WO2005121296A1

WO2005121296A1 - Bleaching composition

Info

Publication number: WO2005121296A1
Application number: PCT/EP2005/005122
Authority: WO
Inventors: Denise Broere; Yvonne Maria Wilhelmina Laseur; Joachim Lienke; Patricia Veerman-Petersen
Original assignee: Hindustan Lever Ltd; Unilever NV
Current assignee: Hindustan Unilever Ltd; Unilever NV
Priority date: 2004-06-11
Filing date: 2005-05-06
Publication date: 2005-12-22
Anticipated expiration: 2006-12-11
Also published as: AR048988A1; GB0413058D0; WO2005121296A8

Abstract

The present invention provides a bleaching composition comprising a [3.3.1] bicyclo compound.

Description

BLEACHING COMPOSITION FIELD OF INVENTION

This invention relates to a class of ligand or complex thereof useful as catalysts for catalytically bleaching substrates.

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: WO9965905; O0012667; O0012808; O0029537, and, O0060045.

WO0060045 (Procter and Gamble) discloses a bleaching system comprising: a) from about lppb, by weight of a transiti'on metal catalyst comprising: i) a transition metal; ii) a ligand having formula (I):

wherein each R is independently hydrogen, hydroxyl, C1-C4 alkyl, and mixtures thereof; Rl is C1-C4 alkyl, C6-C10 aryl, and mixtures thereof; R2 is C1-C4 alkyl, C6-C10 aryl, and mixtures thereof; R3 and R4 are each independently hydrogen, C1-C8 alkyl, C1-C8 hydroxyalkyl, -(CH₂)_XC0₂R5 wherein R5 is C1-C4 alkyl, x is from 0 to 4, and mixtures thereof; X is carbonyl, -C(R6)2- wherein each R6 is independently hydrogen, hydroxyl, C1-C4 alkyl, and mixtures thereof; b) optionally a source of hydrogen peroxide; and c) the balance carriers and adjunct ingredients.

With regard to the structure above, we have found that the bleaching activity may be improved and refined by varying the substituents of the core structure. Example of these substituents are found in our applications WO02/48301 and WO03/104234 and GB 0325430.7.

Various [3.3.1] bicyclo compounds and complexes thereof are discussed in the literature, see for example: Comba P. et al., J. Chem. Soc. Dalton Trans, 1998, (23) 3997-4001;

Borzel et al. Chem. Eur. J. 1999, 5, No. 6, 1716 to 1721; review by P. Comba in Coordination Chemistry Reviews 2000,

200-202, 217 to 245, entitled "Coordination compounds in the Entactic State"; and Borzel et al. Chem . Eur. J. , 2000, 6,

914-919. These compounds are discussed in terms of their physical properties.

SUMARY OF INVENTION We have found that an advantage is to be secured by having substituents at particular positions about pyridin-2-yl groups at the 2 and 4 positions of the bicyclostructure . When the pyridin-2-yl is substituted at the 6 or 5 positions the efficacy of the catalyst increases. The compounds of the present invention may be used in bleaching compositions. The bleaching compositions may be those for use in "air mode" or "peroxyl mode". The "air mode" compositions are substantially devoid of peroxyl species.

The bleaching of a stain by a peroxyl species (peroxyl mode) is aided by the presence of an active transition metal catalyst. A peroxyl species commonly found in laundry bleaching compositions is hydrogen peroxide (H₂O₂) or a precursor thereof, e.g., sodium percarbonate or sodium perborate. In many instances an activator/precursor, e.g., TAED (tetraacetylethylene diamine) , is present which serves together with hydrogen peroxide to form a peracid [RC(0)OOH] to facilitate bleaching.

Recently we have found that oily stains are bleached in the presence of selected transition metal catalysts in the absence of an added peroxyl source (air mode) . 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, the term "air bleaching" is used. In "air mode", 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 than 0.5 % wt/wt, most preferably less than 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. In addition, it is preferred that the presence of alkyl hydroperoxides is kept to a minimum in a composition.

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.

It is an object of the present invention to provide alternative and more efficacious ligands and transition metal complexes thereof to those currently available.

The present invention provides a bleaching composition comprising: a monomer ligand or transition metal catalyst thereof of a ligand having the formula (I) :

wherein R is a pyridin-2-yl group, the pyridin-2-yl groups mono-substituted at the 5 or 6 position by a Cl-C4-alkyl group;

Rl and R2 are independently selected from: a -Cl-C22-alkyl; and, a -Cl-C4-alkyl-C6-C10-aryl;

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-C24-alkyl, n is from 0 to 4, and mixtures thereof;

X is selected from: C=0, a ketal or thioketal derivative of

C=0 selected from a group of the form:

, and , and -C(R6)₂ wherein each R6 is independently selected from hydrogen, hydroxyl, 0-C1-C24- alkyl, 0-benzyl, 0- (C=0) -C1-C2 , Cl-C24-alkyl; and, b) the balance carriers and adjunct ingredients.

The present invention also extends to a method of bleaching textiles and commercial packages together with instructions for implementing such methods.

DETAILED DESCRIPTION OF THE INVENTION

The ligand as described herein is capable of dynamic inversion. The ability of the ligand to chelate to a TM depends upon the stereochemistry of the substituents. It is preferred that subsituents are endo-endo, but it is likely that stereochemical conversion takes place by retro-Mannish conversion. Retro-Mannish may be prevented by changing the groups present such that retro-Mannish reactions are unfavoured. Nevertheless, it is likely that endo-exo and exo-exo ligands as described herein coordinate to transition metal ions in many instances and are capable of functioning as air bleaching catalysts. With regard to synthesis particular reference in made to WO02/48301 and references found therein.

The catalyst may be used as a preformed complex of the ligand and a transition metal. Alternatively, the catalyst may be formed from the free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The composition may also be formulated as a composition of the free ligand or a transition metal-substitutable metal- ligand complex, and a source of transition metal, whereby the complex is formed in si tu in the medium.

It is preferred that X selected from the group consisting of: C=0, CH2, C(OH)2, syn-CHOR and anti-CHOR, wherein R is H, Cl-C24-alkyl or C (0) -Cl-C24-alkyl . Most preferred groups of X are C=0, C(0H)2 and CHOH.

It is preferred that R3 and R4 are selected from the group consisting of: -C (0) 0-Cl-C24-alkyl, -C (0) -0-Cl-C24-aryl - CH2OC(O)Cl-C20-alkyl, benzyl ester, phenyl, benzyl, CN, hydrogen, methyl, and C1-C4-0R wherein R is selected from the group consisting of H, Cl-C24-alkyl or C(0)-C1-C24- alkyl. Most preferred groups of R3 and R4 are -CH20H, -C(O) 0-CH2C6H5 and -C (0) 0-Cl-C6-alkyl . Even more preferred groups of R3 and R4 are -C(0)-0-CH3, -C (0) -0-CH2CH3, -C(0)-0- CH2C6H5 and CH20H. For ease of synthesis it is preferred that R3 = R4.

It is preferred that Rl and R2 are independently selected from the group consisting of linear, and branched: -CH3, - C2H5, -C3H7, -C4H9, -C5H11, -C6H13, -C7H15, -C8H17, -C9H19, -C10H21, -C11H23, -C12H25, -C13H27, -C14H29, -C15H31, - C16H33, -C17H35, -C18H37, -C19H39, -C20H41, -C21H43 groups and CH2-C6H5. Of this group C8-C20 alkyl groups are important. For ease of synthesis and economy Rl and R2 are preferred to be independently selected from: Me, and CH2- C6H5.

5

It is preferred that the R groups, pyrιdm-2-yl = , are mono-substituted at the 5 or 6 by a Cl-C4-alkyl group. It is most preferred that the pyridin-2-yl groups are mono- substituted at the 6 position. It is preferred that the mono-substitution is a -CH3 or a -C2H5 group. For ease of synthesis it is preferred that both R are the same.

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. The ligand forms a complex of the general formula (Al) :

[M_aL_kX_n]Y_m (Al)

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 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 O^2", RB0₂ ^2~, RCOO^", RCONR^", OH^", N0₃ ^", NO, S^2", RS^", P0₄ ^3", PO3OR^3", H₂0, C0₃ ^2", HC0₃ ^", ROH, N(R)₃, ROO^", 0₂ ^2", 0₂ ^", RCN, Cl^", Br^", OCN^", SCN^", CN^", N₃ ^", F^", I^", RO^~, C10₄ ^", and CF₃S0₃ ^~, and more preferably selected from O^2", RB0₂ ^2", RCOO^", OH^", N0₃ ^", S^2", RS^", P0₃ ^4", H₂0, C0₃ ^2", 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^", 0₂ ^2", 0₂ ^", Cl^" , Br^", F^", I^", CF₃SO₃ ^", S₂0₆ ^2" , OCN^", SCN^", H₂0, RB0₂ ^2", BF₄ ^" and BPh₄ ^", and more preferably selected from C10₄ ^", BR₄ ^" , [FeCl₄] ^", PF₆ ^", RCOO^", N0₃ ^", RO^", N⁺(R)₄, Cl^" , Br^", F^", I^", CF₃SO₃ ^", S₂0₆ ^2" , 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 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, -Cl, -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(O) (R')₂, -P(O) (OH)₂, - P(O) (OR')₂, -N0₂, -S0₃H, -S0₃ ^" (Na⁺, K⁺) , -S(0)₂R', -NHC(0)R', and -N (R') C (0) R', wherein R' represents cycloalkyl, aryl, arylalkyl, or alkyl optionally substituted by -F, -Cl, -Br, -I, -NH₃ ⁺, -S0₃H, -S0₃ ^"(Na⁺, K⁺) , -COOH, -COO^"(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 Cι-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 ^", C10^", BF^", PF₆ ^", RS0₃ ^", RS0^", S0₄ ^2" , N0₃ ^", F^", Cl^", 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.

Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from R⁷COO^", C10₄ ^", BF^", PF₆ ^", RS0₃ ^" (in particular CF₃SO₃ ^") , RS0^", S0₄ ^2", N0₃ ^", F^~, Cl^", Br^", and I^", wherein R represents hydrogen or optionally substituted phenyl, naphthyl or Cι-C₄ alkyl.

It will be appreciated that the complex (Al) can be formed by any appropriate means, including in si tu formation whereby precursors of the complex are transformed into the active complex of general formula (Al) under conditions of storage or use. Preferably, the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the catalyst may be formed in si tu from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials. In one such example, the active catalyst may be formed in si tu in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent. Thus, for example, if M is iron, an iron salt such as FeS0₄ can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex. Thus, for example, the composition may formed from a mixture of the ligand L and a metal salt MX_n in which preferably n=l- 5, more preferably 1-3. In another such example, the ligand L, or a ligand L-generating species, can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in si tu . Suitable ligand L-generating species include metal-free compounds or metal coordination •complexes that comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (Al) .

The catalysts according to 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 typical washing compositions the level of the organic substance is such that the in-use level is from lμM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 μM. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching. These levels reflect the amount of catalyst that may be present in a wash dose of a detergent composition. The bleaching composition comprises at least 1 ppb of the ligand or complex thereof.

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 alodours 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.

THE PEROXY SPECIES OR SOURCE THEREOF In a "peroxyl mode" the composition of the present invention uses an added 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 to 35% by weight, preferably from 5 to 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 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;

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (PAP); and

(iii) 6-octylamino-β-oxo-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.

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.

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 laundry treatment composition in addition to the bleaching composition comprises the balance carriers and adjunct ingredients to 100 wt % of the composition. It is most preferred that the bleaching composition comprises between 1.5 to 60 wt% of a surfactant

These may be, for example, builders, foam agents, anti-foam agents, further surfactants, solvents, perfumes, fluorescers, other bleaching agents, 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.

When the bleaching composition is a fabric conditioner the bleaching composition comprises cationic surfactants.

The composition comprises a surfactant and may 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%.

In general, the nonionic and anionic surfactants of a 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 "McCutcheon¹ 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 - 11

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 e 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 Cι₈ 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 Cι₈ alcohols, produced for example from tallow or coconut oil, sodium and potassium alkyl Cg to C₂o benzene sulphonates, particularly sodium linear secondary alkyl Cio to 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 Cn to C₁₅ alkyl benzene sulphonates and sodium C_i2 to Cι₈ 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 Ci₆ to Cι₈ primary alcohol sulphate together with a C_i2 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 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.

Most preferred are quaternary ammonium compounds.

It is advantageous if the quaternary ammonium compound is a quaternary ammonium compound having at least one Cι₂ to C₂₂ alkyl chain.

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

in which R¹ is a C_i2 to C₂₂ alkyl or alkenyl chain; R², R³ and R⁴ are independently selected from Ci to C₄ 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 R¹ and R² are independently selected from Cι₂ to C₂₂ alkyl or alkenyl chain; R³ and R⁴ are independently selected from Ci to C₄ 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 quaternary 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 1.5 wt % to 50 wt % of the total weight of the composition. Preferably the cationic compound may be present from 2 wt % to 25 wt %, a more preferred composition range is from 5 wt % to 20 wt %.

BUILDER The bleaching composition of the present invention preferably comprises one or more detergency builders. The total amount of detergency builder in the compositions will preferably range from 5 to 80 wt%, more preferably from 10 to 60 wt%.

Inorganic builders that may be present include sodium carbonate, if desired in combination with a crystallisation seed for calcium carbonate, as disclosed in GB 1 437 950 (Unilever) ; crystalline and amorphous aluminosilicates, for example, zeolites as disclosed in GB 1 473 201 (Henkel) , amorphous aluminosilicates as disclosed in GB 1 473 202

(Henkel) and mixed crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250 (Procter & Gamble) ; and layered silicates as disclosed in EP 164 514B (Hoechst) . Inorganic phosphate builders, for example, sodium orthophosphate, pyrophosphate and tripolyphosphate are also suitable for use with this invention.

The compositions of the invention preferably contain an alkali metal, preferably sodium, aluminosilicate builder. Sodium aluminosilicates may generally be incorporated in amounts of from 10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt% .

The alkali metal aluminosilicate may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8-1.5 Na₂0. A1₂0₃. 0.8-6 Si0₂.

These materials contain some bound water and are required to have a calcium ion exchange capacity of at least 50 mg CaO/g. The preferred sodium aluminosilicates contain 1.5-3.5 Si0₂ units (in the formula above) . Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature. Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1 429 143 (Procter & Gamble) . The preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available zeolite 4A now widely used in laundry detergent powders. However, according to a preferred embodiment of the invention, the zeolite builder incorporated in the compositions of the invention is maximum aluminium zeolite P (zeolite MAP) as described and claimed in EP 384 070A (Unilever) . Zeolite MAP is defined as an alkali metal aluminosilicate of the zeolite P type having a silicon to aluminium ratio not exceeding 1.33, preferably within the range of from 0.90 to 1.33, and more preferably within the range of from 0.90 to 1.20.

Especially preferred is zeolite MAP having a silicon to aluminium ratio not exceeding 1.07, more preferably about 1.00. The calcium binding capacity of zeolite MAP is generally at least 150 mg CaO per g of anhydrous material

Organic builders that may be present include polycarboxylate polymers such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphinates; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates, carboxymethyloxy succinates, carboxymethyloxymalonates, dipicolinates, hydroxyethyliminodiacetates, alkyl- and alkenylmalonates and succinates; and sulphonated fatty acid salts. This list is not intended to be exhaustive.

Especially preferred organic builders are citrates, suitably used in amounts of from 5 to 30 wt%, preferably from 10 to 25 wt%; and acrylic polymers, more especially acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt%, preferably from 1 to 10 wt%.

Builders, both inorganic and organic, are preferably present in alkali metal salt, especially sodium salt, form.

The bleaching compositions according to 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 well as other uses where a bleach is needed, for example waste water treatment or pulp bleaching during manufacture of paper, dye transfer inhibition, starch bleaching, sterilisation and/or whitening in oral hygiene preparation, or contact lens disinfection.

The bleaching composition may comprise other bleach catalysts, for example complex 1 as found in the experimental below. Other bleaching catalysts that may be present in the composition are, for example, found in WO00/12667, WO01/48299, WO02/48301, and WO03/104234.

The invention will now be further illustrated by way of the following non-limiting examples: EXAMPLES Synthesis

Dimethyl 2, 4-di- (2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate (N2Py2) and transition metal catalyst thereof was prepared as disclosed in WO02/48301.

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 (N2Py3o) and transition metal catalyst thereof was prepared as disclosed in WO02/48301.

Dimethyl 2, 4-di- ( 6-methyl-2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate N2(6Mepy)2 was prepared as found in Borzel et al. Chem. Eur. J. , 2000, 6, 914-919.

Dimethyl 2, 4-di- (3-methyl-2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate N2(3Mepy)2 was prepared in an analogous manner to those compounds above.

Dimethyl 2, 4-di- (5-ethyl-2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate N2(5Etpy)2 was prepared in an analogous manner to those compounds above.

BLEACHING EXPERIMENTS (peroxide mode)

In an aqueous solution containing 5 g/1 SKIP, 2003™ in 19 FH water hardness and 1 mM hydrogen peroxide tomato-soya oil (TOL) stained or curry-soya oil (COL) stained cloths were added and kept in contact with the solution whilst agitating for 30 minutes at 30 °C. Comparative experiments were performed using 10 μM of the metal complexes or as a mixture of 20 μM of free ligand with 10 μM MnCl₂ or FeCl₂ salt referred to in the table below. The mixing procedure was carried out in ethanol using 3 mM of metal salt and 6 mM of ligand. After 20 minutes mixing, the solvent is evaporated and the solid is then dissolved in water. The aqueous ligand/metal mixture is added to the bleach solution to yield the desired concentration of metal/ligand.

After the washes, both air and peroxyl mode, the cloths were rinsed with water and subsequently dried at 30 °C and the change in colour was measured immediately after drying for 3 h at 45 oC with a Linotype-Hell scanner (ex Linotype) . The change in colour (including bleaching) is expressed as the ΔE value versus blank (no catalyst) . A higher ΔE value means a cleaner cloth. The measured colour difference (ΔE) between the washed cloth and the unwashed cloth is defined as follows: ΔE = [ (ΔL)² +(Δa)² +(Δb)² ]^{1 2}

wherein ΔL is a measure for the difference in darkness between the washed and unwashed test cloth; Δa and Δb are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de l'Eclairage (CIE) ; Recommendation on Uniform Colour Spaces, colour difference 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.

Curry oil (COL)

BLEACHING EXPERIMENTS (air mode)

In an aqueous solution containing 2 g/1 OMO Multi Acao ™ in 6 FH water hardness tomato-soya oil (TOL) stained or curry- soya oil (COL) stained cloths were added and kept in contact with the solution whilst agitating for 30 minutes at 30 °C. Comparative experiments were performed using 10 μM of the metal complexes or as a mixture of 20 μM of free ligand with 10 μM MnCl₂ or FeCl₂ salt referred to in the table below. The mixing procedure was carried out in ethanol using 3 mM of metal salt and 6 mM of ligand. After 20 minutes mixing, the solvent is evaporated and the solid is then dissolved in water. The aqueous ligand/metal mixture is added to the bleach solution to yield the desired concentration of metal/ligand.

Curry oil (COL)

Claims

Claims :

1. A bleaching composition comprising:

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

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-C24-alkyl, n is from 0 to 4, and mixtures thereof;

X is selected from: C=0, a ketal or thioketal derivative of

C=0 selected from a group of the form:

, and , and -C(R6)₂ wherein each R6 is independently selected from hydrogen, hydroxyl, 0-C1-C24- alkyl, O-benzyl, 0- (C=0) -C1-C24, Cl-C24-alkyl; and,

b) the balance carriers and adjunct ingredients to 100 wt %.

2. A bleaching composition according to claim 1, wherein X selected from the group consisting of: C=0, CH2, C(0H)2, syn-CHOR and anti-CHOR, wherein R is H, Cl-C24-alkyl or C(0)-Cl-C24-alkyl.

3. A bleaching composition according to claim 2, wherein X is C=0 or C(OH)2 or CHOH.

4. A bleaching composition according to according to claim 3, wherein X is C=0.

5. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of: -C (0) 0-Cl-C24-alkyl, -C (0) -0-Cl-C24-aryl - CH2OC(O)Cl-C20-alkyl, benzyl ester, phenyl, benzyl, CN, hydrogen, methyl, and C1-C4-0R wherein R is selected from the group consisting of H, Cl-C24-alkyl or C(0)-C1-C24- alkyl.

6. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of -CH20H, -C (0) -0-CH2C6H5 and -C (0) 0-C1-C6- alkyl .

7. A bleaching composition according to any preceding claim, wherein R3 and R4 are selected from the group consisting of: -C(0)-0-CH3, -C (0) -0-CH2CH3, -C (0) -0-CH2C6H5 and CH20H.

8. A bleaching composition according to any preceding claim, wherein: R3 = R4.

9. A bleaching composition according to any preceding claim, wherein Rl and R2 are independently selected from the group consisting of linear, and branched: -CH3, -C2H5, - C3H7, -C4H9, -C5H11, -C6H13, -C7H15, -C8H17, -C9H19, - C10H21, -C11H23, -C12H25, -C13H27, -C14H29, -C15H31, - C16H33, -C17H35, -C18H37, -C19H39, -C20H41, -C21H43 groups and CH2-C6H5.

10. A bleaching composition according to claim 9, wherein the Rl and R2 are independently linear alkyl groups.

11. A bleaching composition according to claim 9, wherein the Rl and R2 are independently branched alkyl groups.

12. A bleaching composition according to claim 9, wherein the Rl and R2 are independently C8-C20 alkyl groups.

13. A bleaching composition according any one of claims 1 to 8, wherein Rl and R2 are independently selected from the group consisting of: Me, and CH2-C6H5.

14. A bleaching composition according to any one of claims 1 to 13, wherein the pyridin-2-yl groups are mono-substituted at the 6 position.

15. A bleaching composition according to any one of claims 1 to 13, wherein the pyridin-2-yl groups mono-substituted at the 5 position.

16. A bleaching composition according to any preceding claim, wherein the pyridin-2-yl groups are mono-substituted by -CH3 or -C2H5 groups.

17. A bleaching composition according to any preceding claim, wherein R groups are same.

18. A bleaching composition according to any one of claims 1 to 17, wherein the complex with atmospheric oxygen, and upon addition of the bleaching composition to an aqueous medium providing an aqueous bleaching medium substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl- generating bleach system.

19. A bleaching composition according to any one of claims 1 to 17, wherein the composition comprises a peroxygen bleach or source thereof.

20. A bleaching composition according to claim 19, wherein the a peroxygen bleach or source thereof is selected from: sodium percarbonate and sodium perborate.

21. A bleaching composition according to claims 1 to 17, wherein the complex is of the general formula (Al) :

[M_aL_kX_n]Y_m (Al) ^•

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) ; 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 an integer from 0 to 10, m represents zero or an integer from 1 to 20; and L represents a ligand as defined in claims 1 to 17, or its protonated or deprotonated analogue.

22. A bleaching composition according to claim 21, wherein M represents a metal selected from Fe (II) - (III) - (IV) - (V) and Mn (II)-(III)-(IV)-(V) .

23. A bleaching composition according to claim 22, wherein M represents a metal selected from Fe(II), Fe(III), Mn(II) and Mn(III) .

24. A bleaching composition according to claim 23, wherein the ligand is present in the form selected from the group consisting of [FeLCl]Cl ; [FeL (H₂0) ] (PF₆) ₂; [FeLCl]PF₆; [FeL(H₂0) ] (BF₄)₂; [MnLCl]Cl ; [MnL (H₂0) ] (PF₂) ₂; [MnLCl]PF₆; [MnL(H₂0) ] (BF₄)₂.

25. A bleaching composition according to claim 21, wherein M represents Fe .

26. A ligand or transition metal complex as defined in any one of claims 1 to 17 and 21 to 25, with the proviso that Dimethyl 2, -di- ( 6-methyl-2-pyridyl) -3, 7-dimethyl-3, 7-diaza- bicyclo [3.3.1] nonan-9one-l, 5-dicarboxylate N2(6Mepy)2 is excluded.