STAIN REMOVAL

FIELD OP INVENTION

The present invention concerns the use of particularly efficacious sequestrants for the removal of stains from fabrics .

BACKGROUND OF INVENTION

Tea and red wine are the source of many textile stains that are difficult to remove. There is a need for effective stain removal agents for laundry products that function at low temperature. Sequestrants can provide stain removal benefits at low temperatures, however many of these are not weight effective or contain phosphorous which is not desirable on environmental grounds.

SUMMARY OF THE INVENTION

Some of the non-phosphorous sequestrants used in the present invention have been disclosed in WO2002051961 and WO2005001016 as having utility in semiconductor cleaning solutions. We have found that the non-phosphorous sequestrants, primary sequestrant, are surprisingly weight and molar effective when compared to conventional sequestrants used in laundry applications. The non- phosphorous sequestrants have particular utility in removing stains from cotton textiles. The non-phosphorous sequestrants provide a better stain removal profile when used in combination with other sequestrants, particularity in combination with phosphorous based sequestrants.

In one aspect the present invention provides use of a composition, for cleaning a textile stain, in an aqueous medium, the composition comprising between 2 and 60 wt% of a sufactant and between 0.001 to 5 wt %, preferably 0.05 to 1 wt %, of a sequeterent, the non-phosphonate sequestrant having a molecular weight of less than 400 and of the following structure:

wherein X = N-R3;

Ri _> R2 _> end R4 are independently selected from: a sulphonic acid group, an organic group and hydrogen; and,

R3 and R ₅ are independently selected from: an organic group and hydrogen. The aformentioneed composition preferably comprises a phosphonate sequestrant in the range 0.05 to 1 wt % and the present invention extends tpo such composition per se.

In another aspect the present invention provides use of the composition comprising the non-phosphonate sequestrant, wherein the use comprises the following steps: (i) treating a stained textile in an aqueous medium, the aqueous medium comprising composition comprising: from 0.005 to 0.2 g/L of the non-phosphonate sequestrant, a surfactant at a level in the range from

0.1 g/L to 4g/L, the aqueous medium having a pH in the range from 7 to 12;

(ii) rinsing the textile in an aqueous medium; and (iii) drying the textile.

The use of the composition is preferably conducted in the presense of a phosphonate sequestrant that is present in the aqueous medium in the range from 0.005 to 0.2 g/L.

DETAILED DESCRIPTION OF THE INVENTION

The pendant groups Ri to R ₅ may be optionally substituted without detracting from efficacy of the non-phosphonate sequestrant. In particular Ri to R ₅ may be optionally by amines or carboxylic acids, for example R3 = CH ₂ C(NH ₂ )CO ₂ H.

It is preferred that R5 is selected from the group consisting of: H, a keto group, a Cl to ClO-alkyl group, phenyl, and naphthyl . It is preferred that Ri, R ₂ and R ₄ are independently selected from: methyl, ethyl, propyl, butyl, phenyl, naphthyl, methoxy, ethoxy, hydrogen, sulphonic acid, carboxylic acid or salts thereof, ketone group, ester group and an acid amide group;

R ₃ is independently selected from: methyl, ethyl, propyl, phenyl, naphthyl, and hydrogen.

Preferably R _x = R ₂ = R ₅ = H and R ₄ is CH ₃ or C ₂ H ₅ , R ₃ is selected from the group consisting of selected from CH ₃ , C ₂ H ₅ , C ₃ H ₇ , and C ₂ H ₄ COOM, wherein M is H, an alkali metal or alkaline earth metal. It is most preferred that R ₃ is preferably CH ₃ .

A prefered non-phosphonate sequesterent (X =N) is 3-hydroxy- 1, 2-dimethyl-4-pyridone .

Particularly good results may be obtained when the hereinbefore defined sequestrants, primary sequestrant, are used in conjunction with an additional sequestrants in the range 0.001 to 5 wt %, preferably 0.05 to 1 wt %, the additional sequestrant other than the primary sequestrant. Phosphonate sequestrants are prefered as the additional sequestrant, particularly those sold under the Dequest trade name, most preferably 2060-2069, 2010-2019, 2040-2049.

Preferably the primary sequestrant is stored in an acidic granule in high pH powders. In this regard, the granule containing the primary sequestrant possesses a component selected from the group consisting of: a cogranulent, a binder and a coating, wherein the component is an acidic component .

BALANCE CARRIERS AND ADJUNCT INGREDIENTS

The composition in addition to the non-phosphonate sequestrant and surfactant comprises the balance carriers and adjunct ingredients to 100 wt % of the composition.

These may be, for example, builders, foam agents, shading dyes, anti-foam agents, solvents, fluorescers, bleaching agents, and enzymes. Preferably the composition comprises from 0.0001 to 0.1 wt % of a shading dye, from 0.01 to 1 wt % enzyme and from 0.1 to 1 wt % perfume. The use and amounts of these components are such that the composition performs

depending upon economics, environmental factors and use of the composition.

The composition comprises a surfactant and optionally other conventional detergent ingredients. The composition may also comprise an enzymatic detergent composition which comprises from 0.1 to 50 wt %, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 to 95 wt % of one or more anionic surfactants and 5 to 100 wt % of one or more nonionic surfactants. The surfactant system may additionally contain amphoteric or zwitterionic detergent compounds, but this in not normally desired owing to their relatively high cost. The enzymatic detergent composition according to the invention will generally be used as a dilution in water of about 0.05 to 2 wt%.

The composition comprises between 2 to 60 wt % of a surfactant, most preferably 10 to 30 wt %. In general, the nonionic and anionic surfactants of the surfactant system may be chosen from the surfactants described "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current edition of "McCutcheon ¹ s Emulsifiers and Detergents" published by Manufacturing Confectioners Company or in "Tenside-Taschenbuch", H. Stache, 2nd Edn. , Carl Hauser Verlag, 1981.

Suitable nonionic detergent compounds 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. Specific nonionic detergent compounds are C ₆ to C ₂₂ alkyl phenol-ethylene oxide condensates, generally 5 to 25 EO, i.e. 5 to 25 units of ethylene oxide per molecule, and the condensation products of aliphatic C ₈ to Ci ₈ primary or secondary linear or branched alcohols with ethylene oxide, generally 5 to 40 EO.

Suitable anionic detergent compounds 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 Cs to Ci ₈ alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C ₉ to C ₂₀ benzene sulphonates, particularly sodium linear secondary alkyl Cio to C ₁₅ benzene sulphonates; and sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum. The preferred anionic detergent compounds are sodium Cu to Cχ ₅ alkyl benzene sulphonates and sodium C ₁₂ to Ci ₈ alkyl sulphates. Also applicable are surfactants such as those described in EP-A-328 177 (Unilever) , which show resistance to salting-out, the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides .

Preferred surfactant systems are mixtures of anionic with nonionic detergent active materials, in particular the groups and examples of anionic and nonionic surfactants pointed out in EP-A-346 995 (Unilever). Especially preferred is surfactant system that is a mixture of an alkali metal salt of a Ci ₆ to Ciβ primary alcohol sulphate together with a C ₁₂ to Ci ₅ primary alcohol 3 to 7 EO ethoxylate.

The nonionic detergent is preferably present in amounts greater than 10%, e.g. 25 to 90 wt % of the surfactant system. Anionic surfactants can be present for example in amounts in the range from about 5% to about 40 wt % of the surfactant system.

CATIONIC COMPOUND

When the present invention is used as a fabric conditioner it needs to contain a cationic compound. The preferred pH when for a fabric conditioner is in the range from 3 to 5.

Most preferred are quaternary ammonium compounds.

It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one Cχ ₂ to C ₂₂ alkyl chain.

It is preferred if the quaternary ammonium compound has the following formula:

in which R ¹ is a Ci ₂ to C ₂₂ alkyl or alkenyl chain/ R ² , R ³ and R ⁴ are independently selected from Ci to C ₄ alkyl chains and X ^~ is a compatible anion. A preferred compound of this type is the quaternary ammonium compound cetyl trimethyl quaternary ammonium bromide.

A second class of materials for use with the present invention are the quaternary ammonium of the above structure in which R ¹ and R ² are independently selected from C ₁₂ to C22 alkyl or alkenyl chain; R ³ and R ⁴ are independently selected from Ci to C ₄ alkyl chains and X ^~ is a compatible anion.

A detergent composition according to claim 1 in which the ratio of (ii) cationic material to (iv) anionic surfactant is at least 2:1.

Other suitable quatenary ammonium compounds are disclosed in EP 0 239 910 (Proctor and Gamble) .

It is preferred if the ratio of cationic to nonionic surfactant is from 1:100 to 50:50, more preferably 1:50 to 20:50.

The cationic compound may be present from 0.02 wt % to 20 wt % of the total weight of the composition.

Preferably the cationic compound may be present from 0.05 wt % to 15 wt %, a more preferred composition range is from 0.2 wt % to 5 wt %, and most preferably the composition range is from 0.4 wt % to 2.5 wt % of the total weight of the composition.

If the product is a liquid it is preferred if the level of cationic surfactant is from 0.05 wt % to 10 wt % of the total weight of the composition. Preferably the cationic compound may be present from 0.2 wt % to 5 wt %, and most preferably from 0.4 wt % to 2.5 wt % of the total weight of the composition.

If the product is a solid it is preferred if the level of cationic surfactant is 0.05 wt % to 15 wt % of the total weight of the composition. A more preferred composition range is from 0.2 wt % to 10 wt %, and the most preferred composition range is from 0.9 wt % to 3.0 wt % of the total weight of the composition.

BLEACHING SPECIES

The laundry treatment composition may comprise bleaching species. The bleaching species, for example, may selected from perborate and percarbonate . These peroxyl species may be further enhanced by the use of an activator, for example, TAED or SNOBS. Alternatively or in addition to, a transition metal catalyst may used with the peroxyl species. A transition metal catalyst may also be used in the absence of peroxyl species where the bleaching is termed to be via atmospheric oxygen, see, for example WO02/48301. Photobleaches, including singlet oxygen photobleaches, may be used with the laundry treatment composition. A preferred photobleach is vitamin K3.

FLUORESCENT AGENT The composition most preferably comprises 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 laundry treatment 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-β- (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-l, 3, 5-triazin-2- yl)] amino} stilbene-2-2 ¹ disulfonate, and disodium 4,4'- bis (2-sulfoslyryl) biphenyl .

Examples

Example 1

Black tea beverage was created by placing 1 PG Tips pyramid tea bag in 400ml of boiled ultrapure water for 5 minutes. The tea bag was then removed and the beverage allowed to cool to room temperature. Desized non-mercerised non- fluorescent white cotton sheeting was dipped in the cold tea and removed. The cloth was left to dry for 1 day in the dark, then used for experiments.

The tea stained cotton cloths were washed in pH 8.5 buffer containing 0.1g/L of the compounds listed in the table

below, for 30 minutes. Compounds were selected to provide a comparison of the pyridone compounds to current non-P containing sequesterants. The liquor to cloth ratio was 50:1. The cloth was removed rinsed and dried and the DeltaE values measured relative to a clean cloth. Whether the compound gave a benefit or a negative in terms of stain removal was quantified using the equation deltaE (benefit) = deltaE (control) - deltaE (compound) The 2 pyridones provided the highest benefit

Example 2

Tea stained cloth was created as per example 1. The tea stained cloth was washed in the following commercial laundry products: Persil Performance (ex UK), OMO MA (ex Brasil) and Persil Liquid concentrate (ex UK) . Persil Performance is a zeolite based product with anionic and non-ionic surfactants which contain the TAED/percarbonate bleaching system. OMO MA is a sodium tri-polyphosphate based product with anionic surfactant and does not contain bleach. Persil liquid concentrate contains surfactants, it does not contain bleach and operates at a lower pH than the powders . The washes were conducted at 30°C for 30 minutes using 2.5g/L product and a liquor to cloth ration of 35:1. All cloth was stained. Following the wash the clothes were rinsed, dried and the clothes measured using a reflectometer and the staining of the cloth expressed as deltaE relative to unwashed clean white cloth. Experiments were repeated with addition of varying levels of 3-hydroxy-l, 2-dimethyl-4-pyridone (CAS No 30652-11-0).

The deltaE results are shown in the table below:

Product [3-hydroxy-l , 2-dimethyl- 4-pyridone] in g/L

0 0.01 O.( 35 0. 1

Persil 15. 8 14.5 13 6 11 .8 Performance

OMO MA 16. 4 15.2 13 6 12 .9

Persil 17. 9 16.3 13 4 12 .7 Liquid

Addition of 3-hydroxy-l, 2-dimethyl-4-pyridone increases the tea stain removal seen with all products, as shown by a decrease in the deltaE value.

Example 4

3-hydroxy-l, 2-dimethyl-4-pyridone increased the stain removal of the tea and wine stains when washed in pH buffer solution at 8.5 and 10.

Example 5

Tea stains were created as per example 1. Red wine stains were created in an analogous manner, except here the cloth was dipped into red wine (Australian, Shiraz Cabinet 2003) . The stains were washed at 30 ⁰ C for 30 minutes using 4g/L of ECE reference detergent with a liquor to cloth ratio of 50:1. 6°FH (Ca: Mg 2:1) water was used in the experiment. After washing, rinsing and drying the colour of the cloth was measured and expressed as the DeltaE relative to clean white cloth. The experiment was then repeated with the addition of 0.05 g/L of the sequesterants listed below.

- IA -

ECE reference detergents contains 0.80% of the phosphorous based sequesterant Dequest 2066. Dequest 2016 and Dequest 2060 are also phosphorous based sequestrant. Dequest 2060 and 2066 are analagous except 2060 is the phosphonic acid, and 2066 is Na salt.

From the results 3-hydroxy-l, 2-dimethyl-4-pyridone increases the stain removal by the largest amount. For example for tea and additional stain removal of 2.1 units is observed compared to a maximum of 0.2 units for the other sequestrants .