Field of the Invention

The present invention relates to a stain removing composition and, in particular for removing mud-soil stains from fabrics.

Background of the Invention

Stains are something that people try to avoid, yet they are unavoidable. Nonetheless, people still prefer to wear clothes with lesser stains or no stains at all. Fabric stains ranges from food spills, body stains and stains coming from contact with mud; stains are classified into various categories mainly enzymatic, oily, particulate and bleachable.

Consequently, improved stain removal is one of the constant goals of the detergent industry. There is always an interest to improve the detergency effect, especially on fabric stains. Fabric stains such as particulate stains, especially mud or clay containing iron oxides, aqueous/ bleachable stains such as tea stains or oily stains such as motor oil stains, grease are difficult to remove during main wash. Even if such stains are removed during the wash process, re-deposition of the removed dirt onto the fabric is hard to avoid. Surfactants and polymers are utilized in many stain removing compositions particularly laundry detergent composition for increasing soil removal and soil suspension or anti- redeposition. Polyacrylate polymers are also known for mud stain removal.

Clay soils particles generally comprise negatively charged layers of aluminosilicates and positively charged cations (e.g. calcium) which are positioned between and hold together the negatively charged layers. A variety of models can be proposed for compounds which would have clay soil removal properties. One model requires that the compound have two distinct characteristics. The first is the ability of the compound to adsorb onto the negatively charged layers of the clay particle. The second is the ability of the compound, once adsorbed, to push apart (swell) the negatively charged layers so that the clay particle loses its cohesive force and can be removed in the wash water. Polyethoxy zwitterionic surfactants are one class of mud soil or clay soil removing compounds which are known to perform from the prior art documents. However most anionic surfactants are known to interfere with the clay soil removing performance of the polyethoxy zwitterionic surfactants. Lack of compatibility between the polyethoxy zwitterionic surfactants and the anionic surfactants affects the performance where clay or mud soil removal is desired. US2016/0046892 A1 (Ecolab USA Inc.) discloses a detergent composition having acrylic acid polymers which provides increased soil removal and soil suspension when treating textiles.

US2004/0097394 A1 (Burrows et al.) discloses a detergent composition having a combination of anionic and specified nonionic surfactants for providing improved stain removal.

Accordingly, there is a continuing need to develop compositions, which provide improved mud soil removal benefits and are compatible with anionic surfactants.

Thus, it is an object of the present invention to provide an efficacious stain removing for removing particulate soil, in particular benefits on clay soil or mud soil.

A further object of the invention is to provide a method for removing mud stains and suspending soils in the wash liquor without resulting in any yellowing or greying due to the presence of the mud soil.

A further object of the invention is to provide stain removing composition and methods of use thereof employing a combination of polymer or copolymer of carboxylic acid or salts thereof and anionic alkoxylated surfactant for laundering fabrics. Summary of the Invention

We have determined that signification benefits on mud stain removal from fabrics is achieved by a stain removing composition having a combination of polymer or copolymer of carboxylic acid or salts thereof and an alkoxylated anionic surfactant in a composition having specific amounts of alkaline agent selected from alkaline inorganic salt, organic salt or mixtures thereof.

Detailed Description of the Invention

According to a first aspect of the present invention disclosed is a stain removing composition having a polymer or copolymer of carboxylic acid or salts thereof, an alkoxylated anionic surfactant and an alkaline agent.

The stain removing composition in accordance with the present invention can be formulated into any of the several commercially desirable composition forms for example in the form of particles, granular, flake, powder, liquid, gel, and tablet. More preferably, the stain removing composition of the present invention is in the form of a powder or liquid.

Stain removing composition according to the invention are preferably phosphate free. Phosphate-free means a composition according to the present invention that includes less than 0.5 wt. %, more particularly, less than 0.1 wt. %, and even more particularly less than 0.01 wt. % phosphate based on the total solids content of the stain removing composition.

Stain removing composition according to the present invention are free of amphoteric surfactant. By the term free of amphoteric surfactant it is meant that the composition includes upto 1 wt. %, more preferably upto 0.9 wt. %, still preferably upto 0.5 wt. % and even more preferably up to 0.05 wt.% and most preferably 0 wt.% amphoteric surfactant based on the total solid content of the stain removing composition. It is believed that the presence of amphoteric surfactant may complex with the polyacrylate hence reducing the sites available for adsorption on mud surface or may precipitate the polymer both of these are not desirable.

Preferably, the composition according to the present invention is in particulate or liquid form, preferably, the composition according to the present invention has a water content ranging from 0 to 90wt%. Preferably when the composition is in the form of a liquid the water content is in the range from 30% to 90% more preferably 40% to 90% still preferably from 50% to 90% and most preferably from 60% to 90% by weight of the total composition.

Preferably when the composition is in the solid form, the water content is in the range from 0% to 20%, more preferably from 0% to 15%, still preferably 3% to 10% and most preferably 5% to 12% by weight of the total composition. Polymer or copolymer of carboxylic acid or salts thereof

Disclosed invention includes a polymer or copolymer of carboxylic acid or salts thereof.

Polymer or copolymer of carboxylic acid or salts thereof which can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, are preferably admixed in their acid form. The polymer or copolymer of carboxylic acid or salts thereof according to the present invention is a homopolymer or copolymer (composed of two or more co-monomers) of an alpha, beta-ethylenically unsaturated acid monomer such as acrylic acid, methacrylic acid or a diacid such as maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesoconic acid, citraconic acid and methylene malonic acid. Preferably, the salts are the water-soluble salts of the corresponding polymers, includes the alkali metal, ammonium, and substituted ammonium salts.

Preferably the copolymer of carboxylic acid or salts thereof may be obtained from more than one of the foregoing unsaturated acid monomers. Suitable examples includes a copolymer of acrylic acid and maleic acid or a copolymer of at least one of such unsaturated acid monomers with at least one non-carboxylic alpha, beta-ethylenically unsaturated monomer which may be either non-polar such as styrene or an olefinic monomer such as ethylene, propylene or butane-1 , or which has a polar functional group such as vinyl acetate, vinyl chloride, vinyl alcohol, alkyl acrylates, vinyl pyridine, vinyl pyrrolidone, or an amide of one of the delineated unsaturated acid monomers such as acrylamide or methacrylamide. Copolymer of at least one unsaturated carboxylic acid monomer with at least one non-carboxylic co-monomer should contain at least 50mol. % of polymerised carboxylic acid monomer.

The polymer or copolymer of carboxylic acid is completely or partially neutralised with alkali metal ion, preferably sodium ions. The weight average molecular weight of a polymer or copolymer of carboxylic acid or salts thereof is preferably in the range from 1 ,000 to 20,000, more preferably 1000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.

Particularly suitable polymer or copolymer includes those where the carboxylic acid is an acrylic acid or a salt thereof. Such acrylic acid-based polymers, which are useful herein, are the water-soluble salts of polymerized acrylic acid.

Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Pat. No. 3,308,067, issued Mar. 7, 1967. In the present invention, the preferred polycarboxylic acid or salt thereof is polyacrylic acid or polyacrylate more preferably sodium polyacrylate.

Also preferred are the acrylic/maleic-based copolymers and the water-soluble salts of the copolymer of acrylic acid and maleic acid. Water-soluble salts of such acrylic acid/maleic acid copolymers includes but is not limited to the alkali metal, ammonium and substituted ammonium salts.

Examples of suitable polycarboxylic acid or salts thereof includes modified or unmodified polyacrylates, polyacrylate/maleates, or polyacrylate/methacrylates.

In one aspect, suitable polycarboxylates may be selected from the group comprising acrylic acid such as Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 (ex. BASF GmbH, Ludwigshafen, Germany), Acusol™ 45N, 480N, 460N and 820 (sold by Rohm and Haas, Philadelphia, Pennsylvania, USA), also polyacrylic acids, such as Acusol™ 445 and Acusol™ 420 (sold by Rohm and Haas, Philadelphia, Pennsylvania, USA) acrylic/maleic co-polymers, such as Acusol™ 425N and acrylic/methacrylic

copolymers.

Co-polymers of acrylamide and acrylate with an acrylamide content of upto 50%, preferably upto 20%, by weight of the polymer can also be used. Most preferably, the co-polymer has a weight average molecular weight of from about 4,000 to about 20,000 and an acrylamide content of from about 0% to about 15%, by weight of the polymer. Preferably the polymer or copolymer of carboxylic acid or salts thereof is present in the stain removing composition in an amount ranging from 0.5 to 15 wt% of the

composition, more preferably 1 wt% to 10wt% of the composition.

Alkoxylated anionic surfactant

Disclosed composition includes an alkoxylated anionic surfactant, in which the anionic group is a carboxylate or phosphate moiety.

The composition in accordance with the present invention comprises from 1 to 20 wt.%; preferably from 1 to 15 wt.%, more preferably from 2 to 15 wt.% of alkoxylated anionic surfactant.

Preferably, the alkoxylated anionic surfactant has an anionic group selected from the group consisting of sulphate moiety, phosphate moiety or a carboxylate moiety or anionic derivatives of carboxylate moiety. More preferably, the alkoxylated anionic surfactant is an alkyl alkoxylated carboxylate or a mixture of alkoxylated carboxylate and sulphated alkoxylated alcohol

Preferably, the alkoxylated anionic surfactant has an average degree of alkoxylation ranging from 1 to 40, preferably from 1 to 21 , more preferably 3 to 21. The average degree of alkoxylation is defined as the average number of moles of alkylene oxide per mole of the alkoxylated anionic surfactant of the present invention. Preferably the alkoxylated anionic surfactant is an ethoxylated and/or propoxylated anionic surfactant more preferably ethoxylated. Preferably the alkoxylated anionic surfactant is derived from a fatty alcohol, wherein at least 80%, preferably at least 82%, more preferably at least 85%, most preferably at least 90% by weight of said fatty alcohol is linear. By linear, it is meant is that the fatty alcohol comprises a single backbone of carbon atoms, with no branching.

Preferably, said alkoxylated anionic surfactant has the formula (I):

Ri-(OCH ₂ CH ₂ )n-0-X- M ⁺ (I) wherein:

Ri = a saturated or unsaturated Cs to C22 alkyl chain, preferably Cs to Ci6 alkyl chain, preferably C12 to C14 alkyl chain; preferably, Ri is a saturated Cs to C16, more preferably a saturated C12 to C14 alkyl chain;

X = is an anionic group selected from a sulphonate group, a carboxylate group or respective derivatives thereof;

M = a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and

n = averages from 1 to 40.

The required carbon chain length distribution can be obtained by using alcohols with the corresponding chain length distribution prepared synthetically or from natural raw materials or corresponding pure starting compounds. Preferably, the alkoxylated anionic surfactant of the present invention is derived from a naturally sourced alcohol. Natural sources, such as plant or animal esters (waxes), can be made to yield linear chain alcohols with a terminal (primary) hydroxyl, along with varying degrees of unsaturation. Such fatty alcohols comprising alkyl chains ranging from Cs to C16, may be prepared by any known commercial process, such as those deriving the fatty alcohol from fatty acids or methyl esters, and occasionally triglycerides. For example, the addition of hydrogen into the carboxyl group of the fatty acid to form fatty alcohol, by treating with hydrogen under high pressure and in the presence of suitable metal catalysts. By a similar reaction, fatty alcohols can be prepared by the hydrogenation of glycerides or methyl esters. Methyl ester reduction is a suitable means of providing saturated fatty alcohols, and selective hydrogenation with the use of special catalysts such as copper or cadmium oxides can be used for the production of oleyl alcohol. Synthetic or petroleum-based processes, such as the Ziegler process, are useful for producing suitable straight chain, even-numbered, saturated alcohols. Paraffin oxidation is a suitable process for making mixed primary alcohols. The fatty alcohol may be reacted with ethylene oxide to yield ethoxylated fatty alcohols. The ethoxylated alkyl anionic surfactant(s) of formula Ri-(OCH2CH2)n-0-X ^" M ⁺ may then be obtained by the sulphonation or carboxylation of the corresponding ethoxylated fatty

alcohol(s). Preferably the alkoxylated anionic surfactant has a hydrocarbyl carbon containing 8 to 18 carbon atoms.

A preferred alkoxylated anionic surfactant is the alkoxylated alkyl sulphates having the general structural formula (II): Ri-(OCH ₂ CH ₂ )n-0-S0 ₃ - M ⁺ (II)

The alkoxylated alkyl sulphates are preferably ethoxylated alkyl sulphates having from 8 to 18, preferably 10 to 16, more preferably 12 to 14 carbon atoms in the alkyl chain, and are from 80% to 100% linear. Such surfactants can be made by any known processes, using suitable feedstock. For instance, from linear fatty alcohols which are preferably naturally derived, such as n-dodecanol, n-tetradecanol and mixtures thereof. If desired, such surfactants can contain linear alkyl moieties derived from synthetic sources, or can comprise mixtures of the linear ethoxylated alkyl sulphates with lightly branched, e.g., methyl branched analogues. The ethoxylated alkyl sulphates can be in the form of their sodium, potassium, ammonium or alkanolamine salts. Suitable alcohol precursors for the ethoxylated anionic surfactants include Ziegler-derived linear alcohols, alcohols prepared by hydrogenation of oleochemicals, and 80% or more linear alcohols prepared by enrichment of the linear component of oxo derive alcohols, such as Neodol<®> or Dobanol<®> from Shell. Other preferred ethoxylated anionic surfactants are those from Sasol, sold under the tradenames: Alfol<®>, Nacol<®>, Nalfol<®>, Alchem<®>.

Ethoxylated alkyl sulphate surfactant(s) of formula Ri-(OCH2CH2)n-0-SC>3 ^" M ⁺ , may be derived from coconut oil. Coconut oil usually comprises triglycerides which can be chemically processed to obtain a mixture of C12 to C18 alcohols. A mixture of alkyl sulphates comprising a higher proportion of C12 to C14 alkyl sulphates may be obtained by separating the corresponding alcohols before the ethoxylation or sulphation step, or by separating the obtained ethoxylated alcohol or ethoxylated alkyl sulphate

surfactant(s). Suitable ethoxylated alkyl sulphate surfactants include saturated Cs to C16 alkyl ethoxy sulphates, preferably saturated C12 to C16 alkyl ethoxy sulphates. Preferably Ri is an alkyl chain having from 12 to 16 carbon atoms, M is sodium and n averages from 1 to 3, this is the anionic surfactant sodium lauryl ether sulphate (SLES). It is the sodium salt of lauryl ether sulphonic acid in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3 moles of ethylene oxide per mole.

In the present invention, also preferred as the alkoxylated anionic surfactant are the alkoxylated carboxylate anionic surfactant. The alkoxylated carboxylate anionic surfactant useful in the practice of the disclosed invention include those having the general structural formula (III):

Ri-(0-CH ₂ -CH ₂ )n-0-R-COO-M ⁺ (Ill) wherein Ri is a straight or branched, long chain, alkyl group containing from 8 to 18 carbon atoms, n is an integer from 1 to 40, R is CH2, CH2CH2, or CH2CH2CH2, and M is a counterion such as an organic or inorganic cation including singly valent cations as well as polyvalent cations. Exemplary cations include cations of an alkali metal including sodium or lithium, or organic cations such as ammonium, diethylammonium, or triethylammonium cations, as well as other cations not particularly recited here.

In the compositions according to the instant invention, preferably n ranges from 1 to 20 preferably from 1 to 15, more preferably from 1 to 12 and most preferably from 2 to 10. Preferably Ri is Cs to C22, R is CH2 preferably R= n-alkyl, alkenyl, isoalkyl, cycloalkyl, alkylaryl, arylalkyl and/or aryl and the Ri radical preferably derives from fatty alcohols, Ziegler alcohols, oxo alcohols, Guerbet alcohols and alkylphenols. Preference is given to Cs to C18 alkoxylated carboxylates, and octyl-, nonyl- and tributylphenyl alkoxylated carboxylates.

Particularly preferred Ri radicals are Cs alkyl, C12/14 alkyl, ISO-C13 alkyl, C /is oxoalkyl, C16/18 alkyl, lauryl, oleyl and/or tallow fat alkyl. M is the cation of an alkali metal or alkaline earth metal, sodium polyoxyethylene (6 mol addition) hydrogen, ammonium and/or alkanolammonium, especially triethanolammonium. Such alkoxylated carboxylate surfactant are presently commercially available under the trade name Sandopan® (Clariant Chemical Corp., Charlotte NC), Neodox®25-6 and Neodox®23-4 (Shell Chemical Co., Houston, TX), as well as Surfine® WLG(Finetex Inc., Elmwood Park, NJ), Emuslogen® COL 100 (Clariant).

While the alkoxylated carboxylate anionic surfactant may be provided in its free acid form, it is most preferable to provide this surfactant in its salt form as it has been observed that the surfactant do not reduce the pH level of the detergent formulation or wash liquor. When in free acid form, the alkoxylated carboxylate anionic surfactant is preferably neutralized for example by adding NaOH, KOH, or other base to the composition of the invention.

The alkoxylated carboxylate anionic surfactant are present in the disclosed composition in an amount ranging from 1 to 20 weight%, preferably present in an amount of 2 to 15 weight%, still preferably 1wt% to 10wt% of the composition.

It is highly preferred that the alkoxylated anionic surfactant is an oleyl polyoxethyl acetate, SLES or mixtures thereof. Alkaline agent

Disclosed stain removing composition includes 2 to 70 wt. % alkaline agent. Generally, a sufficient amount of an alkaline agent is added to raise the pH of an aqueous solution of the composition to a pH of at least 8. Preferably the alkaline agent may be present in an amount ranging from 5% to 50% by weight of the disclosed composition, more preferably from 10% to 45% by weight of the composition, still preferably 20 to 40% by weight of the composition.

The alkaline agent in accordance with the present invention is selected from an alkaline inorganic salt, an organic salt or mixtures thereof. The stain removing composition in accordance with the present invention has an alkaline agent and the pH of the resulting composition when dissolved in demineralised water at 25°C and at a concentration of 1wt. % in the solution yields a pH of at least 8. Preferably the measured pH of a 1wt% solution of the composition in demineralised water at 25°C has a pH of 8 to 13 more preferably 9 to 13 and still more from 9 to 12 and most preferably 10 to 12. The composition in accordance with the present invention may employ a combination of alkaline inorganic salt and organic salt. Preferably a combination of alkali metal carbonate and alkali metal citrate is used. When using the stain removing composition of the present invention in the form of a powder to wash clothes, the wash liquor has a pH of at least 8 and preferably from 9 to 12.

Alkaline inorganic salt:

In accordance with the present invention, the alkaline agent is an alkaline inorganic salt. Specific examples of alkaline inorganic salt includes but is not limited to hydroxide, phosphate, orthophosphate, pyrophosphates, tripolyphosphate,

polyphosphates, carbonate, sesquicarbonate, bicarbonate, borate, tetraborate, perborate, metaborates, sulphate, sulfide, cyanide, silicate, orthosilicate, metasilicate, pyrolate or borax salt of alkali metal or alkaline earth metals. Preferably the alkaline inorganic salt which can be employed alone, or preferably in admixture with the silicate includes water-soluble carbonates, bicarbonates and borates.

Preferably the alkaline inorganic salt selected is such that it buffers the pH of an aqueous solution of a 1wt% solution of the composition of the present invention at pH 8 or more. More preferably the alkaline inorganic salt of the present invention is a salt of a strong base and a weak acid. Preferably the alkaline inorganic salts are hydratable salts and can be used in the anhydrous form, or in a partially hydrated form. Preferably the alkaline inorganic salt is selected from the group consisting of carbonate, bicarbonate or silicate of an alkali metal salt or alkaline earth metal.

Preferably the alkali metal is Na or K. It is highly preferred that the alkaline inorganic salt is a non-phosphate inorganic salt. Preferably the alkaline inorganic salt is a silicate of an alkaline metal salt or alkaline earth metal. Such silicate can contain up to 50% by weight of water in the form of water by hydration. Preferred silicates are sodium metasilicate, sodium sesquisilicate or sodium orthosilicate or mixtures thereof. In a preferred composition, the silicate salt (inclusive of any water of hydration) makes up from 2% to 70 wt% of the composition, preferably from 2% to 30 wt% and still more preferably 2 to 20 wt% of the composition. Preferably the silicate is a orthosilicate or a metasilicate which are highly effective strong alkaline reacting substances. Preferably the silicate has a mole ratio of S1O2 to Na ₂ 0 from 1 :1 to 4:1 preferably from 2:1 to 2.5:1 . Preferably the composition according to the present invention includes a combination of a carbonate salt of an alkali metal salt or alkaline earth metal and a silicate salt of an alkali metal salt or alkaline earth metal. Preferably the alkali metal is Na or K.

Preferably the combination includes carbonate salt of an alkali metal salt or alkaline earth metal at a concentration of 5 to 50 wt% of the composition more preferably 10 to 40wt% of the composition and preferably the combination has a silicate salt of an alkali metal salt or alkaline earth metal in an amount from 2% to 30 wt% and still more preferably 2 to 20 wt% of the composition. Preferably, a combination of sodium silicate and sodium carbonate is used. Organic Salt:

In accordance with the present invention, the alkaline agent may be an organic salt. Examples of organic salts includes salts of alkali metal, alkaline earth metal, ammonium and substituted ammonium with polyacetates, carboxylates, polyacetal carboxylates and polyhydoxysulphonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of

ethylenendiaminetetracetic acid, succinic acid, tartaric acid, nitrilotriacetic acid, oxydisuccinic acid, melitic acid, benzene polycarboxylic acid and citric acid.

Preferably the organic salt of the present invention is a salt of a strong base and a weak organic acid. It is preferred that the organic salt is a buffer and maintains the pH of an aqueous solution of a 1wt% solution of the composition of the present invention at at least pH 8.

Preferably the organic salt is a short-chain organic salt and can be either aliphatic salts or aromatic salts or mixtures hereof and is preferably selected from the group consisting of alkali metal salt and/or alkaline earth metal salts of short-chain alkyl-or aryl carboxylic acids comprising a hydrocarbyl chain of no more than 7 carbons.

Preferably the organic salt in the composition according to the present invention is selected from alkali metal salt or alkaline earth metal salt of citrate, maleate or fumarate. Preferably the alkali metal is Na or K. The organic salt is preferably a trisodium salt of a tricarboxylic acid, and more preferably sodium citrate. Most preferably the organic salt is sodium citrate.

Preferably the composition according to the present invention includes organic salt in an amount of 2 to 30 wt%, more preferably 2 to 25 wt% and still more 2 to 20 wt% of the composition.

Optional Ingredients Further surfactants:

The compositions of the invention may further comprise other surfactants over and above the surfactants described earlier. The compositions of this invention may comprise further surfactants selected from anionic, amphoteric, zwitterionic and combinations thereof. Cationic surfactants are not preferred.

Examples of such further surfactants suitable for inclusion herein can be found in "Surface Active Agents" Vol. 1 , by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn., Carl Hauser Verlag, 1981 .

Suitable anionic surfactant which may be used are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher Ce to Ci8 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C20 benzene sulphonates, particularly sodium linear secondary alkyl C10 to C15 benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from palm kernel, tallow or coconut oil, methyl ester sulfonates, and synthetic alcohols derived from petroleum. Most preferred anionic surfactants are sodium C10 to C15 alkyl benzene sulphonates and sodium C12 to C18 alkyl sulphates. The chains of the surfactants may be branched or linear. Suitable nonionic surfactant which may be used include, in particular, the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Preferred nonionic detergent compounds are C6 to C22 alkyl phenol-ethylene oxide condensates, generally 5 to 9 EO, i.e. 5 to 9 units of ethylene oxide per molecule, and the condensation products of aliphatic Cs to C18 primary or secondary linear or branched alcohols with ethylene oxide, with 5 to 9 EO. The non-ionic surfactant preferably contains an alkyl alkoxylate. The alkyl alkoxylate is preferably and alkyl ethoxylate, with formula

Ri(OCH2CH2)pOH : where Ri is an alkyl group that may be primary or secondary and contains C10 to C16 carbon atoms. Most preferably Ri is a C12-C15 primary alkyl chain, p is from 5 to 9, preferably from 7 to 9.

In addition, the composition may include one or more optional ingredients to enhance performance and properties. While it is not necessary for these elements to be present, the use of such materials is often very helpful in rendering the formulation acceptable for consumer use. Examples of optional components include, but are not limited to: hydrotropes, fluorescent whitening agents, photobleaches, fibre lubricants, reducing agents, enzymes, enzyme stabilising agents (such as polyols), powder finishing agents, defoamers, bleaches, bleach catalysts, soil release agents, especially soil release polymers for cotton or polyester or both, antiredeposition agents, especially antiredeposition polymers, dye transfer inhibitors, buffers, colorants, fragrances, pro- fragrances, rheology modifiers, anti-ashing polymers, preservatives, insect repellents, soil repellents, water-resistance agents, suspending agents, aesthetic agents, structuring agents, sanitisers, solvents, including aqueous and non-aqueous solvents, fabric finishing agents, dye fixatives, wrinkle-reducing agents, fabric conditioning agents and deodorizers.

Dye:

As noted above, shading dye can be used to improve the performance of the composition of the present invention. Any dye used in the composition for treating fabric or hard surfaces known to the person skilled in the art may be used. When the composition is for treating fabrics preferred dyes are violet or blue. It is believed that the deposition on fabrics of a low level of a dye of these shades, masks yellowing of fabrics. A further advantage of shading dyes is that they can be used to mask any yellow tint in the composition itself. Examples of suitable dye includes direct dye, acid dye, hydrophobic dyes, basic dye, reactive dye and dye conjugates. Preferred acid dyes includes azine acid dyes selected from acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98, non-azine acid dyes selected from acid violet 17, acid black 1 and acid blue 29. Preferred hydrophobic dyes include solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77. Preferred examples of basic dyes include

triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 . Preferred examples of reactive dyes include Preferred examples include reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96. Dye conjugates are formed by binding direct, acid or basic dyes to polymers or particles via physical forces.

Dependent on the choice of polymer or particle they deposit on cotton or synthetics. A description is given in WO2006/055787. Particularly preferred dyes are: direct violet 7, direct violet 9, direct violet 1 1 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , direct violet 99, acid blue 98, acid violet 50, acid blue 59, acid violet 17, acid black 1 , acid blue 29, solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63, disperse violet 77 and mixtures thereof.

Flourescent agents:

The composition preferably may include a fluorescent agent (optical brightener).

Fluorescent agents are well known and many such fluorescent agents are available commercially. Usually, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2 wt %, more preferably 0.01 to 0.1 wt %. Preferred classes of fluorescer are: Di-styryl biphenyl compounds, e.g. Tinopal (Trade Mark) CBS-X, Di-amine stilbene di-sulphonic acid compounds, e.g. Tinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4- styryl-3-sulfophenyl)-2H-napthol[1 ,2-d]trazole, disodium 4,4'-bis{[(4-anilino-6-(N methyl- N-2 hydroxyethyl) amino 1 ,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, disodium 4,4'-bis{[(4-anilino-6-morpholino-1 ,3,5-triazin-2-yl)]amino}stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.

Polymers:

The compositions of the invention may further comprise other polymer over and above the polymer described earlier as an essential component of the present invention. These polymers can assist in the cleaning process by helping to retail soil in solution or suspension and/or preventing the transfer of dyes. Polymers can also assist in the soil removal process. Dye transfer, anti-redeposition and soil-release polymers are described in further detail below.

Dye transfer inhibitors:

Detergent compositions often employ polymers as so-called 'dye-transfer inhibitors'. These prevent migration of dyes, especially during long soak times. Any suitable dye- transfer inhibition agents may be used in accordance with the present invention.

Generally, such dye-transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. Nitrogen-containing, dye binding, DTI polymers are preferred. Of these polymers and co-polymers of cyclic amines such as vinyl pyrrolidone (PVP), and/or vinyl imidazole (PVI) are preferred.

Anti-redeposition polymer:

Any polymeric soil release agent known to those skilled in the art can optionally be employed in compositions according to the invention. Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibres, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures. Polyethylene glycol (PEG) can act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1 ,000 to about 50,000, more preferably from about 3,000 to about 10,000. Soil release polymer:

Generally the soil release polymers for polyester will comprise polymers of aromatic dicarboxylic acids and alkylene glycols (including polymers containing polyalkylene glycols). If utilized, soil release agents will generally comprise from about 0.01 wt. % to about 10.0 % by weight, of the composition, typically greater than or equal to 0.2 wt % even from 3 wt % to 9 wt %, but more preferably they are used at greater than 1 wt %, even greater than 2 wt % and most preferably greater than 3 wt %, even more preferably greater than 5 wt %, say 6 to 8 wt % in the composition. Still another preferred soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units. The repeat units form the backbone of the oligomer and are preferably terminated with modified isethionate end-caps. A particularly preferred soil release agent of this type comprises about one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2- propyleneoxy units in a ratio of from about 1 .7 to about 1 .8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent also comprises from about 0.5% to about 20%, by weight of the oligomer, of a crystalline-reducing stabilizer, preferably selected from the group consisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, and mixtures thereof. Suitable soil release polymers are described in WO 2008095626 (Clariant); WO 2006133867 (Clariant); WO 2006133868 (Clariant); WO 2005097959 (Clariant); WO 9858044 (Clariant); WO 2000004120

(Rhodia Chimie); U.S. Pat. No. 6,242,404 (Rhodia Inc); WO 2001023515 (Rhodia Inc); WO 9941346 (Rhodia Chim); WO 9815346 (Rhodia Inc); WO 9741 197 (BASF); EP 728795 (BASF); U.S. Pat. No. 5,008,032 (BASF); WO 2002077063 (BASF); EP 483606 BASF); EP 442101 (BASF); WO 9820092 (Proctor & Gamble); EP 201 124 (Proctor & Gamble); EP 199403 (Proctor & Gamble); DE 2527793 (Proctor & Gamble); WO 9919429 (Proctor & Gamble); WO 9859030 (Proctor & Gamble); U.S. Pat. No. 5,834,412 (Proctor & Gamble); WO 9742285 (Proctor & Gamble); WO 9703162 (Proctor & Gamble); WO 9502030 (Proctor & Gamble); WO 9502028 (Proctor & Gamble); EP 357280 (Proctor & Gamble); U.S. Pat. No. 4,1 16,885 (Proctor & Gamble); WO 9532232 (Henkel); WO 9532232 (Henkel); WO 9616150 (Henkel); WO 9518207 (Henkel); EP 1099748 (Henkel); FR 2619393 (Colgate Palmolive); DE 341 1941 (Colgate Palmolive); DE 3410810 (Colgate Palmolive); WO 2002018474 (RWE-DEA MINERALOEL & CHEM AG; SASOL GERMANY GMBH); EP 743358 (Textil Color AG); PL 148326 (Instytut Ciezkiej Syntezy Organicznej "Blachownia", Pol.); JP 2001 181692 (Lion Corp); JP 1 1 193397 A (Lion Corp); RO 1 14357 (S.C. "Prod Cresus" S. A., Bacau, Rom.); and U.S. Pat. No. 7,1 19,056 (Sasol).

Bleach:

Detergent compositions according to the invention may comprise a bleach system. The present invention may be used in a formulation that is used to bleach via air, or an air bleach catalyst system. Suitable complexes and organic molecule (ligand) precursors for forming complexes are available to the skilled worker, for example, from: WO 98/39098; WO 98/39406, WO 97/48787, WO 00/29537; WO 00/52124, and

WO00/60045, incorporated by reference. An example of a preferred catalyst is a transition metal complex of MeN4Py ligand (N,N-bis(pyridin-2-yl-methyl)-1-,1 - bis(pyridin-2-yl)-1 -aminoethane). Suitable bispidon catalyst materials and their action are described in WO02/48301 . Photobleaches may also be employed. In the context of the present invention a "photobleach" is any chemical species that forms a reactive bleaching species on exposure to sunlight, and preferably is not permanently consumed in the reaction. Preferred photo-bleaches include singlet oxygen photo- bleaches and radical photo-bleaches. Suitable singlet oxygen photo-bleaches may be selected from, water soluble phthalocyanine compounds, particularly metallated phthalocyanine compounds where the metal is Zn or AI-Z1 where Z1 is a halide, sulphate, nitrate, carboxylate, alkanolate or hydroxyl ion. Preferably the phthalocyanin has 1 to 4 SO3X groups covalently bonded to it where X is an alkali metal or ammonium ion. Such compounds are described in WO2005/014769 (Ciba). When present, the bleach catalyst is typically incorporated at a level of about 0.0001 to about 10 wt %, preferably about 0.001 to about 5 wt %.

Electrolyte:

The next optional component that can be included in the composition is an electrolyte which, if chosen well, can also serve as a builder and pH booster. Depending on formulation constraints, electrolytes such as sodium sulfate may be added to the composition.

Use of the composition and method

In another aspect of the present invention disclosed is a stain removing composition of the first aspect for use in a fabric washing process involving cotton or polycotton fabric stained with particulate stains, to provide enhancement in Stain Removal Index (SRI) by at least one unit. The term SRI is well known to persons skilled in the art and is widely used in patent and non-patent technical literature. In substance, the SRI indicates efficacy of any laundry product or laundry treatment composition. Greater the index better is the composition.

In yet another aspect of the present invention disclosed is use of a combination of polymer or copolymer of carboxylic acid or salts thereof and an alkoxylated anionic surfactant in which the anionic group is a carboxylate or phosphate moiety in a stain removing composition having 2 to 70wt% alkaline agent selected from alkaline inorganic salt, organic salt or mixtures thereof for removing particulate stains.

In accordance with an aspect of the present invention disclosed is a method of removing particulate stain from a stained fabric comprising the step of adding the stain removing composition of the first aspect to water to form a wash liquor followed by washing the stained fabric in the wash liquor having the stain removing composition according to the first aspect of the present invention, and thereafter rinsing the fabric of the previous step in an aqueous medium. Preferably the wash liquor is an aqueous laundry wash liquor. The method preferably comprises a soaking step in which before washing, the stain fabric is soaked in the wash liquor having the stain removing composition according to the first aspect of the present invention, preferably for 20 minutes, more preferably for 10 minutes. In accordance with another aspect of the present invention disclosed is a method of removing a particulate stain from a stained fabric having the step of: contacting a portion of said stained fabric with the stain removing composition according to the first aspect in a neat form or diluted form followed by cleaning the stained fabric in an aqueous laundry wash liquor or by dry cleaning.

According to yet another aspect, disclosed is a method of removing a particulate stain from a stained fabric comprising the steps of: preparing a paste by mixing an aqueous medium and the stain removing composition in particulate or granular form as claimed in any one of the preceding claims, preferably in a ratio of 1 :1 ; contacting the prepared paste to a stained portion of the fabric; cleaning the stained fabric in an aqueous laundry wash liquor or by dry cleaning.

When the stain removing composition is in particulate form the composition is diluted with aqueous liquid in a ratio of 1 :1 to form a paste.

The method preferably comprises an aqueous washing process. The stained fabrics may be soaked in the composition according to the invention, or alternatively, the composition may be applied either neat or in diluted form to the stained fabrics.

Alternatively or additionally, the pretreatment step may comprise the step of soaking the substrate in an aqueous solution to which the treatment composition has been added.

The second step of the method of the invention may be a 'main' wash and may be a manual washing process or a washing in a machine. The second step may use any suitable detergent composition. Preferably this detergent composition comprises one or more surfactants and/or other functional ingredients.

The following specific examples further illustrate the invention, but the invention is not limited thereto.

The amounts mentioned in the example below are the exact amounts of the actives present in the composition.

Examples

Example 1 : Evaluation of mud stain removal benefits provided by compositions inside and outside the invention

Table 1 shows some of the important parameters/variables related to Example 1 , followed by some explanation of the term SRI. Table 1

Procedure to determine SRI:

SRI is a measure of how much of a stain on textile is removed during washing. The intensity of any stain can be measured by means of a Reflectometer in terms of the difference between the stain and a clean cloth giving ΔΕ ^* for each stain. SRI value was calculated after measuring L ^* ,a ^* ,b ^* using Artix Scan F1 , Microtek. It is defined as ΔΕ ^* and is calculated as given below: , Τ * Ιϊ ^* »

T m≠, _≠r > ^J cl m

SRI = 100 - ΔΕ ⁴ afterwas

L ^* , a ^* , and b ^* are the coordinates of the CIE 1976 ( L ^* , a ^* , b ^* ) colour space, determined using a standard reflectometer . ΔΕ ^* 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. ΔΕ after wash is the difference in L a b colour space between the clean (unwashed) fabric and the stain after wash. So a ΔΕ 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 "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 the determination of the SRI, a standard protocol was used, called the Tergometer (also called Tergotometer) wash protocol.

Said Tergometer wash protocol has the following steps:

1. Measurement of the colour of the stain on the textile cloth (before washing).

2. Switch on the Tergometer and set to a temperature of 28°C.

3. Add water of required hardness, leave to heat to 28°C for 10 minutes.

4. Add formulation (provided in Table 2) to each pot and then agitate at 100 rpm for 1 minute.

5. Add the stained swatches and ballast into each pot.

6. Start the wash, agitate at 100 rpm and leave to wash for 15 minutes.

7. Rinse with fresh water (6°FH) for 2 minutes.

8. Repeat rinse.

9. Dry overnight in the dark.

10. Read stains after wash.

The details of the compositions that were prepared and subjected to SRI studies thereafter, is shown in Table 2.

Table 2

this formulation is outside the presenl invention. * Polyacrylate used was Sokalan PA-30 CL from BASF which is a polyacrylic acid has an average molecular weight of 8000 and is partially neutralised as the sodium salt.

# SLES used has a mol ure below where

^Λ the alkoxylated carboxylate surfactant has a structure as provided below where n=7 to 9 and M is sodium cation. The data given in Table 2 indicates that the SRI values of compositions outside the invention are lower than the SRI provided by composition inside the invention (Ex 1 ), thus the composition (Ex 1 ) of the present invention provides better mud soil stain removal benefits as compared to the comparative compositions (A,B, C andEx 2).