Bleach catalyst carrier formulations and compositions

Abstract

The present invention provides a bleach catalyst formulation comprising, a bleach catalyst and a solid support carrier, wherein the bleach catalyst comprises at least one metal coordinated to at least one ligand of formula (I), a detergent composition comprising the bleach catalyst formulation and a surfactant, and uses of the formulation and composition thereof.

Description

[0001] BLEACH CATALYST CARRIER FORMULATIONS AND COMPOSITIONS

[0002] TECHNICAL FIELD

[0003] The present invention concerns carrier formulations and compositions for bleach catalysts and uses thereof.

[0004] BACKGROUND

[0005] Bleach catalyst carriers are used in detergent and cleaning compositions to deliver highly active, often transition-metal-based bleach catalysts into the wash in a stable, processable and consumer acceptable form. These carriers address the incompatibility between sensitive bleach catalysts and the harsh physical and chemical environment of modern granular and unit dose products while enabling effective low-temperature bleaching.

[0006] Bleaching is defined as the degradation of a stain via oxidation, in which the process either removes the stain entirely by improving aqueous solubility, or oxidation of the stain, such that it is no longer coloured.

[0007] Detergent formulations typically contain a range of different components, and alongside surfactants and bleaches, builders, enzymes, and other auxiliaries are typically also present, each with a unique action for obtaining an enhanced visual clean for the consumer. Detergent formulations are commonly used in laundry and automatic dishwashing applications. In such applications, the detergent formulations in this application commonly include a bleach catalyst. A bleach catalyst is a compound that accelerates the oxidation reactions of bleaching agents like hydrogen peroxide or peracids, allowing effective stain removal at lower temperatures and shorter washing times.

[0008] Automatic dishwashing is one example of an application in which bleaching is an essential component. In this application, the most commonly used bleaching system is based on hydrogen peroxide (H₂O₂), and such systems are termed as active oxygen detergents. Whilst these peroxide-based systems are a superior alternative to chlorine-based bleaching systems such as hypochlorate, they often exhibit limited performance below 50 °C and, thus there has been research into alternative oxidation catalysts and catalyst formulations, in a field known as bleach catalysis. Today, consumers frequently wish to operate cleaning processes, such as automatic dishwashing at lower temperatures or on shorter cycles to reduce costs and help the environment. The performance of current bleaching formulations, such as hydrogen peroxide-based systems, is limited at lower temperatures and one way to improve the bleaching performance of a H₂O₂ / activator formulation is to incorporate the use of a bleach catalyst.

[0009] Existing efforts to develop bleach catalysts have focused on the use of homogeneous transition metal catalysts to oxidise the polyphenolic chromophores in stains. Manganese based catalysts have been at the forefront of many of these studies, as they are non-toxic and commonly found in nature. The most well-known example of a bleach catalyst is manganese l,4,7-trimethyl-l,4,7-triazacyclononane (Mn(Me3-TACN, CAS 116633-53-5)), which was first launched by Unilever as a component in Persil Power in 1994. It catalytically activates hydrogen peroxide via oxygen transfer to stains, producing highly reactive species for oxidation. Alternative industry standard bleach catalysts in the dishwashing detergent industry include manganese oxalate (CAS 640-67-5), manganese oxalate dihydrate (CAS 6556-16-7), and certain cobalt-based complexes.

[0010] Selectivity is a key issue in the field of bleach catalysis, especially for laundry applications, as dyes in textiles often have similar structures to the chromophores in stains. Whilst still used in dishwashing, Mn(Me3-TACN) was removed from the market for laundry applications due to unacceptable fibre damage.

[0011] Despite the wide range of bleach catalysts reported in the art, few have been commercialised, due to challenges in high costs, fabric damage, formulation stability, being manufactured from fossil fuels, being non-biodegradable, being toxic, and that performance is not as good as other industry standards characterised by one or more of the aforesaid disadvantages.

[0012] The present invention aims to provide bleach catalyst formulations that provide improvements in at least one of these respects for use in at least laundry and automatic dishwashing applications.

[0013] There is some recognition in the prior art that certain formulations can be useful in certain types of bleach catalysis.

[0014] W003072691A1 describes a bleaching composition comprising an organic ligand which forms a complex with a transition metal for bleaching a substrate with atmospheric oxygen, an oxidizable substrate consisting of an unsaturated acid or a generating system for producing an unsaturated acid in situ, and a lipoxygenase enzyme for oxidizable precursor.

[0015] WO2007115979A1 describes a bleach system comprising at least one component selected from bleach, bleach activator and bleach catalyst, characterized in that the bleach system has been enveloped by at least one polymeric layer and the polymer has urethane and urea groups. The bleach system and detergent formulations comprising this bleach system are suitable, for example, for washing or cleaning textiles or dishware.

[0016] WO2012145062A1 describes a liquid cleaning compositions that includes a metal bleach catalyst which is a complex of a transition-metal and a macrocyclic ligand, and a formulation enabling fraction comprising at least one formulation enabling ingredient.

[0017] Notably, bleach catalyst formulations are effective to enhance the activity of peroxygen bleaches such as hydrogen peroxide, hydrogen peroxide liberating or generating compounds, and / or inorganic and organic peroxyacids by stabilising or working in synergy with the bleach catalyst.

[0018] The present invention seeks to provide bleach catalyst formulations with comparable performance to the best of the above-mentioned industry standard formulations, but with fewer environmental drawbacks.

[0019] SUMMARY OF THE INVENTION

[0020] According to a first aspect of the invention, there is provided a bleach catalyst formulation comprising:

[0021] a bleach catalyst; and

[0022] a solid support carrier,

[0023] wherein the bleach catalyst comprises at least one metal coordinated to at least one ligand of formula (I) having the structure:

[0024]

[0025] (I)

[0026] wherein n is 1 or 2;

[0027] m is 1 to 4, when the or each R independently represents H, or m is 1 or 2, when the or each R independently represents CH3, C2H5, C3H7, C4H9, OH, OR1, or NR22;

[0028] wherein R1represents CH3(CH2)V, wherein v is 0 to 17, which chain may be hydroxy- or alkoxy-terminated;

[0029] wherein R2represents H or CH3(CH2)W, wherein w is 0 to 17, or wherein R2represents alkoxyalkyl;

[0030] R' represents H, CH3, CH2CH3, CH(CH3)2, (CH2)yOH, or (CH2)yCOOH, wherein y is 0 to 17; R" represents H, CH3, CH2CH3, CH2OH, CH2CH2OH, CH2OCH3, or CH2CH2OCH3;

[0031] R'" represents H, or C(O)R3,

[0032] wherein R3represents (CH2)ZR4or -R5-R6, wherein z is from 1 to 18 and R4is H, OH or COOH; or, wherein R5represents Ci to C4alkyl; and R6represents H, CH3, OH, COOH, OCH3, OCH2CH2OH, OCH2CH2OCH3, or CH(OH)CH2OH.

[0033] Advantageously, use of bleach catalyst complexes of formula (I) as described above in formulations, provided enhanced effects as they are, in general, more hydrophobic and, in general, less water-soluble than the most commonly used oxidative bleaching catalyst, MnMes-TACN, otherwise known as Dragon. Further advantageously, the bleach catalysts of formula (I) may be biodegradable.

[0034] According to a second aspect of the invention, there is provided a detergent composition comprising the formulated bleach catalyst with carrier according to the first aspect of the invention, and a surfactant.

[0035] Advantageously, the combination of the formulated bleach catalyst and a surfactant enhance the activity of the catalyst, as the surfactant enables the surface of the catalyst complex, in a solid state, to be wetted. Coupled with the increased hydrophobicity and reduced water solubility of the catalyst complexes, the composition gives rise to two main advantages in detergent compositions, namely that the catalyst in the form of the chelates can dissolve progressively during a cleaning operation, such as dishwashing, providing a constant level of catalyst rather than a high level at the beginning of a wash, which is particularly the coldest, with decreasing activity during the wash.

[0036] A further advantage of the combination of the formulated bleach catalyst and a surfactant is that the increased hydrophobicity of the catalyst complexes provides additional adsorption onto hydrophobic surfaces, such as greasy surfaces, enabling better cleaning of such surfaces. According to a third aspect of the invention, there is provided use of the formulation or composition according to the first or second aspects of the invention as a bleach catalyst.

[0037] The use of the formulation or composition may be in any of, but not limited to, the following, laundry detergents, automatic dishwashing, the bleaching of paper, textiles, stains, hair, and teeth or in wastewater treatment.

[0038] The formulations and compositions of the present invention is particularly beneficial in automatic dishwashing compositions, where bleaching hydrophobic surfaces such as plastic plates and bowls enable better surface bleaching (likely due to hydrophobicity) and so difficult to remove stains, such as curry stains on plastics bowls are improved.

[0039] According to a fourth aspect of the invention, there is provided a method for bleach catalysis comprising contacting the formulation or composition according to the first or second aspects of the invention with a bleach under conditions effective to allow the compound to enhance a bleaching process.

[0040] According to a fifth aspect of the invention, there is provided a system for enhancing bleach catalysis, comprising the formulation of a bleach catalyst with a solid support.

[0041] Advantageously, by formulating the bleach catalyst with a solid support, the lifespan of the catalyst is prolonged by preventing the degradation of the catalyst, particularly at high pH conditions.

[0042] Any feature discussed in reference to one of the aspects of the present invention applies equally to all of the other aspects discussed herein.

[0043] DETAILED DESCRIPTION

[0044] Catalysts are used in reactions to increase kinetic rates, this is achieved by lowering the activation energy of the reaction, as the catalyst offers a lower energy alternative pathway to transform the reactants to the products. The thermodynamics of the reaction are not changed by a catalyst as the initial energy of the reactants and final energy of the products is not changed. A bleach catalyst is a substance that accelerates the bleaching process, typically by activating a bleaching agent like hydrogen peroxide to break down stains more effectively. Common examples include manganese and iron complexes, which are used in laundry detergents and dishwashing products to enable effective stain removal at lower temperatures and in less harsh conditions than would otherwise be required.

[0045] Solid Support Carrier

[0046] According to the invention, the bleach catalyst formulation comprises a solid support carrier.

[0047] A solid support carrier is a material that provides a surface for a bleach catalyst to be dispersed on, making it easier to use and more effective, especially in applications like laundry and dishwashing. Catalysts that are supported by a solid support carrier help activate bleaching agents like hydrogen peroxide more efficiently, leading to better stain removal.

[0048] In some embodiments, the solid support carrier may substantially be an inorganic carrier or a carbonbased carrier. By the term "substantially" it is meant that the solid support carrier largely but not completely comprises the inorganic carrier or carbon-based carrier. For example, in some embodiments, the solid support carrier may be substantially an inorganic carrier, such as titanium dioxide, with some other support, such as silica for example, comprising the rest.

[0049] The solid support carrier may comprise at least about 85%, at least about 90%, at least about 92%, at least about 93%, at least about 94%, at least about 96%, or at least about 98% inorganic carrier or carbon-based carrier.

[0050] When the solid support carrier is an inorganic carrier, it may be selected from a titanium oxide, an aluminium oxide, silicas, zeolites, or a mixture thereof. In preferred embodiments the solid support carrier is a titanium or zeolites.

[0051] When the solid support carrier is a titanium oxide, it is preferably titanium dioxide (TiO2). In some particular embodiments, the titanium oxide may be modified or surface-treated titanium oxide. For example, the titanium oxide may comprise inorganic and / or organic surface-treatments to improve their dispersion in formulations and their physical and chemical stability. When the solid support carrier is an aluminium oxide, it is preferably aluminium(lll) oxide (AI2O3), it may be acidic, basic, neutral, activated, or otherwise treated alumina. Preferably, the alumina is neutral and / or activated.

[0052] When the solid support carrier is a zeolite, it is a crystalline aluminium silicate. It may be a crystalline aluminium silicates of natural or synthetic origin. When the solid support carrier is a zeolite it may preferably be a hydrated alumina sodium silicate, more preferably an hydrated alumina sodium silicate of type A, P, X, AX, where A, P, X have close chemical composition but differ by their pore size and their respective binding capacity for Calcium and Magnesium ions, most preferably an hydrated alumina sodium silicate of type A also called Zeolite NaA or Zeolite 4A.

[0053] In a further preferred embodiment, the zeolite may be a hydrated alumina sodium silicate of type P, X, or AX. Zeolites of types P, X and AX, have all recently been introduced into the market, and have improved adsorptive capacity relative to zeolites of type A. For example, zeolites of type Xare capable of absorbing up to about 88 % of linseed oil, relative to about 35 % for type A zeolites.

[0054] When the solid support carrier is a carbon-based carrier, it may preferably be selected from activated carbon, mesoporous carbonaceous material, cellulose and its derivatives, starch, lignin, lignosulfonates, kraft softwood lignin, hydrochar, biochar, or a mixture thereof.

[0055] Advantageously, by formulating the bleach catalyst compounds with a carrier as described herein, the carrier prolongs the lifespan, and thus, activity of the bleach catalyst by protecting the bleach catalyst from the high-pH environments in which a bleach catalyst is typically used, which prevents, or at least delays the degradation of the catalysts that is typically observed over time, for example, over the course of a dishwashing cycle.

[0056] In some particular embodiments, the solid support carrier may be insoluble, or partially insoluble, in water. By being insoluble, or partially insoluble, in water, the solid support carrier may slow or control the release of the adsorbed bleach catalyst into water, such as the wash liquor in a laundry or automatic dishwashing application.

[0057] In some embodiments, the solid support carrier may be further treated with additives to provide further functionality, to modify its properties with regards to adsorption and release of bleach catalyst, to enhance physical or chemical stability, and / or to modify its behaviour in end-formulations or applications. For example, the solid support carrier may be treated to make its surface hydrophobic (i.e. water repellent), lipophilic (i.e. oil dispersible), both hydrophobic and lipophilic, or hydrophilic (i.e. water dispersible).

[0058] In some embodiments, the solid support carrier may be provided as a particulate material.

[0059] In some embodiments, the particulate material may have a particle size of less than about 250 pm, preferably less than about 100 pm, more preferably less than about 50 pm, most preferably less than about 25 pm. In some embodiments, the particulate material may have a particle size of from about 0.25 pm to about 250 pm, from about 0.25 pm to about 200 pm, from about 0.25 pm to about 150 pm, from about 0.25 pm to about 100 pm, from about 0.5 pm to about 50 pm, from about 0.5 pm to about 25 pm, from about 0.5 pm to about 15 pm, 0.5 pm to about 10 pm.

[0060] In some embodiments, the particulate material may have a mean surface area of from about 2 to about 800 m2 / g, preferentially from about 50 to about 400 m2 / g, most preferentially from about 100 to about 300 m2 / g.

[0061] Bleach Catalyst

[0062] According to the invention, the bleach catalyst formulation comprises a bleach catalyst, wherein the bleach catalyst comprised within formulations and compositions of the invention comprises at least one metal coordinated to at least one ligand of formula (I) having the structure:

[0063]

[0064] (I)

[0065] wherein

[0066] n is 1 or 2;

[0067] m is 1 to 4, when the or each R independently represents H, or m is 1 or 2, when the or each R independently represents CH3, C2H5, C3H7, C4H9, OH, OR1, or NR22;

[0068] wherein R1represents CH3(CH2)v, wherein v is 0 to 17, which chain may be hydroxy- or alkoxyterminated; wherein R2represents H or CH3(CH2)W, wherein w is 0 to 17, or wherein R2represents alkoxyalkyl;

[0069] R' represents H, CH3, CH2CH3, CH(CH3)2, (CH2)yOH, or (CH2)yCOOH, wherein y is 0 to 17;

[0070] R" represents H, CH3, CH2CH3, CH2OH, CH2CH2OH, CH2OCH3, or CH2CH2OCH3;

[0071] R'" represents H, or C(O)R3,

[0072] wherein R3represents (CH2)ZR4or -R5-R6, wherein z is from 1 to 18 and R4is H, OH or COOH; or, wherein R5represents Ci to C4alkyl; and R6represents H, CH3, OH, COOH, OCH3, OCH2CH2OH, OCH2CH2OCH3, or CH(OH)CH2OH.

[0073] In embodiments of the bleach catalyst of formula (I), the or each R may be H, CH(CH3)2, C(CH3)3, CH2CH3and OH. In most preferred embodiments, the or each R is H.

[0074] In embodiments of the bleach catalyst of formula (I), wherein when the or each R represents NR22and R2represents H or CH3(CH2)W, w is preferably 0. Alternatively, in embodiments of the bleach catalyst of formula (I), wherein when the or each R represents NR22and R2represents alkoxyalkyl, the alkoxyalkyl may be preferably selected from hydroxyethyl ((CH2)2OH), or hydroxypropyl. In most preferred embodiments, R preferably represents OH or NH2, most preferably OH, to provide a more hydrophilic structure with improved biodegradability.

[0075] In embodiments of the bleach catalyst of formula (I), R may be preferably located in positions 4, 5 or 6 of the aromatic ring.

[0076] In embodiments of the bleach catalyst of formula (I), R' is preferably H, and R" is preferably H.

[0077] In embodiments of the bleach catalyst of formula (I), wherein R'" represents C(O)R3and R3represents(CH2)zR4, R4is preferably OH. Alternatively, wherein R'" represents -R5-R6, R5is preferably methylene.

[0078] In addition, an ether or amine may preferably be present, providing the more labile ether or amine functionality between an alkyl (chain) and the benzene ring in which case:

[0079] R1represents CH3(CH2)V,

[0080] wherein v is 0 to 17; or v is preferably 6 to 12 thus providing hydrophobicity without the potential for evolution of volatile short alkyl components, such as during high alkaline washing operation in which catalyst may be used;

[0081] R2represents CH3(CH2)w, wherein w is 0 to 17; or

[0082] R1or R2represents (CH2)vOH.

[0083] The terminal hydroxy group improves biodegradability and ensures high water solubility.

[0084] The compound may be esterified or etherified. In some cases, R'" is preferably an ester, which improves the biodegradability of the compound. In other embodiments R'" is preferably an ether, rendering the compound more stable in an alkaline environment, such as during the washing process.

[0085] The ester or ether may be distanced from the benzene ring by means of a spacer chain R5, R6, respectively. This spacer chain may enable a wider range of metal ions to be chelated, such as Co in addition to Mn, ions.

[0086] R'" may comprise an alkyl chain, this may provide a degree of hydrophobicity to the ligand and thereby to a chelate created using the ligand. This can be advantageous in enabling catalytic bleaching of hydrophobic substrates.

[0087] Thus, it can be seen that the bleach catalysts present in formulations of the present invention are based upon a common structural element of (4,5-dihydro-l,3-oxazol-2-yl)benzene and more preferably upon a o-(4,5-dihydro-l,3-oxazol-2-yl)phenol core, which may also be referred to as a dihydro-oxazol-phenol or DOP structure, shown in formula (II):

[0088]

[0089] In particular embodiments, formula (II) may be ring substituted with ancillary groups, esterified, or etherified. When an ancillary group is present on the benzene (phenolic) ring it is preferably present in positions 4, 5 or 6, more preferably 4 or 5. The compound may be optionally substituted with ancillary groups, where ancillary groups are considered to be groups which do not fundamentally alter the chelating ability of the compound. Advantageously, the inclusion of ancillary groups is helpful in tailoring and altering the hydrophobicity, hydrophilicity, and steric hindrance of the catalytic centre. Adjusting these parameters is able to enhance the overall biodegradability of the ligand. In general, shorter alcohol chains and alkyl chains with a hydrophilic element are preferred so as to enable those characteristics to be achieved without presenting often poorly degradable long alcohol chains.

[0090] To illustrate:

[0091] 6

[0092] N

[0093]

[0094] This is understood to provide better bleaching by the chelate, particularly on hydrophobic surfaces as the catalytic centre is less hindered whilst the overall complex is more hydrophobic.

[0095] In this light, when R is in positions 4, 5 or 6, R can represent (CH2)xCH3, wherein x is 0 to 17, x is preferably 6 to 12 thus providing hydrophobicity without the potential for evolution of volatile short alkyl components, such as during high alkaline washing operation in which catalyst may be used.

[0096] According to the invention, the bleach catalyst comprises at least one metal coordinated to at least one ligand of formula (I), such as may be suitable for catalysing oxidative bleaching. The compounds are biodegradable and thus prevent catalyst build up in the environment.

[0097] In embodiments of the bleach catalyst, the at least one metal coordinated to formula (I) may be a transition metal. In particular embodiments, the transition metal may be selected from iron (Fe), manganese (Mn), copper (Cu), or cobalt (Co).

[0098] The catalytic activity of the bleach catalyst depends on the redox properties of the metal centre and the nature of the ligands. These catalysts generally work by generating high-valent metal-oxo species or facilitating radical pathways that enhance peroxide-based bleaching, while minimizing nonproductive peroxide decomposition. In preferred embodiments of the bleach catalyst, the transition metal ions may be iron(II), iron(III), manganese(II), manganese(III), copper(II), cobalt(II) or cobalt(III).

[0099] In most preferred embodiments, the transition metal may be manganese or cobalt, most preferably manganese, still more preferably manganese (II) or (III). The bleach catalyst chelate may be preferably a chelate of the transition metal element manganese, preferably wherein Mn is in the Mn3+, Mn(lll), oxidation state. Manganese is widely used due to high catalytic activity and selectivity in peroxide activation, especially effective in catalysing bleaching at neutral to alkaline pH.

[0100] In a preferred embodiment, the bleach catalyst comprises an Mn(lll) metal ion coordinated to two ligands of formula (II) having the structure:

[0101]

[0102] In some embodiments, the chelate may be preferably a hexadentate complex. In other embodiments, the chelate may comprise two ligands of formula (I) chelated to one transition metal element, for example.

[0103] In some embodiments, the bleach catalyst chelate may comprise one or more further ligands not being the ligands of formula (I). For example, the catalyst may comprise of two further ligands not being the ligands of the invention. The further ligands may be selected from H2O, carbonate, hydroxide, a halide, or an organic acid. In preferred examples, the further ligands may be selected from, H2O, Cl, and acetate.

[0104] If any of the compounds set out in the table below does not conform to the abbreviated list of requirements for the substituent, then the compound still remains part of the invention. The requirements in each claim are presented for clarity of presentation.

[0105] In accordance with the above, preferred examples of the bleach catalyst ligands of formula (I) are provided in the table below: Table 1: Summary of Structures

[0106] Codes Structure and Description

[0107] 1000- 1041 r<^r> N /

[0108] R’" u 1

[0109] In embodiments of general formula la, the compounds may particularly have one of the following particular structures:

[0110]

[0111] 1100- In further embodiments according to the present invention, the compounds may have a 1532 structure combining one of the oxazolyl ring systems with one of the substituted aromatic ring systems.

[0112]

[0113]

[0114] Bleach Catalyst Synthesis

[0115] The compounds of formula (I) comprised within the formulations and compositions of the present invention may be prepared by known synthetic techniques.

[0116] Given the wide range of compounds (ligands) within the scope of the present invention, a general scheme is provided, from which the skilled person would be well able to reasonably adapt the procedure for any given specific compound preparation.

[0117] The preferred synthetic route or compounds of the present invention uses the scheme: RA^

[0118] OR RA^

[0119] H

[0120] Amidine

[0121]

[0122] o

[0123]

[0124] RA^O^ reagent reagent

[0125]

[0126] and / or o RBand / or

[0127] OR catalyst

[0128]

[0129] RA^ catalyst Oxazoline o

[0130] JJ Amide

[0131] RAOH

[0132] The reaction of a carboxylic acid or its derivatives, such as its methyl ester or its nitrile, with an alpha substituted beta hydroxy amine can take place in two separate stages or a single stage, "one pot" reaction, i.e. telescoping both stages and producing the basic oxazoline unit of the present invention. The required raw materials are readily available from sustainable sources, such as biological or bioderived feedstocks, and therefore are bio-renewable.

[0133] As used herein, the term "bio-renewable" refers to materials and resources derived from natural sources, such as plants or animals, i.e. recently living organisms (biomass), that can be replenished at a rate that makes them available for future use. Examples of bio-renewable materials include, but are not limited to, algae, sugars, starches, corns, natural fibres, sugarcanes, beets, citrus fruits, woody plants, cellulosics, lignocelluosics, hemicelluloses, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, and pullulan, and a combination thereof.

[0134] The above reaction scheme is related to the Pinner reaction for the condensation of a carboxylic acid with an a-substituted -hydroxy amine to form an oxazoline. Reagents and catalysts include but are not restricted to thionyl chloride (SOCl2), oxalyl chloride (C2O2CI2), p-toluene sulfonic acid, methane sulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, or hydrogen chloride. The skilled person would be able to readily adapt the above reaction scheme to access a range of chemical structures in accordance with formula (I).

[0135] Example combinations of reagents that may be used to produce compounds of the present invention is provided in the following table, Table 2. Table 2: Example combinations of substrates and amines

[0136] Amine

[0137] Substrate H2N H2N -

[0138] OH

[0139] C^ CX^Ncr

[0140] cA

[0141] A

[0142] O-A

[0143] HOX'^XXOH

[0144] ay

[0145] V A A

[0146] °X ^ y YT° yV X n

[0147] YY

[0148] pA

[0149] r

[0150] j£X JCX^NXX^N

[0151]

[0152] The bleach catalyst complex of formula (I) is provided by coordination of the at least one metal coordinated to at least one ligand of formula (I).

[0153] Given the wide range of chelates within the scope of the present invention a general scheme, more specific scheme and a particular synthesis are provided, from which a person skilled in the art would be able to reasonably adapt for any given specific chelate preparation.

[0154] Bleach Catalyst Formulation

[0155] According to the invention, there is provided a bleach catalyst formulation comprising the bleach catalyst, and the solid support carrier.

[0156] In some embodiments, the bleach catalyst formulation may further comprise a binder, a filler, and / or a dispersing agent. In embodiments according to the first aspect, the formulation may comprise at least about 1 wt.% bleach catalyst. In particular embodiments, the bleach catalyst may be present in the formulation for example in an amount of from about 1 to about 15 wt.%, preferably from about 1 to about 10 wt.%, or more preferably from about 1 to about 5 wt.%.

[0157] In embodiments according to the first aspect, the formulation may comprise the bleach catalyst compounds on a carrier with a ratio of catalyst over solid support carrier of from about 1:1 to about 1:100, preferentially from about 1:5 to about 1:40.

[0158] In alternative embodiments according to the first aspect, the formulation may comprise at least 10 wt.% solid support carrier. In particular embodiments the formulation may comprise from about 10 to about 95 wt.%, from about 25 to about 95 wt.%, or from about 25 to about 50 wt.% solid support carrier.

[0159] In preferred embodiments, the bleach catalyst formulation according to the first aspect is stable at a pH of at least about 7, optionally wherein the formulation is stable at a pH of at least about 8, at least about 9, at least about 10, or at least about 11. Thus, the bleach catalyst formulation of the present invention provides a means of stabilizing the oxidative bleach catalyst of formula (I).

[0160] Particularly in concentrated and granular detergent compositions, compositions are typically provided to an end user for use as a diluted or dissolved solution, the pH that an oxidative bleach catalyst is exposed to prior to use can be particularly high and this can give rise to issues of storage stability. Advantageously, formulation of the bleach catalyst with a solid support carrier stabilises and preserves the bleach catalyst at high pH.

[0161] In some embodiments, the bleach catalyst formulation may additionally comprise at least one ancillary compound, optionally selected from one or more of:

[0162] surfactant(s);

[0163] detergent(s);

[0164] bleach(es);

[0165] carrier compound(s);

[0166] stabilizer(s); and / or

[0167] dispersant(s). Detergent Formulations and Compositions

[0168] According to the invention, there is provided a detergent composition comprising the formulated bleach catalyst with carrier according to the first aspect of the invention, and a surfactant.

[0169] In embodiments according to the second aspect, the detergent composition may comprise at least about 0.001 wt.% bleach catalyst formulation according to the first aspect.

[0170] In particular embodiments, the bleach catalyst may be present in the detergent composition for example in an amount of from about 0.001 to about 5 wt.%, preferably from about 0.1 to about 4 wt.%, more preferably from about 0.1 to about 2 wt.%, even more preferably from about 0.1 to about 1 wt.%, most preferably from about 0.1 to about 0.5 wt.%.

[0171] The detergent composition may comprise the surfactant in an amount of from about 1 to about 25 wt.%. In particular embodiments, the composition may comprise from about 2 to about 15 wt.%, or from about 3 to about 10 wt.% surfactant. Advantageously, these levels enable effective transport of the catalyst to substrate surfaces, such as hydrophobic surfaces to enable improved oxidative bleaching.

[0172] The surfactant is preferably a detersive surfactant, and may be anionic, non-ionic, zwitterionic or cationic. Importantly, the choice of surfactant determines the adsorption of chelate onto substrates during detergency and hence bleaching efficiency on a surface, as compared to in solution which is generally ineffective in detergency operations to clean surfaces.

[0173] In most preferred embodiments, the surfactant is a non-ionic surfactant. Advantageously, such surfactants are used in automatic dishwashing to avoid excessive foaming for ease of rinsing. For example, in automatic dishwashing, most current surfactants used on the market are non-ionic surfactants and may be present in these applications the range from about 2.5 to about 7 wt.%, and these surfactants are typically Cio to Cig linear or branched ethoxylated and / or propoxylated alcohols.

[0174] In alternative embodiments, the surfactant may be a mix of surfactant types. For example, in laundry applications, most current surfactant formulations comprise a mix of anionic (about 5 to about 15 wt.%), non-ionic (about 2 to about 8 wt.%), and soap (about 0 to about 4 wt.%). The surfactant may comprise at least one surfactant. Preferably, the surfactant is a mixture of surfactants. In particular, a mixture of an anionic or non-ionic surfactants may be desirable.

[0175] In preferred embodiments, the composition may further comprise a bleach activator.

[0176] A bleach activator, which may also be known as a bleach catalyst activator, is a compound that enhances the reactivity of bleaching agents, such as hydrogen peroxide, by promoting the in-situ formation of more potent oxidants such as peroxy acids. These activators or catalysts serve to lower the effective bleaching temperature, improve efficiency, and reduce energy consumption in laundry and textile processing systems. While bleach activators are consumed stoichiometrically to generate peroxy acids, bleach catalysts operate in a catalytic cycle with hydrogen peroxide or percarbonates.

[0177] In embodiments of the invention, the bleach activator may predominantly be selected from any suitable N- and O-acyl compounds that yield peroxy acids.

[0178] In such embodiments, the bleach activator may be selected from, but not limited to, for example, tetraacetylethylenediamine (TAED), tetraacetylglycoluril (TAGU), tetraacetylhexane diamine (TAHD), / V, / V, / V', / V'-tetramethyl-6-dodecylamidinouronium chloride (DADMAC), / V, / V, / V', / \ / '-tetrabenzyl-6-dodecylamidinouronium chloride (BADMAC), / V, / V, / V', / \ / '-tetrabenzyloxycarbonyl-6-dodecylamidinouronium chloride (BODMAC), / V, / V-diacetyl-4,5-diazafluoren-9-one (DADHF), N, N'-diacetyl-4,5-diazafluoren-9-yl peroxybenzoate (DADPA), l,5-diacetyl-2,4-dioxohexahydro-l,3,5-triazine (DADHT), or / V, / V-diacetyl-3,5-dimethyl-l,4-dioxohexahydro-l,3,5-triazine (DADHT-DM), nonanoyloxybenzenesulfonate sodium salt (NOBS), 4-lauroyloxybenzenesulfonic acid sodium salt (LOBS), acetyl triethylcitrate (ATEC), triacetin, ethylene glycol diacetate, pentaacetylglucose (PAG), gluconolactone, / V-acetylcaprolactam, 6-phthalimido peroxyhexanoic acid (PAP), succinimide, succinic anhydride, or a combination thereof. In most preferred embodiments, the bleach activator is TAED or PAG, or a combination thereof.

[0179] The bleach activator advantageously enables a proportion of the oxidative bleach to be provided as other activated (i.e., lower temperature active species) in addition to the catalytically mediated oxidation of the complex of formula (I). This enables species such as peracids to be created during a washing process (such as after dissolution of a dishwashing powder detergent.

[0180] In some embodiments, the composition may further comprise a sequestrant. A sequestrant is a substance that binds and forms complexes with transition metal ions such as copper, iron, manganese and nickel. By doing so, it prevents these metals from catalysing oxidation reactions. Essentially, sequestrants act as preservatives by stabilizing the formulation and improving its quality and shelf life through metal ion chelation.

[0181] Common sequestrants include, but are not limited to, sodium gluconate, and various phosphates and EDTA salts.

[0182] In such embodiments, the sequestrant may be selected from, for example, ethylenediaminetetraacetic acid (EDTA), diethylene glycol monobutyl ether- / V, / V-diacetic acid (DGBE-NDA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyl ethylenediaminetriacetic acid (HEDTA), l-hydroxyethylidene-l,l-diphosphonic acid (HEDP), citric acid, gluconic acid or aminopolycarboxylic acids (APCA) derivatives, such as iminodisuccinic acid (IDS), methylglycinediacetic acid (MGDA), (S, S)-ethylenediaminedisuccinic acid (EDDS), or glutamic acid N, N-diacetic acid (GLDA), or a combination thereof. In most preferred embodiments, the sequestrant may be selected from citric acid, gluconic acid, IDS, MGDA, EDDS, or GLDA, as these sequestrants are more sustainable and biodegradable.

[0183] The use of a sequestrant is desired because it obviates the undesired decomposition of peroxides species when there are transition metals in the water supply used in a cleaning operation. It is important to strike a balance to be made between removing those unwanted transition metal ions and removal of the transition metal iron of the chelate of the present invention.

[0184] Advantageously, it has been surprisingly found that a number of common sequestrants, such as used up to a one-to-one rate ratio with the catalyst of formula (I) in a detergent composition of the second aspect of the invention may not hinder the catalyst significantly.

[0185] In some embodiments, the composition may further comprise an oxidative bleach.

[0186] An oxidative bleach works by releasing oxygen atoms to break down the chemical bonds of coloured molecules in stains. Advantageously, an oxidative bleach is a non-toxic, biodegradable, and environmentally safe alternative to chlorine bleach. In such embodiments, the oxidative bleach may be selected from sodium percarbonate, sodium perborate, sodium perphosphate, sodium hypochlorite, hydrogen peroxide, sodium dichloroisocyanurate (NaDCC), sodium chlorite, potassium monopersulfate (MPS), sodium carbonate peroxyhydrate, sodium persulfate, or a combination thereof. In most preferred embodiments of the present invention, the oxidising agents may be sodium percarbonate or sodium perborate. In the most preferable embodiments, the oxidising agent is sodium percarbonate.

[0187] In such embodiments, the composition may comprise from about 1 to about 50 wt.% of an oxidative bleach, from about 3 to about 30 wt.%, preferably from about 5 to about 20 wt.%, more preferably from about 5 to about 15 wt.%, most preferably from about 5 to about 10 wt.%.

[0188] Specifically, whilst the presence of an oxidative bleach is required for the compound of formula (I) of the present invention to act as a catalyst, the detergent composition can be provided in component form, such as in the well-known Baukasten system and are therefore not necessarily mandatory.

[0189] In some embodiments, the composition may further comprise a proteolytic enzyme or a lipolytic enzyme.

[0190] In such embodiments, a synergistic effect can be observed between the enzyme and the catalyst in the composition.

[0191] In some embodiments, the composition may further comprise a binder, a filler, and / or a dispersing agent.

[0192] Suitable binders may be selected from fatty acids or their soaps, water-soluble polymers (e.g. ethoxylated fatty alcohols, which are also used as non-ionic surfactant in ADW detergents), polysaccharides (e.g., alginates, and cellulose derivatives such as carboxymethyl cellulose), starch, modified starch, and polyvinyl alcohol.

[0193] Binders and stabilizers enhance the formulated bleach catalyst as they form a network that encapsulates the bleach catalyst. In doing so they provide a stable matrix that holds the bleach catalyst formulation together and control its particle size distribution, avoiding break-down of granules and preventing dust formation, thereby reducing reactivity with air, moisture, or the rest of the detergent components during storage of compositions. Suitable fillers or dispersing agents may be selected from cellulose, sodium carbonate, sodium bicarbonate, sodium sulphate, methyl ester sulfonates, alkyl polyglycolides, or other plant-based surfactants.

[0194] Fillers help control the bulk density of the catalyst formulation and keep it in range with other detergent solid ingredients in detergent compositions to avoid segregation and uneven distribution during detergent manufacture. Surfactants can act as dispersants and stabilizers for the manganese bleach catalyst contained within the bleach catalyst formulation. They improve wettability and dispersibility, especially in low-water formulations, enhancing both stability and effectiveness of the composition.

[0195] Advantageously, detergent compositions according to the second aspect achieve a balance between controlling catalyst content, distribution within its formulation, formulation bulk density, whilst ensuring stability of powder or granule form and size during storage, detergent manufacture and consumer end-product storage, achieving an even distribution within detergent composition, efficient release and distribution of catalyst on support from detergent into dishwasher water, and controlled release of catalyst from its support into wash liquor.

[0196] In some embodiments, the composition may additionally comprise at least one ancillary compound, optionally selected from one or more of:

[0197] surfactant(s);

[0198] detergent(s);

[0199] bleach(es);

[0200] carrier compound(s);

[0201] stabilizer(s); and / or

[0202] dispersant(s).

[0203] In a particular embodiment, the detergent composition according to the second aspect may be a laundry detergent composition, such as includes fabric softeners, whitening agents, pre-treatment agents as well as conventional solid, liquid, gel, pouch detergent compositions heavy duty, light duty 'whites' and 'colours' detergent compositions. In a particular embodiment, the detergent composition according to the second aspect may be a fabric washing detergent composition is selected from one or more of a laundry detergent, a laundry fabric softener, a bleach, or a booster laundry aid (such as whitening agent).

[0204] The detergent composition of the second aspect of the invention may be in the physical form of a powder (granulate), liquid, a gel, a pouch, a tablet, or solid sheet. In most preferred embodiments, the composition is a solid.

[0205] In formulations and compositions of the present invention, a particularly significant benefit is the preservation of the active component of formula (I) prior to use. Bleaching compositions are typically distributed in concentrated form which must be capable of being stored for, typically, many months whereas in a washing situation bleaching action is required in a relatively short time and particularly relevant to bleach catalysts at a low temperature. There is therefore a problem of providing a delivery mechanism for oxidative bleach catalysis, which formulation of the catalyst with a solid carrier provides, as it prolongs the lifespan of the catalyst by preventing the degradation of the catalyst, particularly at high pH conditions.

[0206] The invention provides formulations and detergent compositions, such as for example dishwashing compositions or laundry compositions.

[0207] Oxidative bleaching catalyst formulations are typically used in a variety of detergent compositions and particularly in automatic dishwashing or fabric washing detergent compositions. Whilst oxidative bleaching catalysts may be incorporated directly in a fabric washing detergent composition this does not guarantee that the oxidative bleaching catalyst will either remain stable over time, given that fabric washing compositions are typically prepared having a pH greater than pH 7, often at a pH of approximately 10. Therefore, by formulating the bleach catalyst with a solid support carrier, such as TiO2, a stable formulation that is compatible with environmentally acceptable oxidative bleaching catalysts is provided that prolongs stability of the bleach catalyst.

[0208] Particularly in concentrated and granular detergent compositions, compositions are typically provided to an end user for use as a diluted or dissolved solution, and the pH that an oxidative bleaching catalyst is exposed to prior to use can be particularly high and this can give rise to issues of storage stability. By formulating the catalyst with solid support carrier, an improved delivery compositions compatible with environmentally acceptable oxidative bleaching catalysts, particularly those structures defined in this present application is provided.

[0209] For example, when the detergent composition is a dishwashing detergent composition, the dishwashing detergent composition may be a solid composition or a liquid composition.

[0210] Example dishwashing compositions are provided in the below tables, for both solid and liquid compositions.

[0211] Table 3: Dishwashing detergent composition (solid)

[0212] Ingredients Tablets (wt.%) Tablets 2 (wt.%) Powder (wt.%) Bleach catalyst formulation (of

[0213] 0.1-4 0.1-4 0.1-4 the present invention)

[0214] Bleach activator 0-5 1-2 Oxygen-based bleaching

[0215] 10-20 15-40 5-10 agents

[0216] Surfactants <5 <5 1-5 Builders (Alkali silicates &

[0217] 5-30 0-55 50-85 carbonates)

[0218] Builders (Organic

[0219] 0-45 0-45 - sequestrants)

[0220] Builders (Polycarboxylates) 2-7 <5 - Colourants <1 <1 <1 Enzymes <1 0-10 1-3 Enzyme coating (e.g., NaCI) 1-10 1 Fragrance <0.5 <1 <1 Glass protectors, silver

[0221] 0-1 - - protectors

[0222] Lime scale inhibitor 0-10 - - Bulking agents balance to 100% balance to 100% balance to 100%

[0223]

[0224] Table 4: Dishwashing detergent composition (pods or capsules)

[0225] Ingredients Amount (wt.%)

[0226]

[0227] Bleach catalyst formulation (of

[0228] 0.1-4

[0229] the present invention)

[0230] Bleach activator (e.g. TAED) 0.5-2.5

[0231] Chelating agents (e.g. GLDA) 28-32

[0232] Sodium carbonate 30

[0233] Sodium percarbonate 12-15

[0234] Builders (e.g. PESA,

[0235] Polyepoxysuccinic acid 5-10

[0236] sodium)

[0237] Surfactants (e.g. Linear fatty

[0238] 4-6

[0239] alcohol ethoxylate)

[0240] Sodium sulphate 2-3

[0241] Enzymes 1-2

[0242] Solvents (e.g. Glycerol) 0.2-2

[0243] Glasse protectors (e.g. Zinc

[0244] 0.3-0.6

[0245] citrate)

[0246] Fragrances < 0.5

[0247] Polyvinyl alcohol (pods or

[0248] 2-3

[0249] capsules water soluble film)

[0250]

[0251] Fabric washing detergent compositions are typically provided in a number of different formats, such as compositions relevant for hand washing, machine washing, uncoloured garments and coloured garments. Compositions which provide an oxidising agent and widely used, and these can also give rise to stability problems regarding environmentally acceptable oxidative bleaching catalysts, such as those structures defined in the present application. There is therefore a need for delivery compositions which mitigate or ameliorate issues caused by oxidising agents in fabric washing detergent compositions.

[0252] A further consideration is that whilst oxidative bleaching catalysts may be incorporated into fabric washing detergent compositions this does not guarantee that the oxidative bleaching catalyst will absorb onto a fabric being washed. The function of a detergent composition, particularly in laundry, is to absorb on the surfaces of fabrics and preferentially adhere, such that oils and other residues are removed. This is carried out by the means of surfactants in the composition, surfactants typically being classified as anionic, non-ionic, and cationic. It can be a challenge to formulate a fabric washing detergent composition to incorporate an oxidative bleaching catalyst such that the oxidative bleaching catalyst can remain absorbed on a fabric surface after a washing process, washing process typically being followed up by a rinsing process, by formulating the compound with solid state carrier this is provided.

[0253] For example, when the detergent composition is a laundry detergent composition, the dishwashing detergent composition may be a solid composition or a liquid composition.

[0254] Example laundry compositions are provided in the below tables, for both solid and liquid compositions.

[0255] Table 5: Laundry powder composition

[0256] Conventional

[0257] Ingredients Compact (wt.%)

[0258] (wt.%)

[0259] Anionic and non-ionic

[0260] 8-15% 10-30%

[0261] surfactant

[0262] Builders 20-50% 20-40%

[0263] Cobuilders 1-5% 1-7% Bleaching agents 10-25% 10-20% Bleach activators 1-3% 2-8% Antiredeposition agents 1% 1%

[0264] Corrosion inhibitors 2-6% 2-6%

[0265] Bleach Stabilizers 0-1% 0-1% Bleach catalyst formulation (of

[0266] 0.1-2.5% 0.1-2.5%

[0267] the present invention)

[0268] Foam regulators 0.1-1% 0.1-2%

[0269] Enzymes 0.3-1% 0.5-2%

[0270] Minors, water Balance to 100% Balance to 100%

[0271] Bulk density, g / L 500-650 600-900

[0272]

[0273] Table 6: Detergent tablet composition

[0274] Zeolite-based Phosphate-based Ingredients

[0275] (wt.%) (wt.%)

[0276] Surfactants 13-18% 15-18%

[0277]

[0278] Bleaching agents 13-15% 12-16% TAED 3-7% 4-7% Bleach catalyst formulation

[0279] 0.1-2.5% 0.1-2.5% (of the present invention)

[0280] Zeolite 15-30% - Sodium triphosphate - 25-45% Layered silicate 0-9% 0-9% Sodium polycarboxylate 2-3% 2% Disintegrants 5-17% 0-12% Enzymes 2-4% 1-3% Minors, water Balance to 100% Balance to 100% Bulk density, g / L 500-650 600-900

[0281]

[0282] Table 7: Laundry powder composition Homogeneous

[0283] Ingredients Structured (wt.%)

[0284] (wt.%)

[0285] Anionic surfactants 7-18% 10-25% Non-ionic surfactants 15-30% 6-10% Soaps 10-25% 4-8% Builders 0-5% 15-30% Solubilisers 0-12% 0-5% Alcohols 5-12% 0-5% Bleach catalyst formulation (of

[0286] 0.1-2.5% 0.1-2.5% the present invention)

[0287] Enzymes 0-2.5% 0-1.5% Minors, water Balance to 100% Balance to 100%

[0288]

[0289] Table 8: Fabric washing bleach detergent composition Ingredients Powder (wt.%) Liquid (wt.%) Anionic surfactants 5-15% 2-10% Non-ionic surfactants 0-1% 3-5% Builders 60-75% - Bleach 3-15% 3-4%

[0290]

[0291] Bleach catalyst formulation (of

[0292] 10% 10%

[0293] the present invention)

[0294] Filler 5-20% - Enzymes 0-1% - Minors, water Balance to 100% Balance to 100%

[0295]

[0296] A particularly significant aspect of the formulations and compositions of invention is the preservation of the active component prior to use. Bleaching compositions are typically distributed in concentrated form which must be capable of being stored for, typically, many months whereas in a washing situation bleaching action is required in a relatively short time and particularly relevant to bleach catalysts at a low temperature. There is therefore a problem of providing a delivery mechanism for oxidative bleach catalysis.

[0297] In one embodiment, formulations or compositions of the invention may be used in fabric manufacturing. Formulations may be used in finishing processes for cotton. Preferably in the treatment of griege (loom-state) cloth into finished fabric. Formulations of the present invention may be used in melt spinning thing synthetic fibres.

[0298] Table 9: Representative raw cotton bleaching composition

[0299] Ingredient Amount (wt.%)

[0300] Hydrogen Peroxide (H2O2) 10-25%

[0301] Bleach catalyst formulation (of the present

[0302] 0.05-3%

[0303] invention)

[0304] Sodium Hydroxide (NaOH) 1-5%

[0305] Sodium Metasilicate (Na2SiO3) 1-5%

[0306] Sodium Hypochlorite (NaOCI) 0.05-0.5%

[0307] Sequestering Agent (Sodium

[0308] 0.5-2% Hexametaphosphate)

[0309] Stabilizer (Sodium Phosphate) 0.1-1%

[0310] Balance to 100% water

[0311]

[0312] In one embodiment, formulations or compositions of the invention may be used in paper manufacturing. Preferably during "wet" manufacturing processes as detergent compositions. Formulations of the present invention may be used in paper finishing as detergent compositions, for example to treat cellulose fibre before paper manufacture.

[0313] Table 10: Representative paper pulp bleaching composition

[0314] Ingredient Amount (wt.%)

[0315] Hydrogen Peroxide (H2O2) 3-15%

[0316] Bleach catalyst formulation (of the present

[0317] 0.05-3%

[0318] invention)

[0319] Chelating agent (e.g. EDTA) 0.1-2%

[0320] Sodium Hydroxide (NaOH) 0.1-2%

[0321] Sodium Metasilicate (Na2SiO3) 0.1-2%

[0322] Sodium Hypochlorite (NaOCI) 0.005-0.5%

[0323] Stabilizer (Sodium Silicate) 0.1-1%

[0324] Balance to 100% water

[0325]

[0326] In one embodiment, formulations or compositions of the invention may be used in conjunction with emollient to provide cosmetics compositions as detergent compositions. Formulations of the present invention may be used to produce detergent and bleaching compositions, for example as hair bleaching products, teeth whitening products, nail bleaching treatments or spot correctors. Oxidative bleaches, such as hydrogen peroxide-based formulations, are widely used in hair bleaching products to lighten the colour of the hair. These products are used to achieve highlights, balayage, and overall hair lightening effects. Such a composition typically comprises a source of hydrogen peroxide, a surfactant and the chelate of the present invention.

[0327] Table 11: Representative hair bleaching composition

[0328] Ingredient Amount (wt.%)

[0329] Hydrogen Peroxide (H2O2) 6-12%

[0330] Bleach catalyst formulation (of the present

[0331] 0.05-2%

[0332] invention)

[0333] Ammonium Persulfate ((NH4)2S2O8) 20-30%

[0334] Potassium Persulfate (K2S2O8) 20-30%

[0335] Sodium Metasilicate (Na2SiO3) 1-5%

[0336] Sodium Carbonate (Na2CO3) 1-3%

[0337] Kaolin Clay 1-3%

[0338]

[0339] Conditioning Agent 1-3%

[0340] Stabilizer (Sodium Phosphate) 0.5-2%

[0341] Balance to 100% water

[0342]

[0343] In other embodiments, formulations or compositions of the invention may, may also be utilized in teeth whitening products. These products help remove stains and discoloration from the teeth. Such a composition typically additionally comprises a source of hydrogen peroxide, a surfactant and the chelate of the present invention.

[0344] In other embodiments, formulations or compositions of the invention may also be employed in nail bleaching treatments designed to lighten and brighten discoloured or stained nails. These treatments help restore the natural colour and appearance of the nails.

[0345] The advantages of the present invention in cosmetics are that they provide an increase bleaching of cosmetics whilst retaining low levels of hydrogen peroxide, in an environmentally acceptable format whilst also reducing skin irritation.

[0346] The present invention may be exemplified by a bleaching booster composition which is added, such as a separate addition on preparing a washing liquor. The composition consisting of the detergent composition of the present invention, preferably anionic surfactant and chelate, The surfactant enabling efficient dispersion of the catalyst so as to avoid localised bleaching, such as may give rise to spots (such as white spots) on objects to be bleached.

[0347] Use of the Bleach Catalyst Formulation or Composition

[0348] According to the invention, there is provided use of the formulation or composition as a bleach catalyst.

[0349] The use of the formulation or composition may be in any of, but not limited to, the following, laundry detergents, automatic dishwashing, the bleaching of paper, textiles, hair, and teeth or in wastewater treatment.

[0350] Preferably, the use of the formulation or composition is in laundry detergents or automatic dishwashing, for the discolouration, oxidation and solubilisation of stains and other soiling. The formulations and compositions of the present invention is particularly beneficial in automatic dishwashing compositions, where bleaching hydrophobic surfaces such as plastic plates and bowls enable better surface bleaching (likely due to hydrophobicity) and so difficult to remove stains, such as curry stains on plastics bowls are improved.

[0351] EXAMPLES

[0352] Example 1 - Synthesis of Bleach Catalyst of Formula (II):

[0353] The ligand of formula (II) was prepared as follows:

[0354] A mixture of methyl salicylate (273.9g, 1.8mol) and ethanolamine (115.8g, 1.9mol) is heated to 130°C and the methanol of reaction is distilled until no further distillation is observed and the reaction is complete. The resulting residue is then cooled to room temperature and suspended in dichloromethane (IL, 4 vol). After cooling to 5°C, thionyl chloride (237.5g, 2.0mol) is then added dropwise to the mixture. After complete addition, the reaction is stirred for 16h at 25°C. Resulting solids are then filtered and neutralized with 10% NaHCOs solution before being extracted with methyl tert-butyl ether (3 X 150mL). Organic extract is then concentrated to dryness under vacuum to give to give product as a red oil which crystallizes to peach / pink solid on standing. Solids ground to give a peach / pink powder in 68% yield (292.5g, 1.22mol).

[0355] A

[0356]

[0357] nalytical Data: GC purity: 99.5%; FT-IR: nC=N 1636cm1; NMR (Methanol-cU, 300 = MHz, d): 7.56 (dd, 1H), 7.29 (ddd, 1H), 6.89 (dd, 1H), 6.79 (ddd, 1H), 4.28 (t, 2H), 3.93ppm (t, 2H); ^CfH} NMR (methanol-d4, 75MHz, d): 165.87, 159.45, 132.90, 127.75, 118.32, 116.01, 110.57, 66.61, 52.91ppm; Elemental analysis: C 65.66%, H 5.45%, N 8.62%.

[0358] The formula (II) Mn-complex, was prepared as follows:

[0359] Oxazoline ligand of Formula (II) (30g, 180mmol, 2 eq.) was dissolved in MeOH (300g, 10% wt. solution). Solid manganese acetate tetrahydrate (21.9g, 90 mmol, 1 eq.) was charged to the ligand solution to give an instant colour change to dark green / black. After 0.25h stirring the mixture was concentrated in vacuo to give an initial residue. Material was resuspended in 300ml and concentrated to dryness twice more to give the final catalyst complex. The sample was ground in a pestle and mortar to give the catalyst product as a green-brown free-flowing powder (41.3g). Analytical Data: FT-IR: nC=N 1621cm1; UV-Vis: lmax = 264nm, 216nm; ICP: 13% Mn content; Elemental analysis: C 53.40%, H 4.59%, N 5.77%

[0360] Analysis of Formula (II) Mn-Complex:

[0361] Structural X-Ray Diffraction measurements are shown in Tables 12 - 19:

[0362] Table 12: Crystal data and structure refinement for Formula (II) Mn-complex

[0363] Identification code Formula (II) complex

[0364] Empirical formula C22H23MnN20g

[0365] Formula weight 498.36

[0366] Temperature / K 120.00

[0367] Crystal system Triclinic

[0368] Space group P-1

[0369] a / A 6.3884(2)

[0370] b / A 9.4519(3)

[0371] c / A 9.5141(3)

[0372] a / ° 80.7500(10)

[0373] P / ° 71.9660(10)

[0374] v / ° 71.0250(10)

[0375] Volume / A3515.42(3)

[0376] Z 1

[0377] Pcalcg / Cm31.606

[0378] p / mm10.696

[0379] F(000) 258.0

[0380] Crystal size / mm30.21 x 0.11 x 0.025

[0381] Radiation Mo Ka (X = 0.71073)

[0382] 20 range for data collection / 06.634 to 63.994

[0383] Index ranges -9 < h < 9, -14 < k < 14, -14 < 1 < 14 Reflections collected 20885

[0384] Independent reflections 3567 [Ririt = 0.0297, Rsigma= 0.0202] Data / restraints / parameters 3567 / 0 / 196

[0385] Goodness-of-fit on F21.147

[0386] Final R indexes [ l>=2o (1)] Ri = 0.0288, WR2= 0.0740

[0387]

[0388] Final R indexes [all data] Ri = 0.0303, WR2= 0.0747

[0389] Largest diff. peak / hole / e A-30.42 / -0.28

[0390]

[0391] Table 13: Fractional atomic coordinates (xlO4) and equivalent isotropic displacement parameters (A2X103) for Formula (II) Mn-complex. Ueqis defined as 1 / 3 of the trace of the orthogonalised Uu tensor

[0392] Atom X y z U(eq)

[0393] Mnl 5000 0 5000 11.33(6)

[0394] 01 3351.5(15) 86.0(9) 3657.1(9) 15.44(15) 02 6453.7(15) 3569.2(9) 2133.1(10) 17.11(16) 03 1935.7(15) 1609.3(9) 6456.8(10) 18.09(17) 04 1294.2(16) 3730.8(10) 5057.3(10) 21.68(19) N1 6171.8(16) 1663.2(10) 3833.1(10) 12.28(16) Cl 7428(2) 2444.9(13) 4339.4(13) 16.5(2)

[0395] C2 7728(2) 3690.5(14) 3120.8(14) 18.3(2)

[0396] C3 5673.4(18) 2372.2(12) 2646.5(12) 12.33(18) C4 4365.4(19) 2016.4(12) 1828.2(12) 12.74(18) C5 3303.0(19) 867.9(12) 2378.6(12) 13.06(18) C6 2054(2) 561.2(13) 1532.7(13) 17.0(2)

[0397] C7 1914(2) 1343.6(15) 192.5(14) 20.5(2)

[0398] C8 2949(2) 2494.8(15) -338.7(13) 20.7(2)

[0399] C9 4139(2) 2829.8(13) 480.8(13) 16.8(2)

[0400] CIO 767.6(19) 2914.4(12) 6254.1(12) 14.35(19)

[0401]

[0402] Cll -1368(2) 3587.6(15) 7449.5(14) 20.6(2)

[0403] Table 14: Anisotropic displacement parameters (A2xl03) for Formula (II) Mn-complex. The Anisotropic displacement factor exponent takes the form: -2n2[h2a*2Un+2hka*b*Ui2+...]

[0404] Atom Uu u22U33 U23 U13 Ui2

[0405] Mnl 12.13(11) 11.27(10) 12.29(11) 1.92(7) -5.81(8) -4.64(8) 01 18.1(4) 16.4(4) 15.7(4) 4-1(3) -9-5(3) -8.1(3) 02 19.2(4) 15.5(4) 20.2(4) 4.3(3) -8.5(3) -9-5(3) 03 17.9(4) 13.9(4) 17.9(4) -0.7(3) -3.2(3) -0.5(3) 04 21.5(4) 14.7(4) 19.2(4) 2.0(3) 0.0(3) 0.5(3) N1 11.6(4) 11.9(4) 14.2(4) -0.8(3) -4.6(3) -3.6(3) Cl 18.6(5) 16.3(5) 19.0(5) 0.4(4) -8.6(4) -8.5(4) C2 19.9(5) 16.0(5) 23.5(5) 1.0(4) -9.5(4) -8.9(4) C3 10.6(4) 10.8(4) 14.1(4) -1.0(3) -2-1(3) -2.3(3) C4 12.5(4) 13.0(4) 12.3(4) -0.9(3) -3.5(3) -3.1(3) C5 13.2(4) 12.3(4) 13.5(4) -0.1(3) -5-1(4) -2-5(3) C6 20.2(5) 16.4(5) 17.9(5) 0.1(4) -9.4(4) -6.7(4) C7 25.2(6) 22.4(6) 18.3(5) 0-2(4) -11.7(5) -8.3(5) C8 26.0(6) 24.4(6) 14.2(5) 3-2(4) -9.1(4) -9-3(5) C9 19.0(5) 17.8(5) 13.5(5) 1-7(4) -4.7(4) -6.3(4) CIO 13.7(4) 13.5(4) 16.3(5) -2.6(4) -4.8(4) -3-1(4)

[0406]

[0407] Cll 17-7(5) 18.4(5) 19.1(5) -1.8(4) -0.5(4) -0.8(4) Table 15: Bond lengths for Formula (II) Mn-complex

[0408] Atom Atom Length / A Atom Atom Length / A Mnl Ol11.8687(8) Nl Cl 1.4699(14) Mnl 01 1.8687(8) Nl C3 1.2906(14) Mnl 03 2.2646(8) Cl C2 1.5289(17) Mnl 0312.2646(8) C3 C4 1.4447(15) Mnl Nl11.9884(9) C4 C5 1.4105(15) Mnl Nl 1.9884(9) C4 C9 1.4075(15) 01 C5 1.3215(13) C5 C6 1.4113(15) 02 C2 1.4587(14) C6 C7 1.3802(16) 02 C3 1.3437(13) C7 C8 1.4004(18) 03 CIO 1.2368(13) C8 C9 1.3741(17) 04 CIO 1.2862(14) CIO Cll 1.5057(17)

[0409]

[0410] Table 16: Bond angles for Formula (II) Mn-complex

[0411] Atom Atom Atom Angle / " Atom Atom Atom Angle / " Ol1Mnl 01 180.0 C3 Nl Cl 108.94(9) Ol1Mnl O3191.76(4) Nl Cl C2 103.19(9) Ol1Mnl 03 88.24(4) 02 C2 Cl 104.53(9) 01 Mnl 03 91.76(4) 02 C3 C4 117.21(9) 01 Mnl O3188.24(4) Nl C3 02 115.94(10) Ol1Mnl Nl190.50(4) Nl C3 C4 126.85(10) 01 Mnl Nl 90.50(4) C5 C4 C3 120.34(10) 01 Mnl Nl189.50(4) C9 C4 C3 119.68(10) Ol1Mnl Nl 89.50(4) C9 C4 C5 119.98(10) O31Mnl 03 180.0 01 C5 C4 124.11(10) Nl Mnl O3187.83(3) 01 C5 C6 117.80(10) Nl1Mnl 03 87.83(3) C4 C5 C6 118.06(10) Nl1Mnl O3192.17(3) C7 C6 C5 120.90(11) Nl Mnl 03 92.17(3) C6 C7 C8 120.72(11) Nl1Mnl Nl 180.00(3) C9 C8 C7 119.29(11) C5 01 Mnl 131.43(7) C8 C9 C4 121.01(11) C3 02 C2 107.16(9) 03 CIO 04 122.79(11) CIO 03 Mnl 133.84(8) 03 CIO Cll 119.13(11) Cl Nl Mnl 124.20(7) 04 CIO Cll 118.08(10)

[0412]

[0413] C3 Nl Mnl 126.09(8)

[0414] Table 17: Hydrogen bonds for Formula (II) Mn-complex

[0415] D H A d(D-H) / A d(H-A) / A d(D-A) / A D-H-A / °

[0416]

[0417] 04 H4 O411.2196(9) 1.2196(9) 2.4393(17) 180.000(0)

[0418]

[0419] Table 18: Selected torsion angles for Formula (II) Mn-complex

[0420] A B C D Angle / " A B C D Angle / "

[0421] 02 C3 Nl Mnl 172.74(7) C5 01 Mnl Nl1-173.60(10) Cl Nl C3 02 2.44(13) C5 01 Mnl Nl 6.40(10)

[0422] C3 C4 C5 01 2.14(17) C5 C4 C3 02 -173.81(10) C3 C4 C5 C6 -179.74(10) C5 C4 C3 Nl 5.85(17)

[0423] C4 C3 Nl Mnl -6.92(16) C6 C5 01 Mnl 173.10(8) C4 C3 Nl Cl -177.22(10) C6 C5 C4 C9 0.76(16)

[0424] C4 C5 01 Mnl -8.77(17) C9 C4 C3 02 5.69(15)

[0425] C5 01 Mnl 03 98.59(10) C9 C4 C3 Nl -174.64(11)

[0426]

[0427] C5 01 Mnl O31-81.41(10) C9 C4 C5 01 -177.37(10)

[0428] Table 19: Hydrogen atom coordinates (AxlO4) and isotropic displacement parameters (A2xl03) for Formula (II) Mn-complex

[0429] Atom X y z U(eq.)

[0430] H1A 8850(30) 1780(19) 4441(19) 22(4)

[0431] H1B 6490(30) 2840(20) 5300(20) 25(4)

[0432] H2A 9270(30) 3540(20) 2540(20) 22(4)

[0433] H2B 7030(30) 4640(20) 3470(20) 23(4)

[0434] H4 0 5000 5000 47(9)

[0435] H6 1330(30) -200(19) 1913(19) 21(4)

[0436] H7 1040(30) 1100(20) -340(20) 25(4)

[0437] H8 2800(30) 3050(20) -1280(20) 33(5)

[0438] H9 4860(30) 3610(20) 140(20) 26(4)

[0439] H11A -2340(50) 4450(30) 7160(30) 65(8)

[0440] HUB -990(50) 3610(30) 8300(30) 76(9)

[0441] H11C -2230(50) 2930(30) 7740(30) 74(9)

[0442]

[0443] Example 2 - Preparation Bleach Catalyst Formulation (Bleach Catalyst of Formula (II) adsorbed on carrier):

[0444] General Catalyst on carrier preparation:

[0445] Catalyst is dissolved in enough MeOH to ensure slurry formed with carrier stays mobile when carrier is charged and slurry stirred. After 0.25 h stirring at room temperature, the mixture is concentrated in vacuo to give a powder. Catalyst (formula (II) Mn-complex) on TiOz was prepared as follows:

[0446] Catalyst (50 g, 100 mmol, 9 wt.%) was dissolved in MeOH (300 mL, 6 vol.). Titanium oxide (500 g, 91 wt.%) was charged to the catalyst solution. After 0.25 h stirring at room temperature, the mixture was concentrated in vacuo to give a free-flowing powder in quantitative yield.

[0447] Pre-formulation with TAED of catalyst (formula (II) Mn-complex) on TiOz was prepared as follows: There is a benefit for the automatic dishwash detergent industry to use a pre-formulated catalyst ingredient to improve consistent dosing of catalyst into tablet or its evenly distribution into detergent powder. This pre-formulation can also provide low-dust material for safer detergent manufacture.

[0448] Prepared catalyst on solid support (50 g, 34.5 wt.%) was charged to a low shear mixer with TAED (81 g, 55.9 wt.%) and Eumulgin B25 as binder (14 g, 9.6 wt.%). The formulation was then mixed with an external temperature of 50 °C applied to melt the binder for 0.5 h. After cooling the pre-formulated product is isolated as a monodisperse granular solid.

[0449] Catalyst (formula (II) Mn-complex) on zeolite was prepared as follows:

[0450] Catalyst (50 g, 100 mmol, 9 wt.%) was dissolved in MeOH (300 mL, 6 vol.). Zeolite support (500 g, 91 wt.%) was charged to the catalyst solution. After 0.25 h stirring at room temperature, the mixture was concentrated in vacuo to give a free-flowing powder in quantitative yield.

[0451] Pre-formulation with TAED of catalyst (formula (II) Mn-complex) on zeolite was prepared as follows:

[0452] There is a benefit for the automatic dishwash detergent industry to use a pre-formulated catalyst ingredient to improve consistent dosing of catalyst into tablet or its evenly distribution into detergent powder. This pre-formulation can also provide low-dust material for safer detergent manufacture.

[0453] Prepared catalyst on solid support (50 g, 34.5 wt.%) was charged to a low shear mixer with TAED (81 g, 55.9 wt.%) and Eumulgin B25 as binder (14 g, 9.6 wt.%). The formulation was then mixed with an external temperature of 50 °C applied to melt the binder for 0.5 h. After cooling the pre-formulated product is isolated as a monodisperse granular solid.

[0454] Example 3 - Stain bleaching tests

[0455] General Bleach Catalyst Stain Removal Test Standard pre-stained melamine tiles (DM-14, Highly discriminative tea; DM-81, Coffee; DM-82, Espresso coffee; DM-51 Red wine; and DM-62, Curry) from the Center for Testmaterials (CFT, The Netherlands) were used for this test to demonstrate stain removal in automatic dishwashing application.

[0456] Bleach performance test by stain removal from pre-stained tile pieces was achieved by dissolving 1 g of standard detergent Type D IEC 60436 (from supplier Centre For Testmaterials BV, composition shown in table 20) in 1 L of tap water at 40 °C.

[0457] Table 20: Standard detergent Type D composition.

[0458] Component Amount (wt.%)

[0459] Sodium citrate dihydrate 30.0

[0460] Maleic acid / Acrylic acid 12.0

[0461] Sodium percarbonate 7.0

[0462] TAED 2.0

[0463] Sodium disilicate 10.0

[0464] Linear fatty alcohol ethoxylate 2.0

[0465] Protease (Savinase 6T) 1.0

[0466] Amylase (Termamyl 120T) 0.5

[0467] Sodium carbonate 35.5

[0468]

[0469] When testing catalysts in solution, 5 mL of a prepared 1 mmol catalyst solution in deionized water was charged to the above IL Type D solution; and for solid catalyst testing a mass equivalent to 5 mmol catalyst was charged directly to the solution.

[0470] The stain test plate of interest was then half submerged in the stirred solution at 40 °C before adding 5 mL of a 0.75 M H2O2 solution. Test pieces were submerged for a total of 10 minutes from the addition of H2O2 before rinsing with deionised water and allowed to dry in air.

[0471] Stain removal from stained plates was conducted using the above method, with the performance quantified by colorimetric analysis using L*a*b* values to calculate the stain removal index (SRI), which uses the below formula:

[0472] SRI = 100 — E A

[0473]

[0474] E — (LtLQ)2+ (ata0)2+ (btb0)2

[0475] t = clean tea-stained tile

[0476] 0 = unstained tile

[0477] The average L*a*b* values and average SRI are provided in Table 21 below, which compares the ratio of bleach catalyst to carrier:

[0478] Table 21: Comparison of different ratio of Formula (II) Mn-complex: TiCh in the bleaching of DM14 tea stains vs benchmark (MnTACN) or pure Formula (II) Mn-complex.

[0479] Average

[0480] Sample L* a* b* S. D.

[0481] SRI

[0482] Unstained 92.7 -0.9 2.3

[0483] Blank 88.3 0.50 14.0 87.4 0.82 MnTACN - 5mL,

[0484] 91.1 0.29 lmmol. 90.6 -0.33 10.9

[0485] Formula (II) Mn- 89.6 0.42 complex (6mg) 89.2 0.13 12.0

[0486] Formula (II) Mn- complex: TiO290.0 -0.32 11.9 90.0 0.21 l:20 (120mg)

[0487] Formula (II) Mn- complex: TiO289.6 -0.40 10.5 91.2 0.37 1:10 (60mg)

[0488] Formula (II) Mn- complex: TiO289.5 -0.07 11.4 90.3 0.61 1:8 (48mg)

[0489] Formula (II) Mn- complex: TiO289.0 -0.38 11.4 90.1 0.37 1:6 (36mg)

[0490]

[0491] The above results show an improved bleaching performance for Formula (II) Mn-complex supported on TiO2over pure catalyst. Optimum 1:10 ratio allows to match performance of benchmark. The average L*a*b* values and average SRI are provided in Table 22 below, which compares the ratio of different bleach catalysts when adsorbed onto a carrier:

[0492] Table 22: Comparison of different ratio of different Mn complexes on the bleaching of DM14 tea stains when adsorbed on a carrier.

[0493] Average

[0494] Sample L* a* b* S. D.

[0495] SRI

[0496] Unstained 92.7 -0.9 2.3

[0497] Blank 89.2 0.05 12.1 89.5 0.38

[0498] TiO2blank (60mg) 88.7 -0.02 11.9 89.6 0.52 AI2O3 blank (60mg) 88.4 -0.15 11.8 89.5 0.44 MnTACN (5mL of

[0499] 90.6 -0.33 10.9 91.1 0.29 lmmol. Solution)

[0500] MnTACN: TiO2

[0501] 89.5 -0.30 9.8 91.8 0.36

[0502] 1:10 (50mg)

[0503] MnTACN: AI2O31: 10

[0504] 89.9 0.10 10.5 91.3 0.20 (50mg)

[0505] Formula (II) Mn- 89.4 -0.17 11.0 90.7 0.23 complex (6mg)

[0506] Formula (II) Mn- complex: TiO21:10 90.1 -0.50 10.2 91.7 0.26 (60mg)

[0507] Formula (II) Mn- complex: AI2C>3 1:10 89.4 -0.25 10.4 91.2 0.32 (60mg)

[0508] Formula (II) Mn- complex: zeolite 1:10 89.6 0.3 13.0 88.7 0.33

[0509] (60mg)

[0510]

[0511] TiO2or AI2O3 alone (respective blanks) has no effect on stain bleaching. Yet we see an improvement on average SRI when these carriers are used with MnTACN or Formula (II) Mn-complex. The largest average SRI improvement is for use with Formula (II) Mn-complex. The average L*a*b* values and average SRI are provided in Table 23 below, which compares the performance of commercial benchmarks against formula(ll) formulations of bleach catalyst to carrier:

[0512] Table 23: Comparison of different MnTACN benchmark or Formula (II) Mn-complex pre-formulations on the bleaching of DM14 tea stains.

[0513] Average

[0514] Sample L* a* b* S. D.

[0515] SRI

[0516] Unstained 92.7 -0.90 2.3

[0517] Blank 88.3 0.50 14.0 87.4 0.82 WeylClean

[0518] FDO XP

[0519] (~1.9%

[0520] 91.1 -0.10 10.6 91.5 0.67 MnTACN,

[0521] ~71% TAED)

[0522] (200mg)

[0523] WeylClean

[0524] FDO PP6

[0525] (~6.0% 90.6 -0.12 9.9 92.1 0.34 MnTACN)

[0526] (70mg)

[0527] Formula (II)

[0528] Mn-complex

[0529] 89.6 -0.40 10.5 91.2 0.37

[0530] : TiO2

[0531] 1:10 (60mg)

[0532] Preformulated

[0533] Formula (II)

[0534] Mn-complex 90.9 -0.25 10.1 91.9 0.43 on TiO2with

[0535] TAED

[0536] (200mg)

[0537] Preformulated 90.7 0.2 10.9 91.0 0.66 Formula (II)

[0538]

[0539] Mn-complex

[0540] on zeolite

[0541] with TAED

[0542] (200mg)

[0543]

[0544] " Pre-formulated Formula (II) Mn-complex on TiO2with TAED" closely matches bleaching performances of MnTACN pre-formulation (FDO XP and FDO PP6) benchmarks.

[0545] The average L*a*b* values and average SRI are provided in Table 24 below, which compares the performance of benchmarks and formula(ll) formulations on different stains:

[0546] Table 24: Comparison the bleaching performance of MnTACN benchmark, Formula (II) Mn-complex and their pre-formulations on the bleaching of different stains.

[0547] Average

[0548] Sample L* a* b* S. D.

[0549] SRI

[0550] Unstained 92.7 -0.9 2.3

[0551] Curry 92.0 -3.1 18.2 83.9 0.15

[0552] Red

[0553] 86.5 0.67 9.4 90.5 0.44 Blank wine

[0554] Coffee 90.9 -0.97 9.6 92.5 0.21 Espresso 92.6 -0.97 7.8 94.5 0.05 Curry 92.3 -3.6 18.3 83.8 0.30 MnTACN (5mL Red

[0555] 93.4 0.34 of lmmol. wine 89.4 -0.37 8.0

[0556] solution) Coffee 92.5 -0.93 7.5 94.8 0.16 Espresso 93.1 -1.1 7.3 95.0 0.14 WeylClean Curry 92.7 -2.9 13.7 88.5 0.19 FDO XP (~1.9% Red

[0557] 88.8 0.17 10.2 91.1 0.20 MnTACN, wine

[0558] ~71% TAED) Coffee 91.8 -1.1 8.1 94.1 0.17 (200mg) Espresso 92.4 -1.1 7.9 94.4 0.06 Formula (II) Curry 92.3 -2.9 17.7 84.5 0.46 Mn-complex Red

[0559] 87.6 0.47 8.9 91.6 0.37 (6mg) wine

[0560]

[0561] Coffee 90.6 -1.0 8.7 93.2 0.21

[0562] Espresso 92.2 -1.1 7.3 94.9 0.14 Curry 92.3 -3.4 17.6 84.5 0.23 Formula (II)

[0563] Red

[0564] Mn-complex: 87.9 0.23 8.5 92.1 0.18

[0565] wine

[0566] TiO2

[0567] Coffee 92.0 -1.1 7.4 94.8 0.32

[0568] 1:10 (60mg)

[0569] Espresso 92.3 -0.90 7.4 94.8 0.07

[0570]

[0571] On above stains, catalyst on TiO2 achieve slightly better or similar bleaching as the pure catalyst. Both have comparable performances to MnTACN and its pre-formulation benchmarks.

Claims

CLAIMS1. A bleach catalyst formulation comprising:a bleach catalyst; anda solid support carrier,wherein the bleach catalyst comprises at least one metal coordinated to at least one ligand of formula (I) having the structure:whereinn is 1 or 2;m is 1 to 4, when the or each R independently represents H, or m is 1 or 2, when the or each R independently represents CH3, C2H5, C3H7, C4H9, OH, OR1, or NR22;wherein R1represents CH3(CH2)V, wherein v is 0 to 17, which chain may be hydroxy- or alkoxy-terminated;wherein R2represents H or CH3(CH2)W, wherein w is 0 to 17, or wherein R2represents alkoxyalkyl;R' represents H, CH3, CH2CH3, CH(CH3)2, (CH2)yOH, or (CH2)yCOOH, wherein y is 0 to 17; R" represents H, CH3, CH2CH3, CH2OH, CH2CH2OH, CH2OCH3, or CH2CH2OCH3; R'" represents H, or C(O)R3,wherein R3represents (CH2)ZR4or -R5-R6, wherein z is from 1 to 18 and R4is H, OH, or COOH; or, wherein R5represents Ci to C4alkyl; and R6represents H, CH3, OH, COOH, OCH3, OCH2CH2OH, OCH2CH2OCH3, or CH(OH)CH2OH.

2. The bleach catalyst formulation according to Claim 1, wherein the bleach catalyst comprises an Mn(lll) metal ion coordinated to two ligands of formula (II) having the structure:(ID-3. The bleach catalyst formulation according to either Claim 1 or Claim 2, wherein the solid support carrier is an inorganic carrier or a carbon-based carrier.

4. The bleach catalyst formulation according to Claim 3, wherein, when the solid support carrier is an inorganic carrier, it is from a titanium oxide, an aluminium oxide, silicas, zeolites, or a mixture thereof, optionally wherein it is TiO2or Al2O3.

5. The bleach catalyst formulation according to Claim 3, wherein, when the solid support carrier is a carbon-based carrier, it is activated carbon, mesoporous carbonaceous material, cellulose and its derivatives, starch, lignin, lignosulfonates, kraft softwood lignin, hydrochar, biochar, or a mixture thereof.

6. The bleach catalyst formulation according to any one of Claims 1 to 5, wherein the solid support carrier is insoluble, or partially insoluble.

7. The bleach catalyst formulation according to any one of Claims 1 to 6, wherein the solid support carrier is treated with additives to enhance or provide further functionality, to modify its properties with regards to adsorption and release of bleach catalyst, to enhance physical or chemical stability, and / or to modify its behaviour in end-formulations or applications.

8. The bleach catalyst formulation according to any one of Claims 1 to 7, wherein the solid support carrier is provided as a particulate material, optionally wherein the particulate material has a particle size of less than about 250 pm, and / or wherein the particulate material has a mean surface area of from about 2 to about 800 m2 / g.

9. The bleach catalyst formulation according to any one of Claims 1 to 8, wherein the formulation comprises an amount of from about 1 to about 15 wt.% bleach catalyst.

10. The bleach catalyst formulation according to any one of Claims 1 to 9, wherein the formulation comprises a ratio of bleach catalyst to solid support carrier of about 1:1 to about 1:100.

11. The bleach catalyst formulation according to any one of Claims 1 to 10, wherein the formulation comprises at least 10 wt.% solid support carrier.

12. A detergent composition comprising the bleach catalyst formulation according to any one of Claims 1 to 11, and a surfactant.

13. The detergent composition according to Claim 12, wherein the detergent composition comprises at least 0.001 wt.% bleach catalyst formulation according to any one of Claims 1 to 11.

14. The detergent composition according to either Claim 12 or 13, wherein the composition comprises the surfactant in an amount of from about 1 to about 25 wt.%.

15. The detergent composition according to any one of Claims 12 to 14, wherein the surfactant is a detersive surfactant, and / or the surfactant is an anionic, non-ionic, zwitterionic or cationic surfactant.

16. The detergent composition according to any one of Claims 12 to 15, wherein the composition further comprises a bleach activator, optionally wherein the bleach activator is TAED.

17. The detergent composition according to any one of Claims 12 to 16, wherein the composition further comprises a sequestrant.

18. The detergent composition according to any one of Claims 12 to 17, wherein the composition further comprises an oxidative bleach, optionally wherein the oxidative bleach is sodium percarbonate.

19. The detergent composition according to any one of Claims 12 to 18, wherein the composition further comprises a binder, a filler, and / or a dispersing agent.

20. The bleach catalyst formulation according to any one of Claims 1 to 11, or the detergent composition according to any one of Claims 12 to 19, wherein the formulation or composition further comprises at least one ancillary compound, optionally selected from one or more of:surfactant(s);detergent(s);bleach(es);carrier compound(s);stabilizer(s); and / ordispersant(s).

21. Use of the formulation according to any one of Claims 1 to 11, or the detergent composition according to any one of Claims 12 to 20 as a bleach catalyst.

22. The use of the formulation or composition according to Claim 21, in laundry detergents, automatic dishwashing, the bleaching of paper, textiles, stains, hair, and teeth or in wastewater treatment, optionally wherein the use of the formulation or composition is in laundry detergents or automatic dishwashing, for the discolouration, oxidation and solubilisation of stains and other soiling.

23. A method for bleach catalysis comprising contacting the formulation according to any one of Claims 1 to 11, or the detergent composition according to any one of Claims 12 to 20 with a bleach under conditions effective to allow the compound to enhance a bleaching process.

24. A system for enhancing bleach catalysis, comprising the formulation of a bleach catalyst with a solid support.

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