Composition containing bleaching catalyst, method for producing the same, and bleaching and cleaning agents containing the same

Abstract

The present invention relates to compositions comprising a manganese-containing catalyst salt, a water-soluble polymer, and a polysaccharide absorbent. The present invention also relates to methods for preparing such compositions, preferably in granular form, and to bleaching compositions comprising the salt and a peroxy compound or a precursor thereof. Compositions containing the catalyst salt and compositions comprising the same are suitable for catalyzing oxidation, for example as components of laundry or dishwasher bleaching compositions. The present invention also relates to cleaning agents comprising the compositions described herein.

Description

Technical Field

[0001] The present invention relates to a composition comprising a water-soluble polymer, an absorbent and a selected water-soluble bleach catalyst, preferably a mononuclear or dinuclear Mn(III) and / or Mn(IV) complex based on a cyclic triamine ligand, the composition being prepared by quantitatively adding a solution of the water-soluble bleach catalyst as a solution to the water-soluble polymer, the absorbent and optionally other ingredients. The present invention also relates to particles comprising such a composition and to bleaching compositions comprising the composition or particles and a peroxy compound. The compositions and bleaching compositions comprising them are suitable for catalytic oxidation, for example as components of laundry or dishwasher bleaching compositions. The present invention also relates to methods for oxidation using the bleaching compositions described herein. Background Art

[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 liquids and dishwashing products and in the treatment of cellulosic substrates, such as wood pulp or raw cotton (see, for example, EP 0 458 397 A2 (Unilever NV and Unilever plc) and WO 2006 / 125517 A1 (Unilever plc et al.).

[0003] Because these catalysts are very effective, only a small amount of catalyst is needed in bleaching detergents or dishwashing compounds, usually at a level below 0.1wt% in detergents or dishwasher compounds. The difficulty in using this low dosage is the precise quantitative and uniform distribution of the catalyst throughout the compound. When the catalyst is unevenly distributed in the compound, using this type of detergent compound in a washing machine or handwashing can result in insufficient (i.e., poor bleaching performance) or excessive (i.e., causing excessive hydrogen peroxide decomposition and possible brown spots) amounts of the catalyst.

[0004] One well known approach to circumvent this potential problem is to present / include a solid catalyst on a solid support in the bleach formulation.

[0005] For example, EP 0544440 A2 (Unilever plc and Unilever NV) describes a bleach catalyst composition provided in the form of non-friable composite particles comprising a manganese complex catalyst; a binder selected from water-soluble and non-oxidizable polymers, alkali metal silicates, fatty acid / soap mixtures and mixtures thereof; and optionally an inert salt, such as a chloride or carbonate salt. The preferred salt is hexafluorophosphoric acid (PF6 - ) salt, and describes the granulation of a mixture of unsieved light soda ash and a binuclear manganese catalyst hexafluorophosphate with an alkaline sodium silicate solution.

[0006] WO 94 / 2177 A1 (Unilever NV and Unilever plc) describes a method comprising a dinuclear manganese complex (typically PF6 - Salt); a carrier material selected from zeolite, alkali metal sulfate, citric acid, succinic acid and starch; and a binder selected from water-soluble non-oxidizable polymers, alkali metal silicates, saturated fatty acids, fatty acid soaps and mixtures thereof.

[0007] Furthermore, WO 95 / 06710 A1 and WO 95 / 06711 A1 (Unilever plc and Unilever NV) describe non-friable granules consisting of a manganese complex catalyst, a water-soluble binder and an inert solid or hydrophobic binder and a non-deliquescent or non-hygroscopic soluble core material.

[0008] WO 95 / 30733 A1 (Unilever NV and Unilever plc) describes a bleaching composition comprising an adsorption product of a porous material having active ionic sites and a manganese complex catalyst. The porous materials described include silica, zeolites, natural silicates, and clays. Silica gels, particularly hydrothermally treated hydrogels, are recommended. The so-called S- and G-types are described as particularly preferred.

[0009] WO 2014 / 202954 A1 (Chemsenti Limited) describes manganese catalysts containing silicate as counterion, which can be included in detergent formulations containing peroxygen bleach.

[0010] WO 2012 / 012494A1 (Procter & Gamble) discloses particles with various coatings. The core of this material can contain a metal catalyst, such as a manganese complex, which is not necessarily ionic. The most preferred manganese compound described in this document is the complex [LMnCl2], where L is a cross-linked tetraazacyclic ligand. In this case, the chloride ion is bound to the manganese ion. Therefore, the complex is neutral and does not represent a water-soluble transition metal ion.

[0011] WO2018 / 011596 (Itaconix Ltd) describes granules containing a manganese bleach catalyst, a water-soluble polymer, an absorbent, and a filler. During the manufacture of these granules, the bleach catalyst is added as a solid during the granulation process. The granules contain crystals of the bleach catalyst. This document discloses manganese complexes with TACN or DTNE ligands as bleach catalysts, such as [Mn IV Mn IV (μ-O)2(μ-CH3COO)(Me4-DTNE)](PF6).

[0012] WO 2011 / 006934 A1 supports the fact that the Mn complex with PF6 as counterion is poorly soluble in water. For a person skilled in the art, it is obvious that large cationic metal complexes (such as Mn complexes with TACN and DTNE) with large counterions (such as PF6) are poorly soluble in water. - or ClO4 - ) combination produces poorly water-soluble metal complexes because the large counterion fits neatly into the solid containing the large cation. This results in very good crystal packing, which is the driving force for precipitation from water. Consequently, these complexes have very low solubility in water.

[0013] WO 2018 / 210442 (Weylchem Wiesbaden GmbH) describes polyvinyl alcohol-coated particles containing a manganese bleaching catalyst. The particles known from this document are characterized in that the coating content is less than 5 wt%. In the examples, polyvinyl alcohol-coated particles containing a MnTACN bleaching catalyst ( FDO-X) particles. The bleaching catalyst is a PF6 - The invention discloses a salt of an anion having a low water solubility of 10.8 g / L at 20°C. In addition to this bleach catalyst, the document discloses other bleach catalysts, some of which are highly water-soluble. The granules disclosed in the document, which contain a small amount of coating and bleach catalyst, exhibit improved storage stability compared to uncoated granules. However, the document does not provide a person skilled in the art with an incentive to modify the bleach catalyst to improve the storage stability or bleaching performance of the granules.

[0014] WO 2014 / 202954 A2 discloses a method for preparing catalyst salts containing manganese ions, which contain non-coordinating silicate-based counterions. The selected manganese complex salt is adsorbed onto an alkaline earth metal silicate. These products are useful as bleach catalysts in laundry and dishwasher compositions.

[0015] EP 3167036 B (Novozymes A / S) describes granules comprising an enzyme, multiple coatings formed from a manganese catalyst, a water-soluble salt and optionally a third coating formed from a film-forming agent such as polyvinyl alcohol.

[0016] EP 2 966 161 A (Dalli Werke GmbH) discloses particles containing an enzyme and a manganese bleach catalyst in a core, the manganese bleach catalyst being coated with a water-soluble coating compound.

[0017] WO 2017 / 118543 (Dalli Werke GmbH) describes co-granules comprising a manganese bleach catalyst and a binder, which are coated with a water-soluble polymer or an acid.

[0018] WO 2017 / 153528 (Unilever NV, Unilever PLC, Conopco, Inc) describes detergent formulations comprising coated particles containing a manganese-containing catalyst.

[0019] WO 2016 / 177439 (Novozymes A / S) describes coated particles, wherein the coating comprises manganese catalyst particles.

[0020] Although various patents describe granules and related compositions in bleach formulations, for example for dishwashing and laundry applications, to ensure accurate dosing of bleach activating catalysts, there remains a need to improve the useful stability of such catalysts in detergent formulations upon storage. The present invention addresses this need. SUMMARY OF THE INVENTION

[0022] We have surprisingly found that when a solution comprising a selected bleach catalyst which is a water-soluble mononuclear or binuclear manganese complex is added to a mixture comprising a water-soluble polymer, a selected absorbent and optionally a filler, a salt and / or a bleach activator, a composition, preferably a granulate, is formed which exhibits a very high bleaching activity over a long storage period. This finding is even more surprising since storage experiments described in WO 2006 / 125517 A1 showed that aqueous solutions of water-soluble catalysts are not completely stable and decompose significantly already after storage for two weeks at 37°C.

[0023] Thus, viewed from a first aspect, the invention provides a composition, preferably a granulate, comprising a water-soluble polymer, a selected absorbent and a water-soluble transition metal ion-containing bleach catalyst, wherein the water-soluble transition metal ion-containing bleach catalyst has a water solubility of at least 30 g / L at 20°C and is a water-soluble mononuclear or dinuclear Mn(III) and / or Mn(IV) complex comprising a ligand of formula (I):

[0024] in:

[0025]

[0026]

[0027] p is 3;

[0028] R is independently selected from hydrogen, C1-C 24 Alkyl, CH2CH2OH and CH2COOH; or one R through a C2-C6 alkylene bridge, C6-C 10 The arylene bridge may contain one or two C1-C3 alkylene units and one C6-C 10 The bridge of the arylene unit is connected to the nitrogen atom of another Q of another ring of formula (I), and the bridge may be optionally independently selected C1-C24 Alkyl substituted one or more times; and

[0029] R1, R2, R3 and R4 are independently selected from H, C1-C4 alkyl and C1-C4 alkylhydroxy.

[0030] Viewed from a second aspect, the invention provides a method of making the composition, preferably in granular form, the method comprising:

[0031] a) providing in a mixing device a composition comprising a water-soluble polymer, a selected absorbent and a solution, said solution comprising from 2 to 75 wt. % of a water-soluble transition metal ion-containing bleach catalyst, relative to the total amount of the solution, said water-soluble transition metal ion-containing bleach catalyst having a water solubility of at least 30 g / L at 20° C. and being a mononuclear or binuclear Mn(III) and / or Mn(IV) complex comprising a ligand of formula (I) above, and

[0032] b) mixing the ingredients of the composition.

[0033] Viewed from a third aspect, the present invention provides a bleaching package comprising a composition according to the first aspect of the invention.

[0034] Viewed from a fourth aspect, the present invention provides a method of cleaning comprising contacting a substrate with water and a bleach formulation according to the third aspect of the invention.

[0035] Other aspects and embodiments of the invention will become apparent from the discussion that follows. Detailed Description of the Invention

[0037] As noted above, the present invention is based in part on the discovery that storage-stable compositions comprising selected bleach catalysts, which are mononuclear or dinuclear manganese complexes comprising a ligand of formula (I) as described herein, can be prepared from an aqueous solution of the bleach catalyst, an absorbent, and a water-soluble polymer.

[0038] Surprisingly, the compositions of the present invention show improved storage stability and increased bleaching activity compared to conventionally prepared compositions comprising crystalline bleach catalysts.

[0039] Experiments have shown that this is due to the bleach catalyst being contained in the composition in a non-crystalline or nanocrystalline form.

[0040] Therefore, the present invention also relates to a composition comprising a water-soluble polymer, a selected absorbent and a water-soluble transition metal ion-containing bleach catalyst, wherein the bleach catalyst is present in the composition in amorphous or nanocrystalline form.

[0041] The term "nanocrystalline" as used in this specification is intended to describe nanocrystalline particles having an average diameter D50 Compounds having crystals below 1 μm, preferably below 500 nm. The average diameter is determined by laser diffraction analysis.

[0042] The term "amorphous" as used in this specification is intended to describe a compound that is free of crystals as determined by scanning electron microscopy analysis.

[0043] The term "water-soluble" as used in this specification is intended to describe a compound that dissolves in water at 20°C at a concentration of at least 30 g / L.

[0044] Transition metal ion-containing bleach catalysts, such as those typically contained in detergent products, are well known, studied, and understood by those skilled in the art. For example, the following non-limiting list provides examples of patent publications describing different classes of transition metal ion-containing bleach catalysts suitable for use in accordance with various aspects of the present invention: EP 0 485 397, WO 97 / 48787, WO 00 / 12667, WO 03 / 104234, EP 1 557 457, US 6 432 900, US 2005 / 0209120, and US 2005 / 0181964.

[0045] Typically, the bleach catalyst is formed from and comprises a multidentate ligand containing 3 to 6 nitrogen atoms coordinated to the manganese ion of the catalyst. The bleach catalyst is typically in the form of a complex of the general formula (A1)

[0046] [M a LG k X n ]Y m (A1)

[0047] in:

[0048] M represents an ion selected from Mn(III)-(IV);

[0049] LG represents a multidentate ligand as described herein, and wherein at least one of the ligands LG is a ligand of formula (I) as described herein;

[0050] Each X independently represents a coordinating species selected from any singly, doubly or triply charged anion and any neutral molecule capable of coordinating a transition metal ion in a monodentate, bidentate or tridentate manner, preferably selected from O 2- 、R a Bo2 2- 、R a COO - 、R a CONR - OH - 、NO3 - 、NO、S2- 、R a S - PO4 3- PO3OR a3- , H2O, CO3 2- 、HCO3 - 、R a OH, N(R a )3. R a OO - 、O2 2- 、O2 - 、R a CN, Cl - Br - 、OCN - 、SCN - 、CN - 、N3 - 、F - , I - 、R a O - 、ClO4 - and CF3SO3 - , more preferably selected from O 2 、R a Bo2 2- 、R a COO - OH - 、NO3 - 、S 2- 、R a S - PO3 4- , H2O, CO3 2- 、HCO3 - 、R a OH, N(R a )3、Cl - Br - 、OCN - 、SCN - 、R a CN、N3 - 、F - , I - 、R a O - 、ClO4 - and CF3SO3 - ;

[0051] Each R a independently represents a group selected from hydrogen, hydroxy, -R" and -OR", wherein R"=C1-C 20 Alkyl, C2-C 20 Alkenyl, C1-C 20Heterocycloalkyl, C6-C 10 Aryl, C6-C 10 Heteroaryl, (C=O)H, (C=O)-C1-C 20 Alkyl, (C=O)-C6-C 10 Aryl, (C=0)OH, (C=0)O-C1-C 20 Alkyl, (C=O)O-C6-C 10 Aryl, (C=O)NH2, (C=O)NH(C1-C 20 alkyl), (C=O)NH(C6-C 10 -aryl), (C=O)N(C1-C 20 -alkyl)2, (C=O)N(C6-C 10 -aryl)2, R" is optionally substituted by one or more functional groups E, wherein E independently represents a functional group selected from the following: -F, -Cl, -Br, -I, -OH, -OR', -NH2, -NHR', -N(R')2, -N(R')3 + , -C(O)R', -OC(O)R', -COOH, -COO - (Na + , K + ), -COOR', -C(O)NH2, -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, -NO2, -SO3H, -SO3-(Na + , K + ), -S(O)2R', -NHC(O)R' and -N(R')C(O)R', wherein R' represents C6-C 10 Aryl, C7-C 20 Arylalkyl or C1-C 20 Alkyl, each of which may be optionally substituted with -F, -Cl, -Br, -I, -NH3 + 、-SO3H、-SO3 - (Na + , K + ), -COOH, -COO - (Na + , K + ), -P(O)(OH)2 or -P(O)(O - (Na + , K + ))2 substituted, preferably each R a independently represent hydrogen, C1-C 40 Alkyl or optionally C1-C 20Alkyl-substituted C6-C 10 Aryl, more preferably hydrogen or optionally substituted phenyl or naphthyl or C 1-4 -alkyl;

[0052] Y is a non-coordinating counterion;

[0053] a is an integer of 1 or 2, most preferably 2;

[0054] k is an integer from 1 to 4; preferably 1 or 2;

[0055] n is an integer from 0 to 4; preferably an integer from 0 to 2;

[0056] m is an integer of 0 or 1 to 20, and is usually an integer of 1 to 8, preferably an integer of 1 to 2.

[0057] As used herein, within the definitions provided above for formula (A1) and elsewhere, references to alkyl moieties (which means saturated hydrocarbon groups) include alkyl groups that may contain branched and / or cyclic moieties, unless the context clearly dictates otherwise. Similarly, references to alkenyl and alkynyl moieties include groups that may contain branched and / or cyclic moieties.

[0058] The counterion Y in formula (A1) balances the charge z on the complex formed by the chelating ligand LG, the metal ion M and the coordinating species X. According to the present invention, if the charge z is positive, then Y is an anion, such as R b COO - , BPh4 - 、ClO4 - 、BF4 - PF6 - 、R b SO3 - 、R b SO4 - 、SO4 2- 、NO3 - 、F - 、Cl - Br - , or I - , where R b is hydrogen, C1-C 40 Alkyl or optionally C1-C 20 Alkyl-substituted C6-C 10 If the charge z is negative, suitable counterions include alkali metals, alkaline earth metals or (alkyl) ammonium cations. Preferably, the charge z is positive, i.e., the bleach catalyst typically containing manganese ions is a catalyst salt comprising one or two manganese ions and one or more non-coordinating counter anions Y.

[0059] The nature of the counter anion is not an essential feature of the present invention. Suitable counter ions Y include those that result in the formation of a water-soluble manganese complex that is storage-stable and solid. Typically, the counter ions, including those for the preferred metal complexes, are selected from the group consisting of Cl - Br - , I - 、NO3 - 、ClO4 - PF6 - 、R c SO3 - 、SO4 2- 、R c SO4 - CF3SO3 - and R c COO - , where R c In this article, selected from H, C 1-12 Alkyl and optionally C 1-6 Alkyl-substituted C6H5 (i.e., wherein C6H5 is replaced by C 1-6 alkyl groups are substituted one or more times (e.g., once); typically, C6H5 is unsubstituted). Typically, these counterions are selected from Cl - 、NO3 - PF6 - , toluenesulfonate, SO4 2- CF3SO3 - , acetate and benzoate. In particular, these counterions are usually selected from Cl - 、NO3 - 、SO4 2- and acetate.

[0060] The manganese ion-containing bleach catalyst of formula (A1) generally comprises one or more tridentate, tetradentate, pentadentate or hexadentate nitrogen donor ligands as chelating ligands LG. It should be understood that the terms tridentate, tetradentate, pentadentate and hexadentate refer to the number of manganese ion-binding donor atoms (in this case, nitrogen donor atoms) that can bind to the manganese ion. For example, a tridentate nitrogen donor refers to an organic molecule containing three nitrogen atoms with lone pairs, which can bind to the manganese ion. These nitrogen donor atoms can be aliphatic nitrogen donors, can be tertiary amines, secondary amines or primary amines, or nitrogen donors belonging to aromatic rings, such as pyridine. Although the name indicates that all nitrogen donors present in the ligand are bound to the manganese ion-containing complex, this is not necessarily the case. For example, when the ligand is a hexadentate nitrogen donor, it indicates 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 with another molecule such as a hydrogen peroxide anion. This discussion assumes that the manganese ion can bind with 6 donor atoms, which is usually the case but not always the case.

[0061] The manganese ion-containing bleach catalyst used according to the invention comprises a chelating ligand of formula (I):

[0062]

[0063] wherein Q, p, R, R1, R2, R3 and R4 are as described above.

[0064] The ligand of formula (I) forms a complex with, for example, one or two manganese ions, which complex may be or form part of a bleach catalyst.

[0065] WO 2006 / 125517 A1 describes transition metal catalyst salts having a significant water solubility, for example at least 30 g / l at 20° C., for example at least 50 g / l at 20° C. or at least 70 g / l at 20° C. Due to their high water solubility, it may be advantageous to use salts such as those containing small counterions such as chloride, nitrate, sulfate, and acetate. In addition, according to specific embodiments of various aspects of the present invention, catalyst salts containing a p-toluenesulfonate anion, such as those described in WO 2011 / 066934A1 and WO 2011 / 066935A1 (both Clariant International GmbH), are also contemplated.

[0066] Preferred mononuclear or dinuclear Mn(III) and / or Mn(IV) complexes comprise one or two ligands of formula (I) as defined herein. Those skilled in the art are well-known for such complexes, which can be prepared in situ without isolation and are well-defined.

[0067] By "well-defined complex" herein (as the term is commonly used in the art) is meant a complex that has been isolated so that it can be readily characterized (i.e., defined) and analyzed (e.g., its structure and purity can be determined). In contrast, an undefined complex is one that has been prepared but not separated from the medium (e.g., reaction medium) in which it was prepared.

[0068] Typically, the Mn(III) and / or Mn(IV) complexes are binuclear complexes, and subsequent discussion focuses on these complexes. However, the use of mononuclear manganese complexes is also within the scope of the present invention. These manganese complexes are primarily used as salts. Examples of such complexes are described in EP 0549271 A1, EP 0549272 A1, EP 0544519 A2, and EP 0544440 A2.

[0069] Another essential feature of the present invention is the absorbent, which absorbs the water used as a carrier for the manganese catalyst. The water-soluble polymer helps maintain the integrity of the particles during the drying process. The water-soluble polymer does not have to be used as a coating material, but can be added along with the absorbent and manganese catalyst solution.

[0070] According to some specific embodiments, each R in the ligand of formula (I) is independently selected from hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH; or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via an ethylene or propylene bridge.

[0071] According to some other preferred embodiments, each R in the ligand of formula (I) is independently selected from hydrogen, C1-C6 alkyl, CH2CH2OH and CH2COOH; or one R is connected to the nitrogen atom of another Q of another ring of formula (I) via an ethylene or propylene bridge.

[0072] According to some other preferred embodiments, R in the ligand of formula (I) is independently selected from C1-C 24 alkyl, CH2CH2OH and CH2COOH; or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via an ethylene or propylene bridge.

[0073] According to some other preferred embodiments, each R in the ligand of formula (I) is independently selected from the group consisting of: CH3, C2H5, CH2CH2OH and CH2COOH.

[0074] According to some other preferred embodiments, each R in the ligand of formula (I) is independently selected from C1-C6 alkyl, in particular methyl; or one R is connected to the nitrogen atom of another Q of another ring of formula (I) via an ethylene or propylene bridge. When one R is connected to the nitrogen atom of another Q of another ring of formula (I), this connection is generally through an ethylene bridge. In such embodiments, the other R groups, including the R groups in the other ring of formula (I), are the same, and are generally C1-C6 alkyl, in particular methyl.

[0075] According to further specific embodiments, including each of those specific embodiments described in the previous paragraph, R1, R2, R3 and R4 in the ligand of formula (I) are independently selected from hydrogen and methyl, and in some specific embodiments R1, R2, R3 and R4 are all hydrogen.

[0076] When a ligand of formula (I) comprises an R group connected via a bridge to a nitrogen atom (i.e., N) of another Q ring of another formula (I), it is understood that in certain embodiments such a ligand of formula (I) comprising an ethylene bridge may alternatively be represented by the following structure:

[0077]

[0078] wherein R, R1, R2, R3 and R4 are as defined herein (including the various specific embodiments described).

[0079] When a bridge is present in a ligand of formula (I), this may be a C2-C6 alkylene bridge. Such alkylene bridges are typically, but not necessarily, linear alkylene bridges, as described below. However, they may be cyclic alkylenes (for example, the bridge may be cyclohexylene). When the bridge is C6-C6 10 When the bridge comprises one or two C1-C3 alkylene units and one C6-C 10 When an arylene unit is present, such a bridge may be, for example, -CH2C6H4CH2- or -CH2C6H4-. It should be understood that each of these bridges may optionally be replaced by an independently selected C1-C 24 Alkyl (e.g. C1-C 18 alkyl) is substituted one or more times, for example once.

[0080] In the ligands of formula (I), the bridge is typically a C2-C6 alkylene bridge. In this case, the bridge is typically a straight chain alkylene, such as ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene. According to some specific embodiments, the C2-C6 alkylene bridge is ethylene or n-propylene. According to some more specific embodiments, the C2-C6 alkylene bridge is ethylene. In this article, unless the context clearly states otherwise, references to propylene are intended to refer to n-propylene (i.e., -CH2CH2CH2-, rather than -CH(CH3)CH2-).

[0081] According to some specific embodiments of the present invention, the ligand of formula (I) is 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononane-1-yl)-ethane (Me4-DTNE). According to some more specific embodiments of the present invention, the ligand of formula (I) is Me3-TACN.

[0082] The salt of the complex can contain a coordinating ligand (ie, which coordinates to one or both manganese ions in the salt complex) and a non-coordinating ligand (ie, which does not coordinate to the manganese ion).

[0083] Preferred mononuclear Mn(III) and / or Mn(IV) complexes comprise one coordinating ligand of formula (I). Preferred binuclear Mn(III) and / or Mn(IV) complexes comprise two coordinating ligands of formula (I), or one coordinating ligand of formula (I) in the case where the coordinating ligand of formula (I) comprises a group R connected via a bridge to the nitrogen atom of another Q of another ring of formula (I) (e.g., Me4-DTNE) as described herein.

[0084] In addition, both mononuclear and dinuclear Mn(III) and / or Mn(IV) complexes can contain additional coordinating ligands. For dinuclear complexes, these additional coordinating ligands are typically oxygen ions (O 2- ) or C 1-6 Carboxylate ions (i.e. RCO2 - , wherein R is an alkyl group), which bridges the two manganese ions. If present, the alkyl carboxylate ion is typically an acetate group. Typically, the dinuclear Mn(III) and / or Mn(IV) complex comprises two or three bridging oxygen ions. For example, a dinuclear manganese-containing complex may comprise two oxygen ions and one acetate ion, each of which bridges the two manganese ions; or a dinuclear manganese-containing complex may comprise three oxygen ions, each of which bridges the two manganese ions.

[0085] According to some specific embodiments of all aspects of the present invention, it is contemplated to use a dinuclear manganese-containing complex comprising two ligands of formula (I) which do not contain a group R connected via a bridge to the nitrogen atom of another Q ring of another formula (I), such as Me3-TACN, wherein the manganese ions are bridged by three oxygen ions. According to some specific embodiments, such a complex comprises two Mn(IV) ions. For example, the complex can be [Mn IV Mn IV (μ-O)3(Me3-TACN)2] 2+ , with “μ” indicating a bridging ligand according to the convention.

[0086] According to some other specific embodiments of all aspects of the present invention, it is contemplated to use a binuclear manganese ion-containing complex comprising a ligand of formula (I) comprising a group R connected via a bridge to the nitrogen atom of another Q ring of another formula (I), for example Me4-DTNE, wherein the manganese ion is bridged by two oxygen ions and an acetate ion. According to some specific embodiments, such a complex comprises a Mn(IV) ion and a manganese(III) ion. For example, the salt complex can be [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4-DTNE)] 2+ .

[0087] 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 counter anions. The counter anions are typically selected from Cl - Br - , I - 、NO3 - 、ClO4 - PF6 - 、RSO3 - 、SO4 2- 、RSO4 - CF3SO3 - and RCOO - , wherein R is selected from H, C 1-12 Alkyl and optionally C 1-6 Alkyl-substituted C6H5 (i.e., C6H5 is replaced by C 1-6 alkyl groups substituted one or more times (e.g., once); typically, C6H5 is unsubstituted). Typically, these counter anions are selected from Cl - 、NO3 - PF6 - , toluenesulfonate, SO4 2- CF3SO3 - , acetate and benzoate. In particular, these counter anions are usually selected from Cl - 、NO3 - 、SO4 2- and acetate.

[0088] Particularly preferred water-soluble bleach catalysts are [Mn2(μ-O)3(Me3TACN)2]SO4 (abbreviated as MnTACNSO4) and [Mn2(μ-O)3(Me3TACN)2](NO3)2.

[0089] WO 2006 / 125517 A1 describes transition metal catalyst salts having a significant water solubility, for example 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. The use of such highly water-soluble salts, for example those containing small counterions such as chloride, nitrate, sulfate and acetate, can be advantageous because their high solubility in water means that, for example, less water-soluble salts (e.g., salts containing PF6) can be used when contacting them with the absorbent and water-soluble polymer solution. - ions) are more concentrated salt solutions. For example, [Mn IV Mn IV (μ-O)3(Me3-TACN)2] 2+ (PF6 - )2 has a water solubility of only 10.8 g / l at 20°C. In addition, anions such as PF6- The salts are usually prepared by introducing the potassium salt form of PF6 after forming a complex with a transition metal ion. - ions, which results in precipitation of the resulting salt. This precipitate is then typically redissolved, for example in water, before contacting with the absorbent and water-soluble polymer. This additional step introduces complexity and cost and often results in the use of relatively large volumes of water, as the catalyst salt containing transition metal ions (e.g., the one described herein containing PF6 - The solubility (in water) of the manganese catalyst salts (with non-coordinating counterions) is very low.

[0090] In one embodiment, the composition comprises 0.1 to 25wt% of mononuclear or binuclear Mn (III) and / or Mn (IV) complex. Suitably, the composition comprises 0.2 to 20wt% of mononuclear or binuclear Mn (III) and / or Mn (IV) complex. More suitably, the composition comprises 0.3 to 10wt% of mononuclear or binuclear Mn (III) and / or Mn (IV) complex. Even more suitably, the composition comprises 0.5 to 7.0wt% of mononuclear or binuclear Mn (III) and / or Mn (IV) complex.

[0091] In one embodiment, the mononuclear or dinuclear Mn(III) and / or Mn(IV) complex is added in the form of a solution having a concentration of at least 2 wt% of the dry complex. Suitably, the solution is an aqueous solution comprising 2 to 75 wt% of the complex. More suitably, the solution is an aqueous solution comprising 2 to 50 wt% of the complex. More suitably, the solution is an aqueous solution comprising 3 to 30 wt% of the complex. More suitably, the solution is an aqueous solution comprising 5 and 25 wt% of the complex. Most suitably, the solution is an aqueous solution comprising 10 and 20 wt% of the complex. Optionally, the aqueous solution comprising the complex may comprise an organic or inorganic buffer, such as acetate, citrate, and benzoate buffers disclosed in WO 2006 / 125517 (Hindustan Lever Ltd.). The pH of the aqueous solution comprising the complex is ideally between 2 and 7, more typically between pH 4 and 6. The aqueous solution comprising the complex contains no solids or contains at most 1 wt% solids, preferably no solids or contains less than 0.1 wt% solids.

[0092] In certain embodiments, non-aqueous alternative suitable solutions may be used. In addition to water, suitable solutions include polar liquids such as alcohols (particularly C 1-6Alcohols such as methanol, ethanol, n-propanol and isopropanol) or mixtures thereof. As described in WO 2011 / 106906 A1, the complexes can be synthesized in water / alcohol (such as water / ethanol) mixtures or even in predominantly non-aqueous solvents.

[0093] The process of the second aspect of the invention comprises contacting a solution comprising a mononuclear or dinuclear Mn(III) and / or Mn(IV) complex as a bleach catalyst, a water-soluble polymer and an absorbent.

[0094] Water-soluble polymers for preparing compositions comprising mononuclear or dinuclear manganese complexes according to the first aspect of the invention include poly(vinyl pyrrolidone), polyalkylene glycols, functionalized poly(vinyl alcohol) polymers and polyacrylates. Other suitable water-soluble polymers are listed, for example, in WO 2018 / 011596 (Itaconix Ltd.). Polyvinyl alcohol (PVOH) polymers are typically used, wherein the molecular weight of the polymer is typically between 10,000 and 200,000, more typically between 20,000 and 100,000, as determined by gel permeation chromatography (GPC) at 20° C., and the viscosity at 4 wt % is about 2 to 70 mPa.s, measured according to DIN 53015. Polyvinyl alcohol polymers are typically prepared by hydrolyzing polyvinyl acetate and have a degree of hydrolysis of 70 to 100 mol %. Suitable degrees of hydrolysis are between 80 and 99 mol %, which results in favorable solubility characteristics. A variety of PVOH polymers having different degrees of polymerization and hydrolysis are available under the trade name of Kuraray Chemicals. Commercially available.

[0095] Modified polyvinyl alcohol polymers may also be used, such as hydrophobic or hydrophilic modified polyvinyl alcohol polymers. For example, hydrophobic polyvinyl alcohol polymers include ethylene modified polyvinyl alcohol polymers such as those from Kuraray Corporation. Furthermore, the vinyl alcohol groups can be partially modified by reaction with aldehydes, in particular C2-C10 aldehydes, as shown in WO 2018 / 011596 (Itaconix Ltd.).

[0096] In one embodiment, the composition comprises 0.1 to 20 wt% of a water-soluble polymer. Suitably, the composition comprises 0.3 to 15 wt% of a water-soluble polymer. More suitably, the composition comprises 0.5 to 10 wt% of a water-soluble polymer. Even more suitably, the composition comprises 1.0 to 8.0 wt% of a water-soluble polymer.

[0097] In one embodiment, the water-soluble polymer is added as an aqueous solution to the composition comprising the absorbent and the solution of the salt of the complex. The concentration of the water-soluble polymer in water is 5 to 50 wt%, more typically 10 to 30 wt%. Most generally, a higher concentration of the polymer dissolved in water is preferred.

[0098] The absorbent included in the composition is essential for obtaining absorbency and / or water removal when aqueous solutions and complex solutions containing water-soluble polymers are added. It also helps to bind the components of the composition together, particularly during the drying process. Suitable absorbents are based on polysaccharides, which are polymers of monosaccharides, with typical polymer chain lengths of 40-3000 monosaccharide units. Examples of suitable polysaccharides include starch, natural gums such as alginate, or cellulose, glycogen, chitin, guaiac, lumarinin, chrysolaminarim, xylan, arabinoxylan, mannan, fucoidan, galactomannan. Modified polysaccharides, such as modified starch or modified cellulose, may also be used. The most suitable absorbent is starch, which is a polymer of glucose in which the pyranose glucose units are bound by α-linkages. Suitable starch sources are potato starch, corn starch, rice starch, wheat starch, and partially pregelatinized starches from the above list. Alternatively, the absorbent may be a modified starch, such as dextrin, or a natural gum such as alginate. Most suitably, the absorbent is corn starch, potato starch or rice starch. Also particularly suitable are cellulosic materials such as cellulose fibers, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose or carboxy-modified celluloses such as carboxymethylcellulose (CMC). Most suitable are celluloses, in particular microcrystalline cellulose (e.g. 101).

[0099] Natural gum is a polysaccharide of natural origin, which can cause a significant increase in solution viscosity. They are mainly plant gums, present in the wood components of plants or seed coatings. The example of natural gum is the natural gum obtained from marine algae, such as agar, alginic acid, sodium alginate and carrageenan, or the natural gum obtained from non-marine plant resources, such as gum arabic, gum ghatti, gum tragacanth, gum karaya, guar gum, locust bean gum, beta-glucan, gum dammar, glucomannan, psyllium husk and tara gum, or the natural gum produced by bacterial fermentation, such as gellan gum or xanthan gum.

[0100] In one embodiment, the composition comprises 5 to 75 wt% of the absorbent. In another embodiment, the composition comprises 10 to 60 wt% of the absorbent. In another embodiment, the composition comprises 15 to 50 wt% of the absorbent. In one embodiment, the absorbent is added in the form of a solid material, which is typically greater than 90 wt%, more typically greater than 95 wt%.

[0101] Fillers that may be included in the composition may be organic fillers or inorganic fillers, or mixtures thereof. Suitable organic fillers are distinct from the polysaccharides used as adsorbents and include saccharides and their derivatives, including sugars. Examples of sugars include glucose, dextrose, fructose, galactose, sucrose, lactose, and maltose. Modified sugars may also be used.

[0102] In another embodiment, the filler is an inorganic filler. Inorganic fillers include talc, mica, zeolite, silicate, silica and clay. Suitably, the inorganic filler is selected from talc, mica, zeolite and silicate.

[0103] In one embodiment, the composition comprises 0 to 85 wt% filler. In another embodiment, the composition comprises 0 to 60 wt% filler. In another embodiment, the composition comprises 0 to 40 wt% filler. In yet another embodiment, the composition comprises 0 to 20 wt% filler. In another embodiment, the composition does not contain any filler.

[0104] Salts that can be included in the composition are typically alkali metal, alkaline earth metal or transition metal bicarbonates, alkali metal, alkaline earth metal or transition metal carbonates, alkali metal, alkaline earth metal or transition metal halides (chlorides, bromides or iodides), alkali metal, alkaline earth metal or transition metal sulfates, alkali metal, alkaline earth metal or transition metal phosphates, alkali metal, alkaline earth metal or transition metal oxides, alkali metal, alkaline earth metal or transition metal acetates, alkali metal, alkaline earth metal or transition metal citrates, or alkali metal, alkaline earth metal or transition metal nitrates.

[0105] In one embodiment, the salt comprises one or more salts selected from sodium bicarbonate, sodium sulfate, sodium chloride, sodium nitrate, sodium acetate, sodium citrate, sodium nitrate, potassium sulfate, potassium chloride, potassium citrate, calcium carbonate, calcium chloride and calcium sulfate. Suitably, the inorganic salt comprises one or more salts selected from sodium sulfate, calcium carbonate and sodium citrate.

[0106] In a preferred embodiment, the salt is water soluble.

[0107] In one embodiment, the composition comprises 0 to 85 wt% of salt. In another embodiment, the composition comprises 0 to 60 wt% of salt. In another embodiment, the composition comprises 0 to 40 wt% of salt. In yet another embodiment, the composition comprises 0 to 20 wt% of salt. In another embodiment, the composition does not contain any salt.

[0108] The composition may also contain a bleach activator. As bleach activators, the composition of the present invention may contain compounds generally known in the prior art. These compounds are preferably polyacylated alkylenediamines (especially tetraacetylethylenediamine (TAED)), acylated triazine derivatives (especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT)), acylated glycoluril (especially tetraacetyl glycoluril (TAGU)), triacetin (glycerol triacetate), N-acylimides (especially N-nonanoylsuccinimide (NOSI)), acylated phenolsulfonates (especially N-nonanoyloxy or N-lauroyloxybenzenesulfonates (NOBS or LOBS)), acylated phenolcarboxylic acids (especially nonanoyloxy or decanoyloxy) bleach activators. Bleach activators include, but are not limited to, benzoic acid (NOBA or DOBA, respectively), carboxylic anhydrides (particularly phthalic anhydride), acylated polyvalent alcohols (preferably triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran, as well as acetylated sorbitol and mannitol, or mixtures thereof, respectively (SORMAN)), acylated sugar derivatives (preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyxylose, and octaacetyllactose, as well as acetylated and optionally N-alkylated glucosamine and gluconolactone), and / or N-acylated lactams such as N-benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams may also be preferably used. Nitrile derivatives such as N-methylmorpholinium-acetonitrile-methylsulfate (MMA) or cyanomorpholine (MOR) may also be used as bleach activators. Combinations of bleach activators may also be used.

[0109] Suitably, the composition may comprise TAED, NOBS, triacetin and DOBA. More suitably, the granulate may comprise TAED.

[0110] In one embodiment, the composition comprises 0-80 wt% of a bleach activator. Suitably, the composition comprises 0-75 wt% of a bleach activator. Compositions that do not contain any bleach activator are also suitable. Also suitable are compositions that comprise 20-70 wt% of a bleach activator and more suitably 30-60 wt% of a bleach activator.

[0111] Thus, according to some specific embodiments of the present invention, the transition metal ion-containing salt can be provided as an aqueous solution, such as a buffered aqueous solution of the type described above. To such a solution (which can be diluted with additional water (or other solvent) if necessary), appropriate amounts of the absorbent and water-soluble polymer solution can be added, and the resulting mixture can be mixed for a suitable period of time, for example, by stirring, sonicating, vortexing, shaking, etc.

[0112] Mixing devices for preparing the compositions of the present invention are well known to those skilled in the art. All industrial mixing equipment capable of mixing liquid-solid mixtures can be used. Mixing can be carried out continuously or in batches.

[0113] Examples of mixing devices are anchor mixers, high shear dispersers, static mixers, liquid whistles, paddle mixers, V-blenders, ribbon blenders, double cone mixers, high shear mixer / granulator, tumble mixers, twin screw mixers, conical spiral mixers, jet mixers, turbine mixers and planetary mixers.

[0114] Suitable conditions, such as the duration and temperature of contact, will depend on the nature and amount of the reactants (salt of the complex, absorbent, and water-soluble polymer) and can be established by the skilled person without undue burden. For example, the duration of contact may be between about 1 minute and about 24 hours. Typically, contact can be carried out at ambient temperature, for example, at about 20 to 25° C., but elevated temperatures, for example, from about 25 to about 50° C., may be used if desired.

[0115] When the contacting portion according to the second aspect of the invention is carried out in a liquid (i.e., a solution of the salt of the complex and the water-soluble polymer), a solid material is formed in the resulting mixture after the addition of the absorbent as defined herein. Thereafter, the material may be further dried, typically at a temperature of about 30°C to 80°C, for example about 40°C to 60°C, for about 1 to 24 hours, optionally under reduced pressure. Appropriate conditions can be established by the skilled person without undue burden.

[0116] Preferred is a method of preparing a bleach catalyst composition, said method comprising the steps of:

[0117] a) providing in a mixing device a composition comprising a water-soluble polymer, an absorbent and a solution comprising from 2 to 75 wt. % of a water-soluble transition metal ion-containing bleach catalyst, relative to the total amount of the solution, said water-soluble transition metal ion-containing bleach catalyst having a water solubility of at least 30 g / L at 20° C. and being a mononuclear or binuclear manganese complex as defined above;

[0118] b) mixing the ingredients of the composition;

[0119] c) forming particles; and

[0120] d) optionally drying the granules obtained in step c).

[0121] In one variant of the process for preparing a bleach catalyst composition comprising steps a) to d), the dried particles or granules are further subjected to a coating treatment in step e).

[0122] The drying step d) is preferably carried out in a fluidized bed dryer.

[0123] The granulate particles of step c) are preferably formed by wet granulation.

[0124] In another preferred embodiment, the mixture obtained in step b) is extruded to form extrudates.

[0125] In a further preferred embodiment, the mixture obtained in step b) is compacted under pressure.

[0126] The catalyst composition of the present invention can be formed by any suitable technique known in the art. In one embodiment, the amount of water used in step a) of the method is such that the particles produced in step c) are granular. In another embodiment, step d) of the method comprises drying the particles obtained in step c) in a fluidized bed dryer. In another embodiment, step d) of the method comprises drying the particles obtained in step c) at a temperature of 25-80°C. Suitably, step d) of the method comprises drying the particles obtained in step c) at a temperature of 35-60°C. Most suitably, step d) of the method comprises drying the particles obtained in step c) at a temperature of 45-55°C. In another embodiment, the water-soluble polymer mixed in step b) of the method is provided as an aqueous solution. Suitably, the water-soluble polymer mixed in step b) of the method is provided in the form of an aqueous solution of 2wt% to 30wt%. More suitably, the water-soluble polymer mixed in step b) of the method is provided in the form of an aqueous solution of 2wt% to 20wt%. Most suitably, the water-soluble polymer mixed in step b) of the method is provided in the form of an aqueous solution of 2wt% to 10wt%. In addition, the water-soluble polymer mixed in step b) of the method can be provided in the form of an aqueous solution of 15 wt% to 25 wt%. The bleaching catalyst, water-soluble polymer, absorbent, filler and water-soluble salt can be mixed together in the desired proportions and then formed into particles by, for example, compression, granulation (wet or dry granulation), spheronization and extrusion techniques. Alternatively, the water-soluble polymer can be applied to preformed particles of the bleaching catalyst in the form of a coating using any suitable coating technique known in the art. Specific examples of suitable granulation techniques are described in the accompanying Examples section of this article. Therefore, in a particular embodiment, the catalyst composition is produced by a granulation technique. In such an embodiment, step a) comprises adding water to the bleaching catalyst, water-soluble polymer, absorbent and other optional ingredients (e.g., filler, water-soluble salt and water) under mixing, wherein the amount of water added is sufficient to form discrete particles of the mixture. Step c) comprises forming the mixture formed by the ingredients provided in step a) into discrete particles or granules; and step d) comprises drying the discrete particles or granules obtained in step c) (e.g., in a fluidized bed dryer). In another specific embodiment, the catalyst composition is produced by extrusion. In such an embodiment, step b) comprises mixing the bleach catalyst, water-soluble polymer, absorbent, and other optional ingredients such as fillers, water-soluble salts, and water to form a mixed material, which is then extruded into an extrudate in step b'); in a further step c), the extrudate from step b') is treated to form discrete particles or granules (e.g., spheronized); and step d) comprises drying the discrete particles or granules obtained in step c). In one embodiment, step c) of the method can be skipped, and the extrudate obtained in step b') can be directly dried.In another specific embodiment, the catalyst composition is produced by a compaction technique. In such an embodiment, step b) comprises mixing the bleach catalyst, the water-soluble polymer, the absorbent, and other optional ingredients such as fillers, water-soluble salts, and water to form a mixed material, which is then compacted under pressure in step c"); and a further step c) comprises treating the compacted mixture of step c") to form discrete particles or granules (e.g., spheronization); and step d) comprises drying the discrete particles or granules obtained in step c).

[0127] The present invention also relates to bleaching packages comprising a composition according to the invention and at least one bleaching agent and / or a precursor thereof.

[0128] The composition according to the invention may be in the form of granules, powder or flake solids, preferably granules.

[0129] The production of the granules according to the invention can be carried out according to methods known per se and has been described in detail in the above-mentioned patent documents.There are fundamentally different granulation methods available.

[0130] In a first preferred process variant, the granules are formed in a mixing device. The components are processed in conventional mixing devices, either batchwise or continuously operated, which are generally equipped with rotating mixing mechanisms. When mixing, all mixing variants are contemplated that ensure thorough mixing of the components.

[0131] In a preferred embodiment, all components are mixed simultaneously.However, multi-stage mixing processes are also contemplated, in which the individual components are fed into the overall mixture individually or together with other additives in different combinations.

[0132] The order of the slow and fast mixers can be interchanged as needed. The residence time in the mixer granulation is preferably 0.5 seconds to 20 minutes, particularly preferably 2 seconds to 10 minutes. The granulation fluid can be pumped into the mixing device via a simple conduit. However, for better distribution, a nozzle system (single material or multi-material nozzle) can also be considered.

[0133] Typically, a drying step is performed immediately after the granulation stage to prevent the particles from sticking. The coarse and fine particles are then separated by sieving. The coarse particles are comminuted by grinding and, like the fine particles, are fed to a new granulation process. The coating is preferably applied in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0134] The solution is thoroughly mixed with the powdered active substance and other optional additives to form a plastically deformable material. The mixing step can be carried out in the above-mentioned mixing equipment, but a kneader or special extruder can also be used. The granulated material is then pressed through the nozzle holes of the press matrix with a tool to form a cylindrical extrudate. The discharged extrudate must be crushed to the required length or particle size through a post-processing step. In many cases, a length / diameter ratio of L / D=1 is desired. For cylindrical particles, the particle diameter is generally between 0.2mm and 2mm, preferably between 0.5mm and 0.8mm, and the particle length is in the range of 0.5 to 3.5mm, ideally between 0.9mm and 2.5mm. The length or size adjustment of the particles can be achieved by, for example, a fixed stripping knife, a rotating cutting knife, a cutting wire or a blade. In order to round the cut edges, the particles can then be rounded again in a rounding machine (rondier).

[0135] After the granules have been sized, a final curing step is usually required to remove the solvent before applying the coating. This step is typically performed in a fluidized bed system, which functions as a dryer. The coarse and fine fractions are then separated by sieving. The coarse particles are comminuted by grinding and, like the fine particles, are fed to the new granulation process. The resulting granules can then be coated in a fluidized bed system, for example, in a fluidized bed mixer.

[0136] Preferred granules according to the invention are further characterized in that the water content, based on the total amount of granules, is less than 3% by weight (measured by Karl Fischer), particularly preferably 0 to 2% by weight.

[0137] As will be appreciated by those skilled in the art, the composition according to the first aspect of the invention may need to be further processed, for example to impart beneficial properties to the particles for inclusion in bleaching compositions of the invention, such as solid detergent compositions. Although the composition according to the first aspect of the invention may be included in a bleaching composition as is due to its excellent storage stability, the formulator may wish to further modify the particles, for example by mixing with a soluble coating agent.

[0138] Thus, according to some embodiments, the composition of the first aspect of the present invention having the desired particle size may be coated with a water-soluble material, which may optionally be provided with a water-dispersible surface powder coating. Suitable water-soluble materials and water-dispersible surface powder coatings are known to those skilled in the art and are fully described in, for example, WO 95 / 06710 A1 and WO 95 / 30733 A1. In addition, polyvinyl alcohol may also be used as a coating material, as described in WO 2018 / 210442.

[0139] Thus, the bleaching composition of the present invention may be in the form of non-friable composition particles comprising a composition according to the first aspect of the invention, optionally with additional inert solids, bleaching agent precursors, fillers and inorganic salts, and optionally with a coating agent. Definitions and descriptions of each essential and optional category of ingredients are given in the detailed description above.

[0140] Coating agents may include materials similar to the water-soluble polymers described above, but they also include materials such as starches, alginates, cellulose derivatives, fatty acids, waxes, paraffins, polyethylene glycols, gelatin, electrolytes, polyelectrolytes, and the like.

[0141] The composition of the first aspect of the invention, optionally in the form of non-friable particles as described above, may be subjected to grinding, pulverization, etc. to provide a dry composition having the desired particle size. As is well known in the art, when such a composition is introduced into a solid bleaching composition (e.g., a washing powder), the agglomerated particles comprising the bleach activating catalyst ideally have approximately the same size and bulk density as the other components of the solid bleaching composition to avoid percolation or flotation separation.

[0142] The composition of the first aspect of the invention or a composition prepared therefrom is typically present in the bleaching composition according to the third aspect in the form of a solid (typically granular) such as a granule or powder, with an average particle size typically between 50 μm and 2500 μm, for example between 100 μm and 1600 μm. The particle size can be measured by a laser diffraction particle size analyzer such as a Malvern HP equipped with a 100 mm lens.

[0143] As is known in the art, the bulk density and size of particles can be controlled by composition, process conditions, or both.

[0144] Those skilled in the art are familiar with suitable particle sizes and densities (and / or can determine suitable sizes and densities by routine experimentation), as well as suitable techniques for achieving these suitable particle sizes and densities, such as by conventional granulation techniques. For example, suitable granules can be prepared by any conventional and / or known granulation technique, such as using a pan granulator, a fluidized bed, a Schugi mixer, Plowshare mixing, rotary drum and other low energy mixers; by compaction, including extrusion and tableting, optionally followed by comminution and grinding; granulation and pelletization using Sandvik Roto molding machines when using molten binders; and high shear energy processes using high speed mixer / granulator equipment with high energy stirring and cutting action. An example of a suitable compactor is equipment from Hosokawa, such as the Bepex L200 / 30. An example of such high speed mixing / granulation equipment is the Fukae TM, FS-G mixer, manufactured by Fukae Powtech Kogyo Co., Ltd., Japan. Other mixers that can be used in the process of the present invention include Diosna TM , manufactured by TKFielder Ltd., UK; Fuji TM VG-C series, manufactured by Fuji Sangyo of Japan; and Roto TM , manufactured by Zanchete&Co Srl, Italy. In addition to batch equipment, high-speed mixer / granulators can also be used, such as Recycler.

[0145] The compositions according to the first aspect of the invention are particularly valuable when used in bleaching compositions, the transition metal ion-containing complexes described herein being used to catalyse the oxidative activity of peroxygen compounds which may be contained in a bleaching composition according to the invention or which may be generated in situ in such a bleaching composition.

[0146] Where a peroxy compound is present in the bleaching composition of the present invention, the peroxy compound may be, and typically is, a compound capable of producing hydrogen peroxide in aqueous solution. Suitable amounts of peroxy compounds to include in the bleaching composition can be determined by a skilled person, although typical amounts are in the range of 1-35 wt%, e.g., 5-25 wt%, based on the solids content of the bleaching composition. Those skilled in the art will recognize that smaller amounts of peroxy compounds may be used where the bleaching composition comprises a bleaching system comprising a peroxy compound and so-called bleach precursors (discussed below).

[0147] Suitable hydrogen peroxide sources are well known in the art. Examples include 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 in the bleaching composite are persalts, such as optionally hydrated sodium perborate (e.g. monohydrate sodium perborate and tetrahydrate sodium perborate) and sodium percarbonate. According to some specific embodiments, the bleaching composite comprises monohydrate sodium perborate or tetrahydrate sodium perborate. Due to its high active oxygen content, it is advantageous to include monohydrate sodium perborate. For environmental reasons, it is most advantageous to use sodium percarbonate.

[0148] Organic peroxyacids can also be used as peroxy compounds. These organic peroxyacids can be mono- or diperoxyacids. Typical mono- or diperoxyacids have the general formula HOO-(C=O)-RY, wherein R is an alkylene or substituted alkylene group containing 1 to about 20 carbon atoms, optionally with a lactam bond or a phenylene or substituted phenylene group; and Y is hydrogen, a halogen, an alkyl group, an aryl group, an imido aromatic or non-aromatic group, a COOH or (C=O)OOH group, or a quaternary ammonium group.

[0149] Typical monoperoxyacids include peroxybenzoic acid, peroxylauric acid, N,N-phthalamidoperoxycaproic acid (PAP) and 6-octylamino-6-oxoperoxycaproic acid. Typical diperoxyacids include, for example, 1,12-diperoxylauric acid (DPDA) and 1,9-diperoxyazelaic acid.

[0150] Besides organic peroxyacids, inorganic peroxyacids are also suitable, for example potassium monopersulfate (MPS).

[0151] If organic or inorganic peroxyacids are included in the bleaching formulation, they are typically added to the bleaching formulation in an amount in the range of about 2-10 wt. %, for example in the range of 4-8 wt. %.

[0152] However, the bleaching composition need not contain a peroxy compound: the bleaching composition of the present invention may alternatively comprise a bleaching system consisting of components which are suitable for the in situ generation of hydrogen peroxide but which are not themselves peroxy compounds. An example of this is the use of C 1-4 Alcohol oxidase and C 1-4 Combinations of alcohols, such as methanol oxidase and ethanol. Such combinations are described in WO 95 / 07972 A1 (Unilever NV and Unilever plc).

[0153] Typically, bleaching substances are generated in situ. For example, organic peroxyacids are often generated in situ rather than included in the bleaching composition, as peroxyacids themselves are often unstable. To this end, bleaching compositions typically comprise a bleaching system containing a persalt (e.g., sodium perborate (optionally hydrated) or sodium percarbonate) that generates hydrogen peroxide in water; and a so-called peroxy bleach precursor that reacts with hydrogen peroxide to form the organic peroxyacid.

[0154] Those skilled in the art are well-versed in the use of bleaching systems comprising peroxygen bleach precursors, which are well known to those skilled in the art and are described in the literature. For example, reference may be made in this regard to British Patents 836988, 864798, 907356, 1003310, and 1519351; EP 0185522 A, EP 0174132 A, EP 0120591 A; and U.S. Patents 1246339, 3332882, 4128494, 4412934, and 4675393. Suitable bleach precursors are listed above.

[0155] Where used, the bleach precursor compound is typically present in the bleach formulation in an amount of up to 12% by weight of the composition, for example from 2 to 10% by weight, based on the solids content of the bleach formulation.

[0156] The peroxygen compound or bleaching system described herein may be stabilized within a bleaching formulation by providing it with a protective coating, such as a coating comprising sodium metaborate and sodium silicate.

[0157] The present invention also relates to a cleaning agent, preferably a dishwashing agent, comprising the bleaching composition described above.

[0158] Cleaning agents, including dishwashing agents, contain, in addition to the compositions according to the invention, the ingredients customarily present in such agents.

[0159] In a preferred embodiment, the cleaning agent according to the invention contains mononuclear or dinuclear Mn(III) and / or Mn(IV) complexes in the range of 0.002 to 1 wt. %, more preferably in the range of 0.005 to 0.3 wt. %, more preferably in the range of 0.01 to 0.1 wt. %, wherein the percentages are based on the total amount of the cleaning agent.

[0160] For automatic dishwasher cleaning, corrosion of glassware during the rinse cycle can be inhibited by using glass corrosion inhibitors. These are, for example, crystalline layered silicates and / or zinc salts. Crystalline layered silicates are commercially available, for example, from WeylChem under the trade name Na-SKS, such as Na-SKS-1 (Na2Si 22 O 45 xH2O, sodium hydroxide silicate), Na-SKS-2 (Na2Si 14 O 29 xH2O, magadiite), Na-SiKS-3(Na2Si8O 17 ·xH2O) or Na-SKS-4 (Na2Si4O9·xH2O, natronite). Particularly suitable are Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, natronite), Na-SKS-9 (NaHSi2O5·H2O), Na-SKS-10 (NaHSi2O5·3H2O, natronite), Na-SKS-11 (t-Na2Si2O5) and Na-SKS-13 (NaHSi2O5), but especially Na-SKS-6 (δ-Na2Si2O3). For example, in "Seifen- An overview of crystalline sheet silicates can be found in the article published in "Schmidt-Wachse, Vol. 116, No. 20 / 1990", pp. 805-808.

[0161] In another preferred embodiment of the present invention, the washing and cleaning compositions according to the invention, in particular dishwasher detergents, incorporate preferably 0.1 to 20 wt. %, more preferably 0.2 to 15 wt. %, more preferably 0.4 to 10 wt. % of crystalline phyllosilicates, relative to the total weight of the composition.

[0162] To control glass corrosion, the washing and cleaning compositions of the present invention, in particular dishwasher detergents, may contain at least one zinc or bismuth salt, preferably selected from organic zinc salts, more preferably from soluble organic zinc salts, even more preferably from soluble zinc salts of monomeric or polymeric organic acids, and even more preferably from zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietic acid, zinc valerate, and zinc p-toluenesulfonate. Bismuth salts, such as bismuth acetate, may be used as an alternative to or in combination with these zinc salts.

[0163] In the context of the present invention, preference is given to washing and cleaning compositions, in particular dishwasher detergents, in which the amount of zinc salt is from 0.1 to 10 wt %, preferably from 0.2 to 7 wt %, more preferably from 0.4 to 4 wt %, relative to the total weight of the composition, regardless of which zinc salt is used, in particular regardless of whether an organic or inorganic zinc salt, a soluble or insoluble zinc salt or a mixture thereof is used.

[0164] The cleaning compositions of the present invention may also contain silver corrosion inhibitors for controlling silver corrosion. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, dihydric or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, zirconium, hafnium, cobalt or cerium, wherein the metal is present in one of the oxidation states II, III, IV, V or VI, depending on the metal.

[0165] According to some specific embodiments, bleaching compounds can be used for bleaching and / or modifying (e.g., degrading) polysaccharides (e.g., cellulose or starch) or substrates containing polysaccharides (e.g., cellulose-containing, also referred to herein as cellulose). Cellulose substrates are widely present in industries such as household, industrial, and institutional laundry, wood pulp, and cotton processing. For example, raw cotton (ginned cotton product) is dark brown due to the natural pigments in plants. The cotton spinning industry recognizes that before cotton is used in textiles and other fields, it needs to be bleached. The purpose of bleaching such cotton fibers is to remove natural and extraneous impurities while producing substantially whiter materials.

[0166] Regardless of the nature of the substrate to be treated according to the method of the fourth aspect of the invention, the purpose of doing so is to bleach, i.e., remove unwanted chromophores (such as stains or solids on cloths used in washing or dishwashing applications; residual lignin in wood pulp or polyphenolic substances present in raw cotton, wood pulp and paper) and / or to degrade materials such as starch or polyphenolic substances in dishwashing. Thus, according to some specific embodiments, the substrate can be, for example, dirty dishes or a polysaccharide or a polysaccharide-containing substrate, wherein the polysaccharide is a cellulosic substrate such as cotton, wood pulp, paper or starch.

[0167] Thus, the bleaching compositions of the present invention may be used in dishwashing methods. Such methods typically involve washing dishes in a mechanical dishwasher, typically to remove starch and polyphenolic components from the surface of the dishes. The term "dishes" as used herein includes within its scope cookware as well as plates, crockery and other dining (e.g., cutlery) and tableware, such as those made of ceramic, metal, or plastic materials. Thus, an embodiment of a fourth aspect of the present invention comprises a method for washing dishes in a mechanical dishwasher, comprising contacting the dishes with water and a bleaching composition according to the third aspect of the present invention.

[0168] Bleaching compound of the present invention can be used in the method for cleaning textile or nonwoven (common textile) equally.So-called textile refers to weaving or knitted fabric here, promptly is knitted, knotted, crocheted or knitted together the fabric with interwoven fibers formed by natural or artificial fiber.As known in the art, the difference between textile and nonwoven is its manufacture method.Nonwoven is also made of fibrous material, and realizes bonding and produces by applying heat, mechanical pressure or chemical (comprising solvent) processing.Therefore, the embodiment of fourth aspect of the present invention comprises the method for cleaning textile or nonwoven usually in mechanical washing machine, and it comprises making textile or nonwoven contact with water and the bleaching compound according to third aspect of the present invention.

[0169] According to some specific embodiments of the present invention, the bleaching compound is suitable for and can be used in a method for cleaning textiles or nonwovens, in particular for cleaning fabrics, i.e. textiles or nonwovens, such as clothes. Although it should be understood that the present invention should not be considered as limited in this way, in the case where the bleaching compound is intended for laundry or hard surface cleaning applications, the bleaching compound typically includes other components well known to those of ordinary skill in the art, such as bleach stabilizers (also known as chelating agents), such as organic chelating agents such as aminophosphates or carboxylate chelating agents; one or more surfactants, such as cationic, anionic or non-anionic (amphiphilic) surfactants; and other components, including but not limited to detergent builders, enzymes and spices.

[0170] The bleaching formulation according to the third aspect of the invention will preferably contain from 0.1 to 50 wt% of one or more surfactants.The bleaching formulation may comprise one or more anionic surfactants and one or more nonionic surfactants. Typically, the anionic and nonionic surfactants of the surfactant system can be selected from the surfactants described in "Surfactant Active Agents, Volume 1, Schwartz & Perry, Interscience 1949, Volume 2, Schwertz, Perry & Berch, Interscience 1958; in the latest 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 be found, for example, in WO 03 / 072690 A1 (Unilever NV et al.), WO 02 / 068574 A1 (Unilever N.V. et al.) and WO 2012 / 048951 A1 (Unilever PLC et al.).

[0171] Those who understand bleaching compounds will be familiar with the application of enzymes in this regard. Enzymes can provide cleaning performance, fabric care and / or hygienic benefits. The enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. The members of these enzymes are described in "1992 Enzyme Nomenclature: Recommendations of the International Union of Biochemistry and Molecular Biology Nomenclature Committee on Enzyme Nomenclature and Classification" (1992, ISBN 0-1202271165-3, Academic Press). Decontamination enzymes are described in more detail in, for example, U.S. Patent No. 6,579,839 (Price et al.).

[0172] Suitable detergent builders, such as those described in WO 00 / 34427 A1, may also be present as optional ingredients. Builders may include aluminosilicates, particularly zeolites, such as zeolites A, B, C, X, and Y, and MAP zeolite as described in EP 0384070 A; and precipitated builders such as sodium carbonate. Such builders are typically present in an amount of from about 5 to about 80% by weight, more preferably from about 10 to 50% by weight, based on the solids content of the bleaching composition.

[0173] Those skilled in the art will be able to easily prepare suitable bleaching compounds for laundry according to their normal skills.Equally, those skilled in the art will be able to easily prepare bleaching compounds that are applicable to other applications described herein.Such compounds can for example comprise active additional metal ion groups or organocatalysts that are suitable for catalyzing peroxy compounds described herein.Non-limiting examples of bleaching catalysts based on transition metals can be found in for example EP 2228429 A1 (Unilever PLC and Unilever NV) and the references cited therein, and the example of organocatalysts can be found in WO 2012 / 071153 A1 (The Procter & Gamble Company).

[0174] The invention also relates to a method for cleaning textiles or nonwovens or for washing dishes, comprising contacting a substrate with water and a bleaching composition as described above.

[0175] Preferred is a method of washing dishes in a mechanical dishwasher, the method comprising contacting the dishes with water and said bleach combination.

[0176] The following non-limiting examples more fully illustrate embodiments of the present invention.

[0177] experiment

[0178] Chemicals used

[0179] Corn starch was obtained from Roth.

[0180] TAED( AC White), FDO X and FDOXP was obtained from Weylchem Performance Products. FDO X and FDOXP contains 2wt% [Mn IV Mn IV Particles of (μ-O)3(Me3-TACN)2](PF6)2.H2O. FDO X is uncoated granules. FDO XP is a coated granule.

[0181] Calcium sulfate is sold under the trade name Obtained from Rettenmaier.

[0182] Polyvinyl alcohol is sold under the trade name 6-88 obtained from Kuraray.

[0183] Trisodium citrate was obtained from Jungbunzlauer.

[0184] Sodium carbonate was obtained from Sigma-Aldrich.

[0185] Sodium percarbonate was obtained from Solvay.

[0186] SKS-6 silicate is sold under the trade name SKS-6 was obtained from Weylchem Performance Products.

[0187] PEG 1500 and PEG 6000 powders were obtained from Clariant.

[0188] PA25C1 and Lutensol T07 were obtained from BASF.

[0189] Protease Blaze Evity 150T and amylase Stainzyme Plus Evity 24T were obtained from Novozymes.

[0190] [Mn2(μ-O)3(Me3TACN)2]SO4 (15 wt% aqueous solution) was prepared as described in WO2006 / 125517 (hereinafter referred to as MnTACNSO4).

[0191] [Mn2(μ-O)3(Me3TACN)2](NO3)2 (14 wt% aqueous solution) was prepared in a similar manner to the [Mn2(μ-O)3(Me3TACN)2]SO4 solution described in WO2006 / 125517.

[0192] [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 (50% purity level after spray drying with addition of NaCl) was prepared as described in WO 2013 / 033864.

[0193] [Mn2(μ-O)3(Me3-TACN)2](PF6)2.H2O was obtained from Weylchem Performance Products under the trade name MnTACN.

[0194] Preparation of granules and ADW tablets.

[0195] Seven particle compositions containing MnTACNSO4 were prepared according to Table 1. A typical procedure for preparing particles according to the table below is as follows (examples are given for particle 1).

[0196] First, a PVOH aqueous solution was prepared according to the information provided by Kururay. Commercially available Poval 6-88 polymer was dissolved in 3 weight equivalents of hot water (90-95°C) and then allowed to cool slowly.

[0197] In an Eirich laboratory mixer (model R02), 536 g of TAED and 400 g of corn starch were added and mixed thoroughly. Then, an aqueous solution of MnTACNSO4 and PVOH was quickly added to the TAED / starch mixture. For granules 3, 6, and 7, TAED was not used, but the inorganic salt CaSO4 was used. For granule 7, microcrystalline cellulose ( 101) instead of starch. The amount of MnTACNSO4 solution (15 wt%) added was 133.3 g for granules 1-3, 200 g for granules 4-6 and 400 g for granule 7. The amount of diluted PVOH (Poval 6-88; 25 wt% aqueous solution) added was 174 g for granules 1-3, 98.5 g for granules 4-6 and 64 g for granule 7. The resulting composition was then further thoroughly mixed for 2 minutes (2500 rpm). The granules were then dried in a fluidized bed (30 minutes at 60°C). The dried granules obtained were sieved; fine particles (<0.2 mm) and coarse particles (>1.6 mm) were discarded (or they could be reused to prepare new granules of appropriate size).

[0198] Table 1. Containing MnTACNSO4, TAED, starch or microcrystalline cellulose ( 101) and polyvinyl alcohol ( 6-88) (in wt% dry matter). Each granule was prepared in 1 kg batches.

[0199] Particle 1 Particle 2 Particle 3 Particle 4 Particle 5 Particle 6 Granules 7 TAED 53.6 43.6 0 54.5 44.5 0 0 <![CDATA[CaSO4]]> 0 0 53.6 0 0 54.5 52.9 corn starch 40.0 50.0 40.0 40.0 50.0 40.0 0 microcrystalline cellulose 0 0 0 0 0 0 39.6 <![CDATA[MnTACNSO4]]> 2.0 2.0 2.0 3.0 3.0 3.0 6.0 Poval 6-88 4.4 4.4 4.4 2.5 2.5 2.5 1.6

[0200] The composition of the ADW formulation to which particles containing a manganese catalyst were added is given in Table 2 below.

[0201] Each granule (80.15 mg of granules 1-3, 53.44 mg of granules 4-6, and 26.72 mg of granule 7) was then placed in a container containing 19.8 g of the ingredients shown in the table below and mixed thoroughly. Tablets weighing 19.88 g (granules 1-3), 19.85 g (granules 4-6), and 19.83 g (granule 7) were then prepared using a Carver Handtablet Press Model 4332 with a pressure of 1.5 tons.

[0202] Table 2: Composition of ingredients used to prepare ADW tablets containing granules 1-7 shown in Table 1.

[0203] Element Wt% Sodium citrate 36.0 sodium carbonate 25.0 Sodium percarbonate 15.0 Peractive AC white(TAED) 5.0* Weylclean SKS-6 5.0 PEG 1500 powder 3.0 PEG 6000 powder 2.0 Sokalan PA25Cl 5.0 Lutensol TO7 1.0 Protease Blaze Evity 150T 1.5 Stainzyme Plus Evity 24T 0.5

[0204] * Appropriate amounts of TAED were added to achieve a total of 5% TAED in the ADW tablets. Since the addition of granules 1, 2, 4, and 5 also introduced TAED but the addition of granules 3, 6, and 7 did not, varying amounts of pure TAED were added to the mixture.

[0205] Tea stain cleaning in ADW

[0206] ADW tablets containing granules 1 to 7 were then tested for tea stain removal on teacups in an automatic dishwasher (Miele G 1223SC GSL2-45°C, standard program R-time 2, at 21° DH water hardness, 50 g IKW soil solution). For all tablets containing granules 1 to 7, the cleaning of the tea-stained cups was 10 (on a scale of 1 to 10).

[0207] Using the same scoring criteria, the blank (no catalyst present) showed a cleaning performance of 4.8, and two reference samples (ADW formulations of the same composition, but now added as commercial granules, one commercial granule without coating ( FDO X) and a commercially available granule with coating ( FDO XP), both showed a cleaning performance of 10.

[0208] These results show that the cleaning performance of the ADW tablets containing the MnTACNSO4-containing particles of the present invention is very good and comparable to that of the ADW formulations containing the commercially available FDO X and FDO XP particles.

[0209] Storage stability test results

[0210] The tablets containing MnTACNSO4 were then stored in an oven at 40°C for 4 weeks and then tested for cleaning performance and visually assessed (color change of the tablets). FDO X and FDO XP commercial particles (each containing 2 wt% [Mn IV Mn IV The same ADW tablets containing [(μ-O)3(Me3-TACN)2](PF6)2.H2O) were used for comparison.

[0211] The dishwashing tablets containing granules 1, 2, 3, 4 and 5 did not show any color change during storage, whereas the tablets containing granules 6 and 7 showed brown spots in the tablet (presumably due to degraded MnTACN catalyst).

[0212] Under the same conditions, containing commercially available FDO X particles (containing [Mn IV MnIV Tablets containing (μ-O)3(Me3-TACN)2](PF6)2.H2O crystals showed black spots of (presumably) MnO2. In addition, the coated Tablets of FDO XP granules (which also contain [Mn IV Mn IV (μ-O)3(Me3-TACN)2](PF6)2.H2O crystals) showed some black spots (but less than those containing dark spots on tablets of FDO X granules).

[0213] Tea stain bleaching performance using the same apparatus as described in the previous section showed that tablets containing Granules 1, 2, 4, 5, and 7 had the same high tea stain performance as the freshly prepared tablets / granules. The tablet containing Granule 3 showed a 15% loss of activity, and the tablet containing Granule 6 showed a 5% loss of activity.

[0214] contain The reference tablets of FDO X showed a 20% decrease in activity, indicating that significant decomposition of the catalyst and / or sodium percarbonate occurred during storage.

[0215] These data clearly show that particles containing MnTACNSO4 show very good stability and bleaching activity in ADW formulations. Surprisingly, the storage test results of uncoated particles containing amorphous MnTACNSO4 in ADW tablets are even better than those of commercially available coated MnTACN catalysts with PF6 as non-coordinating counterion ( FDO XP) as the latter showed brown spots after storage.

[0216] Reference granulation experiment

[0217] An attempt was made to prepare particles using an aqueous solution of [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O according to the same process.

[0218] Similar to the method described above for particles 1-7, an aqueous solution of [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O in water and PVOH were mixed with the other components (corn starch and CaSO4) to prepare particles. Due to the relatively low solubility of [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O in water (1.08 wt% solubility in water at 20°C, see WO2006 / 125517), a large amount of water needs to be added to obtain a mixture with sufficient [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O catalyst to produce particles containing 2 wt% of [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O (this is equivalent to 1.85 L of an aqueous solution of [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O, following the same amounts of chemicals as described in the above examples).

[0219] Two observations were made: First, it proved impossible to dry the resulting mixture in a fluidized bed drying process without significant catalyst decomposition. After drying, dark brown granules were obtained that were unsuitable for use in dishwashing detergent formulations. A second observation was that mixtures of [Mn(μ-O)(MeTACN)](PF).HO and PVOH in water were unstable. Leaving the mixture at room temperature for one day revealed a white precipitate and a colorless solution. This did not occur when solutions of MnTACNSO and PVOH were mixed, where the mixture remained stable for at least four days.

[0220] Attempts to use the same amount of water as described above for MnTACNSO4 (20 g [Mn2(μ-O)3(Me3TACN)2](PF6)2.H2O in 133 g water) resulted in a mixture of dissolved manganese catalyst (1.08 wt% or 1.45 g) and 18.55 g of still crystalline product (in the form of a slurry). Granulating and drying this mixture with PVOH, starch and CaSO4 or TAED will produce granules in which the catalyst is mainly in the form of a crystalline solid material, which has a very different appearance and needs to be coated to obtain stable granules (such as the commercially available coated FDO XP granules). As shown, such granules are much darker in appearance and therefore distinct from granules produced according to the procedure described above for granules 1-7.

[0221] Scanning electron microscopy analysis of particles containing MnTACNSO4

[0222] exist Figures 1 to 6 , a SEM (scanning electron microscope) photograph of the uncoated granules of the present invention is shown. Figure 1 A photograph of granules prepared from the formulation of Granule 4 of Table 1 is shown. Figures 2 to 6 An enlarged portion of the particle is shown.

[0223] exist Figure 1 In the figures, particles comprising primary particles with smooth surfaces were observed. No MnTACNSO4 crystals were detected in these figures. Figures 2 to 6 At increased magnification as shown in , significantly smaller spheres that are not crystals are observed. Figure 5 and Figure 6 At the highest magnifications in the image, one can observe small globules of amorphous material stuck to it, but never any sign of crystals.

[0224] This is understandable from a chemical perspective. During the preparation of the granules, a solution of MnTACNSO4 and PVOH is combined with water-absorbing starch. After mixing the ingredients, the resulting granules dry relatively quickly (30 minutes). Since it typically takes hours or days to obtain a crystalline transition metal complex during the drying process, it is understandable that the rapid drying of the granules would not allow the formation of crystalline bleach catalyst within the granules, especially considering that a highly water-soluble catalyst salt would be more difficult to crystallize than a less water-soluble catalyst salt, as disclosed in WO2006 / 125517.

[0225] Preparation of particles containing [Mn2(μ-O)3(Me3TACN)2](NO3)2

[0226] Similar to the procedure described above for the particles containing [Mn2(μ-O)3(Me3TACN)2]SO4, particles containing TAED, corn starch, and PVOH (Pellets 8) were prepared. The composition of red Pellets 8 was: 53.6 wt% TAED, 4.4 wt% PVOH, 40.0 wt% corn starch, and 2.0 wt% [Mn2(μ-O)3(Me3TACN)2](NO3)2.

[0227] Preparation of ADW tablets containing particles containing [Mn2(μ-O)3(Me3TACN)2](NO3)2

[0228] Next, tablets were compressed according to the above procedure using the composition given in Table 2 above, which also included 79.5 mg of granules 8 containing [Mn2(μ-O)3(Me3TACN)2](NO3)2.

[0229] Determination of bleaching activity in ADW.

[0230] Tablet containing particle 8 containing [Mn2(μ-O)3(Me3TACN)2](NO3)2 was used to clean tea stains from teacups in a dishwasher as described above for tablets containing particles 1-7.

[0231] Similar to the other tablets containing Granules 1-7, complete stain removal was observed, indicating that the cleaning activity of the tablet containing Granules 8 was equivalent to that of tablets containing Granules 1-7 or commercial FDO X particles (containing [Mn2(μ-O)3(Me3TACN)2](PF6)2).

[0232] Storage stability test

[0233] Next, the tablets were stored at 40°C for 4 weeks and then re-evaluated for tea stain bleaching activity. No loss of performance was observed (complete cleaning), indicating that Particle 8 in the ADW tablet was also very stable (as observed for Particles 1-7 containing MnTACNSO4 stored in ADW tablets disclosed above).

[0234] Preparation of particles containing [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2

[0235] Similar to the procedure described above for particles containing [Mn2(μ-O)3(Me3TACN)2]SO4, particles containing [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2, TAED, corn starch and PVOH were prepared (particles 9).

[0236] The composition of Particle 9 is: 53.6 wt% TAED, 4.4 wt% PVOH, 40.0 wt% corn starch, 1.0 wt% NaCl and 1.0 wt% [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2. The color of Particle 9 is light green.

[0237] Determination of the bleaching activity of granules 9.

[0238] BC-1 (tea stains on cotton) bleaching experiments were performed similarly to those described in WO 2014 / 202954. All bleaching experiments were performed in duplicate.

[0239] Bleaching of BC-1 (tea stains on cotton) was evaluated at pH 11.5 in an aqueous solution containing 1 g / L nonionic complex (Lutensol A07), 0, 1 and 2 μM [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2), 1 g / L sodium percarbonate at 40°C for 30 minutes (reference test).

[0240] Similarly, the bleaching activity of Granule 9 was evaluated using the same protocol, except that Granule 9 was dissolved in demineralized water, resulting in the same concentration of catalyst as used in the reference test.

[0241] result

[0242] As can be seen in Table 3 below, the bleaching performance of Granule 9 containing [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 is very similar to the bleaching performance of 50% pure [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2, indicating that the particle containing this catalyst (Granule 9) effectively releases the catalyst in the bleaching solution, resulting in the same tea stain bleaching performance as the pure catalyst.

[0243] Table 3. ΔR*BC-1 (tea stains on cotton), bleached at pH 11.5 and 1 g / L sodium percarbonate at 40°C for 30 min with different amounts of [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 catalyst (higher ΔR* values indicate higher reflectivity at 457 nm and therefore better bleaching results).

[0244]

[0245] Determination of the storage stability of granules 9

[0246] The storage stability of Granule 9 was determined by keeping it in a jar at 40°C for 2 months, after which the BC-1 (tea stain) bleaching activity was measured as described above for the freshly prepared granules containing [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 (Granule 9).

[0247] The results showed that the bleaching performance of particles 9 containing [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 after storage at 40°C for 2 months was similar to that of freshly prepared particles.

[0248] Table 4. ΔR*BC-1 (tea stain on cotton), bleached at pH 11.5, 1 g / L sodium percarbonate at 40°C for 30 min, with different amounts of [Mn2(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 catalyst added to pellet 9, freshly prepared and stored at 40°C for 2 months.

[0249]

[0250]

Claims

1. A composition comprising: 0.1-20 wt% of a water-soluble polymer selected from poly(vinyl alcohol) and modified poly(vinyl alcohol), 5-75 wt% of a polysaccharide absorbent, wherein the polysaccharide absorbent is selected from alginate, starch and modified starch, 0.1-25 wt% of a water-soluble transition metal ion-containing bleach catalyst, wherein the water-soluble transition metal ion-containing bleach catalyst has a water solubility of at least 30 g / L at 20° C. and is a binuclear Mn(III) and / or Mn(IV) complex selected from the group consisting of: [Mn IV 2(µ-O)3(Me3TACN)2]SO4, [Mn IV 2(µ-O)3(Me3TACN)2](NO3)2, [Mn IV 2(µ-O)3(Me3TACN)2](CH3COO)2, [Mn IV 2(µ-O)3(Me3TACN)2](benzoate)2, [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)]Cl2, [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)] SO4, [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)](NO3)2, and [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)](CH3COO)2, wherein Me3TACN represents 1,4,7-trimethyl-1,4,7-triazacyclononane, and Me4DTNE represents 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononane-1-yl)ethane, 0-85 wt% of a filler other than the absorbent; 0-85 wt% of a material selected from the group consisting of an alkali metal, alkaline earth metal, or transition metal bicarbonate, an alkali metal, alkaline earth metal, or transition metal carbonate, an alkali metal, alkaline earth metal, or transition metal halide, an alkali metal, alkaline earth metal, or transition metal sulfate, an alkali metal, alkaline earth metal, or transition metal phosphate, an alkali metal, alkaline earth metal, or transition metal oxide, an alkali metal, alkaline earth metal, or transition metal acetate, an alkali metal, alkaline earth metal, or transition metal citrate, or an alkali metal, alkaline earth metal, or transition metal nitrate; and 20-70 wt% of a bleach activator selected from tetraacetylethylenediamine, N-nonanoyloxybenzenesulfonate, triacetin and capryloyloxybenzoic acid, The percentages are based on the total weight of the composition.

2. The composition according to claim 1, wherein the water-soluble transition metal ion-containing bleach catalyst is selected from [Mn IV 2(µ-O)3(Me3TACN)2]SO4,[Mn IV 2(µ-O)3(Me3TACN)2](NO3)2 and [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)]Cl2.

3. The composition of claim 1 , wherein the water-soluble polymer is poly(vinyl alcohol). The composition according to claim 1 , wherein the polysaccharide absorbent is starch.

5. The composition of claim 1, wherein the polysaccharide absorbent is selected from the group consisting of potato starch, corn starch, rice starch, wheat starch, partially pregelatinized potato starch, partially pregelatinized corn starch, partially pregelatinized rice starch, partially pregelatinized wheat starch, dextrin, and alginate.

6. The composition according to any one of claims 1 to 5, wherein the composition comprises an inorganic filler or an organic filler different from the absorbent, or a mixture thereof, in an amount of up to 85 wt% relative to the total amount of the composition.

7. The composition according to any one of claims 1 to 5, wherein the composition is a granule optionally comprising a coating.

8. The composition of any one of claims 1 to 5, wherein the water-soluble transition metal ion-containing bleach catalyst is present in the composition in an amorphous or nanocrystalline form.

9. The composition according to claim 1, wherein The binuclear Mn(III) and / or Mn(IV) complex is selected from [Mn IV 2(µ-O)3(Me3TACN)2]SO4,[Mn IV 2(µ-O)3(Me3TACN)2](NO3)2 and [Mn III Mn IV (µ-O)2(µ-CH3COO)(Me4DTNE)]Cl2; The water-soluble polymer is poly(vinyl alcohol); The polysaccharide absorbent is starch; and The bleach activator is tetraacetylethylenediamine.

10. A method of making the composition of claim 1, comprising: a) providing a composition comprising the water-soluble polymer, the polysaccharide absorbent, the bleach activator and a solution in a mixing device, the solution comprising between 2 wt% and 75 wt% of a water-soluble transition metal ion-containing bleach catalyst relative to the total amount of the solution, the water-soluble transition metal ion-containing bleach catalyst being soluble in water at 20 o C has a water solubility of at least 30 g / L and is a binuclear Mn(III) and / or Mn(IV) complex as defined in claim 1, b) mixing the ingredients of the composition; c) forming granules or extruding the mixed ingredients into extrudates, and d) optionally drying the composition obtained in step c).

11. The method according to claim 10, wherein the composition comprises between 0.1 wt% and 20 wt% of the water-soluble polymer relative to the total amount of the composition, and wherein the water-soluble polymer is added to the composition comprising the polysaccharide absorbent and the solution comprising a water-soluble transition metal ion-containing bleaching catalyst in the form of an aqueous solution, wherein the concentration of the water-soluble polymer is between 5 wt% and 50 wt% relative to the aqueous solution of the water-soluble polymer.

12. A bleaching package comprising a composition according to any one of claims 1 to 9 and a peroxy compound and / or a peroxy compound precursor.

13. A cleaning agent comprising the composition according to any one of claims 1 to 9 or the bleaching combination according to claim 12. The cleaning agent according to claim 13 , which is a dishwashing agent.

15. A method of cleaning textiles or washing dishes, the method comprising contacting a substrate with water and a cleaning agent according to claim 13 or 14.

16. A method of cleaning a nonwoven fabric, the method comprising contacting a substrate with water and the cleaning agent of claim 13 or 14.

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