BRPI0611889A2 - bleach composition and method of treating a textile product - Google Patents

Abstract

Whitening composition, and method of treating a textile product. The present invention provides a bleach composition comprising transition metal complex and a catechol.

Description

"WHITE COMPOSITION, Ε METHOD OF TREATING TEXTILE PRODUCT"

FIELD OF INVENTION

This invention relates to bleach compositions primarily for use in bleaching laundry.

BACKGROUND OF THE INVENTION

The use of bleach removal catalysts has been developed over recent years. The recent discovery that some catalysts are capable of effectively targeting the absence and presence of a peroxylated species has recently become the focus of some interest, for example: W09965905; WOOO12667; W00012808; W00029537, and W00060045.

SUMMARY OF THE INVENTION

The bleach composition of the present invention has also been used as an anti-dye transfer agent.

In one aspect the present invention provides a bleach composition comprising from 0.001 to 50% by weight of a catechol group transition metal complex together with from 2 to 60% by weight of a surfactant, and at least 2% by weight of a peroxygenated bleaching agent. or your source.

In another aspect the present invention provides a method of treating a textile product, the method comprising the steps of:

(i) treating a textile product with an aqueous solution of a catechol transition metal complex, the aqueous solution having a pH of at least 7 and comprising from 1 μΜ to 50 mM of a catechol transition metal complex, between 1 and 15 mmol hydrogen peroxide and 0.2 g / l to 3 g / l of a surfactant; and,

(ii) rinse and dry the textile product.

A unit dose as used herein is a particular amount of the bleach composition used for a type of wash. The unit dose may be in the form of a defined volume of unit dose detergent powder, granules or tableteliquid.

DETAILED DESCRIPTION OF THE INVENTION

Catechol Group

The catechol group has the 1,2-benzenediol core structure as given immediately below.

<formula> formula see original document page 3 </formula>

The central structure may in essence have any substituents around it, including conjugation with other aromatics, and still be able to coordinate at a transition metal center. Examples of extended conjugated aromatics are those of aromatic structures denaphthalene, indole, anthracene, and indene.

Preferably, however, the catechol group is of the 1,2-benzenediol core structure, that is, it is not in conjunction with other aromatics. In addition it is preferred that the catechol group has only two hydroxyl groups.

The catechol group is preferably water soluble to the extent of at least 5mg / mL. In this regard, the presence of water solubilizing groups is preferred. The water solubilizing group is most preferably a charged species: cationic or anionic. Examples of such water solubilizing groups are: -SO 3, and -COON. A preferred decathecol example is Tiron® which is commercially available (4,5-dihydroxy-m-benzene disulfonic acid disodium salt).

The level of transition metal complex - catechol group in a laundry detergent product will be present in 0.001 to 50 wt%, more preferably 0.1 to 25 wt%, and even more preferably 1 to 15 wt%.

The transition metal of the catechol complex is preferably that of Mn (II) - (III) - (IV) - (V), Fe (II) - (III) - (IV) - (V), Cu (I) - (II) 5 Mo (IV) - (V) - (VI), W (IV) - (V) - (VI), or V (III) (IV) - (V). More preferably Mn (II) - (III) - (IV) - (V) or Fe (II) - (III) - (IV) - (V) and in particular Mn (III) or Mn (IV). The catechol - transition metal complex level is such that the level in use is 1 μΜ to 50 mM, with preferred levels in use for domestic laundry operations falling within the range of 1 μΜ to 100 μΜ. This is preferably provided by a complex formed in the bleach composition. Higher levels may be desired and applied in industrial bleaching processes such as bleaching of textile and paper pulp.

The levels of active agent in the bleach composition are provided by a unit dose of the clothing bleach composition in an aqueous volume designed as directed in the packaging of a commercial formulation. It is also preferred that the aqueous solution has an ionic strength of 0.001 to 0.5 which is imparted by the use of a unit dose of bleach composition. It is more preferred that a unit dose of bleach composition will give a pH to the aqueous wash environment of pelicans 7, more preferably 8 and even more preferably 9.5.

Second Transition Metal Catalyst

In a preferred embodiment the bleach composition comprises a second catalyst which is different from a catechol group as exemplified in WO9965905; W00012667; W00012808; W00029537, and W00060045. The level of the second catalyst is in the same range as that of the transition metal and catechol catalyst.

The second transition metal catalyst is preferably of the form: <formula> formula see original document page 5 </formula>

wherein each R is independently selected from: hydrogen, hydroxyl, -NH-CO-H, -NH-CO-C1-C4-alkyl, -NH2, -NH-C1-C4-alkyl, and C1-C4-alkyl;

R1 and R2 are independently selected from:

C1 to C10 alkyl, preferably C1 -C4 alkyl, C6 -C10 aryl, and a group containing a nitrogen heteroatom with a transition metal;

R 3 and R 4 are independently selected from hydrogen, C 1 -C 8 alkyl, C 1 -C 8 alkyl-O-C 1 -C 8 alkyl, C 1 -C 8 alkyl-C 6 -C 10 aryl, C 6 -C 10 aryl, C 1 -C 8 hydroxyalkyl, and - (CH 2 ) nC (0) 0R5 where R5 is C1 "C4-alkyl, η is from 0 to 4, and mixtures thereof; and,

X is selected from C = O, - [C (R6) 2] y- wherein y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, C1 -C4 alkoxy and C1 -C4 alkyl.

Preferred groups containing the heteroatom may be found in a heterocycle alkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydro-thiophenyl; tetrahydro-furanyl; tetrahydro-pyranyl; and oxazolidinyl, in which the heterocyclealkyl may be attached in a binder via any atom on the ring of the selected heterocyclealkyl, a -C 1 -C 6 alkylheterocycloalkyl, wherein the -C 1 -C 6 heterocycle alkyl heterocycle alkyl is selected from the group consisting of: piperidinyl, piperidine; 1,4-piperazine, tetrahydro-thiophene; tetrahydrofuran; tetrahydro-pyran, wherein the heterocyclealkyl may be attached to the -C 1 -C 6 alkyl via any atom on the ring of the selected heterocycle alkyl, a C 1 -C 6 alkyl heteroaryl, in which a heteroaryl C1 -C6 alkylheteroaryl is selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl;

quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, in which a heteroaryl may be attached to the C1 -C6 alkyl via any atom in the ring of the selected heteroaryl and the selected heteroaryl is optionally substituted by C1 -C4 alkyl. A preferred heteroaryl substituent is pyridin-2-yl methyl.

Examples of more preferred groups containing the optionally substituted tertiary amine heteroatomosion of the form -C 2 -C 4 alkyl-NR 7 R 8, wherein R 7 and R 8 are independently selected from the group consisting of straight chain, branched or cyclic C 1 -C 12 alkyl, benzyl, C 2 -C 4 -alkyl of a C 2 -C 4 -alkyl of NR 7 R 8 may be substituted with 1 to 4 C 1 -C 2 alkyl, or may form part of a C 3 to C 6 alkyl ring, and wherein R 7 and R 8 may together form a saturated ring containing one or more other heteroatoms. Exemplary examples of -C 2 -C 4 -alkyl-NR 7 R 8 are

-CH2CH2-NR7R2, -CH2-CH2-CH2-N2 -CH2CH2-N (ITr) 2,

and

The second transition metal is preferably of the complex of general formula (Al):

<formula> formula see original document page 6 </formula>

wherein: M represents a metal selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III), Fe (II) - (III) - (IV ) - (V), Co (I) - (II) - (III), Ti (II) - (III) - (IV), V (II) - (III) - (IV) - (V), Mo (II) - (III) - (IV) - (V) - (VI) and W (IV) - (V) - (VI), preferably selected from Fe (II) - (IIl) - (IV) - ( V);

L represents a binder as defined herein, or its analogous or deprotonated analog;

X represents a selected coordinating species of any mono, bi or tri-charged anions and any neutral molecules capable of coordinating with the metal in a mono, bi and tridentate manner, preferably selected from O 2 ", RBO22", RCOO ", RCONR-, OH", NO3 ", NO, S2", RS ", PO43", PO3OR3 ", H2O, CO32", HCO3 ", ROH, N (R) 3, ROO", O22 ", O2", RCN, Cl ", Br", OCN ", SCN", CN ", N3", F ", RO", ClO4 ", and CF3SO3", and most preferably selected from O2 ", RBO22", RCOO ", OH", NO3 ", S2", RS ", PO34 ", H2O, CO32", HCO3 ', ROH, N (R) 3, Cf, Br ", OCN", SCN ", RCN, N3", F', I ", RO", ClO4 ", and CF3SO3" ;

Y represents a non-coordinating counterion, preferably selected from ClO4 ", BR4", [MX4] 2 ", PF6", RCOO ", NO3", RO ", N + (R) 4, ROO", O22 ", O2", Br ", F", CF3SO3 ", S2052-OCN", SCN ", H2O, RBO22", BF4 "and BPh4", and more preferably selected from ClO4 ", BR4", [FeCl4] ', PF6 ", RCOO', NO3 ", RO", N + (R) 4, Cl ", Br", F ", - CF3SO3", S2O62 ", OCN", SCN ', H2O and BF4 ";

a represents an integer from 1 to 10, preferably from 1 to 4;

k represents an integer from 1 to 10;

η represents an integer from 1 to 10, preferably from 1 to 4;

m represents zero or an integer from 1 to 20, preferably from 1 to 8; and

each R independently represents a group selected from hydrogen, hydroxyl, -R 1 and -OR ', wherein alkyl, alkenyl, cycloalkyl, heterocyclealkyl, aryl, heteroaryl or a decarbonyl derivative group, R' being optionally substituted by one or more functional groups E, wherein E independently represents a functional group selected from -F 5 -Cl, -Br, -I, -OH 5 -OR ', -NH 2, -NHR', -N (R 1) 2, -N (R ') 3 +, -C (O) R ', -OC (O) R', -COOH, -COO "(Na +, K +), -C (O) NH 2, -C (O) NHR ', -C (O) N (R) 2, heteroaryl, -SH, -P (R 1) 2, -P (O) (R) 2, -P (O) (OH) 2, -NO 2, -SO 3 H, -SO 3 "(Na +, K +), -S (O) 2 R ', -NHC (O) R', and -N (R) C (O) R ', where R is optionally substituted cycloalkyl, aryl, arylalkyl, or alkyl with -F, -Cl, -Br, -I, -NH 3 +, -SO 3 H, -SO 3 "(Na +, K +), -COOH, -COO" (Na +, K +), -P (O) (OH) 2, or -P (0) (0 "(Na +, K +)) 2, and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or phenylopne. optionally substituted naphthyl or C 1-4 alkyl.

The Y counterions in formula (Al) neutralize the charge ζ of the complex formed by ligand L, metal M and coordinating species X. Thus, if the charge ζ is positive, Y could be an anion such as RCOO ", BPh4", ClO4 ", BF4", PF6 ", RSO3", RSO4 ", SO42", NO3 ", F", Cl ", Br", or I ", with Rs hydrogen, optionally substituted alkyl or optionally substituted aryl. If ζ is negative, Y it may be a common cation such as alkali metal, alkaline earth metal or (alkyl) ammonium cation.

The preferred medium for use of the bleach composition is aqueous medium. However, organic solvents may be used, for example methanol or ethanol.

Peroxygen Bleach or Its Source

In a peroxyl bleaching mode the composition of the present invention uses a peroxylated species to target a substrate. The peroxylated bleach species may be a compound which is capable of hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in the art. These include alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts such as alkali metal perborates, percarbonates, phosphosphates, persilicates and persulfates. Mixtures of two or more of such compounds may also be suitable.

Particularly preferred are sodium perborate tetrahydrate and especially sodium perborate monohydrate. Perborate desodium monohydrate is preferred because of its high oxygen content. Sodium percarbonate may also be preferred for environmental rations. Its amount in the composition of the invention will usually be within the range of about 2-35 wt%, preferably 5-25 wt%. One skilled in the art will recognize that these amounts may be reduced in the presence of a bleach precursor e.g., e.g., Ν, Ν ', Ν'-tetraacetyl ethylene diamine (TAED).

Another suitable hydrogen peroxide generating system is a combination of a C1-C4 alkanol oxidase and a C1-C4 alkanol, especially a combination of methanol oxidase (MOX) and ethanol. Such combinations are described in International Application PCT / EP 94/03003 (Unilever), which is incorporated herein by reference.

Alkyl hydroxy peroxides are another class of peroxygenated bleach compounds. Examples of such materials include cumene hydroxy peroxide and t-butyl hydroxy peroxide.

Organic peroxy acids may also be suitable as the peroxygen bleach compound. Such materials usually have the general formula:

<formula> formula see original document page 9 </formula>

wherein R is a substituted alkylene or alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide bond; or a substituted phenylene or phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH group.

<formula> formula see original document page 10 </formula>

or a quaternary ammonium group.

Typical monoperoxy acids useful herein include, for example:

(i) peroxy benzoic acid and ring-substituted peroxy benzoic acids, e.g. peroxy alpha-naphthoic acid;

(ii) substituted aliphatic and arylalkylated monoperoxy acids, e.g. peroxy lauric acid, peroxy stearic acid and α, β-phthaloyl amino peroxy caproic acid (PAP); and

(iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

Typical diperoxy acids useful herein include, for example:

(iv) 1,12-diperoxy dodecanedioic acid (DPDA);

(v) 1,9-diperoxy azelaic acid;

(vi) diperoxy brassylic acid; diperoxy sebasic acid and diperoxy isophthalic acid;

(vii) 2-decyl diperoxy butane-1,4-dioic acid; and

(viii) 4,4'-sulfonyl-bis-peroxy-benzoic acid.

Also inorganic peroxy acid compounds are suitable, such as, for example, potassium monopersulfate (MPS). If organic or inorganic perperoxy acids are used as the peroxygenated compound, the amount thereof will normally be within the range of about 2-10 wt%, preferably 4-8 wt%.

Peroxy acid bleaching precursors are known and widely described in the literature, such as in British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; ΕΡ-Α-0185522; ΕΡ-Α-0174132; ΕΡ-Α-0120591; and U.S. Patent Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

Another useful class of peroxy acid bleaching agent precursors is that of cationics, i.e. quaternary ammonium substituted peroxy acid precursors as described in U.S. Pat. 4,751,015 and 4,397,757, in EP-A-0284292 and EP-A-331.229. Examples of peroxy acid bleach precursors of this class are:

2- (N, N, N-trimethyl ammonium) ethyl sodium-4-sulfonphenyl carbonate chloride (SPCC);

N-octyl-N, N-dimethyl-N 1 O-carbophenoxy decyl ammonium chloride (ODC);

3- (N, N, N-trimethyl-ammonium) -propyl sodium-4-sulfo-phenyl carboxylate; and

Î ±, Î ±, β-trimethyl ammonium toluyloxybenzenesulfonate.

Another class of bleaching agent precursors are formed by cationic nitriles as described in EP-A-303,520 and European Patent Specification Reports No. 458,396 and 464,880.

Any of these peroxy acid bleaching precursors may be used in the present invention, although some may be more preferred than others.

Of the above classes of bleaching precursors, preferred classes are esters, including acyl phenol sulfonates and acyl alkyl phenol sulfonates; acyl amides; and quaternary ammonium substituted peroxy acid precursors including cationic nitriles.

Examples of said preferred peroxy acid bleach precursors or activators are 4-benzoyloxybenzenesulfonate disodium (SBOBS); Ν, Ν, Ν'Ν'-tetraacetyl ethylene diamine (TAED); sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; 4-methyl-3-benzoloxy-benzoate desodium; SPCC; trimethyl ammonium toluyloxybenzenesulfonate; sodium nonanoyloxybenzenesulfonate (SNOBS); Sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (STHOBS); and the substituted cationic nitriles.

Other classes of bleaching agent precursors for use in the present invention are found in WOOO15750, for example 6- (nonanamido-caproyl) -oxybenzenesulfonate.

Precursors may be used in an amount of up to -12%, preferably 2-10% by weight, of the composition.

ASSISTANT INGREDIENTS AND ROCKING VEHICLES

The bleach composition in addition to the catechol / decatechol-transition metal complex comprises the adjunct ingredients and balance vehicles to 100% by weight of the composition.

These may be, for example, surfactants, reinforcers, foaming agents, defoaming agents, solvents, fluorescent, bleaching agents, perfume and enzymes. The use and quantities of these components are such that the composition performs depending on the economy, environmental factors and the use of the composition.

The composition may comprise a surfactant and optionally other conventional detergent ingredients. The composition may also comprise a enzymatic detergent composition comprising from 0.1 to 50% by weight 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 / zuiterionic detergent compounds, but this is usually not desired due to their relatively high cost. The enzyme detergent composition according to the invention will generally be used as a water dilution of about 0.05 to 2 wt%. It is preferred that the composition comprises between 2 and 60 wt% of a surfactant, more preferably 10 30 wt%. . In general, anionic and nonionic surfactant surfactants can be chosen from the surfactants described in "Surface Active Agents" Vol. 1, by Schwartz & Perry, Interscience 1949, Vol. 2 by Schwartz, Perry & Berch, Interscience 1958, in the current issue. from "McCutcheon'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, 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 oxide. ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are condensed from C 2 to C 22 alkyl phenol ethylene oxide, generally 5 to 25 EO, ie 5 to 25 ethylene oxide units per molecule, and C8 to C18 primary or secondary linear or branched ethylene oxide aliphatic condensation products, generally 5 to 40 EO.

Suitable anionic detergent compounds which may be used are normally soluble alkali metal salts of organic sulfate and sulfonates 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 sulfates, especially those obtained by sulfation of higher alcohols Cg to Cjg, produced for example from coconut oil and tallow, C9 to C20 alkylbenzenesulfonates sodium and potassium, particularly C10 to C15 alkyl-linear secondary sodium sodium sulfonates; and sodium alkyl glyceryl ether sulfates, especially those ethers of higher alcohols derived from coconut oil or tallow and synthetic alcohols derived from oil. Preferred anionic detergent compounds are Cn to C15 sodium alkyl benzene sulfonates and C12 to C1 sodium alkyl sulfates. Surfactants such as those described in EP-A-328 177 (Unilever), which show resistance to salting separation, are also applicable to the alkyl polyglycoside surfactants described in EP-A-070 074, and alkyl monoglycosides.

Preferred surfactant systems are mixtures of anionic with nonionic detergent materials, in particular the groups and examples of anionic and nonionic surfactants cited in EP-A-346 995 (Unilever). Especially preferred is the surfactant system which is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulfate together with a C12 to C15 primary alcohol ethoxylate 3 to 7EO.

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

Enzymes

Preferred compositions of the present invention preferably comprise one or more enzymes, which provide cleaning, tissue care and / or sanitizing performance benefits. Reference is made to WO 03/104378 where suitable and preferred enzymes are discussed. Of lipases Lipex® is the preferred enzyme.

FLUORESCENT AGENT

The garment treatment composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Typically, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example sodium ossals. The total amount of fluorescent agent or agents used in the garment treatment composition is generally from 0.005 to 2 wt%, more preferably 0.01 to 0.1 wt%. Preferred classes of fluorescent agents are: Di-styryl-biphenyl-compounds, eg Tinopal (Trade Mark) CBS-X, Di-amine-stilene-disulfonic acid compounds, egTinopal DMS pure Xtra and Blankophor (Trade Mark) HRH, and pyrazoline compounds, eg Blankophor SN. Preferred fluorescent agents are: 2- (4-styryl-3-sulfo-phenyl) -2H-naphthol [1,2-d] sodium sodium, 4,4'-bis ([(4-anilino-6- (N disodium-methyl-N-2-hydroxy-ethyl) amino-1,3,5-triazin-2-yl)] -amine-stilbene-2,2'-disulfonate, 4,4'-bis {[(4 - disodium anilino-6-morpholin-1,3,5-thiazin-2-yl)] amino) stylbene-2- 2'-disulfonate, and disodium 4,4'-bis (2-sulfoslyryl) - Biphenyl.

PERFUME

Preferably the bleach composition comprises a perfume. The perfume is preferably within the range of 0.001 to 3% by weight, more preferably 0.1 to 1% by weight. Many suitable examples of perfumes are provided in the Cosmetic, Toiletry and Fragrance Association (CTFA) 1992 International Buyers Guide, published by CFTAPublications and OPD 1993 Chemicals Buyers Directory 8th Annual Edition, published by Schnell Publishing Co.

Experimental

The synthesis of MnOO 1: (H2bispictn) [Mn2in (Cl4Cat) 4 (DMF) 2) is described by Pradyot Banerjee in Inorganic Chemistry 2004, 43 (19), 5908-5918; This compound was provided by the author.

The synthesis of FeOO1: [Fem (bispicen) (Cl4Cat) (Cl4SQ)] DMF is described by Pradyot Banerjee in Inorganic Chemistry 2004, 43 (19), 5908-5918; This compound was provided by the author.

The synthesis of Mn002: (Bu4N) [Mn (Cl4Cat) 2 (H2O) (EtOH)] and Mn003: (Bu4N) 2 [Mn (Cl4Cat) 3] is described by Tippu S. Sheriff in InorganicaChima Acta 2004, 357, 2494- 2502; This compound was provided by the author.

The synthesis of Mn004: (derived from Tiron®): [Na] 5 [Mn (3,5- (S03) 2Cat) 2] .IO (H2O) (EtOH)] is described by Tippu S. Sheriffem InorganicaChimica Acta 2003, 348, 115-122; This compound was provided by the author.

In the following description Cl 4 Cat = 1,2-dihydroxy-3,4,5,6-tetra-chloro-benzene but one skilled in the art will recognize that groupocatechol when in the form of a complex will release the two phenolic hydrogens.

Measurements

After the washes, the cloths were rinsed with water and the color change was measured immediately after drying for 3 h at 45 ° C. To express the bleaching effect a value called deltaE is used which is defined as the difference between a bench cloth and a stained cloth after being washed. Mathematically, the definition of deltaE is:

deltaE = [(AL) 2 + (Aa) 2 + (Ab) 2] 172

where AL is a measure of the difference in darkness between white and washed opane; Aa and Ab are measurements for the difference between redness and yellowing respectively between both cloths. From this equation, it is clear that the lower the deltaE value, the whiter the opane. With reference to this color measurement technique, reference is made to the "TEclairage International Commission (CIE); Recommendation on Uniform Color Spaces, color difference equations, psychometric colors, supplement No. 2" by CIE Publication, No. 15, Colormetry, BureauCentral de Ia CIE, Paris 1978. The results are shown below in the tables and are listed, in the tables below the bleaching effect is expressed as a stain removal index (SRI): SRI = 100 - deltaE.

Mn-Catechol (MnOQl) bleaching on peroxide-free tea stains at pH 10e without surfactant

<table> table see original document page 17 </column> </row> <table>

Mn-Catechol (MnOOl) targeting on peroxide decurcumin stains at pH 10 and without surfactant

Bleaching experiments were performed on curcumin oily blots using an Mn-catechol complex (MnOOl) in the presence of H2O2. Residual stain was measured on both the stain itself and the surrounding counterweight as a measure of dye transfer inhibition. The higher the counterweight weight SRI value the greater the dye transfer inhibition.

<table> table see original document page 17 </column> </row> <table>

Bleaching experiments were performed on home made tea stains (PG Tips) using the Fe-catechol complex (FeOOl) in the presence of H2O2.

Fe-Catechol (FeOOl) bleaching on peroxide tea stains at pH 10 and without surfactant.

<table> table see original document page 17 </column> </row> <table>

Bleaching experiments were performed on curcumin oily blots using an Fe-catechol complex (FeOOl) in the presence of H2O2. Residual stain was measured both on the stain itself and on the resulting counterweight as a measure of dye transfer inhibition. The higher the counterweight SRI value, the greater the inhibition of dye transfer.

<table> table see original document page 18 </column> </row> <table>

Bleaching experiments were performed on safflower (curry) spice spots at pH 10 with three Mn-catechol complexes. Washing was conducted in an aqueous carbonate buffer environment at pH 10 for 30 minutes.

<table> table see original document page 18 </column> </row> <table>

The fact that catechol formulation per se can be used either with air or peroxyl, as shown above, allows options for dual bleaching. Peroxylated pretreatment of a stained garment followed by addition to the catechol-containing aqueous medium that is substantially devoid of peroxylated species allows the stain to be subjected to two different types of bleach. Alternatively, after treatment of an air-stained garment a peroxylated species may be post-dosed in an aqueous washing medium.

Claims (7)

1. Bleach composition, characterized in that it comprises from 0.001 to 50% by weight of a catechol group-transitioning metal complex together with from 2 to 60% by weight of a surfactant, and at least 2% by weight of a peroxygenated bleaching agent or its source, wherein the catechol of the following formula: <formula> formula see original document page 19 </formula> or its deprotonated form, wherein: R1, R2, R3, and R4 may be independently selected from -H, -Cl , -F, -SO3, -NO3, -COOH, -CH3, -C2H5, -OMe, -OEt and R2 and R3 may together form another five or six membered aromatic ring optionally substituted with one or more selected groups of the group consisting of - H, -Cl, -F, -SO 3, -NO 3, -COOH, -CH 3, -C 2 H 5, -OMe, and -OEt. Bleach composition according to claim 1, characterized in that R1, R2, R3, and R4 are independently selected from SO3 and Cl. Bleach composition according to claim 2, characterized in that a catechol is selected from the group consisting of: <formula> formula see original document page 19 </formula> <formula> formula see original document page 20 </formula> Bleach composition according to claim 1, characterized in that a catechol is Bleach composition according to any one of the preceding claims, characterized in that a catechol is a preformed complex with Mn (II), Mn (III) or Mn (IV). Method of treating a textile product, characterized in that it comprises the steps of: (i) treating a textile product with an aqueous solution of a catechol group transition metal complex as defined in any one of claims 1 to 5, the solution aqueous having a pH of at least 7 and comprising from 1 μΜ to 50 mM catechol-detecting metal complex, between 1 and 15 mmol hydrogen peroxide and from 0.2 g / L to 3 g / L of a surfactant; and claim 6, characterized in that the aqueous solution has an ionic strength of 0.001 to 0.5. (ii) rinse and dry the textile product. 7. Method of treating a textile product according to