C4454/C
FORM - 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See Section 10 and Rule 13)
BLEACHING COMPOSITION
HINDUSTAN UNILEVER LIMITED, a company incorporated under the Indian Companies Act, 1913 and having its registered office at Hindustan Lever House, 165/166, Backbay Reclamation, Mumbai -400 020, Maharashtra, India
The following specification particularly describes the invention and the manner in which it is to be performed

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BLEACHING COMPOSITION
FIELD OF INVENTION
This invention relates to bleaching compositions primarily
for use in laundry bleaching.
BACKGROUND OF INVENTION
The use of bleaching catalysts for stain removal has been developed over recent years. The recent discovery that some catalysts are capable of bleaching effectively in the absence and presence of a peroxyl species has recently become the focus of some interest, for example: WO9965905; WO0012667; WO0012808; WO0029537, and, WO0060045.
SUMMARY OF INVENTION
The bleaching composition of the present invention also has
use as an anti-dye transfer agent.
In one aspect the present invention provides a bleaching composition comprising between 0.001 to 50 wt % of a transition metal complex of a catechol moiety together with between 2 to 60 wt % of a surfactant, and at least 2 % wt/wt of a peroxygen bleach or source thereof.
In another aspect the present invention provides a method of treating a textile, the method comprising the steps of: (i) treating a textile with an aqueous solution of a transition metal complex of a catechol moiety, the aqueous solution have a pH of at least 7 and comprising from 1 mM to 50 mM of a catechol transition metal complex, between 1 to

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15 mmol hydrogen peroxide and from 0.2 g/L to 3 g/L of a
surfactant; and,
(ii) rinsing and drying the textile.
A unit dose as used herein is a particular amount of the bleaching composition used for a type of wash. The unit dose may be in the form of a defined volume of powder, granules or tablet or unit dose detergent liquid.
DETAIL DESCRIPTION OF THE INVENTION
Catechol Moiety
The catechol moiety has the core structure of 1,2-
benzenediol as given immediately below.
The core structure may in essence have any substituents about it, including conjugation with other aromatics, and still be able to co-ordinate to a transition metal centre. Examples of extended conjugated aromatics are those of aromatic structures of naphthalene, indole, antharcene, and indene.
However, preferably the catechol moiety is of the core 1,2-benzenediol structure, that is to say that it is not in conjugation with other aromatics. Further is preferred that the catechol moiety only has two hydroxyl groups.

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The catechol moiety is preferably soluble in water to the extent of at least 5mg/mL. In this regard, the presence of water solubilising groups is preferred. The water solubilizing group is most preferably a charged species: cationic or anionic. Examples of such water solubilising groups are: -S03, and -COOH. An example of a preferred catechol is Tiron® which is commercially available (4,5-dihydroxy-m-benzenedisulfonic acid disodium salt).
The level of the catechol moiety transition metal complex in a laundry detergent product will be present at 0.001 to 50 wt %, most preferably 0.1 to 25 wt %, and even more preferably from 1 to 15 wt %.
The transition metal of the complex of the catechol is preferably that of Mn(II)-(III)-(IV)-(V), Fe(II)-(III)-(IV)-(V), Cu(I)-(II), Mo(IV)-(V)-(VI), W(IV)-(V)-(VI), or V(III)-(IV)-(V). Most preferably Mn(II)-(III)-(IV)-(V) or Fe(II)-(III)-(IV)-(V) and in particular Mn(III) or Mn(IV). The level of the transition metal-catechol complex is such that the in-use level is from 1 mM to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 mM to 100 mM. This is preferably provided by a preformed complex in the bleaching composition. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching.
The levels of active in the bleaching composition are provided by a unit dose of the laundry bleaching composition in a designated aqueous volume as directed on the package of a commercial formulation. It is also preferred that the

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aqueous solution has an ionic strength from 0.001 to 0.5 which is conferred by use of a unit dose of the laundry bleaching composition. It is most preferred that a unit dose of the bleaching composition confers a pH to the aqueous wash environment of at least 7, most preferably 8 and even more preferably 9.5.
Second Transition Metal Catalyst
In a preferred embodiment the bleaching composition comprises a second catalyst which is other than a catechol moiety such as exemplified in WO9965905; WO0012667; WO0012808; WO0029537, and, WO0060045. The level of the second catalyst is in the same range as that for the catechol transition metal catalyst.
The second transition metal catalyst is preferably of the form:

wherein each R is independently selected from: hydrogen,
hydroxyl, -NH-CO-H, -NH-CO-Cl-C4-alkyl, -NH2, -NH-C1-C4-
alkyl, and Cl-C4-alkyl;
R1 and R2 are independently selected from:
C1 to C10-alkyl, preferably Cl-C4-alkyl,
C6-C10-aryl, and,

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a group containing a nitrogen heteroatom capable of coordinating to a transition metal;
R3 and R4 are independently selected from hydrogen, C1-C8 alkyl, Cl-C8-alkyl-0-Cl-C8-alkyl, Cl-C8-alkyl-O-C6-C10-aryl, C6-C10-aryl, Cl-C8-hydroxyalkyl, and -(CH2)nC(0)OR5 wherein R5 is Cl-C4-alkyl, n is from 0 to 4, and mixtures thereof; and,
X is selected from C=0, -[C(R6)2]y- wherein Y is from 0 to 3 each R6 is independently selected from hydrogen, hydroxyl, Cl-C4-alkoxy and Cl-C4-alkyl.
Preferred groups containing the heteroatom may be found in a heterocycloalkyl: selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the ligand via any atom in the ring of the selected heterocycloalkyl,
a -Cl-C6-alkyl-heterocycloalkyl, wherein the heterocycloalkyl of the -Cl-C6-heterocycloalkyl is selected from the group consisting of: piperidinyl; piperidine; 1,4-piperazine,tetrahydrothiophene; tetrahydrofuran; pyrrolidine; and tetrahydropyran, wherein the heterocycloalkyl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heterocycloalkyl, a -Cl-C6-alkyl-heteroaryl, wherein the heteroaryl of the -Cl-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

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isoindolyl, wherein the heteroaryl may be connected to the -Cl-C6-alkyl via any atom in the ring of the selected heteroaryl and the selected heteroaryl is optionally substituted by -Cl-C4-alkyl. A preferred heteroaryl substituent is Pyridine-2-ylmethyl.
Examples of most preferred groups containing the heteroatom are optionally substituted tertiary amine of the form -C2-C4-alkyl-NR7R8, in which R7 and R8 are independently selected from the group consisting of straight chain, branched or cyclo C1-C12 alkyl, benzyl, the -C2-C4-alkyl- of the -C2-C4-alkyl-NR7R8 may be substituted by 1 to 4 C1-C2-alkyl, or may form part of a C3 to C6 alkyl ring, and in which R7 and R8 may together form a saturated ring containing one or more other heteroatoms. Exemplified examples of -C2-C4-alkyl-NR7R8 are -CH2CH2-NR7R8, -CH2CMe2-NR7R8, -CMe2CH2-NR7R8, -CMeHCH2-NR7R8, -CMeHCMeH-NR7R8, -CH2CMeH-NR7R8, -CH2CH2CH2-NR7R8, -CH2CH2CMe2-NR7R8, -CH2CMe2CH2-NR7R8, -CH2CH2-NEt2, -CH2CH2-N(i-Pr)2,

The second transition metal is preferably of the complex of the general formula (Al):
[MaLkXn]Ym (Al)
in which:

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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)-(III)-(IV)-(V) ;
L represents a ligand as herein defined, or its protonated or deprotonated analogue;
X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from O2", RB022~, RCOO", RCONR", OH", N03", NO, S2", RS", P043", PO3OR3", H20, CO32", HC03~, ROH, N(R)3, ROO", 022", 02", RCN, CI", Br", OCN", SCN", CN", N3", F~, I", RO", CIO4", and CF3SO3", and more preferably selected from O2", RB022", RCOO", OH", N03", S2", RS", PO34", H20, C032", HC03", ROH, N(R)3, Cl~ , Br", OCN", SCN", RCN, N3", F", I", RO", C104", and CF3SO3";
Y represents any non-coordinated counter ion, preferably selected from C104", BR4", [MX4]", [MX4]2", PF6", RCOO", N03", RO", N+(R)4, ROO", 022", 02", CI" , Br", F", I", CF3SO3", S2062" , OCN", SCN", H20, RB022", BF4" and BPh4", and more preferably selected from C104", BR4" , [FeCl4] ", PF6~, RCOO", NO3-, RO", N+(R)4, CI" , Br", F", I", CF3SO3", S2062" , OCN", SCN", H20 and BF4~;
a represents an integer from 1 to 10, preferably from 1 to 4;
k represents an integer from 1 to 10;
n 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

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each R independently represents a group selected from hydrogen, hydroxyl, -R' and -OR', wherein R'= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or a carbonyl derivative group, R' being optionally substituted by one or more functional groups E, wherein E independently represents a functional group selected from -F, -CI, -Br, -I, -OH, -OR', -NH2, -NHR', -N(R')2, -N(R')3+, -C(0)R', -OC(0)R', -COOH, -COO" (Na+, K+) , -COOR', -C(0)NH2, -C(0)NHR', -C(0)N(R')2, heteroaryl, -R', -SR', -SH, -P(R')2, -P(0)(R')2, -P(0)(OH)2, -P(O) (OR')2, -N02, -SO3H, -S03"(Na+, K+) , -S(0)2R', -NHC(0)R', and -N(R')C (O)R', wherein R' represents cycloalkyl, aryl, arylalkyl, or alkyl optionally substituted by -F, -CI, -Br, -I, -NH3+, -SO3H, -S03"(Na+, K+) , -COOH, -C00"(Na+, K+) , -P(O) (OH)2, or -P(O) (0~(Na+, K+))2, and preferably each R independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C1-4-alkyl.
The counter ions Y in formula (Al) balance the charge z on the complex formed by the ligand L, metal M and coordinating species X. Thus, if the charge z is positive, Y may be an anion such as RCOO", BPh4", C104", BF4", PF6", RS03", RS04", S042" , N03", F", CI", Br", or I", with R being hydrogen, optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation.

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The preferred medium for use of the bleaching composition is an aqueous medium. However, organic solvents may be used, for example, methanol or ethanol.
Peroxygen Bleach or Source Thereof
In a peroxyl bleaching mode the composition of the present invention uses a peroxyl species to bleach a substrate. The peroxy bleaching species may be a compound which is capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in the art. They include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its high active oxygen content. Sodium percarbonate may also be preferred for environmental reasons. The amount thereof in the composition of the invention usually will be within the range of about 2-35% by weight, preferably from 5-25% by weight. One skilled in the art will appreciate that these amounts may be reduced in the presence of a bleach precursor e.g., N,N,N'N'-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 disclosed in International

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Application PCT/EP 94/03003 (Unilever), which is incorporated herein by reference.
Alkylhydroxy peroxides are another class of peroxy bleaching compounds. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.
Organic peroxyacids may also be suitable as the peroxy bleaching compound. Such materials normally have the general formula:

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


group or a quaternary ammonium group.
Typical monoperoxy acids useful herein include, for example:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-.alpha.-naphthoic acid;

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(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and
(iii) 6-octylaminc~6-oxc—peroxyhexanoic acid.
Typical diperoxyacids useful herein include, for example:
(iv) 1,12-diperoxydodecanedioic acid (DPDA);
(v) 1,9-diperoxyazelaic acid;
(vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;
(vii) 2-decyldiperoxybutane-l, 4-diotic acid; and
(viii) 4,4'-sulphonylbisperoxybenzoic acid.
Also inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10% by weight, preferably from 4-8% by weight.
Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and U.S. Pat. Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

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Another useful class of peroxyacid bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Pat. Nos. 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331,229. Examples of peroxyacid bleach precursors of this class are:
2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride (SPCC);
N-octyl-N,N-dimethyl-N10-carbophenoxy decyl ammonium chloride (ODC);
3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and
N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.
A further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification No.'s 458,396 and 464,880.
Any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.

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Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS); N,N,N'N'-tetraacetyl ethylene diamine (TAED) ; sodium-l-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyl-oxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.
Other classes of bleach precursors for use with the present invention are found in WO0015750, for example 6-(nonanamidocaproyl)oxybenzene sulphonate.
The precursors may be used in an amount of up to 12%, preferably from 2-10% by weight, of the composition.
BALANCE CARRIERS AND ADJUNCT INGREDIENTS
The bleaching composition in addition to the transition
metal-catechol complex/catechol comprises the balance
carriers and adjunct ingredients to 100 wt % of the
composition.
These may be, for example, surfactants, builders, foam agents, anti-foam agents, solvents, fluorescers, bleaching agents, perfume and enzymes. The use and amounts of these components are such that the composition performs depending upon economics, environmental factors and use of the composition.

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The composition may comprise 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%.
It is preferred that 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'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

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compounds are C6 to C22 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 C8 to C18 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 C8 to C18 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C9 to C20 benzene sulphonates, particularly sodium linear secondary alkyl Ci0 to C15 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 Cn to C15 alkyl benzene sulphonates and sodium C12 to CiB 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

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is surfactant system that is a mixture of an alkali metal salt of a C16 to C18 primary alcohol sulphate together with a C12 to C15 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 4 0 wt % of the surfactant system.
Enzymes
The bleaching compositions of the present invention preferably comprise one or more enzymes, which provide cleaning performance, fabric care and/or sanitation benefits. Reference is made to WO 03/104378 where suitable and preferred enzymes are discussed. Of the lipases Lipex® is the preferred enzyme.
FLUORESCENT AGENT
The laundry treatment composition 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

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Pyrazoline compounds, e.g. Blankophor SN. Preferred fluorescers are: sodium 2 (4-styryl-3-sulfophenyl)-2H-napthol[l,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-l,3,5-triazin-2-yl)]amino} stilbene-2-2' disulfonate, and disodium 4,4'-bis(2-sulfoslyryl)biphenyl.
PERFUME
Preferably the bleaching composition composition comprises a
perfume. The perfume is preferably in the range from 0.001
to 3 wt %, most preferably 0.1 to 1 wt %. Many suitable
examples of perfumes are provided in the CTFA (Cosmetic,
Toiletry and Fragrance Association) 1992 International
Buyers Guide, published by CFTA Publications and OPD 1993
Chemicals Buyers Directory 80th Annual Edition, published by
Schnell Publishing Co.
Experimental
The synthesis of MnOOl: (H2bispictn) [Mn2m (Cl„Cat) 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 FeOOl: [Fe111 (bispicen) (Cl4Cat) (C14SQ) ] • 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 (H20) (EtOH) ] and Mn003: (Bu4N) 2 [Mn (Cl4Cat) 3] is described by Tippu S. Sheriff

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in Inorganica Chimica Acta 2004, 357, 2494-2502; this compound was provided by the Author.
The synthesis of Mn004: (Tiron® derivative): [Na]5[Mn(3,5-(S03)2Cat)2] .10 (H20) (EtOH) ] is described by Tippu S. Sheriff in Inorganica Chimica Acta 2003, 348, 115-122; this compound was provided by the Author.
In the following description Cl4Cat = 1,2-dihydroxy-3,4,5,6-tetrachlorobenzene but one skilled in the art will appreciate that the catechol moiety when in the form of a complex will lose the two phenolic hydrogens.
Measurements
After the washes, the cloths were rinsed with water and the change in colour 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 white cloth and that of the stained cloth after being washed. Mathematically, the definition of deltaE is:
deltaE = [ (AL) 2 + (Aa) 2 + (Ab) 2 ]1/2
wherein AL is a measure of the difference in darkness between the washed and white cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. From this equation, it is clear that the lower the value of deltaE, the whiter the cloth will be. With regard to this colour measurement technique, reference is made to Commission International de l'Eclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference

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equations, psychometric colour terms, supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de la CIE, Paris 1978. The results are shown below in the tables and are listed. In the tables below the bleaching effect is expressed in the form of a stain removal index (SRI): SRI = 100 - deltaE.
Mn-Catechol (MnOOl) bleaching on tea stains with peroxide
ant pH 10 and with no surfactant
H202 I Catalyst |SRI (Stain)
mM microM
0 0 81.27
6 10 80.71
5 6 87.29
5 10 90.15
Mn-Catechol (MnOOl) bleaching on curcumin stains with peroxide at pH 10 and with no surfactant
Bleaching experiments were performed on oily curcumin stains using a Mn-catechol complex (MnOOl) in the of H202. The residual stain was measured both on the stain itself, and on the surrounding ballast as a measure of dye transfer inhibition. The higher the value of the SRI value of the ballast the greater the dye transfer inhibition.

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H202 I Catalyst I SRI I SRI
mM microM (Stain) (Ballast)
0 6 53.84 73.01
0 10 62.50 96.05
5 0 51.84 75.72
5 10 72.43 98.76
Bleaching experiments were performed on home-made tea (PG Tips) stains using a Fe-catechol complex (FeOOl) in the presence of H2O2.
Fe-catechol (FeOOl) bleaching on tea stains with peroxide pH 10 and with no surfactant
H202 ICatalystl SRI (Stain) mM microM 6 6 81.27 0 10 80.46 5 6 87.72 5 10 88.21
Bleaching experiments were performed on oily curcumin stains using a Fe-catechol complex (FeOOl) in the presence of H202. The residual stain was measured both on the stain itself, and on the surrounding ballast as a measure of dye transfer inhibition. The higher the value of the SRI value of the ballast the greater the dye transfer inhibition.

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Fe-Catechol (FeOOl) bleaching on curcumin stains with
peroxide at pH 10 and with no surfactant
H202 ICatalystlSRI (Stain)I SRI (Ballast)
mM microM
0 0 47.09 70.81
0 10 53.22 77.72
5 0 48.35 70.25
5 10 56.74 93.72
Bleaching experiments were performed on spicy turmeric (curry) stains at pH 10 with three Mn-catechol complexes. The wash was conducted in an aqueous carbonate buffer environment at pH 10 for 30 minutes.
Complex / uMol pH I SRI
No Complex 0 10 77.65
Mn002 10 10 84.12
MnOOl 10 10 83.77
Mn004 10 10 78.88
The fact that the catechol formulation per se may be used in air or peroxyl mode, as demonstrated above, permits options for duel bleaching. A peroxyl pretreatment of a stained garment followed by addition to an aqueous medium containing catechol which is substantially devoid of peroxyl species permits the stain to be subjected to two different types of bleaching. Alternatively, after treating a stained garment in air mode a peroxyl species may be post dosed to an aqueous washing medium.

We claim:
1. A bleaching composition comprising between 0.001 to 50
wt % of a transition metal complex of a catechol moiety
together with between 2 to 60 wt % of a surfactant, and
at least 2 % wt/wt of a peroxygen bleach or source
thereof, wherein the catechol of the following formula:

or the deprotonated form thereof, wherein: R1, R2, R3, and R4 may be independently selected from -H, -Cl, -F, -S03, -N03, -COOH, -CH3, -C2H5, -OMe, -OEt and R2 and R3 may together form a another five or six membered aromatic ring optionally substituted with one or more groups selected from the group consisting of -H, -Cl, -F, -S03, -N03, -COOH, -CH3, -C2H5/ -OMe, and -OEt.
2. A bleaching composition according to claim 1, wherein R1, R2, R3, and R4 are independently selected from S03 and Cl.
3. A bleaching composition according to claim 2, wherein the catechol is selected from the group consisting of:



4. A bleaching composition according to claim 1, wherein
the catechol is:
5. A bleaching composition according to any preceding claim, wherein the catechol is a preformed complex with Mn (II), Mn (III) or Mn (IV).
6. A method of treating a textile, the method comprising the steps of:
(i) treating a textile with an aqueous solution of a transition metal complex of a catechol moiety as defined in any one of claims 1 to 5, the aqueous solution having a pH of at least 7 and comprising from 1 mM to 50 mM of the catechol transition metal complex, between 1 to 15 mmol hydrogen peroxide and from 0.2 g/L to 3 g/L of a surfactant; and,
(ii) rinsing and drying the textile.
7. A method of treating a textile according to claim 6,
wherein the aqueous solution has an ionic strength from
0.001 to 0.5.