WO2005118763A1

WO2005118763A1 - Bleaching composition

Info

Publication number: WO2005118763A1
Application number: PCT/EP2005/005482
Authority: WO
Inventors: Adrianus Cornelis Maria Appel; Stephen Norman Batchelor; Lucas Gerard Grabijn; Ronald Hage; Stephen Jones; Joachim Lienke; Matthew Parry
Original assignee: Unilever Plc; Unilever Nv; Hindustan Lever Limited
Priority date: 2004-06-02
Filing date: 2005-05-17
Publication date: 2005-12-15
Also published as: AR049290A1; WO2005118763A8; GB0412225D0

Abstract

A stabilised bleaching composition is provided. The bleaching composition provided comprises a transition metal catalyst together with a UV screen.

Description

BLEACHING COMPOSITION

FIELD OF INVENTION

This invention relates to the enhancement of bleaching compositions.

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 of an added peroxyl source has recently become the focus of some interest, for example: O9965905; WO0012667; WO0012808; O0029537, and, O0060045.

A problem with the prior art is the instability of the bleaching compositions upon exposure to incident UV irradiation. Another problem with the prior art is that bleaching may be ascribed to mechanisms other than the action of the bleaching catalyst acting upon a stain.

SUMMARY OF INVENTION

Recently bleaching commercial compositions have been developed that rely on the use of a transition metal catalyst in the substantial absence of a peroxyl species in the composition. The compositions disclosed provide a post bleach effect as discussed in WO00/12808 where a stain continues to be bleached after the wash. The after wash effect is due to the presence of residual trace amounts of bleaching species. The bleaching species are particularly susceptible to degradation by UV. In addition, in order to ascribe bleaching to the recently developed technology and not to other routes, for example, photo-bleaching, the use of a sunscreen is employed. The invention is of importance where washed textiles are dried outside.

The present invention provides a bleaching composition comprising:

a) a transition metal catalyst;

(b) a photostable organic sunscreen having a C Log P value of at least 1.9 and having an extinction coefficient of greater than 2000 mol^"1 cm^"1 at 300 nm and an extinction coefficient of less than 100 mol^"1 cm^-1 at any single wavelength in the range from 400 nm at 750 nm; and

(c) the balance carriers and adjunct ingredients to 100 wt/wt % of. the total bleaching composition, wherein the bleaching composition contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof.

It is preferred that the bleaching composition comprises an antioxidant in the range from 0.0001 to 20 wt/wt %.

It is also preferred that the bleaching composition comprises a surfactant. The surfactant has an HLB (hydrophilic/lipophilic balance) greater that 5, more preferably greater than 10, and most preferably greater than 15. For a discussion of HLB the reader is directed to and article by Griffin, . C. in J. Soc. Cosmetic Chemists Vol. 1 page 311, 1945 and Davies, J. T. and Rideal, E. K. in Interfacial Phenomena, Acad. Press, NY, 1961, pages 371 to 382. The HLB value requirement reflects the importance of the rate of solubility and dispersibility of the surfactant from the bleaching composition to the aqueous wash medium in conjunction with surface activity towards the substrate being washed. The composition comprises between 1.5 to 60 wt % of a surfactant, most preferably 10 to 30 wt %. In an aqueous wash liquor the level of surfactant present in the wash liquor is between 0.05 to 5 g/1, preferably between 0.1 to 2.5 g/1, most preferably 0.5 to 1.5 g/1.

The role sunscreen and the antioxidant may be performed by a single entity but it is preferred the sunscreen and the antioxidant are separate entities such that the sunscreen is other than an antioxidant.

The term "substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system" should be construed within spirit of the invention. It is preferred that the composition has as low a content of peroxyl species present as possible. It is preferred that the bleaching formulation contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, preferably the bleaching formulation contains less that 0.3 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof, most preferably the bleaching composition is devoid of peracid or hydrogen peroxide or source thereof. The same low levels as specified for of peracid or hydrogen peroxide or source thereof apply to any hydroperoxides, e.g., alkyl hydroperoxides, that may be present in the bleaching composition. The present invention extends to a method of bleaching a substrate/textile with a composition of the present invention. The method comprising the steps of treating a substrate with the bleaching composition in an aqueous environment, rinsing the substrate and drying the substrate.

The present invention also extends to a commercial package together with instructions for its use.

Detailed Description of the Invention

The Sunscreen

A Sunscreen in the context of the present invention is an organic compound that absorbs all or part of the UV radiation of the sun (290 to 400 nm) and converts it to heat with a high quantum yield and hence do not undergo photochemical reactions. The photochemical inert nature of the sunscreen results in incident irradiation being reduced upon those moieties that do undergo photochemical reactions.

The use of a sunscreen is applicable to the reduction in incident radiation from the sun and incandescent light.

A sunscreen may function both as an antioxidant and a sunscreen but within the scope the present application the sunscreen is preferably other than an antioxidant. Antioxidants are organic chemicals that chemically quench autoxidation chain reactions. This may occur by a number of chemical routes, for example by termination of reactive radical intermediates, or by decomposition of peroxides and hydroperoxide intermediates. Protection against solar radiation can be achieved with UVA and UVB absorbing materials with high extinction coefficients. These compounds are commonly called sunscreens. However, the use of such materials is preferably limited for protection against UV radiation with a wavelength of 400nm or below as compounds with the whole or part of their spectra above 400nm will be coloured.

It is preferred that the sunscreen has a C Log P value of at least 1.9, more preferably of at least 2.5, most preferably greater than 3.5. If solid the sunscreen should be dispersed in a liquid, the liquid having a C Log P value of at least 1.9, more preferably of at least 2.5, most preferably greater than 3.5. It is preferred that the sunscreen has an upper limit C Log P value of 8.5. It is also beneficial if the liquid in which the solid sunscreen is to be dissolved is immiscible in water or only sparingly soluble. By sparingly soluble a solubility of no more than 0.04 moles/litre is meant.

The C Log P values were calculated using daylight software (PCModels version 4.8) available from Daylight Chemical Information Systems, Inc. Sheraton House - Castle Park - Cambridge, UK CB3 0AX.

The presence of an alkyl chain (s) substituent on the sunscreen serves to increase C Log P of the sunscreen and serves to aid deposition and adhesion to a relatively apolar substrate/textile. It is preferred that the sunscreen or sunscreen mixture is present at levels from 0.0005 wt% to 10 wt% of the total weight of the composition. The more preferred level of sunscreen is from 0.001 wt% to 2.5 wt %, and the most preferably 0.005 wt% to 0.5 wt %.

In the context of this invention a sunscreen is described as any material which absorbs UVA or UVB radiation. It is preferred that the sunscreens have a molar extinction coefficient (ε) of greater than 2000 mol^-1 cm^-1 at 300 nm, most preferably 5000 mol^"1 cm^-1 at 300 nm. Further it is preferred that the extinction coefficient of the sunscreen is less than 100 mol^-1 cm^-1 at any single wavelength in the range from 400 nm at 750 nm.

The International Commission on Illumination (CIE)in 1970 defined the UV wavelength subdivisions as:-

UVA 315-400nm UVB 280-315nm UVC 100-280nm

Preferably the sunscreen absorbs light at a wavelength from about 280-400nm.

Suitable sunscreens are described in:

N.A. Saath, Cosmestics and Toiletries Vol. 102 March 1987 page 21-39 Classifications given as table 2 on page 22,; N.A. Saath, Evolution of modern sunscreen chemicals pages 3- 35; Cosmetics and Toiletries Vol. 107 March 1992. Sunscreen use in cosmetic formulas, pages 45-47; Ultra violet absorbers by S.B. Miller, G.R. Lappin, and CE. Tholstrup in 1968-1969 Modern Plastics Encyclopedia, pages 442-447 and; G.R. Lappin, Encyclopedia of polymer science and technology, vol 14, pages 125-148, Ultra violet radiation absorbers.

Typical examples of sunscreens that may be employed in the present invention are: cinnamates, hydroxybenzophenones, alpha-cyanoacrylates, oxanilides, phenylsalicylates, and 2- hydroxyphenylbenzotriazoles .

Examples of typical sunscreens but not meant to be exclusive are:

UVA absorbers

Oxybenzone Suisobenzone Dioxybenzone tinuvin 329 tinuvin 327 tinuvin 328

UVB absorber aminobenzoic acid amyldimethyl (PABA)

2-Ethoxyethyl-p-methoxycinnimate amyldimethyl PABA (padimate A)

2-Ethylhexyl salicylate (Sunarome WMO)

Ethyl 4-bis (hydroxypropyl) aminiobenzoate 2-Ethylhexyl-2-cyano-3, 3-diphenylacrylate

Ethylhexyl-p-methoxcinnate 2-Ethylhexyl salicylate (Sunarome WMO) Glyceryl aminobenzoate (Glyceryl PABA) Homomenthyl salicylate Lawsone with dihydroxyacetate Octyldimethyl PABA (Padimate 0)

2-Phenylbenzimidazole-5-sulphonic acid Thethanolamine salicylate Cyasorb UV 2908 Cyasorb UV 24 Chimassorb 81

ANTIOXIDANT

The bleaching compositions of the present invention will also preferably comprise an effective amount of an antioxidant. In contrast to the sunscreens, the antioxidant is susceptible to degradation by reacting with hydroperoxyl (ROO.) and alkoxyl (RO. ) radicals.

An effective amount of an antioxidant is in the range 0.001 to 20 wt/wt % depending upon the nature of the antioxidant and subsidiary purpose of the antioxidant, for example as a carrier or solvent. Preferably the antioxidant is present in the range from 0.001 to 2 wt/wt %. When a phenolic antioxidant is present it is preferred that the phenolic antioxidant present in the range from 0.0001 to 3 % wt % of the composition. When an amine antioxidant it is present it is preferred that the phenolic antioxidant present in the range from 0.0001 to 20 % wt % of the composition.

Anti-oxidants are substances as described in Kirk-Othmers (Vol 3, pg 424) and in Uhlmans Encyclopedia (Vol 3, pg 91) . One class of anti-oxidants suitable for use in the present invention is alkylated phenols having the general formula:

R

wherein R is C1-C22 linear or branched alkyl, preferably methyl or branched C3-C6 alkyl; C3-C6 alkoxy, preferably methoxy; Rl is a C3-C6 branched alkyl, preferably tert- butyl; x is 1 or 2. Hindered phenolic compounds are preferred as antioxidant.

Another class of anti-oxidants suitable for use in the present invention is a benzofuran or benzopyran derivative having the formula:

wherein Rl and R2 are each independently alkyl or Rl and R2 can be taken together to form a C5-C6 cyclic hydrocarbyl moiety; B is absent or CH2; R4 is C1-C6 alkyl; R5 is hydrogen or -C(0)R3 wherein R3 is hydrogen or C1-C19 alkyl; R6 is C1-C6 alkyl; R7 is hydrogen or C1-C6 alkyl; X is - CH20H, or -CH2A wherein A is a nitrogen comprising unit, phenyl, or substituted phenyl. Preferred nitrogen comprising A units include amino, pyrrolidino, piperidino, morpholino, piperazino, and mixtures thereof.

Other suitable antioxidants are found as follows. A derivative of α-tocopherol, beta-tocopherol, gamma- tocopherol, delta-tocophero, and alkyl esters of gallic acid, especially octyl gallate and dodecyl gallate.

Another example of suitable antioxidants are the class of hindered amine light stabilisers (HALS) , particularly those based 2,2, 6, 6-tetramethylpipiridines .

Non-limiting examples of anti-oxidants suitable for use in the present invention include phenols inter alia 2,β-di- tert-butylphenol, 2, 6-di-tert-butyl-4-methylphenol, mixtures of 2 and 3- tert-butyl-4-methoxyphenol .

Mixtures of antioxidants may be use and in particular mixtures that have synergic antioxidant effects as found in, for example, WO02/072746.

Hydroperoxide Decomposing Antioxidants

Hydroperoxide Decomposing Antioxidants (HADs) are compounds that cause the degradation of hydroperoxides. Examples of HADs are found in the organic compounds of sulpher and trivalent phosphorous which are commercialised for stabilising compositions and are widely used in combination with phenolic antioxidants. Zinc Dialkyl Dithio phosphate (ZDDP) is an example of a HAD that is used widely in the automotive oil industry. Generally, phosphites decompose hydroperoxides at substantially lower temperatures than sulphides. Triphenylphosphine, a HAD, is a widely recognised reductant for hydroperoxides and functions well at ambient temperatures. Hindered amine light stabilisers (HALS) also function as HADs and is an example of a class of preferred HADs for use with the present invention. A review of HADs are found in: J. Pospisil, P. P. Klemchuk (Eds) Oxidation inhibition in organic materials, Vol. I. CRC Press 1990, pp. 38 to 47. It is preferred that the bleaching composition of the present invention comprises one or more HADs and most preferably in conjunction with a non-HAD antioxidant.

THE BLEACH CATALYST

We have recently found that oily stains are bleached in the presence of selected transition metal catalysts in the absence of an added peroxyl source. The bleaching of an oily stain in the absence of an added peroxyl source has been attributed to oxygen derived from the air. Whilst it is true that bleaching is effected by oxygen sourced from the air the route in which oxygen plays a part is becoming understood. In this regard, a catalyst that functions as such is regarded as an "air bleach catalyst".

We have concluded from our research that bleaching of a chromophore in an oily stain is effected by products formed by adventitious oxidation of components in the oily stain. These products, alkyl hydroperoxides, are generated naturally by autoxidation of the oily stain and the alkyl hydroperoxides together with a transition metal catalyst serve to bleach chromophores in the oily stain. Alkyl hydroperoxides (ROOH) are generally less reactive that other peroxy species, for example, peracids (RC(O)OOH), hydrogen peroxide (H202), percarbonates and perborates. In this regard, the phrase "for bleaching a substrate with atmospheric oxygen" is synonymous with "for bleaching a substrate via atmospheric oxygen" because it is the oxygen in the air that provides the bleaching species used by catalyst to bleach the substrate stain.

The bleach catalyst per se may be selected from a wide range of transition metal complexes of organic molecules

(ligands) . In typical washing compositions the level of the organic substance is such that the in-use level is from 0.05 μM to 50 mM, with preferred in-use levels for domestic laundry operations falling in the range 1 to 100 μM. Higher levels may be desired and applied in industrial textile bleaching processes. A mixture of different catalysts may be employed in the bleaching composition. The bleaching composition comprises at least 1 ppb (0.0000001 wt%) of the ligand or complex thereof, more preferably 100 ppb (0.00001 wt%), yet more preferably 500 ppb (0.00005 wt%), still more preferably about 1 ppm (0.0001 wt%) to about 5 %, still more preferably 500 ppm (0.05 wt%).

Suitable organic molecules (ligands) for forming complexes and complexes thereof are found, for example in:

GB 9906474.3; GB 9907714.1; GB 98309168.7, GB 98309169.5;

GB 9027415.0 and GB 9907713.3; DE 19755493; EP 999050;

W09534628; EP-A-458379; EP 0909809; United States Patent

4,728,455; WO9839098; WO9839406, W09748787, WO0029537; WO0052124, and WO0060045 the complexes and organic molecule

(ligand) precursors of which are herein 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) .

The ligand forms a complex with one or more transition metals, in the latter case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and molybdenum II-VI. Preferred transition metals are iron and manganese, in particular iron.

An example of a preferred catalyst is a monomer ligand or transition metal catalyst thereof of a ligand having the formula (I) :

wtlherein each R is independently selected from: hydrogen, F, CI, Br, hydroxyl, Cl-C4-alkyl0-, -NH-CO-H, -NH-CO-C1-C4- alkyl, -NH2, -NH-Cl-C4-alkyl, and Cl-C4-alkyl; Rl and R2 are independently selected from: Cl-C4-alkyl, C6-C10-aryl, and, a group containing a heteroatom capable of coordinating to a transition metal, wherein at least one of Rl and R2 is the group containing the heteroatom;

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 (O) OR5 wherein R5 is independently selected from: hydrogen, C1-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.

With regard to the above formula (I) it is also particularly preferred that Rl and R2 may also be^' independently selected from: CI to C22-optionally substituted alkyl, and an 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 Cl-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.

Another preferred class of ligands are macropolycyclic rigid ligands of the formula:

wherein m and n are 0 or integers from 1 to 2, p is an integer from 1 to 6, preferably m and n are both 0 or both 1 (preferably both 1 ) , or m is 0 and n is at least 1; and p is 1; and A is a nonhydrogen moiety preferably having no aromatic content; more particularly each A can vary independently and is preferably selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, C5-C20 alkyl, and one, but not both, of the A moieties is benzyl, and combinations thereof.

Preferably, the macropolycyclic ligand is of the formula:

wherein "R¹" is independently selected from H, and linear or branched, substituted or unsubstituted C1-C20 alkyl, alkylaryl, alkenyl or alkynyl; and all nitrogen atoms in the macropolycyclic rings are coordinated with the transition metal.

Of the macropolycyclic ligands 5, 12-dimethyl-l, 5, 8, 12- tetraaza-bicyclo [6.6.2] hexadecane is preferred. This ligand is most preferred as its manganese complex [Mn (Bcyclam) Cl₂] and may be synthesised according to WO9839098.

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

[M_aL_kX_n]Y_m

in which: 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 from Fe(II)-(III)-(IV)-(V); L represents the ligand, preferably N, N-bis (pyridin-2- yl-methyl) -1, 1-bis (pyridin-2-yl) -1-aminoethane, 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; Y represents any non-coordinated counter ion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10; m represents zero or an integer from 1 to 20. BALANCE CARRIERS AND ADJUNCT INGREDIENTS These are generally surfactants, builders, foam agents, anti-foam agents, solvents, and enzymes. The use and amounts of these components are such that the bleaching composition performs depending upon economics, environmental factors and use of the bleaching composition.

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 - 50 % by weight, based on the total detergent composition, of one or more surfactants. This surfactant system may in turn comprise 0 - 95 % by weight of one or more anionic surfactants and 5 to 100 % by weight 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%.

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. - Ii

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 C₆-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- Ciβ 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-Ci8 alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl C₉-C₂₀ benzene sulphonates, particularly sodium linear secondary alkyl Cι₀-Cι₅ 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 C₁₁-C₁5 alkyl benzene sulphonates and sodium C_i2-Ci8 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 Ciβ-Ciβ primary alcohol sulphate together with a ₁₂-C₁₅ primary alcohol 3-7 EO ethoxylate.

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

One skilled in the art will appreciate that some adventitious peroxyl species may be in the composition nevertheless it is most preferred that the bleaching composition of the present invention has less that 1%, preferably less than 0.1%, most preferably less than 0.01%, of a peroxyl species present. These adventitious peroxyl are predominantly alkyl hydroperoxides formed by autoxidation of the surfactants.

The composition may contain additional enzymes as found in WO 01/00768 Al page 15, line 25 to page 19, line 29, the contents of which are herein incorporated by reference. Builders, polymers and other enzymes as optional ingredients may also be present as found in WO0060045.

Suitable detergency builders as optional ingredients may also be present as found in WO0034427.

The composition of the present invention may be used for laundry cleaning, hard surface cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed in waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact lens disinfection.

In the context of the present invention, bleaching should be understood as relating generally to the decolourisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to or otherwise associated with a substrate. Furthermore, in the context of the present invention bleaching is to be understood as being restricted to any bleaching mechanism or process that does not require the presence of light or activation by light. Experimental

The transition metal catalyst present in the liquid formulation was the iron chloride complex of dimethyl 2,4- di- (2-pyridyl) -3-methyl-7- (pyridin-2-ylmethyl) -3, 7-diaza- bicyclo [3.3.1] nonan-9-one-l, 5-dicarboxylate [FeCl (N2Py3o) ] CI which was prepared as described in WO0248301.

The activities of the liquid bleaching compositions were determined at 40 °C in a H202 containing NaH2P04.H20 pH7 buffer and Acid Blue 45 (CAS No. 2861-02-1) as substrate using the following protocol.

Samples of 70 mg liquid were diluted in 10.00 ml MilliQ water. We added 45 μl of this solution to an assay of 230 μL containing 20 mM H202, 75 μM Acid blue 45 and 54 mM NaH2P04.H20 pH7 buffer.

The solutions were mixed and pre incubated for 1 min at 40 °C The changes in absorbance at 600 nm were measured for 8 min at 40 °C using a spectrophotometer .

The absolute changes in absorbance were correlated to activities obtained with freshly prepared calibration samples. The measured activities were expressed as μMol/1.

Polyethylene teraphthalate = PET High density polyethylene = PEHD

The liquid bleaching composition were irradiated on a sun bed having the following measured properties: UV A= 2.7 mW/cm3 and UV B= 0.05 mW/cm3. UV-A is irradiation in the range 320-400 nm and UV-B is irradiation in the range 280 to 320 nm.

Table 1: The concentration bleach catalyst (μMol/1) in liquid A after irradiation in different types of bottles.

Bottle A: PEHD +/- Clariant Sarmastab UV 9M-B@ 2% UV absorber (ex Alpla) Bottle B: PET 8 fl.Oz Resin 7352 +/- UV absorber 117880 (ex Owens Illinois)

Bottle C: PET 20 fl.Oz +/- UV absorber Clearshield UV 400M (5% T@390 nm) (ex Milliken)

Liquid A: 6 % LAS 6 % sLES 3 EO 6 % Nonionic 7 EO 0.016 % Proxel GXL 3.35 % sorbitol 2.30 % Borax.10 H20

4.75 % MPG

0.75 % NaOH

0.4 % Relase 16.0L EXI

Table 2: The concentration bleach catalyst (μMol/1) in liquid B after irradiation in different types of bottles.

Bottle A: PEHD +/- Clariant Sarmastab UV 9M-B@ 2% UV absorber (ex Alpla)

Bottle B: PET 8 fl.Oz Resin 7352 +/- UV absorber 117880 (ex

Owens Illinois)

Bottle C: PET 20 fl.Oz +/- UV absorber Clearshield UV 400M (5% TΘ390 nm) (ex Milliken)

Liquid B:

6 % LAS

6 % sLES 3 EO

6 % Nonionic 7 EO 0..016 % Proxel GXL

3. .35 % sorbitol

2. .30 % Borax.10 H20

4. .75 % MPG

0. .75 % NaOH

0. .5 % Prifac 7908

0. .4 % Relase 16.0L EXI

The above demonstrates the UV instability of the bleach catalyst.

Claims

1. A bleaching composition comprising: (a) a transition metal catalyst;

(b) a photostable organic sunscreen having a C Log P value of at least 1.9 and having an extinction coefficient of greater than 2000 mol^-1 cm^-1 at 300 nm and an extinction coefficient of less than 100 mol^-1 cm^-1 at any single wavelength in the range from 400 nm at 750 nm; and

(c) the balance carriers and adjunct ingredients to 100 wt/wt % of the total bleaching composition, wherein the bleaching composition contains less that 1 % wt/wt total concentration of peracid or hydrogen peroxide or source thereof.

2. A bleaching composition composition according claim 1, wherein the extinction coefficient of the organic sunscreen is greater than 5000 mol^"1 cm^"1 at 300 nm.

3. A bleaching composition composition according claim 1 or 2, wherein the level of sunscreen inhibitor is from 0.0005 wt% to 10 wt% of the total weight of the composition.

4. A bleaching composition according to any preceding claim wherein the bleaching composition further comprises an antioxidant .

5. A bleaching composition according claim 4, wherein the antioxidant is selected from: (i) a phenolic antioxidant, the phenolic antioxidant present in the range 0.0001 to 3 % wt %; and, (ii) an amine antioxidant, the hindered amine antioxidant in the range from 0.0001 to 20%.

6. A bleaching composition according to claim 5, wherein the antioxidant is a hindered phenol.

7. A bleaching composition according to claim 5, wherein the antioxidant is selected from the group consisting of: 2, 6-di-tert-butyl hydroxy toluene, octylgallate, and dodecylgallate .

8. A bleaching composition according to claim 7, wherein the antioxidant is 2, 6-di-tert-butyl hydroxy toluene.

9. A bleaching composition according to claim 4 to 8, wherein the antioxidant is present in the bleaching composition in the range from 0.001 to 2 wt % .

10. A method of bleaching a textile comprising the steps of: (i) contacting a textile with an a bleaching composition, as defined in any one of claims 1 to 9, in aqueous medium; and,

(ii) rinsing the textile with water and drying the textile.