap surfactant selected from primary alkyl sulfate surfactant, alkyl ester fatty acid sulphonate surfactant or mixtures thereof; a water-soluble alkyl carboxylate salt of Cs to Ci₈ fatty acid and nonionic surfactant as described herein above. It is further preferred that the solid cleaning composition includes from 1 wt.% to 20 wt.%. further preferably from 1 wt.% to 15 wt.% surfactant content in the solid cleaning composition.

Other surfactants In addition to the anionic surfactant selected from primary alkyl sulfate surfactant or alkyl fatty ester sulphonate surfactant, water soluble alkyl carboxylate salt of the Cs to Ci₈ fatty acid and the nonionic surfactant as described herein above, the solid cleaning composition according to the invention may include other surfactants. When present other anionic surfactant in the cleaning composition is present in an amount of less than 5 wt.%, still preferably less than 3 wt.%, further preferably less than 2 wt.%, still further preferably less than 1 wt.%, most preferably the solid cleaning composition of the present invention is substantially free of other anionic surfactants.

The composition according to the present invention includes from 0 wt.% to 0.5 wt.% linear alkylbenzene sulfonate surfactant. Preferably the linear alkylbenzene sulfonate surfactant has an Cs to C2₀ alkyl group. The composition preferably includes from 0 wt.% to 0.3 wt.% linear alkylbenzene sulfonate surfactant, more preferably the composition has less than 0.2 wt.%, still more preferably less than 0.1 wt.% linear alkylbenzene sulfonate surfactant and most preferably the composition is free of any deliberately added linear alkylbenzene sulfonate surfactant. The other anionic surfactant may include but is not limited to the anionic sulfonate surfactant. Examples of such other anionic surfactants include, alkyl ether sulfate, alkyl ethoxy sulfate (AES), alkyl ethoxy carboxylates (AEC), secondary alkyl sulfates (SAS) and combinations thereof. More preferably, anionic surfactants selected from sodium dodecyl benzene sulfonate (Na-LAS), sodium lauryl ether sulfate (SLES), and combinations thereof. Preferably the cleaning composition of the present invention includes less than 5 wt.% of anionic surfactant selected from the group consisting of Cio to C20 linear alkyl benzene sulphonates, Cioto C20 linear or branched alkylethoxy sulfates having an average degree of ethoxylation ranging from about 0.1 to about 5 (preferably from about 0.3 to about 4 and more preferably from about 0.5 to about 3), or mixtures thereof.

More preferably the cleaning composition of the present invention are substantially free from other anionic surfactants as described herein above. The terms "substantially free of "substantially free from" used herein means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 wt.%, or less than 0.1 wt.%, or less than 0.01 wt.%, or even 0 wt.%, by weight of the cleaning composition.

Carbonate builder

The composition of the present invention includes a carbonate builder. Examples of the carbonate builder includes alkaline earth metal and alkali metal carbonates as disclosed in the German patent application No. 2,321 ,001. Preferred alkali carbonates are sodium and/or potassium carbonate of which sodium carbonate is particularly preferred. It is further preferred that sodium carbonate makes up at least 75 wt.%, more preferably at least 85 wt.% and even more preferably at least 90 wt.% of the total weight of the alkali carbonate builder.

The cleaning composition of the present invention preferably includes from 15 wt.% to 50 wt.% carbonate builder, more preferably from 30 wt.% to 40 wt.% carbonate builder. Preferably the cleaning composition comprises at least 16 wt.% , still preferably at least 18 wt.% , still preferably at least 20 wt.%, most preferably at least 25 wt.% of the nonionic surfactant, but typically not more than 45 wt.% , still preferably not more than 40 wt.% , most preferably not more than 35 wt.% of carbonate builder based on the weight of the cleaning composition.

Non-carbonate builder In addition to the carbonate builder the solid cleaning composition of the present invention may include other inorganic non-carbonate builder. The other preferred builders may be selected from the group consisting of silicates, silica, zeolites phosphates or mixtures thereof. Yet other non-carbonate builder may be organic builders which includes but are not limited to as succinates, carboxylates, malonates, polycarboxylates, citric acid or a salt thereof. It is highly preferred that the composition of the present invention is substantially free of phosphate containing builders. It is highly preferably that the composition comprises from 0 wt.% to 0.5 wt.% phosphate builders, most preferably there is no deliberately added phosphate builders. Examples of the phosphate builders includes but not limited to alkali metal or ammonium salt of tripolyphosphates, pyrophosphate, pyrophosphate and orthophosphate.

Suitable silicates include the water-soluble sodium silicates with an S1O2: Na2<D ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.4 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an S1O2: Na2<D ratio of 2.0 is the most preferred silicate. Silicates are preferably present in the detergent compositions in accordance with the invention at a level of from 5 wt.% to 50 wt.% by weight of the composition, more preferably from 10 wt.% to 40 wt.% by weight. Water insoluble particles

It is preferred that the cleaning compositions of the invention comprises very limited amount of, i.e. , up to 2 wt.% insoluble particulate matter other than the non-carbonate builder. Such particulate matter may include an abrasive or may even be a silicate like sodium silicate. The compositions may contain one type of particulate matter or a mixture of different particles while still being inside the range of up to 2 wt.% of the total composition.

Whenever such particles are present, it is preferred that Moh's index of such particulate matter is in the range of 2.5 to 6.0. The particulate matter could be one or more of clay, calcite, dolomite, olive stone, feldspar, apatite, fluorite and hematite, kyanite, magnetite, orthoclase and pumice. 15 Whenever present, the average particle size of such particles is 0.5 pm to 400 pm, more preferably 10 pm to 200 pm.

Foam suppressing agent The solid cleaning composition according to the present invention preferably includes a foam suppressing agent. The foam suppressing agent, preferably a non-soap foam suppressing agent is present at a level from 0.01 wt.% to 15 wt.%, preferably from 0.02 wt.% to 10 wt.%, more preferably from 0.05 wt.% to 5 wt.%, most preferably 0.5wt% to 5wt% of the composition.

Suitable foam suppressing agent for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds. By foam suppressing agent it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or foam produced by a solution of a detergent composition, particularly in the presence of agitation of that solution. Particularly preferred foam suppressing agent for use herein are silicone foam suppressing agent 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 foam suppressing agent is a combination of an antifoam compound and silica. In the combination, preferably the antifoam compound is a silicone antifoam compound most preferably polydimethyl siloxane. In the combination the antifoam compound is present at a level of from 50 wt.% to 99 wt.%, preferably 75 wt.% to 95 wt.% of the foam suppressing agent; and silica is present at a level of from 1 wt.% to 50 wt.%, preferably 5 wt.% to 25 wt.% by weight of the foam suppressing agent. The foam suppressing agent having the combination of silica and antifoam compound is incorporated at a level of from 5 wt.% to 50 wt.%, preferably 10 wt.% to 40 wt.% by weight in the detergent composition. Further the foam suppressing agent preferably includes a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72% to 78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1:1.1, at a level of from 0.5% to 10%, preferably 1% to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Coming under the tradename DC0544; Additionally, the foam suppressing agent may include an inert carrier fluid compound, most preferably comprising a C16-C18 ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80%, preferably 10% to 70%, by weight.

Another preferred foam suppressing agent is described in EP-A-0210731 and includes a combination of 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 foam 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 of from 45°C to 80°C.

Still further examples of the foam suppressing agents includes silicone-based foam suppressing agent, hydrocarbon foam suppressing agent, monostearyl phosphate foam suppressing agent or combinations thereof. Other highly preferred foam suppressing agent comprise polydimethylsiloxane or mixtures of silicone, such as polydimethylsiloxane, aluminosilicate and polycarboxylic polymers, such as copolymers of maleic and acrylic acid and monocarboxylate fatty acid. Form of the composition

The composition of the invention thereof can be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tabletting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray drying. The detergent composition may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying. The compositions herein can take a variety of physical solid forms including forms such as powder, granule, ribbon, noodle, paste, tablet, flake, pastille and bar, and preferably the composition is in the form of powder, granules or a tablet, still preferably the composition is in the form of a powder. The composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. The cleaning compositions may have a form selected from powder, unit dose or pouch form, tablet, gel, paste, bar, or flake. Preferably the composition is for manual-washing. Preferably, the cleaning composition of the present invention is a laundry detergent composition. Preferably the composition is in the form of a solid. Further preferably the composition is in the form of a spray - dried powder.

The compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre. pH of the composition The solid cleaning composition according to the present invention preferably has an alkaline pH, generally in the region of pH 9 to 11 when measured with a 10 wt.% dilution in de-ionised water at 25°C.

Suitable pH buffering components for use herein are selected from the group consisting of alkali metal salts of carbonates, bicarbonate, citric, citrate, polycarbonates, sesquicarbonates, silicates, polysilicates, borates, metaborates, phosphate, stannates, aluminates and mixtures thereof.

Optional ingredients The cleaning composition of the present invention may preferably include one or more of the optional ingredients selected from the group consisting of cleaning and care polymers, enzyme, enzyme stabilizing system, brighteners, fabric hueing agents, perfume and bleach. Cleaning polymer

The cleaning polymer includes but is not limited to soil release polymer, carboxylate polymers, antiredeposition polymers, cellulosic polymers, care polymers, dye-transfer inhibiting polymer, amphiphilic alkoxylated grease cleaning polymers, clay soil cleaning polymers, soil suspending polymers or mixtures thereof.

Suitable carboxylate polymer includes polymers such as a maleate/acrylate random copolymer or polyacrylate homopolymer. Suitable carboxylate polymers includes polyacrylate homopolymers having a molecular weight of from 4,000 Da to 9,000 Da; maleate/acrylate random copolymers having a molecular weight of from 30,000 Da to 100,000 Da, or from 50,000 Da to 100,000 Da, or from 60,000 Da to 80,000 Da. Also suitable are homopolymeric or copolymeric carboxylic acids, such as polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or Methacrylic acid with maleic acid and maleic acid with vinyl methyl ether, these polymeric acids being present as free acids or preferably as sodium salts. Preferred representatives of this group are sodium polyacrylate and sodium salts of acrylic acid-maleic acid copolymers having a weight ratio of acrylic acid: maleic acid of 10: 1 to 1 : 1 , preferably 7: 1 to 2: 1. These compounds generally have molecular weights of 3,000 to 150,000, preferably 5,000 to 100,000.

Soil release polymers are designed to modify the surface of the fabric to facilitate the ease of removal of soil. Typically soil release polymers are based on or derivatives of polyethylene glycol/vinyl acetate copolymers or polyethylene glycol terephthalate polyesters and combinations thereof. Preferred soil release polymer includes polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols), as described in WO2009/153184, EP2692842 and WO2014/019903. Suitable soil release polymers are sold by Clariant under the

TexCare® series of polymers, e.g. TexCare® SRN240, TexCare® SRN100, TexCare® SRN170, TexCare® SRN300, TexCare® SRN325, TexCare® SRA100 and TexCare® SRA300. Other suitable soil release polymers are sold by Rhodia under the Repel-o- Tex® series of polymers, e.g. Repel-o-Tex® SF2, Repel-o-Tex® SRP6 and Repel-o- Tex® Crystal. A preferred polymer is selected from the group consisting of polyester soil release polymer, both end-capped and non-end-capped sulphonated PET/POET polymers, both end-capped and non-end-capped unsulphonated PET/POET polymers or combinations thereof. Preferably the levels of these soil release polymer in the adjunct particle is from 3 wt.% to 15 wt.% at least 5 wt.%, still preferably at least 6 wt.%, still preferably at least 6.5 wt.%, most preferably at least 7 wt.%, but typically not more than 14 wt.%, still preferably not more than 13 wt.%, most preferably not more than 12 wt.%.

Anti-redeposition polymers are designed to suspend or disperse soil. Typically, antiredeposition polymers are polyethylene glycol polymers, polycarboxylate polymers, polyethyleneimine polymers or mixtures thereof. Preferably the antiredeposition polymer is an acrylate polymer, maleic anhydride polymer or a copolymer of acrylic acid and maleic acid and combinations thereof. Such polymers are available from BASF under the trade name Sokalan^®CP5 (neutralised form) and Sokalan^®CP45 (acidic form). Suitable antiredeposition polymers are ethoxylated and or propoxylated polyethylene imine or polycarboxylate materials, for example, acrylic acid-based homo or copolymers available under the trade mark ACUSOL from Dow Chemical, Alcosperse from Akzonobel or Sokolan from BASF. Suitable care polymers include cellulosic polymers that are cationically modified or hydrophobically modified. Such modified cellulosic polymers can provide anti- abrasion benefits and dye lock benefits to fabric during the laundering cycle. Suitable cellulosic polymers include cationically modified hydroxyethyl cellulose. Other suitable care polymers include dye lock polymers, for example the condensation oligomer produced by the condensation of imidazole and epichlorhydrin, preferably in ratio of 1 :4: 1. A suitable commercially available dye lock polymer is Polyquart® FDI (Cognis). Preferably the adjunct particle includes from 0.01% to 10%, preferably from 0.05% to 0.5% by weight of care polymer. Examples of suitable sequestering polymers are DEQUEST™, organic phosphonate type sequestering polymers sold by Monsanto and alkanehydroxy phosphonates.

The cleaning composition is preferably substantially free of phosphate based sequestering polymers. By substantially free, it is meant herein that no phosphate based sequestering polymers is deliberately added. Enzymes:

The composition of the present invention preferably includes one or more enzymes. Preferred examples of the enzymes include those which provide cleaning performance and/or fabric care benefits.

Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, xyloglucanase, phospholipases, esterases, cutinases, pectinases, mannanases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, G-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is an enzyme cocktail that may comprise, for example, a protease and lipase in conjunction with one or more of amylase, mannanase and cellulase. When present in a detergent composition, the aforementioned additional enzymes may be present at levels from about 0.00001% to about 2%, from about 0.0001% to about 1% or from 0.001% to about 0.5% enzyme protein by weight of the detergent composition.

In one aspect preferred enzymes would include a protease. Suitable proteases include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisins (EC 3.4.21.62). Suitable proteases include those known to a person skilled in the art and preferably from animal, vegetable or microbial origin.

In one aspect, such suitable protease may be of microbial origin. The suitable proteases include chemically or genetically modified mutants of the aforementioned suitable proteases. In one aspect, the suitable protease may be a serine protease, such as an alkaline microbial protease or/and a trypsin-type protease. Examples of suitable neutral or alkaline proteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus, such as Bacillus lentus, B. alkalophilus, B.subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii. (b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium protease. (c) metalloproteases, including those derived from Bacillus amyloliquefaciens Preferred proteases include those derived from Bacillus gibsonii or Bacillus Lentus.

Suitable commercially available protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®,

Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark), those sold under the tradename Maxatase®, Maxaca®l, Maxapem®, Properase®, Purafect®, Purafect Prime®,

Purafect Ox®, FN3®, FN4®, 10 Excellase® and Purafect OXP® by Genencor International, those sold under the tradename Opticlean® and Optimase by Solvay Enzymes.

Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha- amylase is derived from a strain of Bacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp. , such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ no. 12649, KSM AP1378 (WO 97/00324), KSM K36 or KSM K38 (EP 1,022, 334). Preferred amylases include: a) the variants with substitutions in one or more of the following positions versus the 25 enzyme listed as SEQ ID No. 2 in WO 96/23874: 15, 23, 105, 106, 124, 128, 133, 154, 156, 181 , 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391, 408, and 444. b) the variants with one or more substitutions in the following positions versus the AA560 enzyme listed as SEQ ID No. 12:

26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 30256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311,314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably that also contain the deletions of D183* and G184*. c) variants exhibiting at least 95% identity with the wild-type enzyme from Bacillus sp.707 (SEQ ID NO:7 in US 6,093, 562), especially those comprising one or more of the following mutations M202, M208, S255, R172, and/or M261. Preferably said amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and/or R172Q. Particularly preferred are those comprising the M202L or M202T mutations. d) variants exhibiting at least 90% identity with SEQ ID No. 4 in W006/002643, the wild-type enzyme from Bacillus SP722, especially variants with deletions in the 183 and 184 positions and variants described in WO 00/60060, which is incorporated herein by reference. e) variants described in WO 09/149130, preferably those exhibiting at least 90% identity with SEQ ID NO: 1 or SEQ ID NO:2 in WO 09/149130, the wild-type enzyme from Geobacillus Stearophermophilus or a truncated version thereof.

Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERM AMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S, Bagsvaerd,

Denmark), 15 KEMZYM® AT 9000 Biozym Biotech Trading GmbH Wehlistrasse 27b A- 1200 Wien Austria, RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE® and PURASTAR OXAM® (Genencor International Inc., Palo Alto, California) and KAM® (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan). In one aspect, suitable amylases include NATALASE®, STAINZYME and STAINZYME PLUS® and mixtures thereof.

In one aspect, such enzymes may be selected from the group consisting of: lipases, including "first cycle lipases". In one aspect, the lipase is a first-wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus comprising one or more of the T231 R and N233R mutations. The wild-type sequence is the 269 amino acids (amino acids 23 — 291) of the Swissprot accession number Swiss-Prot 059952 (derived from Thermomyces lanuginosus (Humicola lanuginosa)). Preferred lipases would include those sold under the tradenames Lipex® and Lipolex®.

In one aspect, other preferred enzymes include microbial-derived endoglucanases exhibiting endo-beta-1, 4-glucanase activity (E.C. 3.2. L4), including a bacterial polypeptide endogenous to a member of the genus Bacillus which has a sequence of at least 90%, 94%, 97% and even 99% identity to the amino acid sequence SEQ ID NO:2 in 7,141 ,403B2) and mixtures thereof. Suitable endoglucanases are sold under the tradenames Celluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

Other preferred enzymes include pectate lyases sold under the tradenames Pectawash®, Pectaway®, Xpect® and mannanases sold under the tradenames Mannaway® (all from Novozymes A/S, Bagsvaerd, Denmark), and Purabrite® (Genencor International Inc., Palo Alto, California).

Enzyme stabilizing system

The enzyme-containing compositions described herein may optionally comprise from 0.001% to 10%, in some examples from about 0.005% to about 8%, and in other examples, from about 0.01% to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, chlorine bleach scavengers and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the cleaning composition. In the case of detergent compositions comprising protease, a reversible protease inhibitor, such as a boron compound, including borate, 4-formyl phenylboronic acid, phenylboronic acid and derivatives thereof, or compounds such as calcium formate, sodium formate and 1,2-propane diol may be added to further improve stability.

Brighteners Optical brighteners or other brightening or whitening agents including fluorescers may be incorporated at levels from 0.01% to 1.2%, by weight of the composition.

Commercial brighteners suitable for the present invention can be classified into subgroups, including but not limited to: derivatives of stilbene, pyrazoline, coumarin, benzoxazoles, carboxylic acid, methinecyanines, dibenzothiophene-5, 5- dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Preferred commercially available Brighteners includes Tinopal AMS-GX by Ciba Geigy Corporation, Tinopal UNPA-GX by Ciba-Geigy Corporation, Tinopal 5BM-GX by Ciba- Geigy Corporation. These also includes DASCC and CBSX. The brighteners may be added in particulate form or as a premix with a suitable solvent, for example nonionic surfactant, monoethanolamine, propane diol. Fabric hueing agents

The composition may comprise a fabric hueing agent (sometimes referred to as shading, bluing or whitening agents). Typically the hueing agent provides a blue or violet shade to fabric. Hueing agents can be used either alone or in combination to create a specific shade of hueing and/or to shade different fabric types. This may be provided for example by mixing a red and green-blue dye to yield a blue or violet shade. Hueing agents may be selected from any known chemical class of dye, including but not limited to acridine, anthraquinone (including polycyclic quinones), azine, azo (e.g., monoazo, disazo, trisazo, tetrakisazo, polyazo), including 30 premetallized azo, benzodifurane and benzodifuranone, carotenoid, coumarin, cyanine, diazahemicyanine, diphenylmethane, formazan, hemicyanine, indigoids, methane, naphthalimides, naphthoquinone, nitro and nitroso, oxazine, phthalocyanine, pyrazoles, stilbene, styryl, triarylmethane, triphenylmethane, xanthenes and mixtures thereof. Suitable fabric hueing agents include dyes, dye-clay conjugates, and organic and inorganic pigments.

Perfume

The solid cleaning composition according to the present invention preferably includes a perfume. Examples of suitable perfume includes those well known to the person skilled in the art. The perfume may be in the form of free oils, encapsulated perfume or combinations thereof. Bleach

The solid cleaning composition according to the present invention preferably includes a bleach. Non-limiting examples of bleach suitable for the present invention includes metal percarbonates, particularly sodium salts, organic peroxyacid bleaches, combination of organic peroxyacid bleach precursor and hydrogen peroxide source and combinations thereof. The composition of the present invention preferably includes from 0.1 wt.% 10 wt.% bleach.

According to a second aspect of the present invention, disclosed is process for preparing a solid cleaning composition according to any one of the preceding claims comprising the steps of: i) adding carbonate builder in the mixing chamber; ii) adding an anionic non-soap anionic surfactant selected from a primary alkyl sulfate surfactant, alkyl ester fatty acid sulphonate surfactant or mixtures thereof; water soluble alkyl carboxylate salt of Cs to Cie fatty acid and a nonionic surfactant; from 0 wt.% to 0.5 wt.% linear alkyl benzene sulphonate surfactant and, iii) mixing the above ingredients from 2 to 15 minutes to obtain the solid cleaning composition according to the first aspect.

According to a third aspect of the present invention disclosed is a method of laundering fabrics using a solid cleaning composition according to any one of the preceding claims comprising the step of: i) preparing an aqueous wash liquor by adding or dissolving the solid cleaning composition according to the first aspect or prepared according to the second aspect in a liquid, preferably water; ii) contacting a textile article with the wash liquor during a main wash cycle or washing step of a hand laundering process, which preferably including a soaking and cleaning step of the soiled textile article in the wash liquor for predetermined period of time; and, iii) rinsing the textile article from the step (ii) in clean water where the rinsing step involves less than 3 rinses, preferably a single risne. iv) optionally drying the textile article.

According to a fourth aspect of the present invention disclosed is use of a combination of an anionic non-soap surfactant selected from a primary alkyl sulfate surfactant or alkyl ester fatty acid sulphonate surfactant or mixtures thereof; a water-soluble alkyl carboxylate salt of Cs to Cis fatty acid; a nonionic surfactant; and, a carbonate builder in a solid cleaning composition for providing low or no foam during washing.

The invention will now be illustrated by the following non-limiting Examples in which parts and percentages are by weight except where otherwise indicated.

Examples Example 1 Preparing the compositions:

A comparative cleaning composition (Ex A) with LAS surfactant was prepared having the formulation as provided in Table 1. Two cleaning compositions (Ex 1 and Ex 2) according to the present invention were prepared in which a primary alkyl sulfate, a nonionic surfactant and a alkyl carboxylate salt of Cs to Cis fatty acid (soap) as provided in Table 1 was prepared.

Determination of the foamability of the composition:

A fixed amount of the composition of Comparative example ExA was weighed and diluted in 5 Litres of water taken in a transparent container to provide a wash liquor having a concentration of 2.5 grams of the composition per litre of water. The water used for preparing the wash liquor had a hardness of 24FH (French Hardness; Ca:Mg; 2:1). The prepared wash liquor was whisked vigorously using hand for 20 seconds. Thereafter the height of the foam generated was determined using a measuring scale. The foam height at this stage (pre-soaking stage) was recorded. The foam height data is provided in Table 1. In the wash liquor a 1 Kg wash load of soiled cotton fabric was added and the fabrics were soaked for 30 minutes. The foam height in the container after soaking the fabric was measured and recorded. The foam height (post soaking) data after soaking are provided in Table 1. The soaked fabric was thereafter removed and washed manually.

The soaked fabric was then rinsed in batches. In each rinse batch 9 litres of clean water were used. After each rinse, the foam height (rinse stage) in the rinse container was measured and recorded. The data is provided in Table 1. The above procedure of manually washing the soiled fabric was similarly followed for the solid cleaning composition of Ex 1 and Ex 2 and the data was recorded and provided in Table 1 below.

Stain removal study protocol: A fixed amount of the composition of Comparative example Ex A was weighed and diluted in 10.6 Litres of clean water taken in a transparent container to provide a wash liquor having a concentration of 2.5 grams of the composition per litre of water. The water used for preparing the wash liquor had a hardness of 24FH (French Hardness;Ca:Mg; 2:1).

In the prepared wash liquor 2.3Kg of the wash load was added. The wash load consisted of 50% cotton and 50% polycotton fabric. Additionally, stain swatches with a dimension of 10X 10 cm² of the stain type ICS-1X1 +ICS-2 X1 +Grass KCoX 1 (ex.

TUV Pvt. Ltd.) was added into a wash liquor along with the wash load. The above wash liquor was left undisturbed for a period of 30 minutes, to allow the wash load to soak in the wash liquor. Thereafter the soaked wash load was manually washed and rinsed in batches. In each batch 1.2 litres of clean rinse water was used.

Stain removal measurement: a) Measurement of Soil Release Index (SRI) Soil release index (SRI) is a measure of the amount of a stain present on fabric that is removed during a washing process. The intensity of any stain after washing is measured by means of a reflectometer and expressed in terms of the difference between the stained fabric and a clean fabric giving DE^* for each stain. SRI value was calculated after measuring L*, a*, and b* using Artix Scan F1, Microtek. It is defined as DE^* and is calculated as:

SRI ⁼ 100 - DE afterwash

L*, a*, and b* are the coordinates of the CIE 1976 (L*, a*, b*) colour space, determined using a standard reflectometer. DE* can be measured before and after the stain is washed, to give AE*bw (before wash) and AE*aw (after wash).

SRI of 100 means complete removal of a stain. The higher the SRI value, the greater is the stain removal potential. DE after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stain after wash. So a DE after wash of zero means a stain that is completely removed. Therefore, a SRI aw (aw: after wash) of 100 is a completely removed stain. The clean (or virgin) fabric is an 25 "absolute standard" which is not washed. For each experiment, it refers to an identical piece of fabric to that to which the stain is applied. Therefore, its point in L a b colour space stays constant.

For each of the composition the stain removal performance was recorded and provided in Table 2. Table 1

*Primary alkyl sulfate ex. Galaxy Surfactants Ltd.

^#Nonionic granules ex. Clariant under the trade name Laundroclin Nl 111. ®Soap powder was procured from JLL.

The data in table 1 shows that the foam height of the composition prepared according to the present invention (Ex 1 , Ex 2) is significantly lower than the comparative composition (Ex A), further the amount of water required to completely rinse the fabric washed in the composition according to the present invention is lower (9 litres of clean water) as compared to the comparative composition ( 27 to 36 litres of clean water). Table 2

The above table shows that good results on stain removal are obtained for Ex 1 having the cleaning composition within the scope of the present invention when compared to comparative detergent composition (Comp Ex A) having LAS surfactant at a higher level (14wt%).

Example 2

The solid cleaning composition according to the present invention suitable for use in a front load washing machine was prepared as shown in table 3. Also, a composition according to the present invention where the non-soap anionic surfactant is an alkyl ester fatty acid sulphonate surfactant was prepared and evaluated for foamability according to the method detailed in Example 1. The detailed formulation and the measured foamability data are included in Table 3.

Table 3

The data in table 1 shows that when the composition of the present invention was used in a front load machine no foam was noticed during the main wash cycle as compared to the conventional front load composition (Ex B). Also the hand wash composition in prepared according to the present invention (Ex 4) having MES as the non-soap anionic surfactant shows no foam formation during the soaking and rinse stage and required only 9 litres of water for complete rinsing and required only 1 rinse.

Example 3 A qualitative evaluation of the cleaning performance of the detergent composition according to the present invention (Ex 3) was conducted with a panel of 8 consumers. The consumer evaluated the detergent compositions by washing their daily wash load for 7 days using the composition according to the present invention and then for the next 7 days with their regular conventional detergent composition (Ex B). At the end of the evaluation period the feedback from the consumer were collected and the details are summarized in Table 4 below.

Table 4

Claims

1 A solid cleaning composition comprising: i) an anionic non-soap surfactant selected from a primary alkyl sulfate surfactant or alkyl ester fatty acid sulphonate surfactant or mixtures thereof; ii) a water-soluble alkyl carboxylate salt of Cs to Cie fatty acid; iii) a nonionic surfactant; iv) a carbonate builder and, v) 0 wt.% to 0.5 wt.% linear alkylbenzene sulfonate surfactant.

2 A solid cleaning composition as claimed in claim 1 wherein the composition comprises from 20 wt.% to 50 wt.% carbonate builder.

3 A solid cleaning composition as claimed in claim 1 wherein the primary alkyl sulfate surfactant has a Cs to Cis alkyl chain, more preferably C_M to Cie alkyl chain.

4 A composition as claimed in claim 1 wherein the nonionic surfactant is a C12 to Cisalkoxylated alcohol, comprising 3 to 9 alkylene oxide units per molecule, preferably 3 to 7 alkylene oxide units per molecule.

5 A composition as claimed in any one of the preceding claims, wherein the composition comprises a non-soap antifoaming agent in an amount ranging from 0.5 wt.% to 5 wt.% in the composition.

6 A composition as claimed in any one of the preceding claims, wherein the composition has a pH from 9 to 11, when measured by preparing a 10% solution of the composition in demineralised water at 25°C.

7 A composition as claimed in any one of the preceding claims, comprising a colourant, dye, shading dye, pigment, fabric hueing agent, optical brightener or combinations thereof. A composition as claimed in any one of the preceding claims, comprising a perfume. A composition as claimed in any one of the preceding claims, comprises an enzyme. A composition as claimed in claim 9 wherein the enzyme is selected from the group consisting of amylase, mannanase, lipase, protease, cellulase or combinations thereof. A composition according to any one of the preceding claims, comprises an antiredeposition polymer, preferably acrylate polymer, maleic anhydride polymer or copolymer of acrylic and maleic acid or combinations thereof. A composition according to any one of the preceding claims, comprises a soil release polymer, preferably a PET-POET polymer. A composition according to any one of the preceding claims, comprises a bleach. A method for reducing the number of rinses during a washing cycle, the method comprising the steps of: i) adding a solid cleaning composition according to any one of the preceding claims 1 to 10 to water to form a wash liquor; ii) contacting a textile article with the wash liquor during a main wash cycle of a laundering process; iii) rinsing the textile article with water where the rinsing step involves less than 3 rinses, preferably a single rinse; and, iv) optionally drying the textile article. Use of a combination of an anionic non-soap surfactant selected from a primary alkyl sulfate surfactant or alkyl ester fatty acid sulphonate surfactant or mixtures thereof; a water-soluble salt of Cs to Cie fatty acid; a nonionic surfactant; and, a carbonate builder in a solid cleaning composition for providing low or no foam during washing.