Co-granules comprising bleaching catalyst, bleaching activator, binder and zinc or bismuth salt, and bleaching and cleaning agent comprising same

Abstract

Disclosed are co-granules comprising a) a Manganese complex salt comprising at least one selected carbo-aza-cyclic ligand, a selected non-coordinating counter ion and having a water-solubility of at least 30 g / L at 20° C, b) a seleted zinc or bismuth salt having a water-solubility of at least 30 g / L at 20° C, c) a binder, and d) a bleaching activator. The co-granules and formulations comprising these are suitable for use in catalysing oxidation, for example as a component of a laundry or dishwasher bleaching composition. The invention further relates to cleaning agents, preferably ADW formulations, comprising the co-granules described herein.

Description

FIELD OF THE INVENTION

[0001] The present invention concerns storage-stable co-granules comprising selected ingredients. The invention also concerns bleaching formulations and detergents comprising said co-granules and a peroxy compound. The co-granules and bleaching formulations comprising them are suitable for use in catalysing oxidation, for example as a component of a laundry or dishwasher bleaching composition.BACKGROUND

[0002] Transition metal complexes, such as manganese catalysts based on triazacyclononane ligands are known to be active catalysts in the bleaching of stains in laundry detergent products and in dishwash products and for treatment of cellulosic substrates in e.g. wood-pulp or raw cotton (see for example EP 0 458 397 A2 (Unilever NV and Unilever plc) and WO 2006 / 125517 A1 (Unilever pic et al.).

[0003] Since these catalysts are very effective, only small amounts of them need to be used in bleaching detergent or dishwash formulations, often at levels less than 0.1 wt% in the detergent or dishwasher formulation. A difficulty arising from the use of such low dosing is achieving accurate dosing of the catalyst and homogeneous distribution throughout the formulation. When distribution of the catalyst is heterogeneous in a formulation, the use of such detergent formulations in a washing machine or in handwashing can lead to underdosing (i.e. giving a poorer bleaching performance) or overdosing of the catalyst (i.e. giving rise to excessive hydrogen peroxide decomposition and possibly brown spotting).

[0004] A well-known approach to circumvent this potential problem is the presentation / inclusion of the solid catalyst on a solid support in bleaching formulations.

[0005] Numerous patents and patent applications disclose granules containing bleaching catalyst, bleaching activator and binder. Examples for these documents are EP 0 544 440 A2, WO 94 / 21777 A1, WO 95 / 06710 A1, WO 95 / 06711 A1, WO 2018 / 011596 A1, WO 2018 / 210442 A1, EP 3 167 036 B, EP 2 966 161 A1, WO 2017 / 118543 A1, WO 2017 / 153528 A1 and WO 2016 / 177439 A1.

[0006] Coated granules comprising Mn-catalysts with good water-solubility are disclosed in WO 2022 / 058039 A1. These granules are preferably used in automatic dishwashing (ADW) formulations. In dishwashing formulations often glass protecting agents are contained, for example zinc or bismuth salts.

[0007] Whilst various patent documents describe granules and related compositions in bleaching formulations, for example of use in dishwashing and laundry applications to ensure accurate dosing of bleach activating catalysts, there remains still a need to improve useful stability of said catalysts in detergent formulations upon storage and to provide granules comprising new ingredients. The present invention is intended to address these needs.SUMMARY OF THE INVENTION

[0008] To control glass corrosion, washing and cleaning compositions, in particular dishwasher detergents, incorporate at least one zinc or bismuth salt. In granules for ADW formulations often Manganese-1,4,7-triazacyclononane bleach catalysts comprising PF 6 -< anion (Mn-TACN PF6) and ZnCO 3 are used. In some markets the use of phosphor-containing ingredients is not allowed. As an alternative, bleach catalysts with other anions, e.g. a Manganese-1,4,7-triazacyclononane bleach catalyst comprising SO 4 2-< anion could be used.

[0009] However, experiments have shown that when adding basic zinc salts, such as ZnCO 3 , to granules containing highly soluble Mn bleaching catalysts, such as Manganese-1 ,4,7-triazacyclononane bleach catalyst comprising SO 4 2-< anion, this leads to instability, formation of MnO 2 and less cleaning activity of this granule in the dishwash cleaning formulation.

[0010] Surprisingly we have found that when using less basic zinc or bismuth salts, e.g. zinc sulfate or bismuth sulfate, in combination with a highly water-soluble Mn-containing bleach catalyst this results in a much better performance and also shows a much better storage stability in the ADW formulation compared to a Mn-TACN-PF 6 / ZnCO 3 or a Mn-TACN-PF 6 / BiCO 3 containing formulation.

[0011] Viewed from a first aspect, therefore, the invention provides a co-granule comprising a) a Manganese complex salt comprising at least one ligand of formula (I) wherein: p is 3; R is independently selected from the group consisting of hydrogen, C 1 -C 24 -alkyl, CH 2 CH 2 OH and CH 2 COOH; or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via a C 2 -C 6 alkylene bridge, a C 6 -C 10 arylene bridge or a bridge comprising one or two C 1 -C 3 alkylene units and one C 6 -C 10 arylene unit, which bridge may be optionally substituted one or more times with independently selected C 1 -C 24 alkyl groups; and R 1 , R 2 , R 3 , and R 4 are independently selected from H, C 1 -C 4 alkyl and C 1 -C 4 -alkylhydroxy, wherein the manganese complex salt has a water-solubility of at least 30 g / L at 20° C and has a non-coordinating counter ion selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates and dicarboxylate monoesters, b) a zinc salt or a bismuth salt having a water-solubility of at least 30 g / L at 20° C and being selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates, dicarboxylate monoesters and acetylacetonates, c) a binder, and d) a bleaching activator.

[0012] Viewed from a second aspect, the invention provides a method of manufacturing said co-granules, said method comprising a) providing in a mixing device a composition containing components a), b), c) and d) defined above in solid form or combined with water, and b) mixing the components of said composition until co-granules are formed.

[0013] Viewed from a third aspect, the invention provides a bleaching formulation comprising co-granules according to the first aspect of the invention.

[0014] Viewed from a fourth aspect, the invention provides a cleaning method comprising contacting a substrate with water and a bleaching formulation according to the third aspect of the invention.

[0015] Further aspects and embodiments of the present invention will be evident from the discussion that follows below.DETAILED DESCRIPTION

[0016] As summarised above, the present invention is based, in part, on the finding that storage-stable co-granules may be prepared by combining selected bleaching catalysts, which are selected manganese complex salts comprising at least one ligand of formula (I) and at least one selected anion, preferably mononuclear or dinuclear manganese complexes comprising ligands of formula (I) described herein, bleaching activators, binders and selected zinc or bismuth salts.

[0017] Surprisingly, the co-granules of the present invention show improved storage stability and increased bleaching activity, compared to co-granules containing conventional PF 6 -< containing bleaching catalysts and basic zinc salts.

[0018] The term "water-soluble" when used in this description is meant to describe a bleaching catalyst a) which is soluble in water of 20 °C at a concentration of at least 30 g / L.

[0019] Typically, the bleaching catalyst a) is formed from and comprises a polydentate ligand containing 3 to 6 nitrogens atoms, which atoms coordinate to a manganese ion of the catalyst. The bleaching catalyst is typically in the form of a complex of the general formula (A1)         [M a LG k X n ]Y m      (A1) in which: M represents a ion selected from Mn(III)-(IV); LG represents a polydentate ligand as described herein and wherein at least one of the ligands LG is a ligand of formula (I) as described herein; each X independently represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate a transition metal ion in a mono, bi or tridentate manner, preferably selected from O 2-< , R 8< BO 2 2-< , R a< COO -< , R a< CONR -< , OH -< , NO 3 -< , NO, S 2-< , R a< S -< , PO 4 3-< , PO 3 OR a3-< , H 2 O, CO 3 2-< , HCO 3 -< , R a< OH, N(R a< ) 3 , R a< OO -< , O 2 2-< , O 2 -< , R a< CN, Cl -< , Br -< , OCN -< , SCN -< , N 3 -< , F -< , I -< , R a< O -< , ClO 4 -< , and CF 3 SO 3 -< , and more preferably selected from O 2< , R a< BO 2 2-< , R 8< COO -< , OH -< , NO 3 -< , S 2-< , R 8< S -< , PO 3 4-< , H 2 O, CO 3 2-< , HCO 3 -< , R a< OH, N(R a< ) 3 , Cl -< , Br -< , OCN -< , SCN -< , R a< CN, N 3 -< , F -< , I -< , R a< O -< , ClO 4 -< , and CF 3 SO 3 -< ; each R a< independently represents a group selected from hydrogen, hydroxyl, -R" and -OR", wherein R" is selected from C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 20 -heterocycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -heteroaryl, (C=O)H, (C=O)-C 1 -C 20 -alkyl, (C=O)-C 6 -C 10 -aryl, (C=O)OH, (C=O)O-C 1 -C 20 -alkyl, (C=O)O-C 6 -C 10 -aryl, (C=O)NH 2 , (C=O)NH(C 1 -C 20 -alkyl), (C=O)NH(C 6 -C 10 -aryl), (C=O)N(C 1 -C 20 -alkyl) 2 , (C=O)N(C 6 -C 10 -aryl) 2 , 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', -NH 2 , -NHR', -N(R') 2 , -N(R') 3 +< , -C(O)R', -OC(O)R', -COOH, -COO -< (Na +< , K +< ), -COOR', -C(O)NH 2 , -C(O)NHR', -C(O)N(R') 2 , heteroaryl, -R', -SR', -SH, -P(R') 2 , -P(O)(R') 2 , -P(O)(OH) 2 , -P(O)(OR') 2 , -NO 2 , -SO 3 H, -SO 3 -(Na +< , K +< ), -S(O) 2 R', -NHC(O)R', and -N(R')C(O)R', wherein R' represents C 6 -C 10 -aryl, C 7 -C 20 -arylalkyl, or C 1 -C 20 -alkyl each of which may be each of which may be optionally substituted by -F, -Cl, -Br, -I, -NH 3 +< , -SO 3 H, -SO 3 -< (Na +< , K +< ), -COOH, -COO -< (Na +< , K +< ), -P(O)(OH) 2 , or -P(O)(O -< (Na +< , K +< )) 2 , and preferably each R a< independently represents hydrogen, C 1 -C 20 -alkyl or optionally C 1 -C 20 alkyl-substituted C 6 -C 10 -aryl, more preferably hydrogen or optionally substituted phenyl or naphthyl, or C 1-4 -alkyl; Y is a non-coordinating counteranion selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, perchlorate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates and dicarboxylate monoesters, a is an integer from 1 or 2 and most preferred 2; k is an integer from 1 to 4; and preferably 1 or 2; n is an integer from 0 to 4; and preferably 0 to 2; m is an integer from 1 to 8, preferably from 1 to 2.

[0020] As used herein, within the definitions provided above for formula (A1) and elsewhere, unless the context expressly dictates to the contrary, references to alkyl moieties, by which is meant saturated hydrocarbyl radicals, embrace alkyl groups that may comprising branched and / or cyclic portions. Likewise, references to alkenyl and alkynyl moieties embrace groups that may comprise branched and / or cyclic portions.

[0021] The counter anions Y in formula (A1) balance the charge z on the complex formed by the chelating ligand(s) LG, metal ion(s) M and coordinating species X. According to this invention the charge z is positive, and Y is anion as defined above. Preferably, the manganese ion-containing bleaching catalyst is a catalyst salt comprising one or two manganese ions and one or more non-coordinating counteranions Y.

[0022] Suitable counter ions Y include those which give rise to the formation of water-soluble manganese complexes forming storage-stable solids. Often counterions Y are selected from Cl -< , Br -< , I -< , NO 3 -< , ClO 4 -< , R c< SO 3 -< , HSO 4 -< , SO 4 2-< , R c< SO 4 -< , R d< SO 3 -< , CF 3 SO 3 -< , and R c< COO -< , with R c< in this context being selected from H, C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted) and with R d< in this context being selected from C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted). Often, these anions Y will be selected from Cl -< , NO 3 -< , tosylate, SO 4 2-< , CF 3 SO 3 -< , acetate, and benzoate. Particularly often, these anions Y will be selected from the group consisting of Cl -< , NO 3 -< , SO 4 2-< and acetate.

[0023] The manganese ion-containing bleaching catalyst a) according to formula (A1) typically comprises, as chelating ligand(s) LG, one or more tridentate, tetradentate, pentadentate, or hexadentate nitrogen donor ligands. It will be understood that the terms tridentate, tetradentate, pentadentate and hexadentate refer to the number of manganese ion-binding donor atoms (in this case being nitrogen donor atoms) that can bind to a manganese ion. For example, a tridentate nitrogen donor refers to an organic molecule that contains three nitrogen atoms with lone pairs, which can bind to a manganese ion. These nitrogen donor atoms can be either an aliphatic nitrogen donor, either a tertiary, secondary or primary amine, or a nitrogen donor belonging to an aromatic ring, for example pyridine. Whilst the name suggests that all nitrogen donors present in a ligand bind to a manganese ion-containing complex, this need not necessarily be so. For example, when a ligand is a hexadentate nitrogen donor, it suggests that the ligand can bind with 6 nitrogen donor atoms, but it may only bind with 5 nitrogen donor atoms, leaving one coordination site open to bind to another molecule, such as the hydrogen peroxyl anion. This discussion presumes that a manganese ion can bind to 6 donor atoms, which is generally, but not always, the case.

[0024] The manganese ion containing bleaching catalyst a) used according to the invention comprises a chelating ligand of formula (I): wherein Q, p, R, R 1 , R 2 , R 3 , and R 4 are as hereinbefore described.

[0025] Ligands of formula (I) form complexes with, for example, one or two manganese ions, which complexes may be, or constitute part of, the bleaching catalyst.

[0026] Transition metal catalyst salts having significant water-solubility, such as at least 30 g / l at 20 °C, e.g. at least 50 g / l at 20 °C or at least 70 g / l at 20 °C, are described in WO 2006 / 125517 A1. On account of their high water solubility, the use of such salts, for example those comprising small counterions such as chloride, nitrate, sulfate and acetate, can be advantageous. Also, catalyst salts comprising the tosylate anion, such as those described in WO 2011 / 066934 A1 and WO 2011 / 066935 A1 (both Clariant International Ltd) are also contemplated according to specific embodiments of the aspects of the present invention.

[0027] Preferred components a) are mononuclear or dinuclear Mn(III) and / or Mn(IV) complexes comprising one or two ligands of formula (I) as herein defined.

[0028] Typically, the Mn(lll) and / or Mn(IV) complex is a dinuclear complex and the subsequent discussion focuses on these. However, the use of mononuclear manganese complexes is also within the scope of the present invention. These manganese complexes are mostly applied as salts. Examples of such complexes are described in EP 0 549 271 A1, EP 0 549 272 A1, EP 0 544 519 A2 and EP 0 544 440 A2.

[0029] According to particular embodiments, each R in the ligand of formula (I) is independently selected from: CH 3 , C 2 H 5 , CH 2 CH 2 OH and CH 2 COOH.

[0030] According to further preferred embodiments R 1 , R 2 , R 3 , and R 4 in the ligand of formula (I) are independently selected from hydrogen and methyl, in particular embodiments in which each of R 1 , R 2 , R 3 , and R 4 is hydrogen.

[0031] When a ligand of formula (I) comprises one group R linked to the nitrogen atom (i.e. N) of another Q of another ring of formula (I) via a bridge, it will be understood that such ligands of formula (I) in particular embodiments comprising an ethylene bridge may alternatively be represented by the following structure: wherein R, R 1 , R 2 , R 3 , and R 4 are as herein defined, including the various specific embodiments set out.

[0032] According to particular embodiments of the invention, the ligand of formula (I) is 1,4,7-triazacyclononane (TACN), 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triaza-cyclonan-1-yl)-ethane (Me 4 -DTNE). According to still more particular embodiments of the invention, the ligand of formula (I) is TACN or Me 3 -TACN.

[0033] The salt of the complex may comprise both coordinating ligands (i.e. which coordinate to one or two manganese ions in the complex of the salt) and non-coordinating ligands (i.e. which do not coordinate to a manganese ion).

[0034] Preferred mononuclear Mn(lll) and / or Mn(IV) complexes comprise one coordinating ligand of formula (I). Preferred dinuclear Mn(lll) and / or Mn(IV) complexes comprise either two coordinating ligands of formula (I), or one coordinating ligand of formula (I) where this comprises one ethylene or propylene group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, as described herein, e.g. is Me 4 -DTNE.

[0035] Additionally, Mn(III) and / or Mn(IV) complexes may comprise additional coordinating ligands. For dinuclear complexes, these are typically oxide (O 2-< ) or C 1-6 carboxylate (i.e. RCO 2 -< wherein R is an alkyl group) ions, which bridge the two manganese ions. Where present, an alkylcarboxylate ion is typically acetate. Typically, dinuclear Mn(III) and / or Mn(IV) complexes comprise two or three bridging oxide ions. For example, dinuclear manganese ion-containing complexes may comprise two oxide ions and one acetate ion, each of which bridges the two manganese ions; or three oxide ions, each of which bridges the two manganese ions.

[0036] According to particular embodiments of all aspects of the invention, there is contemplated the use of dinuclear manganese ion-containing complexes comprising two ligands of formula (I) which do not comprise one group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, for example TACN or Me 3 -TACN, in which the manganese ions are bridged by three oxide ions. According to particular embodiments, such complexes comprise two Mn(IV) ions. For example, the complex may be [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ] 2+< , "µ" denoting, according to convention, a bridging ligand.

[0037] According to other particular embodiments of all aspects of the invention, there is contemplated the use of dinuclear manganese ion-containing complexes comprising one ligand of formula (I) which does comprise one ethylene or propylene group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, for example Me 4 -DTNE, in which the manganese ions are bridged by two oxide ions and one acetate ion. According to particular embodiments, such complexes comprise one Mn(IV) ion and one Mn(III) ion. For example, the complex of the salt may be [Mn III< Mn IV< (µ-O) 2 (µ-CH 3 COO)(Me 4 -DTNE)] 2+< .

[0038] The mononuclear or dinuclear manganese ion-containing complex of the salt has an overall positive charge, which is balanced by one or more non-coordinating counteranions Y defined above. The counteranion(s) Y will typically be selected from Cl -< , Br -< , I -< , NO 3 -< , ClO 4 -< , R'SO 3 -< , HSO 4 -< , SO 4 2-< , RSO 4 -< , CF 3 SO 3 -< , and RCOO -< , with R in this context being selected from H, C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted) and R'in this context being selected from C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted). Often, these anions Y will be selected from Cl -< , NO 3 -< , tosylate, SO 4 2-< , CF 3 SO 3 ', acetate, and benzoate. Particularly often, these anions Y will be selected from the group consisting of Cl -< , NO 3 -< , SO 4 2-< and acetate.

[0039] Particularly preferred water-soluble bleaching catalysts a) are [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ]SO 4 (abbreviated as Mn-TACN SO 4 ) and [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ](NO 3 ) 2 (abbreviated as Mn-TACN NO 3 ).

[0040] Manganese catalyst salts a) having significant water-solubility, such as at least 30 g / l at 20 °C, or at least 50 g / l at 20 °C or at least 70 g / l at 20 °C, are described in WO 2006 / 125517 A1. The use of such highly water-soluble salts, for example those comprising small counterions such as chloride, nitrate, sulfate and acetate, can be advantageous since their high solubilities in water mean, for example, that more concentrated solutions of the salts can be used when contacting them with the other ingredients of the co-granules of this invention than when using poorly water-soluble salts, such as those comprising the PF 6 -< ion. For example, [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ] 2+< (PF 6 -< ) 2 has a water solubility of only 10.8 g / l at 20 °C. Moreover, salts of anions such as PF 6 -< are typically formed by introduction of the PF 6 -< ion as a potassium salt after the formation of the transition metal ion-containing complex, which leads to precipitation of the resultant salt. This precipitate is then typically redissolved, for example in water, prior to contacting with the other ingredients of the co-granules of this invention. Such additional steps introduce complexity and cost, as well as often occasioning the use of relatively large volumes of water in view of the low solubility in water of the manganese catalyst salts comprising PF 6 -< non-coordinating counterions.

[0041] Combinations of manganese complex salts a) can also be used.

[0042] In an embodiment, the co-granules comprise between 0.1 and 25 wt-% of the manganese complex salt a). Preferably, the co-granules comprise between 0.5 and 20 wt-%, more preferred between 1 and 15 wt-%, and still more preferred between 1.5 and 5 wt-% of the manganese complex salt a). The percentages relate to the total mass of the co-granules.

[0043] In an embodiment, the manganese complex salt a) is dosed as a solution with a concentration of at least 2 wt-% of dried complex. Suitably, the solution is an aqueous solution comprising between 2 wt-% and 75 wt-%, preferably between 2 wt-% and 50 wt-%, more preferred between 3 wt-% and 30 wt-% still more preferred between 5 wt-% and 25 wt-%, and most preferred between 10 wt-% and 20 wt-% of said manganese complex salt a). Optionally, said aqueous solutions comprising the complex salt, may contain organic or inorganic buffers, such as acetate, citrate and benzoate buffers as disclosed in WO2006 / 125517 (Hindustan Lever Ltd.). Optimally the pH of the aqueous solution comprising the complex is between 2 to 7 and more typically between pH 4 and 6. The aqueous solutions comprising said complex salt do contain no solids or up to 1 wt.-% of solids, preferably no solids or less than 0.1 wt.-% of solids.

[0044] In certain embodiments, alternative a suitable solution can be used that is not aqueous. Besides water, suitable solutions include polar liquids, such as alcohols (in particular C 1-6 alcohols, for example methanol, ethanol and n- and isopropanol), or mixtures thereof. As described in WO 2011 / 106906 A1, the complexes may be synthesised in water / alcohol (e.g. water / ethanol) mixtures, or even in mainly non-aqueous solvents.

[0045] The zinc salt or bismuth salt b) is a salt of high water-solubility of at least 30 g / L at 20° C. This salt contains one or more anions which are selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates, dicarboxylate monoesters and acetylacetonates. Combinations of salts b) can also be used.

[0046] Salts b) used in the co-granules of this invention are non-basic. Preferably these salts when dissolved in water of 20 °C and forming a 10 % by weight solution have a pH-value of 8 or below, preferably of 7.5 and below and most preferred between 4 and 7.5.

[0047] These salts b) differ from basic zinc carbonates or from bismuth carbonates. Basic salts when dissolved in water of 20 °C and forming a 10 % by weight solution have a pH-value of more than 8.

[0048] Preferred salts b) are selected from the group of zinc or bismuth salts of monomeric or polymeric organic acids and yet still more preferably selected from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc citrate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate, bismuth acetate, bismuth acetylacetonate, bismuth benzoate, bismuth citrate, bismuth formate, bismuth lactate, bismuth gluconate, bismuth oxalate, bismuth ricinoleate, bismuth abietate, bismuth valerate and bismuth p-toluenesulfonate. Most preferred components b) are zinc salts.

[0049] Very preferred salts b) are zinc salts.

[0050] In an embodiment, the co-granules comprise between 5 and 60 wt-% of the zinc or bismuth salt b). Preferably, the co-granules comprise between 10 and 50 wt-%, more preferred between 15 and 40 wt-%, and still more preferred between 20 and 35 wt-% of the zinc or bismuth salt b). The percentages relate to the total mass of the co-granules.

[0051] As a further ingredient the co-granules according to the invention contain a binder c) to improve the cohesion of the co-granules.

[0052] As binders, preferably substances selected from fatty acids, alcohol ethoxylates and organic polymers can be used. Mixtures of different binders or different binders of the same type can also be used.

[0053] As organic polymers in the context of the present description synthetic and natural polymers are understood as well as modified polymers of natural origin.

[0054] Binders c) can be neutral or acidic organic polymers or even low-molecular organic compounds having, for example, molecular weights below 1.000 Daltons. Preferably used are acidic organic compounds thus acidic low-molecular organic compounds or acidic polymeric organic compounds. These can be used either in the form of free acid or in neutralized form. In the context of the present invention, therefore, the term "organic acid " encompasses both organic acids in free form and in neutralised form.

[0055] As counterions alkaline metal ions, especially Na ions, are preferred.

[0056] Suitable binders c) include, among others, organic fatty acids with 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Organic polymers are also preferred. The organic polymers can be of neutral or acidic nature. Natural organic polymers and modified organic polymers of natural origin can be used, as well as synthetic organic polymers.

[0057] The group of organic polymers c) very preferably used as a binder includes polyvinyl alcohols including their hydrophilically or hydrophobically modified derivatives, polyvinyl pyrrolidones and polyalkylene glycols, especially polyethylene glycols.

[0058] The acidic polymers used with preference as binders c) are in particular homo-or copolymeric polycarboxylates. Preferably, polyacrylic acids or polymethacrylic acids, especially those with a relative molecule mass of 500 to 70,000 g / mol are used.

[0059] Among these preferred are polyacrylates which preferably have a molecular mass of 2,000 to 20,000 g / mol. Due to their solubility, the short-chain polyacryates having molar masses from 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol are preferred from this group.

[0060] Other acidic polymers preferably used as binders c) are sulphonic acid-group-containing polymers, in particular copolymers from unsaturated carboxylic acids, sulphonic acid group containing monomers and optionally other ionogenic or non-ionogenic monomers.

[0061] Other preferred binders c) are C 8 -C 22 alcohol ethoxylate solid at room temperature, preferably C 8 -C 22 alcohol ethoxylates with an average of 10 to 100 ethylene oxide units in the molecule, such as Genapol ®< T 500 from Clariant.

[0062] As binders c) also cellulose ethers can be used. Cellulose ethers are derivatives of cellulose, which are produced by partial or complete substitution of the hydrogen atoms of the hydroxy groups in the cellulose. Kind of substituents, number of substituted hydroxy groups and their distribution in the cellulose ethers used according to the invention can be varied in wide ranges. Preferably, cellulose ethers are used, which are soluble in water. This is understood to mean a solubility of at least 10 g of cellulose ether in 1 L of water of 20 °C.

[0063] Examples of cellulose ethers that can be used as component b) are carboxymethylcellulose (CMC), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC) or mixed cellulose ethers, such as methyl ethyl cellulose (MEC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), ethylhydroxyethyl cellulose or carboxymethylhydroxyethylcellulose. Preferred component c) is carboxymethylcellulose.

[0064] As binder c) a starch can be used. A starch is a polymer of glucose in which the glucopyranose units are bonded by alpha-linkages. Suitable sources of starch are potato starch, maize starch, rice starch, wheat starch and partially pregellatinised starches from the aforementioned list. Alternatively, the binder c) may be a modified starch, such as dextrin, a natural gum, such as alginate. Most suitably, the binder c) is maize starch, potato starch or rice starch.

[0065] Very preferrred binders c) are polyvinylalcohols including or hydrophilically or hydrophobically modified polyvinylalcohol derivatives.

[0066] Typical polyvinyl alcohols used for formation as a binder c) according to the invention have an average numerical weight of molecular weight in the range between 10,000 and 200,000 (as measured at 20 °C using the method of gel permeation chromatography (GPC)) (corresponding to a viscosity of a 4 % aqueous solution at 20 °C of about 2 to 70 mPa * s; measured by falling ball ball viscosimeter according to Höppler, DIN 53015).

[0067] Polyvinyl alcohol is generally produced by saponification of polyvinyl acetate.

[0068] Particularly suitable polyvinyl alcohol has a hydrolysis degree of 70 to 100 mol % and its aqueous solution has a viscosity according to Höppler at 20 °C of 2 to 70 mPa * s.

[0069] Examples of hydrophobically modified polyvinyl alcohols containing non-water-soluble monomer blocks in their main chain include ethylene-containing polyvinyl alcohols of type Exceval ®< from Kuraray.

[0070] Another option is to modify by grafting reactions at the alcohol groups, such as by partial acetalisation of the alcohol groups of the polyvinyl alcohol, whereby the polyvinyl alcohols can be equipped with any residues that may be either hydrophobic or hydrophilic, such as Mowiflex ®< type polyvinyl alcohols from Kuraray.

[0071] The modifying residues can be block-like or statistically arranged.

[0072] Preferably used polyvinyl alcohols and acetalised polyvinyl alcohols have molecular weights in the range of 10,000 to 200,000 g / mol, preferably from 11,000 to 90,000 g / mol, especially preferred from 12,000 to 80,000 g / mol and especially preferred from 13,000 to 70,000 g / mol. Preferably used polyethylene glycols have molar masses ranging from 200 to 5.000.000 g / mol, corresponding to polymerisation degrees of 5 to >100,000.

[0073] As binders c) mixtures of different polyvinyl alcohols or mixtures of polyvinyl alcohols with other organic polymers or low-molecular compounds can be used. The vast majority of the binder c) preferably consists of polyvinyl alcohol or mixtures thereof, thus to at least 80% of polyvinyl alcohol or mixtures thereof, in relation to the total weight of the binder c).

[0074] The low-molecular organic acids, which are also preferred as binders c), can be used either in the form of free acid or in neutralized form. Preferably used low-molecular organic acids are citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, fatty acids as well as mixtures from these.

[0075] Particularly preferred low-molecular organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids.

[0076] In an embodiment, the co-granules comprise between 1 and 50 wt-% of the binder c). Preferably, the co-granules comprise between 2 and 30 wt-%, more preferred between 3 and 15 wt-%, and still more preferred between 3.5 and 10 wt-% of the binder c). The percentages relate to the total mass of the co-granules.

[0077] Very preferred the co-granules of the invention comprise between 3.5 and 10 wt.-% of polyvinylalcohol as binder c).

[0078] Binders c) used in the co-granules of the invention are preferably water-soluble compounds forming aqueous solutions containing 10 g of binder c) in 100 g water of 20°C,

[0079] The co-granules also comprise one or more bleaching activator(s) d). These are compounds generally known from the prior art. Bleaching activators d) are preferably multiple acylated alkylene diamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1.5-diacetyl-2, 4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), glycerol-triacetate (triacetin), N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolic sulfonates, in particular n-nonanoyloxi- or n-lauroyloxibenzene-sulfonate (NOBS or LOBS), acylated phenolic carboxylic acids, in particular nonanoyloxi- or decanoyloxi-benzoic acid (NOBA or DOBA, respectively), carboxylic acid anhydrides, in particular phthalic acid anhydride, acylated multivalent alcohols, preferably triacetine, ethylene-glycol diacetate and 2.5-diacetoxy-2,5-dihydrofurane as well as acetyliertated sorbitol and mannitol or their mixtures, respectively (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated and optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acylacetales and acyllactames can also preferably be used. In addition, nitrile derivatives such as n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleaching activators d). Combinations of bleaching activators d) can also be used.

[0080] Suitably the co-granules comprise TAED, NOBS, triacetin, and DOBA. More suitably the co-granules comprise TAED.

[0081] In an embodiment, the co-granules comprise between 10 and 80 wt-% of the bleaching activator d). Preferably, the co-granules comprise between 15 and 70 wt-%, more preferred between 20 and 60 wt-%, and still more preferred between 30 and 35 wt-% of the bleaching activator d). The percentages relate to the total mass of the co-granules.

[0082] The co-granules of the invention may be uncoated or are preferably coated. Preferably a coating of cellulose ether is used (so-called coating or protective layer), whereby the storage stability is improved and the co-granules can be optionally coloured. The proportion of the coating referring to the total amount of co-granules may vary in wide ranges, but should not exceed 30 wt.-%, based on the total mass of the coated co-granule. Preferably, the proportion of the coating is 1 to 20 wt.-%, more preferred between 3 nd 10 wt.-%, based on the total mass of the coated co-granulate.

[0083] As materials forming the coating the materials used as a binder c) can be used.

[0084] Preferably cellulose ethers can be used for the coating. As coating material, methyl cellulose, carboxymethyl cellulose, hydroxymethylpropyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose or mixtures of two or more thereof are preferred.

[0085] In another embodiment polyvinylalcohol or hydrophilically or hydrophobically modified derivatives thereof are used for the coating. Preferrred polyvinylalcohols for the coating are disclosed above for binder c).

[0086] Optionally, the coating may additionally contain small amounts of additives, such as water-soluble or water-insoluble organic dyes and / or other film-forming polymers (i.e. film-forming polymers that are not cellulose ethers). However, the total proportion of such additives and / or other film-forming polymers in the total mass of the coating should not exceed 10 wt.-%, preferably 5 wt.-%. Preferably, the coating contains no additives and no further film-forming polymers.

[0087] In another embodiment, the co-granule of the invention may be provided with two or more coatings, of which at least one consists of cellulose ether. Thus, the co-granule of the invention may be provided with a first coating, preferably from hydroxypropyl methylcellulose (HPMC) and / or from methyl cellulose (MC), and with a second protective layer, preferably from a fatty acid or a fatty acid mixture, most preferably from stearic acid and palmitic acid.

[0088] Preferably used coating material is hydroxymethyl cellulose and polyvinylalcohol.

[0089] Optionally dyes can also be added to the co-granules according to the invention. Dyes can be in the co-granulate core and / or in the coating. Preferably, dyes are added to the co-granules before they have been coated.

[0090] In another preferred embodiment, the invention concerns co-granules containing other additives in addition to the components described above.

[0091] In this embodiment, the co-granules according to the invention can therefore have components a), b), c) and d) in combination with other additives e).

[0092] Fillers or sikkatives may be used as other additives e).

[0093] The filler that may be included in the co-granules can be either an organic filler or an inorganic filler, or a mixture thereof. Suitable organic fillers are saccharides and derivatives thereof, including sugars. Examples of sugars include glucose, dextrose, fructose, galactose, sucrose, lactose and maltose. Also modified saccharides may be used.

[0094] In another embodiment the filler is an inorganic filler. Inorganic fillers include talcs, micas, zeolites, silicates, silicas and clays. Suitably, the inorganic filler is selected from talcs, micas, zeolites, and silicates.

[0095] As siccatives, earth alkaline metal sulfates may be used, preferably calcium sulfate.

[0096] In an embodiment, the co-granules comprise between 0 and 80 wt-% of other additives e). Preferably, the co-granules comprise between 0 and 60 wt-%, more preferred between 0 and 40 wt-%, and still more preferred between 5 and 20 wt-% of other additives e). The percentages relate to the total mass of the co-granules.

[0097] The production of the co-granules according to the invention can be carried out according to methods known per se and has already been described in detail in the above-mentioned patent documents. There are basically different granulation methods available.

[0098] In a first preferred process variant, building-up of the co-granules takes place in a mixing apparatus. The components are processed in usual mixing devices operating batch-by-batch or continuously, which are usually equipped with rotating mixing organs. When mixing, all mixing variants are conceivable, which ensure a sufficient mixing of the components.

[0099] In a preferred embodiment, all components are mixed at the same time. However, multistage mixing processes are also conceivable, in which the individual components are entered in the overall mixture individually or together with other additives in different combinations.

[0100] The order of slow and fast mixers can be exchanged according to requirements. The dwell times in the mixer granulation are preferably 0.5 s to 20 min, especially preferred 2 s to 10 min. The granulation fluid can be pumped into the mixing apparatus via simple conduction tubes. For better distribution, however, nozzle systems (single- or multi-material nozzles) are also conceivable.

[0101] Typically, a drying step follows the granulation stage to avoid conglutination of the co-granules. Then, by sieving the coarse grain parts and the fine grain parts are separated. The coarse grain content is crushed by grinding and, like the fine grain content, is fed to a new granulation process. The application of a coating is preferably provided in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0102] Solutions are intensively mixed with powdery active substances and other additives optionally present, resulting in a plastically deformable mass. The mixing step can be performed in the above-mentioned mixing apparatus, but also kneaders or special extruder types are conceivable. The granulation mass is then pressed by means of tools through the nozzle holes of a press matrix, creating cylindrically shaped extrudates. The exiting extrudates must be crushed to the desired length or particle size by a post-processing step. In many cases, a length / diameter ratio of L / D = 1 is desired. For cylindrical co-granules, the particle diameter is typically between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, the particle length is in the range of 0.5 to 3.5 mm, ideally between 0.9 and 2.5 mm. The length or size adjustment of the co-granules can be obtained, for example, by fixed stripper knives, rotating cut knives, cut wires or blades. To round off the cutting edges, the co-granules can then be rounded again in a rondier.

[0103] After the size adjustment of the co-granules, often a final solidification step is required in which the solvent is removed and a coating is then applied. This step is usually carried out in a fluidized bed apparatus, which is operated as a dryer. Then, by sieving the coarse grain part and the fine grain part is separated. The coarse grain content is crushed by grinding and, like the fine grain content, is fed to a new granulation process. After that, the generated co-granules may be equipped with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0104] Preferred co-granules according to the invention are also characterized by a water content of less than 3 % by weight (measured by Karl Fischer), based on the total amount of co-granules, especially preferred 0 to 1 % by weight.

[0105] According to particular embodiments of the invention, the Manganese complex salt a) may be provided as an aqueous solution, for example a buffered aqueous solution. To such solutions, which may be diluted with additional water (or other solvent) if desired, may be added an appropriate quantity of zinc or bismuth salt b), binder c) and bleaching activator d) and the resultant mixture mixed, for example by stirring, sonication, vortexing, shaking and the like for a suitable period of time.

[0106] Mixing devices for preparing the co-granules of the invention are well known to the skilled artisan. All industrial mixing equipment which is capable to mix liquid-solid blends may be used. Mixing may be performed continuously or batchwise.

[0107] Examples of mixing devices are anchor mixers, high shear dispersers, static mixers, liquid whistles, paddle mixers, V blenders, ribbon blenders, double cone blenders, high shear mixers / granulators, drum-blenders, twin-screw blenders, cone screw blenders, jet mixers, turbomixers and planetary mixers.

[0108] Appropriate conditions such as durations of and temperatures for the contacting will depend on the nature of the ingredients (the complex salt, the zinc or bismuth salt, binder and bleach activator) and their quantities and can be established without undue burden by the skilled person. For example, durations of contacting may be between about 1 min and about 24 hours. Often, the contacting can be carried out at ambient temperature, for example at about 20 to 25 °C although elevated temperatures, for example between about 25 and about 50 °C may be used if desired.

[0109] Where contacting is finished, a solid material is formed in the resultant mixtures. Thereafter, the material may be further dried, optionally under reduced pressure, generally at a temperature of between about 30°C and 80°C, for example between about 40° C and 60°C, for between about 1 and 24 hours. Appropriate conditions can be established without undue burden by the skilled person.

[0110] The co-granules of this invention are preferably formed by wet granulation.

[0111] The invention also relates to bleaching formulations comprising the co-granules of the invention and at least one bleaching agent and / or a precursor thereof.

[0112] As will be appreciated by the person skilled in the art, it may be desirable to subject the co-granules according to the first aspect of the invention to further processing, for example to include co-granules in the bleaching formulations of the invention, for example solid detergent formulations. Whilst co-granules according to the first aspect of the invention can be included in the bleaching formulations as such owing to their excellent storage stability, the formulator may want to modify these co-granules further, for example, by mixing with a soluble coating agent.

[0113] The co-granules of the first aspect of the invention are typically present in bleaching formulations according to the third aspect with mean particle sizes typically between 50 and 2500 µm, preferably between 100 and 1600 µm. Particle sizes may be measured by a laser diffraction particle size analyser, for example a Malvern HP equipped with a 100 mm lens.

[0114] Bulk density and size of the co-granules can be controlled via the composition, the process conditions or both, as is known in the art.

[0115] The co-granules according to the first aspect of the invention are of particular value when used in bleaching formulations. Tthe manganese ion-containing complexes described herein serving to catalyse the oxidising activity of a peroxy compound, which may either be included within a bleaching formulation according to the present invention, or may be generated from such a bleaching formulation in situ.

[0116] Where a peroxy compound is present in a bleaching formulation of the invention, this may be, and typically is, a compound which is capable of yielding hydrogen peroxide in aqueous solution. Suitable amounts of peroxy compounds included within the bleaching formulation may be determined by the skilled person although typical quantities will be within the range of 1-35 wt%, for example 5-25 wt%, based on the solids content of the bleaching formulation. One of skill in the art will appreciate that smaller quantities of peroxy compounds may be used where the bleaching formulation comprises a bleaching system comprising a peroxy compound and a so-called bleach precursor.

[0117] Suitable hydrogen peroxide sources are well known in the art. Examples include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates, and persulfates. Typical peroxy compounds included within bleaching formulations are persalts, for example optionally hydrated sodium perborate (e.g. sodium perborate monohydrate and sodium perborate tetrahydrate) and sodium percarbonate. According to particular embodiments, the bleaching formulation comprises sodium perborate monohydrate or sodium perborate tetrahydrate. Inclusion of sodium perborate monohydrate is advantageous owing to its high active oxygen content. Use of sodium percarbonate is most advantageous for environmental reasons.

[0118] Organic peroxy acids may also serve as the peroxy compound. These may be mono- or diperoxyacids. Typical mono- or diperoxyacids are of the general formula HOO-(C=O)-R-Y, 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 (C=O)OOH group or a quaternary ammonium group.

[0119] Typical monoperoxy acids include peroxy benzoic acids, peroxy lauric acid, N,N-phtaloylaminoperoxy caproic acid (PAP) and 6-octylamino-6-oxo-peroxyhexanoic acid. Typical diperoxy acids include for example: 1,12-diperoxydodecanoic acid (DPDA) and 1,9-diperoxyazeleic acid.

[0120] As well as organic peroxyacids, inorganic peroxyacids are also suitable, for example potassium monopersulfate (MPS).

[0121] If organic or inorganic peroxyacids are included within bleaching formulations, the amount of them incorporated in a bleaching formulation will typically be within the range of about 2-10 wt%, for example 4-8 wt%.

[0122] The bleaching formulation need not comprise a peroxy compound, however: a bleaching formulation of the invention may instead comprise a bleaching system constituted by components suitable for the generation of hydrogen peroxide in situ, but which are not themselves peroxy compounds. An example of this is the use of a combination of a C 1-4 alcohol oxidase enzyme and a C 1-4 alcohol, for example a combination of methanol oxidase and ethanol. Such combinations are described in WO 95 / 07972 A1 (Unilever N.V. and Unilever plc).

[0123] Often, a bleaching species is generated in situ. For example, organic peroxyacids are often generated in situ, as opposed to being included within the bleaching formulation, peroxyacids themselves tending to be insufficiently stable. For this reason, bleaching formulations often comprise a bleaching system comprising a persalt (e.g. sodium perborate (optionally hydrated) or sodium percarbonate), which yields hydrogen peroxide in water; and a so-called peroxy bleach precursor capable of reacting with the hydrogen peroxide to generate an organic peroxyacid.

[0124] The skilled person is very familiar with the use of bleaching systems comprising peroxy bleach precursors, peroxy bleach precursors being well known to the skilled person and described in the literature. For example, reference in this regard is made to British Patents 836988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 0 185 522 A, EP 0 174 132 A, EP 0 120 591 A; and U.S. Patent Nos. 1,246,339, 3,332,882, 4,128,494, 4,412,934 and 4,675,393. Suitable bleach precursors have been listed above.

[0125] Where used, bleach precursor compounds are typically present in the bleaching formulation in an amount of up to 12 wt%, for example from 2-10 wt%, of the composition, based on the solids content of the bleaching formulation

[0126] Peroxy compounds or bleaching systems as described herein can be stabilised within the bleaching formulation by providing them with a protective coating, for example a coating comprising sodium metaborate and sodium silicate.

[0127] The invention also relates to a cleaning agent comprising a bleaching formulation described herein before, preferably a diswashing agent.

[0128] Cleaning agents including dishwashing agents contain - besides the compositions of the invention - ingredients that are normally present in such agents.

[0129] In a preferred embodiment the cleaning agent according to the invention contains the manganese complex salt a) defined above within the range of 0.002 and 1 wt-%, more preferred within the range of 0.005 and 0.3 wt-% and still more preferred within the range of 0.01 and 0.1 wt-%, wherein the percentages refer to the total amount of the cleaning agent.

[0130] For automatic dishwash cleaning, corrosion on glassware during the rinsing stages can be suppressed by using glass corrosion inhibitors These are, for example, crystalline layered silicates and / or zinc or bismuth salts. Crystalline layered silicates are available for example from WeylChem under the trade name of Na-SKS, e.g. Na-SKS-1 (Na 2 Si 22 O 45 ·xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ·xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ·xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ·xH 2 O, makatite). Suitable among these are in particular Na-SKS-5 (alpha-Na 2 Si 2 O 5 ), Na-SKS-7 (beta-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ·H 2 O), Na-SKS-10 (NaHSi 2 O 5 ·3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but in particular Na-SKS-6 (delta-Na 2 Si 2 O 5 ). An overview of crystalline sheet-silicates is found, for example, in the article published in "Seifen-Öle-Fette-Wachse, 116 volume, No. 20 / 1990", on pages 805-808.

[0131] In a further preferred embodiment of the invention, the washing and cleaning compositions of the present invention, in particular the dishwasher detergents, incorporate the crystalline layered silicate at preferably 0.1 to 20 wt%, more preferably 0.2 to 15 wt% and more preferably 0.4 to 10 wt%, all relative to the overall weight of the composition.

[0132] To improve glass corrosion control, washing and cleaning compositions of the present invention, in particular dishwasher detergents, may incorporate - besides component b) available from the co-granules of the invention - in addition at least one zinc or bismuth salt, preferably selected from the group of organozinc or organobismuth salts, more preferably selected from the group of soluble organozinc or organobismuth salts, yet more preferably selected from the group of soluble zinc or bismuth salts of monomeric or polymeric organic acids and yet still more preferably selected from the group consisting of zinc or bismuth acetate, zinc or bismuth acetylacetonate, zinc or bismuth benzoate, zinc or bismuth citrate, zinc or bismuth formate, zinc or bismuth lactate, zinc or bismuth gluconate, zinc or bismuth oxalate, zinc or bismuth ricinoleate, zinc or bismuth abietate, zinc or bismuth valerate and zinc or bismuth p-toluenesulfonate.

[0133] Preference in the context of the present invention is given here to washing and cleaning compositions, in particular dishwasher detergents, where the amount of zinc or bismuth salt, relative to the overall weight of this composition, is from 0.1 to 10 wt%, preferably from 0.2 to 7 wt% and more preferably from 0.4 to 4 wt%, irrespective of which zinc salts are used, specifically irrespective that is as to whether organic or inorganic zinc or bismuth salts, soluble or insoluble zinc or bismuth salts or mixtures thereof are used.

[0134] Cleaing agents of the invention may also contain silver corrosion inhibitors for silver corrosion control. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, of zirconium, of hafnium, of cobalt or of cerium wherein the metals referred to are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.

[0135] According to particlar embodiments, bleaching formulations may be used for bleaching and / or modifying (e.g. degrading) polysaccharides (for example cellulose or starch) or polysaccharide-containing (for example cellulose-containing, also referred to herein as cellulosic) substrates. Cellulosic substrates are found widely in domestic, industrial and institutional laundry, wood-pulp, cotton processing industries and the like. For example, raw cotton (gin output) is dark brown in colour owing to the natural pigment in the plant. The cotton and textile industries recognise a need for bleaching cotton prior to its use in textiles and other areas. The object of bleaching such cotton fibres is to remove natural and adventitious impurities with the concurrent production of substantially whiter material.

[0136] Irrespective of the nature of the substrate treated in accordance with the method of the fourth aspect of the invention, it is the objective when doing so to effect bleaching, i.e. to remove unwanted chromophores (be they, for example, stains or solids on cloth in laundering or dishwashing applications; residual lignin in wood pulp or polyphenolic materials present in raw cotton and wood pulp and paper) and / or to degrade material, for example starch or polyphenolic materials in dishwashing. According to particular embodiments, therefore, the substrate may be a dirty dish or a polysaccharide- or polysaccharide-containing substrate, for example wherein the polysaccharide is a cellulosic substrate, such as cotton, wood pulp, paper or starch.

[0137] The bleaching formulation of the present invention may thus be used in a method of dishwashing. Such a method typically involves cleaning dishes in a mechanical dishwasher, often to remove starch and polyphenolic components from the dishes' surfaces. The term "dishes" herein embraces within its scope cookware as well as plates, crockery and other eating (e.g., cutlery) and serving tableware, for example items made of ceramic, metallic or plastics materials. Accordingly, embodiments of the fourth aspect of the invention include methods of cleaning dishes in a mechanical dishwasher, which comprise contacting the dishes with water and a bleaching formulation in accordance with the third aspect of the invention.

[0138] The bleaching formulation of the present invention may likewise be used in a method of cleaning textiles or non-woven fabrics, typically textiles. By textile is meant herein a woven or knitted fabric, that is to say a fabric with interlacing fibres resultant from weaving, knotting, crocheting or knitting together natural or artificial fibres. As is known in the art, textiles are distinguished by virtue of their method of manufacture from non-woven fabrics, which are also made of fibrous material and produced through bonding achieved by application of heat, mechanical pressure or chemical (including solvent) treatment. Accordingly, embodiments of the fourth aspect of the invention include methods of cleaning textiles or non-woven fabrics, typically in a mechanical washing machine, which comprise contacting a textile or non-woven fabric with water and a bleaching formulation in accordance with the third aspect of the invention.

[0139] According to particular embodiments of the invention, the bleaching formulation is suitable for use, and may be used in, a method of cleaning textiles or non-woven fabrics, in particular for use in cleaning fabric, i.e. textiles or non-woven fabrics, for example clothes. Although it is to be understood that the invention is not to be considered to be so limited, where a bleaching formulation is intended for use in laundry or hard-surface cleaning applications, the bleaching formulation will typically comprise other components well understood by those of normal skill in the art, such as bleach stabilisers (also known as sequestrants), for example organic sequestrants such as aminophosphonate or a carboxylate sequestrants; one or more surfactants, for example cationic anionic or non-anionic (amphiphilic) surfactants; as well as other components, including (but not limited to) detergency builders, enzymes and perfuming agents.

[0140] A bleaching formulation according to the third aspect of the invention, will contain preferably between 0.1 and 50 wt-% of one or more surfactants. This bleaching formulation may comprise one or more anionic surfactants and one or more non-ionic surfactants. In general the anionic and nonionic surfactants of the surfactant system may be chosen from the surfactants described in "Surfactant Active Agents, Vol 1 by Schwartz & Perry, Interscience 1949, vol 2 by Schwartz, Perry & Berch, Interscience 1958; in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company; or in Tenside Taschenbuch, H. Stache, Carl Hauser Verlag, 1981. Examples of descriptions of suitable anionic and nonionic surfactants can for example be found in WO 03 / 072690 A1 (Unilever N.V. et al.), WO 02 / 068574 A1 (Unilever N.V. et al.) and WO 2012 / 048951 A1(Unilever PLC et al.)

[0141] Those knowledgeable of bleaching formulations will be familiar with the use of enzymes in this context. Enzymes can provide cleaning performance, fabric care and / or sanitation benefits. Said enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Members of these enzyme classes are described in Enzyme Nomenclature 1992: Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the Nomenclature and Classification of Enzymes, 1992, ISBN 0-1202271165-3, Academic Press. Detersive enzymes are described in greater detail in for example US Patent No 6,579,839 (Price et al.).

[0142] Suitable detergency builders as optional ingredients may also be present, for example as described in WO 00 / 34427 A1. Builders may include aluminosilicates, in particular zeolites, e.g. zeolite A, B, C, X and Y types, as well as zeolite MAP as described in EP 0 384 070 A; and precipitating builders such as sodium carbonate. Such builders are typically present in an amount from about 5 to about 80 wt-%, more preferably from about 10 to 50 wt-%, based on the solids content of the bleaching formulation.

[0143] The skilled person will be readily able to formulate a suitable bleaching formulation for use in laundry in accordance with his normal skill. Likewise, the skilled person will be readily able to formulate bleaching formulations suitable for use in the other applications described herein. Such formulations may, for example, comprise additional metal-ion based or organic catalysts suitable for catalysing the activity of the peroxy compounds described herein. Non-limiting examples of transition-metal based bleaching catalysts can be found for example in EP 2 228 429 A1 (Unilever PLC and Unilever N.V.), and references cited therein and examples of organic catalysts can be found in WO 2012 / 071153 A1 (The Procter & Gamble Company).

[0144] The invention also relates to a method of cleaning textiles or non-wovens or of dishwashing comprising contacting a substrate with water and a bleaching formulation as defined above.

[0145] Preferred is a method of cleaning dishes in a mechanical dishwasher, the method comprising contacting the dishes with water and the bleaching formulation.

[0146] The non-limiting examples below more fully illustrate the embodiments of this invention.EXPERIMENTALChemicals used.

[0147] [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ] SO 4 (as a 15 wt-% aqueous solution) was prepared as described in WO2006 / 125517 (abbreviated below as Mn-TACN SO 4 ).

[0148] Corn starch was obtained from Roth.

[0149] TAED (Peractive ®< AC White) was obtained from Catexel, Wiesbaden.

[0150] Polyvinyl alcohol was obtained from Kuraray, under the trade name Poval ®< 6-88.

[0151] Zinc sulfate monohydrate and Zinc carbonate were obtained from Sigma Aldrich.

[0152] Weylclean ®< FDO X and Weylclean ®< FDO XP were obtained from Catexel, Wiesbaden. Weylclean ®< FDO X and Weylclean ®< FDO XP are granules each containing 2 wt-% of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O. Weylclean ®< FDO X are uncoated granules and Weylclean ®< FDO XP are granules coated with polyvinylalcohol.

[0153] Calcium sulfate was obtained from Roth.

[0154] Trisodium citrate and Zinc citrate were obtained from Jungbunzlauer.

[0155] Sodium carbonate and Bismuth citrate were obtained from Sigma Aldrich.

[0156] Sodium percarbonate was obtained from Solvay.

[0157] SKS-6 silicate was obtained from Catexel, Wiesbaden under the tradename Weylclean ®< SKS-6.

[0158] PEG 1500 and PEG 6000 powder were obtained from Clariant.

[0159] Sokalan ®< PA25 Cl and Lutensol T07 were obtained from BASF.

[0160] Protease Blaze Evity 150T and Amylase Stainzyme Plus Evity 24T were obtained from Novozymes.Preparation of co-granulesExample 1

[0161] Co-granules containing Mn-TACN SO 4 , TAED and Zinc sulfate were prepared as follows: First an aqueous polyvinyl alcohol (PVOH) solution is prepared, according to the information given by Kuraray. The commercial Poval 6-88 polymer was dissolved in 3 weight equivalent of hot water (90-95 °C) and then slowly allowed to cool down.

[0162] In an Eirich laboratory mixer (Type EL1), 125 g of TAED, 89.40 g of Zinc sulfate monohydrate and 20.5 g of corn starch were added and mixed thoroughly. Then, the aqueous solution of Mn-TACN SO 4 and PVOH were quickly added to the TAED / Zn sulfate / starch mixture. The amount of Mn-TACN SO 4 in an aqueous solution (15 wt-%) was 5.0 g. The amount of diluted PVOH (Poval 6-88; 25 wt-% in water) added was 10.0 g. The amount of water in the resulting composition was 68.33 g. This composition was then further mixed thoroughly for 2 min (1200 rpm). Then the co-granules were dried as a fluidized bed (40 min at 60 °C). The dried co-granules obtained were sieved; coarse co-granules (>1.25 mm) were discarded (or could be re-used to prepare new co-granules of the right size). The amount of the co-granules with particle sizes between 1250 and 200 µm was 86.8 wt.-% and with particle sizes below 200 µm was 13.2 wt.-%.

[0163] The dried co-granules contained 4 wt.-% of PVOH, 50.02 wt.-% of TAED, 8.20 wt.-% of corn starch, 2.00 wt.-% of Mn-TACN SO 4 and 35.78 wt.-% of Zn sulfate monohydrate.Example 2 (Comparative)

[0164] Co-granules with a similar composition as co-granules of Example 1 were prepared as described for Example 1. Instead of Zinc sulfate monohydrate the same amount of Zinc carbonate was used.Preparation of ADW tablets.

[0165] The composition of the ADW formulation to which the co-granules comprising the manganese catalyst, the bleach activator with and without Zinc salt are added is given in the table below. 73 mg of each of the co-granules were brought into a vessel that contained 17 g of the ingredients as indicated in the table below and this was mixed well. Tablets of 19.8 g each were then prepared by using a Carver Handtablettenpresse Model 4332 using a 1.5 ton press force. Table: Composition of the ingredients to prepare ADW tablets comprising co-granules of Examples 1 and 2, Weylclean ®< FDO X and Weylclean ®< FDO XPIngredient Wt-% Sodium citrate36.0Sodium carbonate25.0Sodium percarbonate15.0Peractive AC white (TAED)5.0*Weylclean SKS-65.0PEG 1500 Powder3.0PEG 6000 Powder2.0Sokalan PA25 Cl5.0Lutensol TO71.0Protease Blaze Evity 150T1.5Amylase Stainzyme Plus Evity 24T0.5* The appropriate amount of TAED was added to obtain in total 5% TAED in the ADW tablet. Storage stability test

[0166] The tablets containing Mn-TACN SO 4 , TAED and Zinc salt were stored in an oven at 40 °C during 12 weeks and were visually assessed (color changes of the tablets) at the start of the storage test and after 12 weeks of storage. Comparison was made with the same ADW tablets comprising Weylclean ®< FDO X and Weylclean ®< FDO XP commercial granules (which contain each 2-wt% of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O).

[0167] The dishwash tablets containing co-granules of Example 1 did not show any change in color during storage, whilst the tablets containing co-granules of Example 2 showed brown spots in the tablets after a few days of storage (presumably due to degraded Mn-TACN SO 4 catalyst). Moreover, the release of Mn-TACN SO 4 catalyst in the tablets containing Zinc carbonate after storage was only 0.6 % instead of 2.0 % demonstrating that the catalyst had been degraded during or soon after the granulation process. When using zinc sulfate instead of zinc carbonate no degradation of the catalyst could be detected after storage.

[0168] Under the same storage conditions tablets containing commercial Weylclean ®< FDO X granules (containing crystals of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O) showed dark spots of (presumably) MnO 2 . Also, tablets containing coated Weylclean ®< FDO XP granules, which also contain crystals of [Mn IV< Mn IV< (µ- O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O, showed some dark spots (but less than for the tablets with Weylclean ®< FDO X granules).Tea-stain cleaning in ADW

[0169] ADW tablets comprising different granules were tested for tea-stain removal of tea cups in an automatic dishwasher (Miele G 1223 SC GSL2 - 45 °C, standard programme R-time 2, at 21 °DH water hardness, with 50 g of IKW soil - protocol).

[0170] The cleaning on tea-stained cups for tablets containing granules of commercial Weylclean ®< FDO XP (containing crystals of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O) which had not been subjected to storage testing was set to 100 %. Besides granules of Weylclean ®< FDO XP co-granules of Examples 1 and 2 were used. The results are given in the following table.Test Results: Performance in ADW formulation

[0171] storage at 40°C (months)Weylclean ®< FDO XPCo-granules of Example 1Co-granules of Example 2 (comparative)0100 %100 %75 %369 %79 %*)*) The granules comprising Zinc carbonate degraded after preparation, which resulted in formation of brown granules with a low cleaning performance as shown in the table; therefore no performance test after 3 month of storage was performed

[0172] These results show that the cleaning performance of the ADW tablets comprising co-granules containing Mn-TACN SO 4 , TAED and zinc sulfate according to this invention is very good and after storage is even better as the ADW formulation containing the commercial FDO XP granules.

[0173] The reference tablet comprising co-granules containing Mn-TACN SO 4 , TAED and zinc carbonate showed a diminished activity after preparation of the co-granules, suggesting significant decomposition of the catalyst in the co-granules.

[0174] These data demonstrate clearly that co-granules comprising Mn-TACN SO 4 , TAED and Zinc sulfate show very good stability and bleaching activity in ADW formulations.

Examples

example 1

Example 1

[0161]Co-granules containing Mn-TACN SO 4 , TAED and Zinc sulfate were prepared as follows: First an aqueous polyvinyl alcohol (PVOH) solution is prepared, according to the information given by Kuraray. The commercial Poval 6-88 polymer was dissolved in 3 weight equivalent of hot water (90-95 °C) and then slowly allowed to cool down.

[0162]In an Eirich laboratory mixer (Type EL1), 125 g of TAED, 89.40 g of Zinc sulfate monohydrate and 20.5 g of corn starch were added and mixed thoroughly. Then, the aqueous solution of Mn-TACN SO 4 and PVOH were quickly added to the TAED / Zn sulfate / starch mixture. The amount of Mn-TACN SO 4 in an aqueous solution (15 wt-%) was 5.0 g. The amount of diluted PVOH (Poval 6-88; 25 wt-% in water) added was 10.0 g. The amount of water in the resulting composition was 68.33 g. This composition was then further mixed thoroughly for 2 min (1200 rpm). Then the co-granules were dried as a fluidized bed (40 min at 60 °C). The dried co-granules obtained ...

FIELD OF THE INVENTION

[0001] The present invention concerns storage-stable co-granules comprising selected ingredients. The invention also concerns bleaching formulations and detergents comprising said co-granules and a peroxy compound. The co-granules and bleaching formulations comprising them are suitable for use in catalysing oxidation, for example as a component of a laundry or dishwasher bleaching composition.BACKGROUND

[0002] Transition metal complexes, such as manganese catalysts based on triazacyclononane ligands are known to be active catalysts in the bleaching of stains in laundry detergent products and in dishwash products and for treatment of cellulosic substrates in e.g. wood-pulp or raw cotton (see for example EP 0 458 397 A2 (Unilever NV and Unilever plc) and WO 2006 / 125517 A1 (Unilever pic et al.).

[0003] Since these catalysts are very effective, only small amounts of them need to be used in bleaching detergent or dishwash formulations, often at levels less than 0.1 wt% in the detergent or dishwasher formulation. A difficulty arising from the use of such low dosing is achieving accurate dosing of the catalyst and homogeneous distribution throughout the formulation. When distribution of the catalyst is heterogeneous in a formulation, the use of such detergent formulations in a washing machine or in handwashing can lead to underdosing (i.e. giving a poorer bleaching performance) or overdosing of the catalyst (i.e. giving rise to excessive hydrogen peroxide decomposition and possibly brown spotting).

[0004] A well-known approach to circumvent this potential problem is the presentation / inclusion of the solid catalyst on a solid support in bleaching formulations.

[0005] Numerous patents and patent applications disclose granules containing bleaching catalyst, bleaching activator and binder. Examples for these documents are EP 0 544 440 A2, WO 94 / 21777 A1, WO 95 / 06710 A1, WO 95 / 06711 A1, WO 2018 / 011596 A1, WO 2018 / 210442 A1, EP 3 167 036 B, EP 2 966 161 A1, WO 2017 / 118543 A1, WO 2017 / 153528 A1 and WO 2016 / 177439 A1.

[0006] Coated granules comprising Mn-catalysts with good water-solubility are disclosed in WO 2022 / 058039 A1. These granules are preferably used in automatic dishwashing (ADW) formulations. In dishwashing formulations often glass protecting agents are contained, for example zinc or bismuth salts.

[0007] Whilst various patent documents describe granules and related compositions in bleaching formulations, for example of use in dishwashing and laundry applications to ensure accurate dosing of bleach activating catalysts, there remains still a need to improve useful stability of said catalysts in detergent formulations upon storage and to provide granules comprising new ingredients. The present invention is intended to address these needs.SUMMARY OF THE INVENTION

[0008] To control glass corrosion, washing and cleaning compositions, in particular dishwasher detergents, incorporate at least one zinc or bismuth salt. In granules for ADW formulations often Manganese-1,4,7-triazacyclononane bleach catalysts comprising PF 6 -< anion (Mn-TACN PF6) and ZnCO 3 are used. In some markets the use of phosphor-containing ingredients is not allowed. As an alternative, bleach catalysts with other anions, e.g. a Manganese-1,4,7-triazacyclononane bleach catalyst comprising SO 4 2-< anion could be used.

[0009] However, experiments have shown that when adding basic zinc salts, such as ZnCO 3 , to granules containing highly soluble Mn bleaching catalysts, such as Manganese-1 ,4,7-triazacyclononane bleach catalyst comprising SO 4 2-< anion, this leads to instability, formation of MnO 2 and less cleaning activity of this granule in the dishwash cleaning formulation.

[0010] Surprisingly we have found that when using less basic zinc or bismuth salts, e.g. zinc sulfate or bismuth sulfate, in combination with a highly water-soluble Mn-containing bleach catalyst this results in a much better performance and also shows a much better storage stability in the ADW formulation compared to a Mn-TACN-PF 6 / ZnCO 3 or a Mn-TACN-PF 6 / BiCO 3 containing formulation.

[0011] Viewed from a first aspect, therefore, the invention provides a co-granule comprising a) a Manganese complex salt comprising at least one ligand of formula (I) wherein: p is 3; R is independently selected from the group consisting of hydrogen, C 1 -C 24 -alkyl, CH 2 CH 2 OH and CH 2 COOH; or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via a C 2 -C 6 alkylene bridge, a C 6 -C 10 arylene bridge or a bridge comprising one or two C 1 -C 3 alkylene units and one C 6 -C 10 arylene unit, which bridge may be optionally substituted one or more times with independently selected C 1 -C 24 alkyl groups; and R 1 , R 2 , R 3 , and R 4 are independently selected from H, C 1 -C 4 alkyl and C 1 -C 4 -alkylhydroxy, wherein the manganese complex salt has a water-solubility of at least 30 g / L at 20° C and has a non-coordinating counter ion selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates and dicarboxylate monoesters, b) a zinc salt or a bismuth salt having a water-solubility of at least 30 g / L at 20° C and being selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates, dicarboxylate monoesters and acetylacetonates, c) a binder, and d) a bleaching activator.

[0012] Viewed from a second aspect, the invention provides a method of manufacturing said co-granules, said method comprising a) providing in a mixing device a composition containing components a), b), c) and d) defined above in solid form or combined with water, and b) mixing the components of said composition until co-granules are formed.

[0013] Viewed from a third aspect, the invention provides a bleaching formulation comprising co-granules according to the first aspect of the invention.

[0014] Viewed from a fourth aspect, the invention provides a cleaning method comprising contacting a substrate with water and a bleaching formulation according to the third aspect of the invention.

[0015] Further aspects and embodiments of the present invention will be evident from the discussion that follows below.DETAILED DESCRIPTION

[0016] As summarised above, the present invention is based, in part, on the finding that storage-stable co-granules may be prepared by combining selected bleaching catalysts, which are selected manganese complex salts comprising at least one ligand of formula (I) and at least one selected anion, preferably mononuclear or dinuclear manganese complexes comprising ligands of formula (I) described herein, bleaching activators, binders and selected zinc or bismuth salts.

[0017] Surprisingly, the co-granules of the present invention show improved storage stability and increased bleaching activity, compared to co-granules containing conventional PF 6 -< containing bleaching catalysts and basic zinc salts.

[0018] The term "water-soluble" when used in this description is meant to describe a bleaching catalyst a) which is soluble in water of 20 °C at a concentration of at least 30 g / L.

[0019] Typically, the bleaching catalyst a) is formed from and comprises a polydentate ligand containing 3 to 6 nitrogens atoms, which atoms coordinate to a manganese ion of the catalyst. The bleaching catalyst is typically in the form of a complex of the general formula (A1)         [M a LG k X n ]Y m      (A1) in which: M represents a ion selected from Mn(III)-(IV); LG represents a polydentate ligand as described herein and wherein at least one of the ligands LG is a ligand of formula (I) as described herein; each X independently represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate a transition metal ion in a mono, bi or tridentate manner, preferably selected from O 2-< , R 8< BO 2 2-< , R a< COO -< , R a< CONR -< , OH -< , NO 3 -< , NO, S 2-< , R a< S -< , PO 4 3-< , PO 3 OR a3-< , H 2 O, CO 3 2-< , HCO 3 -< , R a< OH, N(R a< ) 3 , R a< OO -< , O 2 2-< , O 2 -< , R a< CN, Cl -< , Br -< , OCN -< , SCN -< , N 3 -< , F -< , I -< , R a< O -< , ClO 4 -< , and CF 3 SO 3 -< , and more preferably selected from O 2< , R a< BO 2 2-< , R 8< COO -< , OH -< , NO 3 -< , S 2-< , R 8< S -< , PO 3 4-< , H 2 O, CO 3 2-< , HCO 3 -< , R a< OH, N(R a< ) 3 , Cl -< , Br -< , OCN -< , SCN -< , R a< CN, N 3 -< , F -< , I -< , R a< O -< , ClO 4 -< , and CF 3 SO 3 -< ; each R a< independently represents a group selected from hydrogen, hydroxyl, -R" and -OR", wherein R" is selected from C 1 -C 20 -alkyl, C 2 -C 20 -alkenyl, C 1 -C 20 -heterocycloalkyl, C 6 -C 10 -aryl, C 6 -C 10 -heteroaryl, (C=O)H, (C=O)-C 1 -C 20 -alkyl, (C=O)-C 6 -C 10 -aryl, (C=O)OH, (C=O)O-C 1 -C 20 -alkyl, (C=O)O-C 6 -C 10 -aryl, (C=O)NH 2 , (C=O)NH(C 1 -C 20 -alkyl), (C=O)NH(C 6 -C 10 -aryl), (C=O)N(C 1 -C 20 -alkyl) 2 , (C=O)N(C 6 -C 10 -aryl) 2 , 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', -NH 2 , -NHR', -N(R') 2 , -N(R') 3 +< , -C(O)R', -OC(O)R', -COOH, -COO -< (Na +< , K +< ), -COOR', -C(O)NH 2 , -C(O)NHR', -C(O)N(R') 2 , heteroaryl, -R', -SR', -SH, -P(R') 2 , -P(O)(R') 2 , -P(O)(OH) 2 , -P(O)(OR') 2 , -NO 2 , -SO 3 H, -SO 3 -(Na +< , K +< ), -S(O) 2 R', -NHC(O)R', and -N(R')C(O)R', wherein R' represents C 6 -C 10 -aryl, C 7 -C 20 -arylalkyl, or C 1 -C 20 -alkyl each of which may be each of which may be optionally substituted by -F, -Cl, -Br, -I, -NH 3 +< , -SO 3 H, -SO 3 -< (Na +< , K +< ), -COOH, -COO -< (Na +< , K +< ), -P(O)(OH) 2 , or -P(O)(O -< (Na +< , K +< )) 2 , and preferably each R a< independently represents hydrogen, C 1 -C 20 -alkyl or optionally C 1 -C 20 alkyl-substituted C 6 -C 10 -aryl, more preferably hydrogen or optionally substituted phenyl or naphthyl, or C 1-4 -alkyl; Y is a non-coordinating counteranion selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, perchlorate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates and dicarboxylate monoesters, a is an integer from 1 or 2 and most preferred 2; k is an integer from 1 to 4; and preferably 1 or 2; n is an integer from 0 to 4; and preferably 0 to 2; m is an integer from 1 to 8, preferably from 1 to 2.

[0020] As used herein, within the definitions provided above for formula (A1) and elsewhere, unless the context expressly dictates to the contrary, references to alkyl moieties, by which is meant saturated hydrocarbyl radicals, embrace alkyl groups that may comprising branched and / or cyclic portions. Likewise, references to alkenyl and alkynyl moieties embrace groups that may comprise branched and / or cyclic portions.

[0021] The counter anions Y in formula (A1) balance the charge z on the complex formed by the chelating ligand(s) LG, metal ion(s) M and coordinating species X. According to this invention the charge z is positive, and Y is anion as defined above. Preferably, the manganese ion-containing bleaching catalyst is a catalyst salt comprising one or two manganese ions and one or more non-coordinating counteranions Y.

[0022] Suitable counter ions Y include those which give rise to the formation of water-soluble manganese complexes forming storage-stable solids. Often counterions Y are selected from Cl -< , Br -< , I -< , NO 3 -< , ClO 4 -< , R c< SO 3 -< , HSO 4 -< , SO 4 2-< , R c< SO 4 -< , R d< SO 3 -< , CF 3 SO 3 -< , and R c< COO -< , with R c< in this context being selected from H, C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted) and with R d< in this context being selected from C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted). Often, these anions Y will be selected from Cl -< , NO 3 -< , tosylate, SO 4 2-< , CF 3 SO 3 -< , acetate, and benzoate. Particularly often, these anions Y will be selected from the group consisting of Cl -< , NO 3 -< , SO 4 2-< and acetate.

[0023] The manganese ion-containing bleaching catalyst a) according to formula (A1) typically comprises, as chelating ligand(s) LG, one or more tridentate, tetradentate, pentadentate, or hexadentate nitrogen donor ligands. It will be understood that the terms tridentate, tetradentate, pentadentate and hexadentate refer to the number of manganese ion-binding donor atoms (in this case being nitrogen donor atoms) that can bind to a manganese ion. For example, a tridentate nitrogen donor refers to an organic molecule that contains three nitrogen atoms with lone pairs, which can bind to a manganese ion. These nitrogen donor atoms can be either an aliphatic nitrogen donor, either a tertiary, secondary or primary amine, or a nitrogen donor belonging to an aromatic ring, for example pyridine. Whilst the name suggests that all nitrogen donors present in a ligand bind to a manganese ion-containing complex, this need not necessarily be so. For example, when a ligand is a hexadentate nitrogen donor, it suggests that the ligand can bind with 6 nitrogen donor atoms, but it may only bind with 5 nitrogen donor atoms, leaving one coordination site open to bind to another molecule, such as the hydrogen peroxyl anion. This discussion presumes that a manganese ion can bind to 6 donor atoms, which is generally, but not always, the case.

[0024] The manganese ion containing bleaching catalyst a) used according to the invention comprises a chelating ligand of formula (I): wherein Q, p, R, R 1 , R 2 , R 3 , and R 4 are as hereinbefore described.

[0025] Ligands of formula (I) form complexes with, for example, one or two manganese ions, which complexes may be, or constitute part of, the bleaching catalyst.

[0026] Transition metal catalyst salts having significant water-solubility, such as at least 30 g / l at 20 °C, e.g. at least 50 g / l at 20 °C or at least 70 g / l at 20 °C, are described in WO 2006 / 125517 A1. On account of their high water solubility, the use of such salts, for example those comprising small counterions such as chloride, nitrate, sulfate and acetate, can be advantageous. Also, catalyst salts comprising the tosylate anion, such as those described in WO 2011 / 066934 A1 and WO 2011 / 066935 A1 (both Clariant International Ltd) are also contemplated according to specific embodiments of the aspects of the present invention.

[0027] Preferred components a) are mononuclear or dinuclear Mn(III) and / or Mn(IV) complexes comprising one or two ligands of formula (I) as herein defined.

[0028] Typically, the Mn(lll) and / or Mn(IV) complex is a dinuclear complex and the subsequent discussion focuses on these. However, the use of mononuclear manganese complexes is also within the scope of the present invention. These manganese complexes are mostly applied as salts. Examples of such complexes are described in EP 0 549 271 A1, EP 0 549 272 A1, EP 0 544 519 A2 and EP 0 544 440 A2.

[0029] According to particular embodiments, each R in the ligand of formula (I) is independently selected from: CH 3 , C 2 H 5 , CH 2 CH 2 OH and CH 2 COOH.

[0030] According to further preferred embodiments R 1 , R 2 , R 3 , and R 4 in the ligand of formula (I) are independently selected from hydrogen and methyl, in particular embodiments in which each of R 1 , R 2 , R 3 , and R 4 is hydrogen.

[0031] When a ligand of formula (I) comprises one group R linked to the nitrogen atom (i.e. N) of another Q of another ring of formula (I) via a bridge, it will be understood that such ligands of formula (I) in particular embodiments comprising an ethylene bridge may alternatively be represented by the following structure: wherein R, R 1 , R 2 , R 3 , and R 4 are as herein defined, including the various specific embodiments set out.

[0032] According to particular embodiments of the invention, the ligand of formula (I) is 1,4,7-triazacyclononane (TACN), 1,4,7-trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triaza-cyclonan-1-yl)-ethane (Me 4 -DTNE). According to still more particular embodiments of the invention, the ligand of formula (I) is TACN or Me 3 -TACN.

[0033] The salt of the complex may comprise both coordinating ligands (i.e. which coordinate to one or two manganese ions in the complex of the salt) and non-coordinating ligands (i.e. which do not coordinate to a manganese ion).

[0034] Preferred mononuclear Mn(lll) and / or Mn(IV) complexes comprise one coordinating ligand of formula (I). Preferred dinuclear Mn(lll) and / or Mn(IV) complexes comprise either two coordinating ligands of formula (I), or one coordinating ligand of formula (I) where this comprises one ethylene or propylene group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, as described herein, e.g. is Me 4 -DTNE.

[0035] Additionally, Mn(III) and / or Mn(IV) complexes may comprise additional coordinating ligands. For dinuclear complexes, these are typically oxide (O 2-< ) or C 1-6 carboxylate (i.e. RCO 2 -< wherein R is an alkyl group) ions, which bridge the two manganese ions. Where present, an alkylcarboxylate ion is typically acetate. Typically, dinuclear Mn(III) and / or Mn(IV) complexes comprise two or three bridging oxide ions. For example, dinuclear manganese ion-containing complexes may comprise two oxide ions and one acetate ion, each of which bridges the two manganese ions; or three oxide ions, each of which bridges the two manganese ions.

[0036] According to particular embodiments of all aspects of the invention, there is contemplated the use of dinuclear manganese ion-containing complexes comprising two ligands of formula (I) which do not comprise one group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, for example TACN or Me 3 -TACN, in which the manganese ions are bridged by three oxide ions. According to particular embodiments, such complexes comprise two Mn(IV) ions. For example, the complex may be [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ] 2+< , "µ" denoting, according to convention, a bridging ligand.

[0037] According to other particular embodiments of all aspects of the invention, there is contemplated the use of dinuclear manganese ion-containing complexes comprising one ligand of formula (I) which does comprise one ethylene or propylene group R linked to the nitrogen atom of another Q of another ring of formula (I) via a bridge, for example Me 4 -DTNE, in which the manganese ions are bridged by two oxide ions and one acetate ion. According to particular embodiments, such complexes comprise one Mn(IV) ion and one Mn(III) ion. For example, the complex of the salt may be [Mn III< Mn IV< (µ-O) 2 (µ-CH 3 COO)(Me 4 -DTNE)] 2+< .

[0038] The mononuclear or dinuclear manganese ion-containing complex of the salt has an overall positive charge, which is balanced by one or more non-coordinating counteranions Y defined above. The counteranion(s) Y will typically be selected from Cl -< , Br -< , I -< , NO 3 -< , ClO 4 -< , R'SO 3 -< , HSO 4 -< , SO 4 2-< , RSO 4 -< , CF 3 SO 3 -< , and RCOO -< , with R in this context being selected from H, C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted) and R'in this context being selected from C 1-12 alkyl, and optionally C 1-6 alkyl-substituted C 6 H 5 (i.e. wherein C 6 H 5 is substituted one or more times with a C 1-6 alkyl group; often C 6 H 5 is unsubstituted). Often, these anions Y will be selected from Cl -< , NO 3 -< , tosylate, SO 4 2-< , CF 3 SO 3 ', acetate, and benzoate. Particularly often, these anions Y will be selected from the group consisting of Cl -< , NO 3 -< , SO 4 2-< and acetate.

[0039] Particularly preferred water-soluble bleaching catalysts a) are [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ]SO 4 (abbreviated as Mn-TACN SO 4 ) and [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ](NO 3 ) 2 (abbreviated as Mn-TACN NO 3 ).

[0040] Manganese catalyst salts a) having significant water-solubility, such as at least 30 g / l at 20 °C, or at least 50 g / l at 20 °C or at least 70 g / l at 20 °C, are described in WO 2006 / 125517 A1. The use of such highly water-soluble salts, for example those comprising small counterions such as chloride, nitrate, sulfate and acetate, can be advantageous since their high solubilities in water mean, for example, that more concentrated solutions of the salts can be used when contacting them with the other ingredients of the co-granules of this invention than when using poorly water-soluble salts, such as those comprising the PF 6 -< ion. For example, [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ] 2+< (PF 6 -< ) 2 has a water solubility of only 10.8 g / l at 20 °C. Moreover, salts of anions such as PF 6 -< are typically formed by introduction of the PF 6 -< ion as a potassium salt after the formation of the transition metal ion-containing complex, which leads to precipitation of the resultant salt. This precipitate is then typically redissolved, for example in water, prior to contacting with the other ingredients of the co-granules of this invention. Such additional steps introduce complexity and cost, as well as often occasioning the use of relatively large volumes of water in view of the low solubility in water of the manganese catalyst salts comprising PF 6 -< non-coordinating counterions.

[0041] Combinations of manganese complex salts a) can also be used.

[0042] In an embodiment, the co-granules comprise between 0.1 and 25 wt-% of the manganese complex salt a). Preferably, the co-granules comprise between 0.5 and 20 wt-%, more preferred between 1 and 15 wt-%, and still more preferred between 1.5 and 5 wt-% of the manganese complex salt a). The percentages relate to the total mass of the co-granules.

[0043] In an embodiment, the manganese complex salt a) is dosed as a solution with a concentration of at least 2 wt-% of dried complex. Suitably, the solution is an aqueous solution comprising between 2 wt-% and 75 wt-%, preferably between 2 wt-% and 50 wt-%, more preferred between 3 wt-% and 30 wt-% still more preferred between 5 wt-% and 25 wt-%, and most preferred between 10 wt-% and 20 wt-% of said manganese complex salt a). Optionally, said aqueous solutions comprising the complex salt, may contain organic or inorganic buffers, such as acetate, citrate and benzoate buffers as disclosed in WO2006 / 125517 (Hindustan Lever Ltd.). Optimally the pH of the aqueous solution comprising the complex is between 2 to 7 and more typically between pH 4 and 6. The aqueous solutions comprising said complex salt do contain no solids or up to 1 wt.-% of solids, preferably no solids or less than 0.1 wt.-% of solids.

[0044] In certain embodiments, alternative a suitable solution can be used that is not aqueous. Besides water, suitable solutions include polar liquids, such as alcohols (in particular C 1-6 alcohols, for example methanol, ethanol and n- and isopropanol), or mixtures thereof. As described in WO 2011 / 106906 A1, the complexes may be synthesised in water / alcohol (e.g. water / ethanol) mixtures, or even in mainly non-aqueous solvents.

[0045] The zinc salt or bismuth salt b) is a salt of high water-solubility of at least 30 g / L at 20° C. This salt contains one or more anions which are selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates, dicarboxylate monoesters and acetylacetonates. Combinations of salts b) can also be used.

[0046] Salts b) used in the co-granules of this invention are non-basic. Preferably these salts when dissolved in water of 20 °C and forming a 10 % by weight solution have a pH-value of 8 or below, preferably of 7.5 and below and most preferred between 4 and 7.5.

[0047] These salts b) differ from basic zinc carbonates or from bismuth carbonates. Basic salts when dissolved in water of 20 °C and forming a 10 % by weight solution have a pH-value of more than 8.

[0048] Preferred salts b) are selected from the group of zinc or bismuth salts of monomeric or polymeric organic acids and yet still more preferably selected from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc citrate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate, bismuth acetate, bismuth acetylacetonate, bismuth benzoate, bismuth citrate, bismuth formate, bismuth lactate, bismuth gluconate, bismuth oxalate, bismuth ricinoleate, bismuth abietate, bismuth valerate and bismuth p-toluenesulfonate. Most preferred components b) are zinc salts.

[0049] Very preferred salts b) are zinc salts.

[0050] In an embodiment, the co-granules comprise between 5 and 60 wt-% of the zinc or bismuth salt b). Preferably, the co-granules comprise between 10 and 50 wt-%, more preferred between 15 and 40 wt-%, and still more preferred between 20 and 35 wt-% of the zinc or bismuth salt b). The percentages relate to the total mass of the co-granules.

[0051] As a further ingredient the co-granules according to the invention contain a binder c) to improve the cohesion of the co-granules.

[0052] As binders, preferably substances selected from fatty acids, alcohol ethoxylates and organic polymers can be used. Mixtures of different binders or different binders of the same type can also be used.

[0053] As organic polymers in the context of the present description synthetic and natural polymers are understood as well as modified polymers of natural origin.

[0054] Binders c) can be neutral or acidic organic polymers or even low-molecular organic compounds having, for example, molecular weights below 1.000 Daltons. Preferably used are acidic organic compounds thus acidic low-molecular organic compounds or acidic polymeric organic compounds. These can be used either in the form of free acid or in neutralized form. In the context of the present invention, therefore, the term "organic acid " encompasses both organic acids in free form and in neutralised form.

[0055] As counterions alkaline metal ions, especially Na ions, are preferred.

[0056] Suitable binders c) include, among others, organic fatty acids with 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Organic polymers are also preferred. The organic polymers can be of neutral or acidic nature. Natural organic polymers and modified organic polymers of natural origin can be used, as well as synthetic organic polymers.

[0057] The group of organic polymers c) very preferably used as a binder includes polyvinyl alcohols including their hydrophilically or hydrophobically modified derivatives, polyvinyl pyrrolidones and polyalkylene glycols, especially polyethylene glycols.

[0058] The acidic polymers used with preference as binders c) are in particular homo-or copolymeric polycarboxylates. Preferably, polyacrylic acids or polymethacrylic acids, especially those with a relative molecule mass of 500 to 70,000 g / mol are used.

[0059] Among these preferred are polyacrylates which preferably have a molecular mass of 2,000 to 20,000 g / mol. Due to their solubility, the short-chain polyacryates having molar masses from 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol are preferred from this group.

[0060] Other acidic polymers preferably used as binders c) are sulphonic acid-group-containing polymers, in particular copolymers from unsaturated carboxylic acids, sulphonic acid group containing monomers and optionally other ionogenic or non-ionogenic monomers.

[0061] Other preferred binders c) are C 8 -C 22 alcohol ethoxylate solid at room temperature, preferably C 8 -C 22 alcohol ethoxylates with an average of 10 to 100 ethylene oxide units in the molecule, such as Genapol ®< T 500 from Clariant.

[0062] As binders c) also cellulose ethers can be used. Cellulose ethers are derivatives of cellulose, which are produced by partial or complete substitution of the hydrogen atoms of the hydroxy groups in the cellulose. Kind of substituents, number of substituted hydroxy groups and their distribution in the cellulose ethers used according to the invention can be varied in wide ranges. Preferably, cellulose ethers are used, which are soluble in water. This is understood to mean a solubility of at least 10 g of cellulose ether in 1 L of water of 20 °C.

[0063] Examples of cellulose ethers that can be used as component b) are carboxymethylcellulose (CMC), methyl cellulose (MC), ethyl cellulose (EC), hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC) or mixed cellulose ethers, such as methyl ethyl cellulose (MEC), hydroxyethyl methyl cellulose (HEMC), hydroxypropyl methyl cellulose (HPMC), ethylhydroxyethyl cellulose or carboxymethylhydroxyethylcellulose. Preferred component c) is carboxymethylcellulose.

[0064] As binder c) a starch can be used. A starch is a polymer of glucose in which the glucopyranose units are bonded by alpha-linkages. Suitable sources of starch are potato starch, maize starch, rice starch, wheat starch and partially pregellatinised starches from the aforementioned list. Alternatively, the binder c) may be a modified starch, such as dextrin, a natural gum, such as alginate. Most suitably, the binder c) is maize starch, potato starch or rice starch.

[0065] Very preferrred binders c) are polyvinylalcohols including or hydrophilically or hydrophobically modified polyvinylalcohol derivatives.

[0066] Typical polyvinyl alcohols used for formation as a binder c) according to the invention have an average numerical weight of molecular weight in the range between 10,000 and 200,000 (as measured at 20 °C using the method of gel permeation chromatography (GPC)) (corresponding to a viscosity of a 4 % aqueous solution at 20 °C of about 2 to 70 mPa * s; measured by falling ball ball viscosimeter according to Höppler, DIN 53015).

[0067] Polyvinyl alcohol is generally produced by saponification of polyvinyl acetate.

[0068] Particularly suitable polyvinyl alcohol has a hydrolysis degree of 70 to 100 mol % and its aqueous solution has a viscosity according to Höppler at 20 °C of 2 to 70 mPa * s.

[0069] Examples of hydrophobically modified polyvinyl alcohols containing non-water-soluble monomer blocks in their main chain include ethylene-containing polyvinyl alcohols of type Exceval ®< from Kuraray.

[0070] Another option is to modify by grafting reactions at the alcohol groups, such as by partial acetalisation of the alcohol groups of the polyvinyl alcohol, whereby the polyvinyl alcohols can be equipped with any residues that may be either hydrophobic or hydrophilic, such as Mowiflex ®< type polyvinyl alcohols from Kuraray.

[0071] The modifying residues can be block-like or statistically arranged.

[0072] Preferably used polyvinyl alcohols and acetalised polyvinyl alcohols have molecular weights in the range of 10,000 to 200,000 g / mol, preferably from 11,000 to 90,000 g / mol, especially preferred from 12,000 to 80,000 g / mol and especially preferred from 13,000 to 70,000 g / mol. Preferably used polyethylene glycols have molar masses ranging from 200 to 5.000.000 g / mol, corresponding to polymerisation degrees of 5 to >100,000.

[0073] As binders c) mixtures of different polyvinyl alcohols or mixtures of polyvinyl alcohols with other organic polymers or low-molecular compounds can be used. The vast majority of the binder c) preferably consists of polyvinyl alcohol or mixtures thereof, thus to at least 80% of polyvinyl alcohol or mixtures thereof, in relation to the total weight of the binder c).

[0074] The low-molecular organic acids, which are also preferred as binders c), can be used either in the form of free acid or in neutralized form. Preferably used low-molecular organic acids are citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, fatty acids as well as mixtures from these.

[0075] Particularly preferred low-molecular organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids.

[0076] In an embodiment, the co-granules comprise between 1 and 50 wt-% of the binder c). Preferably, the co-granules comprise between 2 and 30 wt-%, more preferred between 3 and 15 wt-%, and still more preferred between 3.5 and 10 wt-% of the binder c). The percentages relate to the total mass of the co-granules.

[0077] Very preferred the co-granules of the invention comprise between 3.5 and 10 wt.-% of polyvinylalcohol as binder c).

[0078] Binders c) used in the co-granules of the invention are preferably water-soluble compounds forming aqueous solutions containing 10 g of binder c) in 100 g water of 20°C,

[0079] The co-granules also comprise one or more bleaching activator(s) d). These are compounds generally known from the prior art. Bleaching activators d) are preferably multiple acylated alkylene diamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1.5-diacetyl-2, 4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), glycerol-triacetate (triacetin), N-acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolic sulfonates, in particular n-nonanoyloxi- or n-lauroyloxibenzene-sulfonate (NOBS or LOBS), acylated phenolic carboxylic acids, in particular nonanoyloxi- or decanoyloxi-benzoic acid (NOBA or DOBA, respectively), carboxylic acid anhydrides, in particular phthalic acid anhydride, acylated multivalent alcohols, preferably triacetine, ethylene-glycol diacetate and 2.5-diacetoxy-2,5-dihydrofurane as well as acetyliertated sorbitol and mannitol or their mixtures, respectively (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated and optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. Hydrophilic substituted acylacetales and acyllactames can also preferably be used. In addition, nitrile derivatives such as n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleaching activators d). Combinations of bleaching activators d) can also be used.

[0080] Suitably the co-granules comprise TAED, NOBS, triacetin, and DOBA. More suitably the co-granules comprise TAED.

[0081] In an embodiment, the co-granules comprise between 10 and 80 wt-% of the bleaching activator d). Preferably, the co-granules comprise between 15 and 70 wt-%, more preferred between 20 and 60 wt-%, and still more preferred between 30 and 35 wt-% of the bleaching activator d). The percentages relate to the total mass of the co-granules.

[0082] The co-granules of the invention may be uncoated or are preferably coated. Preferably a coating of cellulose ether is used (so-called coating or protective layer), whereby the storage stability is improved and the co-granules can be optionally coloured. The proportion of the coating referring to the total amount of co-granules may vary in wide ranges, but should not exceed 30 wt.-%, based on the total mass of the coated co-granule. Preferably, the proportion of the coating is 1 to 20 wt.-%, more preferred between 3 nd 10 wt.-%, based on the total mass of the coated co-granulate.

[0083] As materials forming the coating the materials used as a binder c) can be used.

[0084] Preferably cellulose ethers can be used for the coating. As coating material, methyl cellulose, carboxymethyl cellulose, hydroxymethylpropyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose or mixtures of two or more thereof are preferred.

[0085] In another embodiment polyvinylalcohol or hydrophilically or hydrophobically modified derivatives thereof are used for the coating. Preferrred polyvinylalcohols for the coating are disclosed above for binder c).

[0086] Optionally, the coating may additionally contain small amounts of additives, such as water-soluble or water-insoluble organic dyes and / or other film-forming polymers (i.e. film-forming polymers that are not cellulose ethers). However, the total proportion of such additives and / or other film-forming polymers in the total mass of the coating should not exceed 10 wt.-%, preferably 5 wt.-%. Preferably, the coating contains no additives and no further film-forming polymers.

[0087] In another embodiment, the co-granule of the invention may be provided with two or more coatings, of which at least one consists of cellulose ether. Thus, the co-granule of the invention may be provided with a first coating, preferably from hydroxypropyl methylcellulose (HPMC) and / or from methyl cellulose (MC), and with a second protective layer, preferably from a fatty acid or a fatty acid mixture, most preferably from stearic acid and palmitic acid.

[0088] Preferably used coating material is hydroxymethyl cellulose and polyvinylalcohol.

[0089] Optionally dyes can also be added to the co-granules according to the invention. Dyes can be in the co-granulate core and / or in the coating. Preferably, dyes are added to the co-granules before they have been coated.

[0090] In another preferred embodiment, the invention concerns co-granules containing other additives in addition to the components described above.

[0091] In this embodiment, the co-granules according to the invention can therefore have components a), b), c) and d) in combination with other additives e).

[0092] Fillers or sikkatives may be used as other additives e).

[0093] The filler that may be included in the co-granules can be either an organic filler or an inorganic filler, or a mixture thereof. Suitable organic fillers are saccharides and derivatives thereof, including sugars. Examples of sugars include glucose, dextrose, fructose, galactose, sucrose, lactose and maltose. Also modified saccharides may be used.

[0094] In another embodiment the filler is an inorganic filler. Inorganic fillers include talcs, micas, zeolites, silicates, silicas and clays. Suitably, the inorganic filler is selected from talcs, micas, zeolites, and silicates.

[0095] As siccatives, earth alkaline metal sulfates may be used, preferably calcium sulfate.

[0096] In an embodiment, the co-granules comprise between 0 and 80 wt-% of other additives e). Preferably, the co-granules comprise between 0 and 60 wt-%, more preferred between 0 and 40 wt-%, and still more preferred between 5 and 20 wt-% of other additives e). The percentages relate to the total mass of the co-granules.

[0097] The production of the co-granules according to the invention can be carried out according to methods known per se and has already been described in detail in the above-mentioned patent documents. There are basically different granulation methods available.

[0098] In a first preferred process variant, building-up of the co-granules takes place in a mixing apparatus. The components are processed in usual mixing devices operating batch-by-batch or continuously, which are usually equipped with rotating mixing organs. When mixing, all mixing variants are conceivable, which ensure a sufficient mixing of the components.

[0099] In a preferred embodiment, all components are mixed at the same time. However, multistage mixing processes are also conceivable, in which the individual components are entered in the overall mixture individually or together with other additives in different combinations.

[0100] The order of slow and fast mixers can be exchanged according to requirements. The dwell times in the mixer granulation are preferably 0.5 s to 20 min, especially preferred 2 s to 10 min. The granulation fluid can be pumped into the mixing apparatus via simple conduction tubes. For better distribution, however, nozzle systems (single- or multi-material nozzles) are also conceivable.

[0101] Typically, a drying step follows the granulation stage to avoid conglutination of the co-granules. Then, by sieving the coarse grain parts and the fine grain parts are separated. The coarse grain content is crushed by grinding and, like the fine grain content, is fed to a new granulation process. The application of a coating is preferably provided in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0102] Solutions are intensively mixed with powdery active substances and other additives optionally present, resulting in a plastically deformable mass. The mixing step can be performed in the above-mentioned mixing apparatus, but also kneaders or special extruder types are conceivable. The granulation mass is then pressed by means of tools through the nozzle holes of a press matrix, creating cylindrically shaped extrudates. The exiting extrudates must be crushed to the desired length or particle size by a post-processing step. In many cases, a length / diameter ratio of L / D = 1 is desired. For cylindrical co-granules, the particle diameter is typically between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, the particle length is in the range of 0.5 to 3.5 mm, ideally between 0.9 and 2.5 mm. The length or size adjustment of the co-granules can be obtained, for example, by fixed stripper knives, rotating cut knives, cut wires or blades. To round off the cutting edges, the co-granules can then be rounded again in a rondier.

[0103] After the size adjustment of the co-granules, often a final solidification step is required in which the solvent is removed and a coating is then applied. This step is usually carried out in a fluidized bed apparatus, which is operated as a dryer. Then, by sieving the coarse grain part and the fine grain part is separated. The coarse grain content is crushed by grinding and, like the fine grain content, is fed to a new granulation process. After that, the generated co-granules may be equipped with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0104] Preferred co-granules according to the invention are also characterized by a water content of less than 3 % by weight (measured by Karl Fischer), based on the total amount of co-granules, especially preferred 0 to 1 % by weight.

[0105] According to particular embodiments of the invention, the Manganese complex salt a) may be provided as an aqueous solution, for example a buffered aqueous solution. To such solutions, which may be diluted with additional water (or other solvent) if desired, may be added an appropriate quantity of zinc or bismuth salt b), binder c) and bleaching activator d) and the resultant mixture mixed, for example by stirring, sonication, vortexing, shaking and the like for a suitable period of time.

[0106] Mixing devices for preparing the co-granules of the invention are well known to the skilled artisan. All industrial mixing equipment which is capable to mix liquid-solid blends may be used. Mixing may be performed continuously or batchwise.

[0107] Examples of mixing devices are anchor mixers, high shear dispersers, static mixers, liquid whistles, paddle mixers, V blenders, ribbon blenders, double cone blenders, high shear mixers / granulators, drum-blenders, twin-screw blenders, cone screw blenders, jet mixers, turbomixers and planetary mixers.

[0108] Appropriate conditions such as durations of and temperatures for the contacting will depend on the nature of the ingredients (the complex salt, the zinc or bismuth salt, binder and bleach activator) and their quantities and can be established without undue burden by the skilled person. For example, durations of contacting may be between about 1 min and about 24 hours. Often, the contacting can be carried out at ambient temperature, for example at about 20 to 25 °C although elevated temperatures, for example between about 25 and about 50 °C may be used if desired.

[0109] Where contacting is finished, a solid material is formed in the resultant mixtures. Thereafter, the material may be further dried, optionally under reduced pressure, generally at a temperature of between about 30°C and 80°C, for example between about 40° C and 60°C, for between about 1 and 24 hours. Appropriate conditions can be established without undue burden by the skilled person.

[0110] The co-granules of this invention are preferably formed by wet granulation.

[0111] The invention also relates to bleaching formulations comprising the co-granules of the invention and at least one bleaching agent and / or a precursor thereof.

[0112] As will be appreciated by the person skilled in the art, it may be desirable to subject the co-granules according to the first aspect of the invention to further processing, for example to include co-granules in the bleaching formulations of the invention, for example solid detergent formulations. Whilst co-granules according to the first aspect of the invention can be included in the bleaching formulations as such owing to their excellent storage stability, the formulator may want to modify these co-granules further, for example, by mixing with a soluble coating agent.

[0113] The co-granules of the first aspect of the invention are typically present in bleaching formulations according to the third aspect with mean particle sizes typically between 50 and 2500 µm, preferably between 100 and 1600 µm. Particle sizes may be measured by a laser diffraction particle size analyser, for example a Malvern HP equipped with a 100 mm lens.

[0114] Bulk density and size of the co-granules can be controlled via the composition, the process conditions or both, as is known in the art.

[0115] The co-granules according to the first aspect of the invention are of particular value when used in bleaching formulations. Tthe manganese ion-containing complexes described herein serving to catalyse the oxidising activity of a peroxy compound, which may either be included within a bleaching formulation according to the present invention, or may be generated from such a bleaching formulation in situ.

[0116] Where a peroxy compound is present in a bleaching formulation of the invention, this may be, and typically is, a compound which is capable of yielding hydrogen peroxide in aqueous solution. Suitable amounts of peroxy compounds included within the bleaching formulation may be determined by the skilled person although typical quantities will be within the range of 1-35 wt%, for example 5-25 wt%, based on the solids content of the bleaching formulation. One of skill in the art will appreciate that smaller quantities of peroxy compounds may be used where the bleaching formulation comprises a bleaching system comprising a peroxy compound and a so-called bleach precursor.

[0117] Suitable hydrogen peroxide sources are well known in the art. Examples include the alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates, and persulfates. Typical peroxy compounds included within bleaching formulations are persalts, for example optionally hydrated sodium perborate (e.g. sodium perborate monohydrate and sodium perborate tetrahydrate) and sodium percarbonate. According to particular embodiments, the bleaching formulation comprises sodium perborate monohydrate or sodium perborate tetrahydrate. Inclusion of sodium perborate monohydrate is advantageous owing to its high active oxygen content. Use of sodium percarbonate is most advantageous for environmental reasons.

[0118] Organic peroxy acids may also serve as the peroxy compound. These may be mono- or diperoxyacids. Typical mono- or diperoxyacids are of the general formula HOO-(C=O)-R-Y, 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 (C=O)OOH group or a quaternary ammonium group.

[0119] Typical monoperoxy acids include peroxy benzoic acids, peroxy lauric acid, N,N-phtaloylaminoperoxy caproic acid (PAP) and 6-octylamino-6-oxo-peroxyhexanoic acid. Typical diperoxy acids include for example: 1,12-diperoxydodecanoic acid (DPDA) and 1,9-diperoxyazeleic acid.

[0120] As well as organic peroxyacids, inorganic peroxyacids are also suitable, for example potassium monopersulfate (MPS).

[0121] If organic or inorganic peroxyacids are included within bleaching formulations, the amount of them incorporated in a bleaching formulation will typically be within the range of about 2-10 wt%, for example 4-8 wt%.

[0122] The bleaching formulation need not comprise a peroxy compound, however: a bleaching formulation of the invention may instead comprise a bleaching system constituted by components suitable for the generation of hydrogen peroxide in situ, but which are not themselves peroxy compounds. An example of this is the use of a combination of a C 1-4 alcohol oxidase enzyme and a C 1-4 alcohol, for example a combination of methanol oxidase and ethanol. Such combinations are described in WO 95 / 07972 A1 (Unilever N.V. and Unilever plc).

[0123] Often, a bleaching species is generated in situ. For example, organic peroxyacids are often generated in situ, as opposed to being included within the bleaching formulation, peroxyacids themselves tending to be insufficiently stable. For this reason, bleaching formulations often comprise a bleaching system comprising a persalt (e.g. sodium perborate (optionally hydrated) or sodium percarbonate), which yields hydrogen peroxide in water; and a so-called peroxy bleach precursor capable of reacting with the hydrogen peroxide to generate an organic peroxyacid.

[0124] The skilled person is very familiar with the use of bleaching systems comprising peroxy bleach precursors, peroxy bleach precursors being well known to the skilled person and described in the literature. For example, reference in this regard is made to British Patents 836988, 864,798, 907,356, 1,003,310 and 1,519,351; EP 0 185 522 A, EP 0 174 132 A, EP 0 120 591 A; and U.S. Patent Nos. 1,246,339, 3,332,882, 4,128,494, 4,412,934 and 4,675,393. Suitable bleach precursors have been listed above.

[0125] Where used, bleach precursor compounds are typically present in the bleaching formulation in an amount of up to 12 wt%, for example from 2-10 wt%, of the composition, based on the solids content of the bleaching formulation

[0126] Peroxy compounds or bleaching systems as described herein can be stabilised within the bleaching formulation by providing them with a protective coating, for example a coating comprising sodium metaborate and sodium silicate.

[0127] The invention also relates to a cleaning agent comprising a bleaching formulation described herein before, preferably a diswashing agent.

[0128] Cleaning agents including dishwashing agents contain - besides the compositions of the invention - ingredients that are normally present in such agents.

[0129] In a preferred embodiment the cleaning agent according to the invention contains the manganese complex salt a) defined above within the range of 0.002 and 1 wt-%, more preferred within the range of 0.005 and 0.3 wt-% and still more preferred within the range of 0.01 and 0.1 wt-%, wherein the percentages refer to the total amount of the cleaning agent.

[0130] For automatic dishwash cleaning, corrosion on glassware during the rinsing stages can be suppressed by using glass corrosion inhibitors These are, for example, crystalline layered silicates and / or zinc or bismuth salts. Crystalline layered silicates are available for example from WeylChem under the trade name of Na-SKS, e.g. Na-SKS-1 (Na 2 Si 22 O 45 ·xH 2 O, kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ·xH 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 ·xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ·xH 2 O, makatite). Suitable among these are in particular Na-SKS-5 (alpha-Na 2 Si 2 O 5 ), Na-SKS-7 (beta-Na 2 Si 2 O 5 , natrosilite), Na-SKS-9 (NaHSi 2 O 5 ·H 2 O), Na-SKS-10 (NaHSi 2 O 5 ·3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ) and Na-SKS-13 (NaHSi 2 O 5 ), but in particular Na-SKS-6 (delta-Na 2 Si 2 O 5 ). An overview of crystalline sheet-silicates is found, for example, in the article published in "Seifen-Öle-Fette-Wachse, 116 volume, No. 20 / 1990", on pages 805-808.

[0131] In a further preferred embodiment of the invention, the washing and cleaning compositions of the present invention, in particular the dishwasher detergents, incorporate the crystalline layered silicate at preferably 0.1 to 20 wt%, more preferably 0.2 to 15 wt% and more preferably 0.4 to 10 wt%, all relative to the overall weight of the composition.

[0132] To improve glass corrosion control, washing and cleaning compositions of the present invention, in particular dishwasher detergents, may incorporate - besides component b) available from the co-granules of the invention - in addition at least one zinc or bismuth salt, preferably selected from the group of organozinc or organobismuth salts, more preferably selected from the group of soluble organozinc or organobismuth salts, yet more preferably selected from the group of soluble zinc or bismuth salts of monomeric or polymeric organic acids and yet still more preferably selected from the group consisting of zinc or bismuth acetate, zinc or bismuth acetylacetonate, zinc or bismuth benzoate, zinc or bismuth citrate, zinc or bismuth formate, zinc or bismuth lactate, zinc or bismuth gluconate, zinc or bismuth oxalate, zinc or bismuth ricinoleate, zinc or bismuth abietate, zinc or bismuth valerate and zinc or bismuth p-toluenesulfonate.

[0133] Preference in the context of the present invention is given here to washing and cleaning compositions, in particular dishwasher detergents, where the amount of zinc or bismuth salt, relative to the overall weight of this composition, is from 0.1 to 10 wt%, preferably from 0.2 to 7 wt% and more preferably from 0.4 to 4 wt%, irrespective of which zinc salts are used, specifically irrespective that is as to whether organic or inorganic zinc or bismuth salts, soluble or insoluble zinc or bismuth salts or mixtures thereof are used.

[0134] Cleaing agents of the invention may also contain silver corrosion inhibitors for silver corrosion control. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, of zirconium, of hafnium, of cobalt or of cerium wherein the metals referred to are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.

[0135] According to particlar embodiments, bleaching formulations may be used for bleaching and / or modifying (e.g. degrading) polysaccharides (for example cellulose or starch) or polysaccharide-containing (for example cellulose-containing, also referred to herein as cellulosic) substrates. Cellulosic substrates are found widely in domestic, industrial and institutional laundry, wood-pulp, cotton processing industries and the like. For example, raw cotton (gin output) is dark brown in colour owing to the natural pigment in the plant. The cotton and textile industries recognise a need for bleaching cotton prior to its use in textiles and other areas. The object of bleaching such cotton fibres is to remove natural and adventitious impurities with the concurrent production of substantially whiter material.

[0136] Irrespective of the nature of the substrate treated in accordance with the method of the fourth aspect of the invention, it is the objective when doing so to effect bleaching, i.e. to remove unwanted chromophores (be they, for example, stains or solids on cloth in laundering or dishwashing applications; residual lignin in wood pulp or polyphenolic materials present in raw cotton and wood pulp and paper) and / or to degrade material, for example starch or polyphenolic materials in dishwashing. According to particular embodiments, therefore, the substrate may be a dirty dish or a polysaccharide- or polysaccharide-containing substrate, for example wherein the polysaccharide is a cellulosic substrate, such as cotton, wood pulp, paper or starch.

[0137] The bleaching formulation of the present invention may thus be used in a method of dishwashing. Such a method typically involves cleaning dishes in a mechanical dishwasher, often to remove starch and polyphenolic components from the dishes' surfaces. The term "dishes" herein embraces within its scope cookware as well as plates, crockery and other eating (e.g., cutlery) and serving tableware, for example items made of ceramic, metallic or plastics materials. Accordingly, embodiments of the fourth aspect of the invention include methods of cleaning dishes in a mechanical dishwasher, which comprise contacting the dishes with water and a bleaching formulation in accordance with the third aspect of the invention.

[0138] The bleaching formulation of the present invention may likewise be used in a method of cleaning textiles or non-woven fabrics, typically textiles. By textile is meant herein a woven or knitted fabric, that is to say a fabric with interlacing fibres resultant from weaving, knotting, crocheting or knitting together natural or artificial fibres. As is known in the art, textiles are distinguished by virtue of their method of manufacture from non-woven fabrics, which are also made of fibrous material and produced through bonding achieved by application of heat, mechanical pressure or chemical (including solvent) treatment. Accordingly, embodiments of the fourth aspect of the invention include methods of cleaning textiles or non-woven fabrics, typically in a mechanical washing machine, which comprise contacting a textile or non-woven fabric with water and a bleaching formulation in accordance with the third aspect of the invention.

[0139] According to particular embodiments of the invention, the bleaching formulation is suitable for use, and may be used in, a method of cleaning textiles or non-woven fabrics, in particular for use in cleaning fabric, i.e. textiles or non-woven fabrics, for example clothes. Although it is to be understood that the invention is not to be considered to be so limited, where a bleaching formulation is intended for use in laundry or hard-surface cleaning applications, the bleaching formulation will typically comprise other components well understood by those of normal skill in the art, such as bleach stabilisers (also known as sequestrants), for example organic sequestrants such as aminophosphonate or a carboxylate sequestrants; one or more surfactants, for example cationic anionic or non-anionic (amphiphilic) surfactants; as well as other components, including (but not limited to) detergency builders, enzymes and perfuming agents.

[0140] A bleaching formulation according to the third aspect of the invention, will contain preferably between 0.1 and 50 wt-% of one or more surfactants. This bleaching formulation may comprise one or more anionic surfactants and one or more non-ionic surfactants. In general the anionic and nonionic surfactants of the surfactant system may be chosen from the surfactants described in "Surfactant Active Agents, Vol 1 by Schwartz & Perry, Interscience 1949, vol 2 by Schwartz, Perry & Berch, Interscience 1958; in the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company; or in Tenside Taschenbuch, H. Stache, Carl Hauser Verlag, 1981. Examples of descriptions of suitable anionic and nonionic surfactants can for example be found in WO 03 / 072690 A1 (Unilever N.V. et al.), WO 02 / 068574 A1 (Unilever N.V. et al.) and WO 2012 / 048951 A1(Unilever PLC et al.)

[0141] Those knowledgeable of bleaching formulations will be familiar with the use of enzymes in this context. Enzymes can provide cleaning performance, fabric care and / or sanitation benefits. Said enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Members of these enzyme classes are described in Enzyme Nomenclature 1992: Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the Nomenclature and Classification of Enzymes, 1992, ISBN 0-1202271165-3, Academic Press. Detersive enzymes are described in greater detail in for example US Patent No 6,579,839 (Price et al.).

[0142] Suitable detergency builders as optional ingredients may also be present, for example as described in WO 00 / 34427 A1. Builders may include aluminosilicates, in particular zeolites, e.g. zeolite A, B, C, X and Y types, as well as zeolite MAP as described in EP 0 384 070 A; and precipitating builders such as sodium carbonate. Such builders are typically present in an amount from about 5 to about 80 wt-%, more preferably from about 10 to 50 wt-%, based on the solids content of the bleaching formulation.

[0143] The skilled person will be readily able to formulate a suitable bleaching formulation for use in laundry in accordance with his normal skill. Likewise, the skilled person will be readily able to formulate bleaching formulations suitable for use in the other applications described herein. Such formulations may, for example, comprise additional metal-ion based or organic catalysts suitable for catalysing the activity of the peroxy compounds described herein. Non-limiting examples of transition-metal based bleaching catalysts can be found for example in EP 2 228 429 A1 (Unilever PLC and Unilever N.V.), and references cited therein and examples of organic catalysts can be found in WO 2012 / 071153 A1 (The Procter & Gamble Company).

[0144] The invention also relates to a method of cleaning textiles or non-wovens or of dishwashing comprising contacting a substrate with water and a bleaching formulation as defined above.

[0145] Preferred is a method of cleaning dishes in a mechanical dishwasher, the method comprising contacting the dishes with water and the bleaching formulation.

[0146] The non-limiting examples below more fully illustrate the embodiments of this invention.EXPERIMENTALChemicals used.

[0147] [Mn 2 (µ-O) 3 (Me 3 TACN) 2 ] SO 4 (as a 15 wt-% aqueous solution) was prepared as described in WO2006 / 125517 (abbreviated below as Mn-TACN SO 4 ).

[0148] Corn starch was obtained from Roth.

[0149] TAED (Peractive ®< AC White) was obtained from Catexel, Wiesbaden.

[0150] Polyvinyl alcohol was obtained from Kuraray, under the trade name Poval ®< 6-88.

[0151] Zinc sulfate monohydrate and Zinc carbonate were obtained from Sigma Aldrich.

[0152] Weylclean ®< FDO X and Weylclean ®< FDO XP were obtained from Catexel, Wiesbaden. Weylclean ®< FDO X and Weylclean ®< FDO XP are granules each containing 2 wt-% of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O. Weylclean ®< FDO X are uncoated granules and Weylclean ®< FDO XP are granules coated with polyvinylalcohol.

[0153] Calcium sulfate was obtained from Roth.

[0154] Trisodium citrate and Zinc citrate were obtained from Jungbunzlauer.

[0155] Sodium carbonate and Bismuth citrate were obtained from Sigma Aldrich.

[0156] Sodium percarbonate was obtained from Solvay.

[0157] SKS-6 silicate was obtained from Catexel, Wiesbaden under the tradename Weylclean ®< SKS-6.

[0158] PEG 1500 and PEG 6000 powder were obtained from Clariant.

[0159] Sokalan ®< PA25 Cl and Lutensol T07 were obtained from BASF.

[0160] Protease Blaze Evity 150T and Amylase Stainzyme Plus Evity 24T were obtained from Novozymes.Preparation of co-granulesExample 1

[0161] Co-granules containing Mn-TACN SO 4 , TAED and Zinc sulfate were prepared as follows: First an aqueous polyvinyl alcohol (PVOH) solution is prepared, according to the information given by Kuraray. The commercial Poval 6-88 polymer was dissolved in 3 weight equivalent of hot water (90-95 °C) and then slowly allowed to cool down.

[0162] In an Eirich laboratory mixer (Type EL1), 125 g of TAED, 89.40 g of Zinc sulfate monohydrate and 20.5 g of corn starch were added and mixed thoroughly. Then, the aqueous solution of Mn-TACN SO 4 and PVOH were quickly added to the TAED / Zn sulfate / starch mixture. The amount of Mn-TACN SO 4 in an aqueous solution (15 wt-%) was 5.0 g. The amount of diluted PVOH (Poval 6-88; 25 wt-% in water) added was 10.0 g. The amount of water in the resulting composition was 68.33 g. This composition was then further mixed thoroughly for 2 min (1200 rpm). Then the co-granules were dried as a fluidized bed (40 min at 60 °C). The dried co-granules obtained were sieved; coarse co-granules (>1.25 mm) were discarded (or could be re-used to prepare new co-granules of the right size). The amount of the co-granules with particle sizes between 1250 and 200 µm was 86.8 wt.-% and with particle sizes below 200 µm was 13.2 wt.-%.

[0163] The dried co-granules contained 4 wt.-% of PVOH, 50.02 wt.-% of TAED, 8.20 wt.-% of corn starch, 2.00 wt.-% of Mn-TACN SO 4 and 35.78 wt.-% of Zn sulfate monohydrate.Example 2 (Comparative)

[0164] Co-granules with a similar composition as co-granules of Example 1 were prepared as described for Example 1. Instead of Zinc sulfate monohydrate the same amount of Zinc carbonate was used.Preparation of ADW tablets.

[0165] The composition of the ADW formulation to which the co-granules comprising the manganese catalyst, the bleach activator with and without Zinc salt are added is given in the table below. 73 mg of each of the co-granules were brought into a vessel that contained 17 g of the ingredients as indicated in the table below and this was mixed well. Tablets of 19.8 g each were then prepared by using a Carver Handtablettenpresse Model 4332 using a 1.5 ton press force. Table: Composition of the ingredients to prepare ADW tablets comprising co-granules of Examples 1 and 2, Weylclean ®< FDO X and Weylclean ®< FDO XPIngredient Wt-% Sodium citrate36.0Sodium carbonate25.0Sodium percarbonate15.0Peractive AC white (TAED)5.0*Weylclean SKS-65.0PEG 1500 Powder3.0PEG 6000 Powder2.0Sokalan PA25 Cl5.0Lutensol TO71.0Protease Blaze Evity 150T1.5Amylase Stainzyme Plus Evity 24T0.5* The appropriate amount of TAED was added to obtain in total 5% TAED in the ADW tablet. Storage stability test

[0166] The tablets containing Mn-TACN SO 4 , TAED and Zinc salt were stored in an oven at 40 °C during 12 weeks and were visually assessed (color changes of the tablets) at the start of the storage test and after 12 weeks of storage. Comparison was made with the same ADW tablets comprising Weylclean ®< FDO X and Weylclean ®< FDO XP commercial granules (which contain each 2-wt% of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O).

[0167] The dishwash tablets containing co-granules of Example 1 did not show any change in color during storage, whilst the tablets containing co-granules of Example 2 showed brown spots in the tablets after a few days of storage (presumably due to degraded Mn-TACN SO 4 catalyst). Moreover, the release of Mn-TACN SO 4 catalyst in the tablets containing Zinc carbonate after storage was only 0.6 % instead of 2.0 % demonstrating that the catalyst had been degraded during or soon after the granulation process. When using zinc sulfate instead of zinc carbonate no degradation of the catalyst could be detected after storage.

[0168] Under the same storage conditions tablets containing commercial Weylclean ®< FDO X granules (containing crystals of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O) showed dark spots of (presumably) MnO 2 . Also, tablets containing coated Weylclean ®< FDO XP granules, which also contain crystals of [Mn IV< Mn IV< (µ- O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O, showed some dark spots (but less than for the tablets with Weylclean ®< FDO X granules).Tea-stain cleaning in ADW

[0169] ADW tablets comprising different granules were tested for tea-stain removal of tea cups in an automatic dishwasher (Miele G 1223 SC GSL2 - 45 °C, standard programme R-time 2, at 21 °DH water hardness, with 50 g of IKW soil - protocol).

[0170] The cleaning on tea-stained cups for tablets containing granules of commercial Weylclean ®< FDO XP (containing crystals of [Mn IV< Mn IV< (µ-O) 3 (Me 3 -TACN) 2 ](PF 6 ) 2 .H 2 O) which had not been subjected to storage testing was set to 100 %. Besides granules of Weylclean ®< FDO XP co-granules of Examples 1 and 2 were used. The results are given in the following table.Test Results: Performance in ADW formulation

[0171] storage at 40°C (months)Weylclean ®< FDO XPCo-granules of Example 1Co-granules of Example 2 (comparative)0100 %100 %75 %369 %79 %*)*) The granules comprising Zinc carbonate degraded after preparation, which resulted in formation of brown granules with a low cleaning performance as shown in the table; therefore no performance test after 3 month of storage was performed

[0172] These results show that the cleaning performance of the ADW tablets comprising co-granules containing Mn-TACN SO 4 , TAED and zinc sulfate according to this invention is very good and after storage is even better as the ADW formulation containing the commercial FDO XP granules.

[0173] The reference tablet comprising co-granules containing Mn-TACN SO 4 , TAED and zinc carbonate showed a diminished activity after preparation of the co-granules, suggesting significant decomposition of the catalyst in the co-granules.

[0174] These data demonstrate clearly that co-granules comprising Mn-TACN SO 4 , TAED and Zinc sulfate show very good stability and bleaching activity in ADW formulations.

Examples

example 1

Example 1

[0161]Co-granules containing Mn-TACN SO 4 , TAED and Zinc sulfate were prepared as follows: First an aqueous polyvinyl alcohol (PVOH) solution is prepared, according to the information given by Kuraray. The commercial Poval 6-88 polymer was dissolved in 3 weight equivalent of hot water (90-95 °C) and then slowly allowed to cool down.

[0162]In an Eirich laboratory mixer (Type EL1), 125 g of TAED, 89.40 g of Zinc sulfate monohydrate and 20.5 g of corn starch were added and mixed thoroughly. Then, the aqueous solution of Mn-TACN SO 4 and PVOH were quickly added to the TAED / Zn sulfate / starch mixture. The amount of Mn-TACN SO 4 in an aqueous solution (15 wt-%) was 5.0 g. The amount of diluted PVOH (Poval 6-88; 25 wt-% in water) added was 10.0 g. The amount of water in the resulting composition was 68.33 g. This composition was then further mixed thoroughly for 2 min (1200 rpm). Then the co-granules were dried as a fluidized bed (40 min at 60 °C). The dried co-granules obtained ...

Claims

1. A co-granule comprising a) a manganese complex salt comprising at least one ligand of formula (I) wherein: Q = p is 3; R is independently selected from the group consisting of hydrogen, C1-C24-alkyl, CH2CH2OH and CH2COOH; or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via a C2-C6 alkylene bridge, a C6-C10 arylene bridge or a bridge comprising one or two C1-C3 alkylene units and one C6-C10 arylene unit, which bridge may be optionally substituted one or more times with independently selected C1-C24 alkyl groups; and R1, R2, R3, and R4 are independently selected from H, C1-C4alkyl and C1-C4-alkylhydroxy, wherein the manganese complex salt has a water-solubility of at least 30 g / L at 20° C and has a non-coordinating counter ion selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates and dicarboxylate monoesters, b) a zinc salt or a bismuth salt having a water-solubility of at least 30 g / L at 20° C and being selected from the group consisting of halides, nitrate, nitrite, thiocyanate, cyanate, sulfate, hydrogen sulfate, sulfate monoester, alkyl sulfonates, aryl sulfonates, monocarboxylates, dicarboxylates, dicarboxylate monoesters and acetylacetonates, c) a binder, and d) a bleaching activator.

2. The co-granule according to claim 1, wherein the manganese complex salt a) is a mononuclear or dinuclear Mn(III) and / or Mn(IV) complex salt comprising at least one ligand of formula (I), preferably a ligand of formula (I) which is selected from 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclonan-1-yl)ethane (Me4-DTNE).

3. The co-granule according to claim 1 or 2, wherein the non-coordinating counter ion of the manganese complex salt a) is an anion selected from the group consisting of NO3-, SO42-, HSO4-, Cl-, tosylate or RCOO-, whereby R is hydrogen, C1-C8 alkyl or C7-C15 arylalkyl.

4. The co-granule according to claim 3, wherein the non-coordinating counter ion is selected from the group consisting of NO3-, SO42-, HSO4-, Cl-, acetate, tosylate or benzoate, preferably SO42-.

5. The co-granule according to any of claims 1 to 4, wherein the Manganese complex salt a) is selected from the group consisting of [MnIV2(µ-O)3(Me3TACN)2]SO4, [MnIV2(µ-O)3(Me3TACN)2](NO3)2, [MnIV2(µ-O)3(Me3TACN)2](tosylate)2, [MnIIIMnIV(µ-O)2(µ-CH3COO)(Me4DTNE)]SO4, [MnIIIMnIV(µ-O)2(µ-CH3COO) (Me4DTNE)](NO3)2, and [MnIIIMnIV(µ-O)2(µ-CH3COO) (Me4DTNE)]Cl2, preferably selected from the group consisting of [MnIV2(µ-O)3(Me3TACN)2]SO4, [MnIV2(µ-O)3(Me3TACN)2](NO3)2 and [MnIV2(µ-O)3(Me3TACN)2](tosylate)2.

6. The co-granule according to at least one of claims 1 to 5, wherein component b) is a zinc salt.

7. The co-granule according to any of claims 1 to 5, wherein the salt b) is selected from the group consisting of zinc or bismuth halides, zinc or bismuth nitrate, zinc or bismuth nitrite, zinc or bismuth thiocyanate, zinc or bismuth cyanate, zinc or bismuth sulfate, zinc or bismuth hydrogen sulfate, zinc or bismuth sulfate monoester, zinc or bismuth alkyl sulfonates, zinc or bismuth aryl sulfonates, zinc or bismuth monocarboxylates, preferably zinc or bismuth citrate, zinc or bismuth dicarboxylates, zinc or bismuth dicarboxylate monoesters or hydrates of these salts, preferably being selected from the group consisting of zinc or bismuth sulfate, zinc or bismuth hydrogen sulfate, zinc or bismuth acetate, zinc or bismuth chloride, zinc or bismuth citrate or hydrates of these salts.

8. The co-granule of claims 2, 5 and 7, wherein the mononuclear or dinuclear Mn(lll) and / or Mn(IV) complex salt a) is selected from the group consisting of [MnIV2(µ-O)3(Me3TACN)2]SO4, [MnIV2(µ-O)3(Me3TACN)2](NO3)2 and [MnIV2(µ-O)3(Me3TACN)2](tosylate)2 and wherein the zinc or bismuth salt b) is selected from the group consisting of zinc or bismuth sulfate, zinc or bismuth hydrogen sulfate, zinc or bismuth acetate, zinc or bismuth chloride, zinc or bismuth nitrate, zinc or bismuth citrate or hydrates of these salts.

9. The co-granule of any one of the preceding claims, wherein the binder is selected from non-acidic film forming polymers, preferably from polyvinylalcohol.

10. The co-granule of any of the preceding claims, wherein the co-granule contains non-film forming acids which are solid at 25°C, preferably citric acid or its alkali metal salt.

11. The co-granule of any one of the preceding claims, wherein the co-granule contains a coating.

12. The co-granule of any of the preceding claims, wherein the bleaching activator d) is selected from tetraacetylethylene diamine (TAED), n-nonanoyloxybenzene-sulfonate (NOBS) or n-lauroyloxybenzenesulfonate (LOBS), preferably from tetraacetylethylene diamine (TAED).

13. The co-granule according of any one of the preceding claims, wherein the co-granule comprises between 1 and 35 wt.-% of component a), between 1 and 20 wt.-% of component b), between 5 and 80 wt.-% of component c) and between 10 and 80 wt.-% of component d), wherein the percentages refer to the total amount of the co-granule.

14. A bleaching formulation comprising a co-granule of any of claims 1 to 13 and a peroxy compound and / or a precursor thereof.

15. A cleaning agent comprising a co-granule of any of claims 1 to 13 or a bleaching formulation of claim 14, which cleaning agent is preferably a dishwashing agent.

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