Granules comprising a protonated triazacyclic compound and bleaching and cleaning agents comprising the granules

Abstract

The present invention relates to a granule comprising manganese (II) oxalate, a protonated salt of a cyclic triamine, a polysaccharide absorbent and a coating agent. In another embodiment, the present invention relates to a granule comprising a polysaccharide absorbent, a protonated salt of a cyclic triamine and no or little Mn. The present invention also relates to a process for preparing said granule comprising manganese (II) oxalate, a polysaccharide absorbent and such a salt or comprising a polysaccharide absorbent, such a salt and a Mn-free compound, and to a bleaching formulation comprising said granule and a peroxygen compound or a precursor thereof. The granule comprising manganese (II) oxalate, a polysaccharide absorbent and a salt or comprising a polysaccharide absorbent, a salt and a Mn-free compound, and the formulation comprising the same are suitable for catalytic oxidation, for example as a component of a dishwasher bleach composition. The present invention further relates to a process for oxidation with a bleaching formulation as described herein.

Description

TECHNICAL FIELD

[0001] The present invention relates to granules comprising a protonated cyclic triamine compound and other ingredients.

[0002] The present invention also relates to a bleaching formulation comprising said granules and a peroxygen compound or a precursor thereof. The granules and formulations comprising said granules are suitable for catalysing oxidation or bleaching, for example as a component of an automatic dishwasher bleach composition. BACKGROUND

[0003] Manganese catalysts based on triazacyclononane ligands are known to be active catalysts in bleaching stains in laundry detergent products and dishwashing products and in treating cellulose substrates in, for example, wood pulp or raw cotton (see, for example, EP 0458397 A2 (Unilever NV and Unilever pic) and WO 2006 / 125517 Al (Unilever pic, et al).

[0004] As these catalysts are very effective, only small amounts of catalyst are required in a bleaching detergent or dishwashing formulation, typically less than 0.1 wt% in the detergent or dishwashing formulation. A difficulty arising from the use of this low dosage is achieving an accurate amount of catalyst and uniform distribution throughout the formulation. When the distribution of catalyst in the formulation is not uniform, the use of such detergent formulations in a washing machine or hand wash can result in either an underdosing of catalyst (i.e. poor bleaching performance) or an overdosing (i.e. leading to excessive hydrogen peroxide decomposition and possible brownish staining). One well-known method to circumvent this potential problem is to provide / include a solid catalyst on a solid support in the bleaching formulation. Non-limiting examples of methods to develop stable granules comprising a bleach catalyst composition are EP 0544440 A2, WO 94 / 21777 Al, WO 95 / 06710 Al (both Unilever N.V. and Unilever pic), WO 2018 / 011596 (Itaconix Ltd), WO 2018 / 210442 (Weylchem Wiesbaden GmbH), EP 3167036 B and WO 2016 / 177439 (both Novozymes A / S), EP 2966161 A and WO 2017 / 118543 (both Dalli Werke GmbH).

[0005] Typically, a disadvantage of the method using granules comprising a manganese bleach catalyst is that these granules will be strongly coloured. For example, [Mn IV Mn IVThe particles of [Mn(μ-O)3(Me3-TACN)2](PF6)2] (Me3-TACN = 1,4,7-trimethyl-1,4,7-triazacyclononane) are distinctly red / pink, which is not optimal for some detergent formulations. The use of [Mn IV Mn IV An advantage of [Mn(μ-O)3(Me3-TACN)2](PF6)2 is that the complex is relatively stable due to the presence of the kinetically slow Mn(IV) ion. It would be attractive to have a light-coloured or even colourless particle. Typically, only Mn(II) salts are (nearly) colourless, but these salts are often unstable during storage, especially in alkaline oxidizing environments, which leads to the formation of brown MnO2 material.

[0006] WO2010 / 022918A1 (Clariant International Ltd) describes the use of manganese (II) oxalate as a bleach catalyst, which has higher stability and activity compared to other manganese (II) salts. It was observed that manganese (II) oxalate has very low solubility in water.

[0007] EP0549271 B1 (Unilever PLC and Unilever N.V.) describes the use of Me3-TACN ligand (optionally as a protonated salt) in combination with a Mn source (e.g. Mn(nitrate)2 or a Mn-Me3-TACN containing complex) to improve the bleach activity of hydrogen peroxide.

[0008] It is known that the use of Me3-TACN ligand salt without any Mn source in a detergent bleach formulation can find hydrogen peroxide to improve the bleach activity. The presence of manganese ions in certain stains leads to the binding of the ligand to the Mn ion and then the formation of a bleach active species. EP0902021 A2 (Clariant GmbH) describes the use of a cyclic polyamine salt, such as a monoprotonated Me3-TACN ligand salt, in a detergent formulation to improve the bleach performance by hydrogen peroxide. This reference discloses the addition of Me3HTACN bisulfate to an alkaline detergent containing sodium percarbonate and the bleach performance of the detergent was investigated. Furthermore, the use of non-protonated Me3-TACN ligand in a detergent formulation for the same application has been covered in a patent application by Rhodia Operations (WO2018 / 141237A1). The experiments given in the said patent show that the addition of non-protonated Me3-TACN ligand to a detergent formulation with sodium percarbonate improves the stain bleach activity.

[0009] Reinhardt et al. in Household and Personal Care Today, Vol. 9, No. 4, pages 54-57 (2014) describe ligand salts as metal-free bleach boosters in laundry applications. Protonated Me3TACN salts, in particular a series of monoprotonated Me3TACN-salts, such as with HSO4 - , PF6 - , BF4 - , CIO4 - , oxalate, acetate, citrate and polyacrylate are disclosed. Also disclosed in the same publication is a diprotonated salt Me3TACN * 2HCl. As an embodiment, the document discloses ligand salts in particulate form, preferably as co-particulates with enzymes, bleach activators or sodium percarbonate. No details are given about the composition of these particulates or co-particulates and no data are given about their performance, such as storage stability or bleach activity.

[0010] In the field of bleach formulations, such as bleach formulations used in dishwashing applications, there is still a need for colorless or light-colored particulates comprising that exhibit good storage stability and high bleach activity. The present invention aims to solve these needs. SUMMARY

[0012] We have surprisingly found that particulates comprising a protonated cyclic triamine compound and other ingredients show very high bleach activity over a useful storage period.

[0013] In an embodiment, the use of a polysaccharide absorbent, manganese (II) oxalate instead of other commercially available Mn(II) salts in combination with a protonated cyclic polyamine compound salt provides storage stable particulates and their detergent compositions, while providing high bleach activity.

[0014] Thus, from a first aspect, the present invention provides a particulate comprising a coating agent, a polysaccharide absorbent, 0.02-25 wt% manganese (II) oxalate and 0.1-25 wt% of a salt of the following composition: [HL] + (X i- ) 1 / i ,[H2L] 2+ (X i- ) 2 / i ,[H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- )3 / i , [(H2L-BG-LH2)] 4+ (X i- ) 4 / i , [(H3L-BG-LH2)] 5+ (X i- ) 5 / i , and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i wherein L is a monocyclic triamine, BG is a divalent organic bridging group connecting two L groups,

[0015] i is 1 or 2, and

[0016] X i- is a monovalent or divalent anion, preferably selected from the group consisting of CI - , Br - , I - , NO3 - , CI O4 - , PF6 - , BF4 - , OCN - , SCN - , SO4 2- , R’SO4 - , R’COO - , R”oxalate - , oxalate 2- , CF3SO3 - and R’SO3 - , wherein:

[0017] R’ is selected from the group consisting of hydrogen, C1-C8 alkyl, phenyl and methyl- substituted phenyl, and R” is selected from the group consisting of H, Na, K and Li.

[0018] L is preferably a monocyclic triamine, L-BG-L is preferably two monocyclic triamines connected by a divalent organic bridging group, more preferably L is a monocyclic triamine of formula (1) and L-BG-L is a bicyclic triamine of formula (2):

[0019]

[0020] wherein R a , R b and R c are independently of each other hydrogen, alkyl or aryl, which can be substituted by alkyl, alkoxy, hydroxy, sulfo or carboxy or a halogen atom,

[0021] R d , R e and R f are a - CR h R i- a group,

[0022] R g is a C2-C6alkylene bridge, a C6-C 10 arylene bridge, or a bridge comprising one or two C1-C3alkylene units and one C6-C 10 arylene unit, which bridge can optionally be substituted one or more times by independently selected C1-C 24 alkyl groups,

[0023] R h and R i are independently of each other hydrogen, alkyl or aryl, which can be substituted by alkyl, alkoxy, hydroxy, sulfo or carboxy or by a halogen atom, and

[0024] l, m and n are independently of each other 1, 2, 3 or 4.

[0025] Most preferably L is a ring of formula (I) and L-BG-L is two rings of formula (I) connected by an organic divalent group RB:

[0026]

[0027] wherein:

[0028]

[0029] p is 3;

[0030] R is independently selected from the group consisting of hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH; or one R is connected as a divalent group RBto the nitrogen atom of another Q of another ring of formula (I), wherein RBis selected from the group consisting of a C2-C6alkylene bridge, a C6-C 10 arylene bridge, or a bridge comprising one or two C1-C3alkylene units and one C6-C 10 arylene unit, which bridge can optionally be substituted one or more times by independently selected C1-C 24 alkyl groups;

[0031] R1, R2, R3and R4are independently selected from the group consisting of H, C1-C4alkyl and C1-C4alkylhydroxy.

[0032] In another embodiment, the combination of the use of a polysaccharide builder, a protonated monocyclic or bicyclic triamine compound with a low amount of a Mn-containing compound or the use of the protonated monocyclic or bicyclic triamine compound in the absence of a Mn-containing compound provides a storage-stable granule and a detergent composition thereof, while providing high bleach activity.

[0033] Viewed from a second aspect, the present application provides a granule comprising a polysaccharide builder, 0.02-25 wt% of a salt of the following composition: [HL]+ (X i- ) 1 / i [H2L] 2+ (X i- ) 2 / i [H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- ) 3 / i ,[(H2L-BG-LH2)] 4+ (X i- ) 4 / i ,[(H3L-BG-LH2)] 5+ (X i- ) 5 / i , and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i Where L is a monocyclic triamine as defined above, BG is a divalent organic bridging group as described above, preferably L is a ring of formula (I), and L-BG-L are two rings of formula (I) connected by a divalent organic group:

[0034]

[0035] in:

[0036]

[0037] p is 3;

[0038] R is independently selected from hydrogen, C1-C 24 Alkyl, CH2CH2OH and CH2COOH; or an R via a C2-C6 alkylene bridge, C6-C 10 arylene bridge, or containing one or two C1-C3 alkylene units and one C6-C 10 The arylene unit is bridged to the nitrogen atom of another Q in another ring of formula (I), and the bridge may optionally be independently selected C1-C. 24 Alkyl substitution once or multiple times;

[0039] R1, R2, R3, and R4 are independently selected from H, C1-C4 alkyl, and C1-C4 alkylhydroxyl groups.

[0040] i is 1 or 2; and where i is 1 or 2;

[0041] X i- It is a monovalent or divalent anion, preferably selected from Cl.- Br - I - NO3 - ClO4 - PF6 - BF4 - OCN - SCN - SO4 2- R'SO4 - R'COO - R"oxalate - oxalate 2- CF3SO3 - and R'SO3 - anions,

[0042] wherein

[0043] R' is selected from hydrogen, C1-C8 alkyl, phenyl and methyl substituted phenyl, wherein

[0044] R" is selected from H, Na, K and Li, and

[0045] wherein the particles contain less than 0.01 wt% Mn.

[0046] Viewed from a third aspect, the present application provides a bleaching formulation comprising the particles of the first or second aspect of the present application.

[0047] Viewed from a fourth aspect, the present application provides a method comprising contacting a substrate with water and a bleaching formulation according to the third aspect of the present application.

[0048] Viewed from a fifth aspect, the present application provides a method comprising preparing the particles of the first or second aspect of the present application.

[0049] Viewed from a sixth aspect, the present application provides a compound of formula [H2L] 2+ (Y -i- ) 2 / i [H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- ) 3 / i ,[(H2L-BG-LH2)] 4+ (X i- ) 4 / i ,[(H3L-BG-LH2)] 5+ (X i- )5 / i , or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i The salt, wherein L is a monocyclic triamine, BG is a divalent organic bridging group as defined above, preferably L is a ring of formula (I), and L-BG-L are two rings of formula (I) linked by a divalent organic group, Y i- Selected from Br - I, NO3 - ClO4 - PF6 - BF4 - OCN - SCN - SO4 2- R'SO4 - R'COO - CF3SO3 - and R'SO3 - ,

[0050] i is 1 or 2; and

[0051] X i- It is a monovalent or divalent anion, preferably selected from Cl. - ,Br - I - NO3 - ClO4 - PF6 - BF4 - OCN - SCN - SO4 2- R'SO4 - R'COO - ,R” oxalate - oxalate 2- CF3SO3 - and R'SO3 - The anion of , wherein R' is selected from hydrogen, C1-C8 alkyl, phenyl or methyl-substituted phenyl, and R” is selected from H, Na, K and Li.

[0052] Other aspects and embodiments of the invention will become apparent from the following discussion. Invention Details

[0054] As described above, this invention is partly based on the discovery of a particle comprising a polysaccharide absorbent, manganese(II) oxalate, and a salt comprising [HL]. + (X i- ) 1 / i [H2L] 2+ (X i- )2 / i , [H3L] 3+ (X i- ) 3 / i , [(HL-BG-LH)] 2+ (X i- ) 2 / i , [(HL-BG-LH2)] 3+ (X i- ) 3 / i , [(H2L-BG-LH2)] 4+ (X i- ) 4 / i , [(H3L-BG-LH2)] 5+ (X i- ) 5 / i and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i (wherein L, BG, i and X are as previously described, preferably L is a compound of formula (i), or L-BG-L is two compounds of formula (I) linked via a BG group as described herein) and a water-soluble polymer as a coating material. The granules exhibit high stability in a detergent formulation on storage.

[0055] The term "water-soluble" as used in the present specification means a compound that is soluble in water at a concentration of at least 30 g / L at 20 °C.

[0056] The granules of the first aspect of the present application comprise a polysaccharide absorbent, manganese (II) oxalate, a salt of a monocyclic triamine compound L or a compound L-BG-L (preferably a salt of formula (I) or two compounds of formula (I) linked via a BG group) and optionally a processing additive, and wherein the granules comprise a coating agent or are preferably coated with a water-soluble coating.

[0057] The polysaccharide absorbent acts as a processing additive, aiding in the formation of the granules or in the absorption of any water used in the mixing of the ingredients to make the granules.

[0058] The water-soluble polymer as a coating material aids in the maintenance of the integrity of the granules or of the ingredients in the granules during storage in a detergent formulation.

[0059] In manganese (II) oxalate, the oxalate is present as a divalent anion, i.e. both protons of the oxalic acid are not present when combined with the manganese ion. In other words, the oxalate is present as its divalent anion, which can also be written as C2H4O2 2- .

[0060] Typically, manganese (II) oxalate is present as manganese (II) oxalate dihydrate or manganese (II) oxalate trihydrate, with manganese (II) oxalate dihydrate being more typical.

[0061] In one embodiment, the granule comprises 0.02 to 25 wt% manganese (II) oxalate. Suitably, the granule contains 0.1 to 10 wt% manganese (II) oxalate. More suitably, the granule contains 0.2 to 8 wt% manganese (II) oxalate.

[0062] The cyclic triamine compound L or L-BG-L is protonated when present in the granule of the first or second aspect of the application. One nitrogen atom of each polyamine ring can be protonated, i.e. the compound L is mono-protonated in this case. Alternatively, two nitrogen atoms of each triamine ring can be protonated, i.e. the compound L is then di-protonated. Alternatively, however, each nitrogen atom can be protonated, i.e. the ligand is tri-protonated in this case. The first pKa of 1,4,7-trimethyl-1,4,7-triazacyclononane is 11.7, the second pKa is 5.1 and the third pKa is 0.4 (P. Chauduri, K. Wieghardt, Prog. Inorg. Chem., 35, 229-436 (1987)). The granule comprising the salt will typically be between slightly acidic (e.g. pH 4) and neutral, which suggests that predominantly mono-protonated and di-protonated salts will be prevalent in the granule. The unprotonated compound L and L-BG-L are very strong bases and are unstable in the granule of the first aspect of the application; as strong bases, they will readily be protonated to form mono-protonated salts in the granule. The tri-protonated salt is a very strong acid and readily releases the third proton. Thus, if present in the granule, the tri-protonated salt is likely to be present only in a small fraction.

[0063] The mono-protonated, di-protonated or tri-protonated triamine ring of the compound of formula L or L-BG-L will have one or more counterions X i- to balance the charge of the mono-protonated or di-protonated compound L or L-BG-L and can conveniently be represented as [HL] + (X i- ) 1 / i ,[H2L] 2+ (X i- ) 2 / i ,[H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- ) 3 / i ,[(H2L-BG-LH2)] 4+ (X i- ) 4 / i,[(H3L-BG-LH2)] 5+ (X i- ) 5 / i And / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i Together they will be referred to as the salt of compound L or the salt of compound L, or alternatively as the salt of compound L-BG-L or the salt of compound L-BG-L.

[0064] Typically, cyclic triamine ligands will be either monoprotonated or disprotonated, i.e., [HL]. + [H2L] 2+ [H3L] 3+ ,[(HL-BG-LH)] 2+ ,[(HL-BG-LH2)] 3+ , or [(H2L-BG-LH2)] 4+ More typically, the cyclic triamine ligand will be [HL]. + Or [H2L] 2+ Even more typically, the cyclic triamine ligand will be [H2L]. 2+ .

[0065] Counteracting anion X i- The type is not an essential feature of this invention. However, these are generally selected from Cl - ,Br - I - NO3 - ClO4 - PF6 - BF4 - OCN - SCN - SO4 2- R'SO4 - R'COO - ,R” oxalate - oxalate 2- CF3SO3 - and R'SO3 - R' is selected from hydrogen, C1-C8 alkyl, and optionally methyl-substituted phenyl groups, and R” is selected from H, Na, K, and Li. R” is oxalate. - It is a single-charge counterion, where R” can be hydrogen, i.e., HOOC-COO - (hydrooxalate), or selected from Li + Na + and K + Alkali metal ions. If R” oxalate is present. - Then the ligand salt contains the same number of monoanions R” oxalate ions.- The number of protons attached to the triamine ring of L or L-BG-L depends on the number of protons (like any single-charged X group). i- (The groups are the same). Therefore, [HL] + Oxalate with a single anion R” - The [H₂L] group acts as a counter ion. 2+ Or [(HL-BG-LH)] 2+ The R” oxalate group, which has two monoanions, - The group acts as a counter ion; [H3L] 3+ Or [(HL-BG-LH2)] 3+ Oxalate with three monoanions R” - The group acts as a counter ion, [(H2L-BG-LH2)]. 4+ Oxalate with four monoanions R” - The group acts as a counter ion, [(H3L-BG-LH2)]. 5+ Oxalate with five monoanions R” - The group acts as a counter ion, and [(H3L-BG-LH3)] 6+ Oxalate with six monoanions R” - The group acts as a counter ion.

[0066] Oxalate can also exist as its divalent anion, namely (COO)2. 2- Then there will be two unprotonated L compounds ([HL]). + Each of their respective oxalate groups 2- The charge of a divalent anion is 1. + Or, if [H2L] exists. 2+ Or [(HL-BG-LH)] 2+ In this case, there will be a divalent anion oxalate ion. 2- The group [(HL-BG-LH2)] acts as a counter ion. 3+ There will be 1.5 oxalate groups. 2- The group acts as a counter ion (or per 2 [(HL-BG-LH2)]). 3+ The group has 3 oxalate groups. 2- (Group). [(H2L-BG-LH2)] 4+ There will be two oxalate groups. 2- The group acts as a counter ion. [(H3L-BG-LH2)] 5+ There will be 2.5 oxalate groups. 2- The group acts as a counter ion (or per 2[(H3L-BG-LH2)) 5+ The group has 5 oxalate groups. 2- (Group). [(H3L-BG-LH3)]6+ There will be 3 oxalate 2- groups as counterions.

[0067] When present as counterions to a salt of compound L or compound L-BG-L, the divalent anion oxalate is represented as oxalate 2- .

[0068] Hydrooxalate is the most typical oxalate salt used as counterion to compound L or L-BG-L salt.

[0069] Similarly, the sulfate divalent anion is represented as SO4 2- for the same reasons outlined above for the oxalate divalent anion. Typically, the counterion is selected from Cl - , NO3 - , hydrooxalate, HSO4 - , R'COO - and R'SO3 - , where R' is selected from alkyl and aryl, preferably from methyl, phenyl and 4-methylphenyl.

[0070] More frequently, the counterion will be selected from Cl - , hydrooxalate, HSO4 - , acetate and tosylate.

[0071] Particularly common, the counterion will be selected from HSO4, Cl - and hydrooxalate.

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

[0073] According to other embodiments, each R is independently selected from hydrogen, C1-C6alkyl, CH2CH2OH and CH2COOH; or one R is connected to the nitrogen atom of another Q of another ring of formula (I) through an ethylene or propylene bridge. According to other embodiments, R is independently selected from C1-C 24alkyl, CH2CH2OH, and CH2COOH; or one R is attached to the nitrogen atom of another Q of another ring of Formula (I) via an ethylene or propylene bridge. According to other embodiments, each R is independently selected from CH3, C2H5, CH2CH2OH, and CH2COOH. According to other embodiments, each R is independently selected from C1-C6 alkyl, particularly methyl; or one R is attached to the nitrogen atom of another Q of another ring of Formula (I) via an ethylene or propylene bridge. Where one R is attached to the nitrogen atom of another Q of another ring of Formula (I), this is typically via an ethylene bridge. In such embodiments, the other R groups, including those in other rings of Formula (I), are the same, typically C1-C6 alkyl, particularly methyl.

[0074] According to further particular embodiments, including each of those described in the immediately preceding paragraph, R1, R2, R3, and R4are independently selected from hydrogen and methyl, in particular embodiments wherein R1, R2, R3, and R4are hydrogen.

[0075] When a compound of Formula (I) contains one R group attached to the nitrogen atom (i.e., N) of another Q of another ring of Formula (I) via a bridge, it is understood that in particular embodiments including ethylene bridges, such compounds of Formula L-BG-L can alternatively be represented by the following structure:

[0076]

[0077] wherein R, R1, R2, R3, and R4are as defined herein, including the various particular embodiments listed.

[0078] The bridge BG is preferably a C2-C6 alkylene bridge, preferably linking two monocyclic polyamines of Formula (I). Such alkylene bridges are typically straight chain alkylene bridges, although not necessarily straight chain, as described below. However, they can be cyclic alkylene (e.g., the bridge can be a cyclic hexylene). In the case where the bridge is a C6-C 10 In the case of an arylene bridge, this can be, for example, phenylene or the corresponding arylene formed by removing two hydrogen atoms from naphthalene. In the case where the bridge comprises one or two C1-C3 alkylene units and one C6-C 10 In the case of an arylene bridge, this can be, for example, phenylene or the corresponding arylene formed by removing two hydrogen atoms from naphthalene. In the case where the bridge comprises one or two C1-C3 alkylene units and one C6-C 24 In the case of an arylene bridge, this can be, for example, phenylene or the corresponding arylene formed by removing two hydrogen atoms from naphthalene. In the case where the bridge comprises one or two C1-C3 alkylene units and one C6-C 18 In the case of an arylene bridge, this can be, for example, phenylene or the corresponding arylene formed by removing two hydrogen atoms from naphthalene. In the case where the bridge comprises one or two C1-C3 alkylene units and one C6-C

[0079] In compounds L-BG-L, preferably in compounds in which L is a triamine of formula (I), the bridge is usually a C2-C6alkylene bridge. In this case, the bridge is usually a straight-chain alkylene group, for example ethylene, n-propylene, n-butylene, n-pentylene or n-hexylene. According to some particular embodiments, the C2-C6alkylene bridge is ethylene or n-propylene. According to more particular embodiments, the C2-C6alkylene bridge is ethylene. Herein, the propylene group means n-propylene (i.e. -CH2CH2CH2-, and not -CH(CH3)CH2-), unless the context clearly dictates otherwise.

[0080] Examples of preferred compounds L are 1,4,7-triazacyclononane, 1,4,7- triazacyclododecane, 1,4,8-triazacyclododecane, 1,4,7-trimethyl-1,4,7- triazacyclononane and 1,4,7-trimethyl-1,4,7-triazacyclododecane. At the nitrogen atoms and / or the CH groups, these compounds can carry further substituents.

[0081] The following cyclic polyamines are preferred: 1,4,7-triazacyclononane (TACN), 1,4,7-trimethyl-1,4,7-triazacyclononane (1,4,7-Me3TACN), 2-methyl-1,4,7- triazacyclononane (2-MeTACN), 1,4-dimethyl-1,4,7-triazacyclononane, 1,2,4,7- tetramethyl-1,4,7-triazacyclononane (1,2,4,7-Me4TACN), 1,2,2,4,7-pentamethyl-1,4,7- triazacyclononane (1,2,2,4,7-Me5TACN), 2-benzyl-1,4,7-trimethyl-1,4,7- triazacyclononane and 2-decyl-1,4,7-trimethyl-1,6,7-triazacyclononane.

[0082] These cyclic triamines can be synthesized in the manner described, for example, by K. Wieghardt et al. in lnorganic Chemistry 1982, 21, 3086 ff. or in “Macrocycling Chemistry” by Dietrich, Viout, Lehn, Weinheim 1993.

[0083] These cyclic triamines can be converted into the protonated salts by reaction with the corresponding acids.

[0084] According to a particular embodiment of the present application, the compound L of formula (I) is 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or the compound L-BG-L is 1,2-bis(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane (Me4-DTNE). According to a more particular embodiment of the present application, the compound of formula (I) is Me3-TACN.

[0085] In one embodiment, the granules comprise a polysaccharide absorbent and 0.02-25 wt% of a salt of the following composition: [[HL] + (X i- ) 1 / i ,[H2L] 2+ (X i- ) 2 / i ,[H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- ) 3 / i ,[(H2L-BG-LH2)] 4+ (X i- ) 4 / i ,[(H3L-BG-LH2)] 5+ (X i- ) 5 / i , and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i wherein L, BG, i and X i- are defined above, preferably a salt of the ligand L or L-BG-L, wherein L is a compound according to formula (I). More preferably, the granules comprise 0.1-10 wt% of a salt of the ligand L or L-BG-L, preferably a salt of the compound L or L-BG-L, wherein L is a compound according to formula (I). More preferably, the granules comprise 0.3-6.0 wt% of a salt of the compound L or L-BG-L, preferably a salt of the compound L or L-BG-L, wherein L is a compound according to formula (I).

[0086] Without being bound by theory, the manganese ions released upon dissolution of the manganese (II) oxalate in water bind to the cyclic triamine (L) salt. If a triprotonated ligand salt is used, upon dissolution in a mildly basic bleach solution, the triprotonated ligand salt will lose two protons to form a monoprotonated compound species. If a diprotonated ligand salt is used, upon dissolution in a mildly basic bleach solution, the diprotonated ligand salt will lose one proton to form a monoprotonated compound species. In the case where a L-BG-L salt is used, where each L group or one of its L groups is triprotonated, each L group will lose one proton upon dissolution in a mildly basic solution. In the case where a L-BG-L salt is used, where each L group or one of its L groups is triprotonated, each L group or one of its L groups will lose two protons upon dissolution in a mildly basic solution. The monoprotonated compound ([HL] + or [HL-BG-LH] 2+ ) will lose its last proton (per polyamine ring) upon binding to the Mn(II) ion. The Mn ligand species thus formed will further react with the alkaline hydrogen peroxide solution to form the bleach active Mn ligand catalyst species.

[0087] In one embodiment, the present application provides a granule comprising a polysaccharide absorbent and 0.02-25 wt% of a salt of the compound L, the salt of the compound L having the composition [HL] + (X i- ) 1 / i ,[H2L] 2+ (X i- ) 2 / i ,H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- ) 3 / i ,[(H2L-BG-LH2)] 4+ (X i- ) 4 / i ,[(H3L-BG-LH2)] 5+ (X i- ) 5 / i and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i wherein L, BG, i and X i- are as described above, and wherein said granule does not comprise manganese (II) oxalate or any other Mn salt in an amount greater than 0.01 wt% (based on Mn).

[0088] Preferably, less than 0.005 wt% of Mn is present in the granule, more preferably less than 0.002 wt%, even more preferably less than 0.001 wt%, still more preferably less than 0.0003 wt%, most preferably less than 0.0001 wt% of Mn.

[0089] More preferably, the granule comprises 0.1 - 10 wt% of a salt of compound L or L-BG-L, preferably a salt of compound L or L-BG-L, wherein L is a compound according to formula (I). More preferably, the granule comprises 0.3 - 6.0 wt% of a salt of compound L or L-BG-L, preferably a salt of compound L or L-BG-L, wherein L is a compound according to formula (I).

[0090] The granule of this embodiment can have a similar composition as the granule also comprising manganese (II) oxalate (according to the first aspect of the application), as described above. However, it can not be necessary to include a coating material which is necessary to prevent the undesired degradation of manganese (II) oxalate according to the first aspect of the application, but which is not necessarily present in the granule according to the second aspect of the application.

[0091] According to the second aspect of the application, when more than 0.01 wt% of manganese (II) oxalate or any other manganese salt or manganese complex is not present in the granule, the diprotonated ligand ([H2L] 2+ , or its analogous L-BG-L salt, [H2L-BG-LH] 3+ , or [H2L-BG-LH] 4+ ) will easily convert into the monoprotonated ligand cation ([HL + , or its analogous L-BG-L salt, [HL-BG-LH] 2+ ) in solution upon dissolution in an alkaline wash solution, and will remain monoprotonated unless it binds to metal ions present in the stain, as disclosed by G. Reinhardt et al. in "H&PC Today, Vol. 9, July-August 2014, pages 54-57. Similarly, when the triprotonated cyclic triamine ligand (i.e. [H3L] 3+ , or its analogous L-BG-L salt, [H3L-BG-LH2] 5+ , or ([H3L_BG-LH3] 6+ ) is present in the formulation, the protonated cyclic triamine ligand will lose two protons upon dissolution in a mildly alkaline solution, or will lose all protons upon binding to metal ions.

[0092] In one embodiment, the present application provides a granule comprising a salt of compound L or L-BG-L, preferably a salt of compound L or L-BG-L, wherein L is a compound according to formula (I). 2+ (Y i- )2 / i ,[H3L] 3+ i- 3 / i ,L-BG-L (i.e. [(HL-BG-LH] 2+ i- 2 / i ,[(HL-BG-LH2] 3+ i- 3 / i ,[(H2L-BG-LH2] 4+ i- 4 / i ,[(H3L-BG-LH2] 5+ i- 5 / i ,or [(H3L-BG-LH3] 6+ i- 6 / i ) wherein i, X i- , L and L-BG-L are as defined above, preferably L or L-BG-L- is a compound of formula (I) wherein L is a compound of formula (I), Y i- is selected from the group consisting of Br - , I - , NO3 - , ClO4 - , PF6 - , BF4 - , OCN - , SCN - , SO4 2- , R'SO4 - , R'COO - , R"oxalate - , oxalate 2- , CF3SO3 - and R'SO3 - , X i- is selected from the group consisting of Cl - , Br - , I - , NO3 - , ClO4 - , PF6 - , BF4 - , OCN - , SCN - , SO4 2- , R'SO4 - , R'COO - , R"oxalate - , oxalate 2- , CF3SO3 - and R'SO3 - ​​​​​​​​​​​​wherein R' is selected from the group consisting of hydrogen, C1-C8 alkyl and optionally methyl substituted phenyl, and wherein R" is selected from the group consisting of H, Na, K and Li. Typically, L is 1,4,7-tri-C1-C 24 -alkyl-1,4,7-triazacyclononane, more typically, L is 1,4,7-trimethyl-1,4,7- triazacyclononane. Typically, L-BG-L is 1,2-bis(4,7-dimethyl-1,4,7- triazacyclononan-1 -yl)-ethane (Me4-DTNE).

[0093] Typically, Y in the salt is selected from the group consisting of HSO4 i- - - , hydrogen oxalate, R'COO - - and R'SO3 i- wherein R' is selected from the group consisting of methyl, phenyl and 4-methylphenyl. More typically, Y - is selected from the group consisting of HSO4 i- , acetate, hydrogen oxalate and tosylate, and most typically Y - is selected from the group consisting of hydrogen oxalate and HSO4 i- .

[0094] Typically, X in the salt is selected from the group consisting of Cl - , NO3 - , HSO4 - , R'COO - , R'SO3 - and R"oxalate - wherein R' is selected from the group consisting of methyl, phenyl and 4-methylphenyl, and wherein R" is selected from the group consisting of H, Na, K and Li. More typically, X i- is selected from the group consisting of Cl - , HSO4 - , acetate, hydrogen oxalate and tosylate, most typically, X i- is selected from the group consisting of Cl - , hydrogen oxalate and HSO4 - .

[0095] The coating agent present in the granules of the first aspect of the application and optionally present in the granules of the second aspect of the application comprises a water-soluble polymer, preferably polyvinyl alcohol or a polyvinyl alcohol derivative. The coating agent can also comprise materials such as starch, alginate, cellulose derivatives, fatty acids, waxes, paraffins, polyethylene glycol, gelling compounds, electrolytes, polyelectrolytes.

[0096] ​​​The coating material used in the particles of the present invention can form a coating that encapsulates one or more components in the particles and / or can form a coating that encapsulates the particles. Preferably, the particles of the present invention are covered with a protective layer or coating. In another preferred embodiment, manganese(II) oxalate is coated.

[0097] In another preferred embodiment, the particles of the present invention comprise a protective layer or coating, more preferably a coating comprising polyvinyl alcohol.

[0098] Even in tablet formulations, coating materials can improve storage stability.

[0099] The proportion of the coating material in the total particles of the present invention is preferably 25 wt% or less, particularly less than 10 wt%, more preferably 0.3-10 wt%, particularly preferably 0.5-7 wt%, and most preferably 1-4 wt%.

[0100] Typical polyvinyl alcohols used for coating or as binders have a number-average molecular weight of 10,000-200,000 (measured by gel permeation chromatography (GPC) at 20°C) (corresponding to a viscosity of approximately 2-70 mPa·s for a 4 wt% aqueous solution at 20°C; according to (Measured using a droplet viscometer according to DIN 53015), more typically 20,000-100,000.

[0101] Polyvinyl alcohol is usually produced by saponifying polyvinyl acetate.

[0102] A particularly suitable degree of hydrolysis for polyvinyl alcohol is 70-100 mol%, more preferably 80-99 mol%, and its aqueous solution at 20°C is based on... The viscosity ranges from 2 to 70 mPa·s. Various PVOH polymers with different degrees of polymerization and hydrolysis are available from the trade name of Kuraray Chemicals.

[0103] Other suitable polyvinyl alcohols can be modified to be hydrophobic or hydrophilic in any way.

[0104] An example of hydrophobically modified polyvinyl alcohol containing water-insoluble monomers forming blocks in its main chain is Kuraray. Polyvinyl alcohol containing ethylene.

[0105] Another option is to modify polyvinyl alcohol (PVA) through grafting reactions with alcohol groups, such as the partial acetalization of the alcohol groups in PVA, where the PVA is equipped with any residues that can be hydrophobic or hydrophilic, such as Mowiflex PVA from Kuraray. Furthermore, the vinyl alcohol group can be modified by grafting with aldehydes (especially C2-C...). 10which are partially modified by reaction with a compound containing a carbon-carbon double bond (e.g. a diene, a dienophile or an aldehyde) as exemplified in WO2018 / 011596 (Itaconix Ltd.).

[0106] The modified residues can be blockwise or statistically arranged.

[0107] The polyvinyl alcohol and the acetalized polyvinyl alcohol preferably used have a molecular weight in the range of 10 000 to 200 000 g / mol, preferably 11 000 to 90 000 g / mol, particularly preferably 12 000 to 80 000 g / mol, and especially preferably 13 000 to 70 000 g / mol.

[0108] In the preparation of the coating, mixtures of different polyvinyl alcohols or mixtures of polyvinyl alcohol with other organic polymers or low molecular weight compounds can be used. Preferably, the coating comprises in most cases polyvinyl alcohol or a mixture thereof, for example at least 80 wt.-%, based on the total weight of the coating, of polyvinyl alcohol or a mixture thereof.

[0109] The granules of the present application contain at least one polysaccharide absorbent in an amount of 2 to 95 wt.-%, preferably 5 to 60 wt.-%, most preferably 10 to 50 wt.-%, wherein the percentages refer to the total amount of the granules.

[0110] In one embodiment, the granules according to the present application contain at least one of the additional ingredients selected from the group consisting of water-soluble polymers, fillers, salts and bleach activators, and wherein these ingredients are present in an amount of:

[0111] 0 to 20 wt.-% of water-soluble polymers,

[0112] 0 to 85 wt.-% of fillers,

[0113] 0 to 85 wt.-% of inorganic salts,

[0114] 0 to 90 wt.-% of bleach activators;

[0115] wherein the percentages are based on the total amount of the granules.

[0116] The polysaccharide processing additive comprised in the granules of the first or second aspect of the present application helps to achieve suitable processing characteristics, including absorption and / or removal of water which can be present during the processing steps for the preparation of the granules or which is present in the detergent formulation during storage of the detergent formulation. It also helps to bind the components in the granules together. Suitable processing additives are based on polysaccharides, including starch, modified starch, glycogen, natural gums such as alginate or combinations thereof.

[0117] Natural gums are polysaccharides of natural origin, which are capable of increasing the viscosity of a solution substantially. They are mostly plant gums, which are present in the woody parts or seed coats of plants. Examples of natural gums are natural gums obtained from seaweed, such as agar agar, alginic acid, sodium alginate and carrageenan, or natural tree gums obtained from non-marine plant resources, such as gum arabic, gum ghatti, gum tragacanth, karaya gum, guar gum, locust bean gum, beta-glucan, dammar resin, glucomannan, psyllium husks and tara gum, or natural gums produced by bacterial fermentation, such as gellan gum or xanthan gum.

[0118] Most suitable as processing additive is starch, which is a polymer of glucose, wherein the pyranoglucose units are bound by a- linkages. Suitable sources of starch are potato starch, corn starch, rice starch, wheat starch and partially pregelatinized starch from the above listed. Alternatively, the processing additive can be a modified starch, such as dextrin, gum or alginate. Most suitable is corn starch, potato starch or rice starch. Cellulosic materials are also particularly suitable, such as cellulose fibers, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose or carboxy-modified cellulose, such as carboxymethylcellulose (CMC). Most suitable is cellulose, in particular microcrystalline cellulose (e.g. Heweten 101).

[0119] In one embodiment, the granules comprise 5-95 wt% of the processing additive. In another embodiment, the granules comprise 10-60 wt% of the processing additive. In another embodiment, the granules comprise 15-50 wt% of the processing additive. In one embodiment, the processing additive is added as a solid material, which is typically greater than 90 wt%, more typically greater than 95 wt% pure.

[0120] Water-soluble polymers that can be included in the granules comprising the monoprotonated, diprotonated or triprotonated cyclic triamine ligand salt of the first or second aspect of the application include poly(vinylpyrrolidone), polyalkylene glycols, functionalized poly(vinyl alcohol) and polyacrylates. The water-soluble polymer can be present in the coating and / or the bulk of the granules. When preferred embodiments of the coating are disclosed, examples of preferred polyvinyl alcohol or modified polyvinyl alcohol are given above. These preferred (modified) polyvinyl alcohols can also be used in the bulk of the granules.

[0121] In one embodiment, the granules comprise 0.1-20 wt% of the water-soluble polymer. Suitably, the granules comprise 0.3-15 wt% of the water-soluble polymer. More suitably, the granules comprise 0.5-10 wt% of the water-soluble polymer. Even more suitably, the granules comprise 1.0-8.0 wt% of the water-soluble polymer.

[0122] In one embodiment, the water-soluble polymer is added as an aqueous solution to the mixture of processing additive and manganese (II) oxalate. Alternatively, in another embodiment, the water-soluble polymer is added as an aqueous solution to the processing additive, after which the mixture is added to the other components of the granule. The concentration of the water-soluble polymer in water is 5 to 50 wt%, more typically 10 to 30 wt%. Most typically, a higher concentration of the polymer dissolved in water will be preferred.

[0123] In one embodiment, the granules of the first and second aspects of the application comprise a filler, which can be an organic filler or an inorganic filler or a mixture thereof. Suitable organic fillers are different from the polysaccharide absorbent processing additive described above, and include saccharides and derivatives thereof, including sugars. Examples of sugars include glucose, dextrose, fructose, galactose, sucrose, lactose, maltose. Modified saccharides can also be used.

[0124] In another embodiment, the filler is an inorganic filler. Inorganic fillers include talc, mica, zeolite, silicate, silicon oxide and clay. Suitably, the inorganic filler is selected from talc, mica, zeolite and silicate.

[0125] In another embodiment, the granules comprise a cellulose compound, optionally in combination with an inorganic filler as described above.

[0126] In one embodiment, the granules comprise 0 to 85 wt% of a filler. In another embodiment, the granules comprise 0 to 60 wt% of a filler. In another embodiment, the granules comprise 0 to 40 wt% of a filler. In yet another embodiment, the granules comprise 0 to 20 wt% of a filler. In another embodiment, the granules do not comprise any filler.

[0127] In one embodiment, the granules of the first and second aspects of the application comprise a salt, which can typically be a carbonate, bicarbonate, halide (chloride, bromide or iodide), sulphate, phosphate, oxide, acetate, citrate or nitrate of an alkali metal, alkaline earth metal or transition metal.

[0128] In one embodiment, the granules comprise one or more salts selected from sodium bicarbonate, sodium sulphate, sodium chloride, sodium nitrate, sodium acetate, sodium citrate, sodium nitrate, potassium sulphate, potassium chloride, potassium citrate, calcium carbonate, calcium chloride and calcium sulphate. Suitably, the composition comprises one or more salts selected from sodium sulphate, calcium carbonate and sodium citrate.

[0129] In one embodiment, the salt is typically water-soluble.

[0130] In one embodiment, the particles comprise 0-85wt% salt. In another embodiment, the particles comprise 0-60wt% salt. In another embodiment, the particles comprise 0-40wt% salt. In yet another embodiment, the particles comprise 0-20wt% salt. In another embodiment, the particles do not comprise any salt.

[0131] The particles can also comprise a bleach activator. As bleach activator, the particles of the present application can contain compounds generally known in the state of the art. These are preferably a plurality of acylated alkylene diamines, in particular tetraacetyl ethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DAHT), acylated glycoluril, in particular tetraacetyl glycoluril (TAGU), glycerol triacetate (triacetin), N- imides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular N-nonanoyloxy- or N-lauryloxybenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxybenzoic acid (NOBA or DOBA, respectively), carboxylic anhydrides, in particular phthalic anhydride, acylated polyvalent alcohols, preferably glycerol triacetate, ethylene glycol diacetate and 2,5-diacetyloxy-2,5-dihydrofuran as well as acetyliertated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxymyl and octaacetyllactose, and acetylated and optionally N-alkylated glucamides and gluconolactones, and / or N-acylated lactams, for example N-benzoyl caprolactam. It can also be preferred to use hydrophilically substituted acyloxyalkyli- dene and acyl lactams. Furthermore, nitrile derivatives such as n-methylmorpholinium acetonitrile-methylsulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of bleach activators can also be used.

[0132] Suitably, the particles can comprise TAED, NOBS, triacetin and DOBA. More suitably, the particles can comprise TAED.

[0133] In one embodiment, the particles comprise 0-90wt% bleach activator. Suitably, the particles comprise 0-75wt% bleach activator. Also suitable is that the particles do not comprise any bleach activator. Also suitable is that the particles comprise particles comprising 20-70wt% bleach activator and more suitably 30-60wt% bleach activator.

[0134] The granules of the present application are preferably granular or tablet-like formulations which can be prepared in a known manner, for example by mixing, roller compaction and / or by spray-drying the thermoplastic component, and then by adding more sensitive components such as enzymes, bleaches and bleach catalysts.

[0135] The granules of the present application can for example exist as granular or tablet-like solids. Preferred are granular solids.

[0136] The production of the granules of the present application can be carried out according to methods known per se and have been described in detail in the above-mentioned patent literature. Basically different granulation methods can also be employed.

[0137] In a first preferred process variant, the formation of the granules takes place in a mixing apparatus. The components are processed in a generally mixing apparatus which is operated in batch or continuously, which is usually equipped with a rotating mixing mechanism. When mixing, all mixing variants can be considered which ensure a sufficient mixing of the components.

[0138] In a preferred embodiment, all components are mixed simultaneously. However, a multi-stage mixing process can also be considered, in which the individual components are introduced into the overall mixture separately or in different combinations with other additives.

[0139] The sequence of slow and fast mixers can be exchanged as desired. The residence time in the mixer granulation is preferably from 0.5 seconds to 20 minutes, particularly preferably from 2 seconds to 10 minutes. The granulation fluid can be pumped into the mixing apparatus by means of simple conduits. However, in order to achieve a better distribution, a nozzle system (single- or multi-material nozzles) can also be used.

[0140] Generally, a drying step is carried out after the granulation stage in order to avoid sticking of the granules. Then, the coarse and fine granule fractions are separated by sieving. The coarse granulate is comminuted by milling and, like the fine granulate, is fed into the new granulation process. The application of the coating is preferably provided in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0141] The solution is mixed thoroughly with the powdered active material and other optional additives to form a plastic deformable mass. The mixing step can be carried out in the mixing apparatus described above, but a kneader or a special extruder can also be used. The granulated mass is then pressed through the nozzle holes of a press matrix with a tool to form cylindrical extrudates. The extrudates emerging must be comminuted to the desired length or particle size in a post-processing step. In many cases, a length / diameter ratio L / D = 1 is required. For cylindrical particles, the particle diameter is usually between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, and the particle length is between 0.5 and 3.5 mm, desirably between 0.9 and 2.5 mm. The length or size adjustment of the particles can be achieved by, for example, stationary stripping knives, rotating cutting knives, cutting wires or blades. To round off the cut, the particles can be rounded off again in a rondier.

[0142] After the size adjustment of the particles, a final solidification step is usually required, in which the solvent is removed and then a coating is applied. This step is usually carried out in a fluidized bed apparatus, which is operated as a dryer. Then, the coarse and fine particle fractions are separated by sieving. The coarse particles are comminuted by grinding and, like the fine particles, are fed into the new granulation process. After that, the resulting particles can be equipped with a coating in a fluidized bed apparatus, for example in a fluidized bed mixer.

[0143] The preferred particles according to the application are further characterized in that the water content, based on the total amount of the particles, is less than 3 wt% (measured by Karl Fischer), particularly preferably 0 to 2 wt%.

[0144] To prepare the cleaning agent according to the application in the form of tablets, all components are preferably combined and mixed with one another in a mixer. Subsequently, the mixture is compacted by means of a conventional tablet press, for example using a press with a pressure of 200 x 10 5 - 1500 x 10 5 Pa eccentric press or rotary press.

[0145] An anti-frangible tablet is thus obtained which dissolves sufficiently rapidly under the conditions of use and which has a bending strength which is usually greater than 150 N. Preferably, the tablets produced in this way have a weight of 15 to 40 g, in particular 20 to 30 g, and a diameter of 35 to 40 mm.

[0146] The preparation of the composition according to the application in the form of dust-free, storage-stable and free-flowing particles with a high bulk density of 800 to 1000 g / 1 can be carried out as follows: in a first process sub-phase, the builder component is mixed with at least a proportion of the liquid mixture component, the bulk density of this premix is increased and then, if necessary after intermediate drying, the other components of the composition, including the bleach catalyst, are combined with the premix thus obtained.

[0147] Suitable conditions (e.g. duration of contact and temperature) will depend on the properties of the reactants (the salt of compound L or L-BG-L, optional manganese (II) oxalate, and other ingredients to obtain suitable particles) and their amounts, and can be established by the skilled person without undue burden. For example, the duration of contact can be from about 1 minute to about 24 hours. Typically, the contact can be carried out at ambient temperature, e.g. at about 20-25 °C, although elevated temperatures, e.g. about 25-50 °C, can be used if desired.

[0148] As will be appreciated by the skilled person, it can be desirable to further process the compositions of the first and second aspects of the application, e.g. to include the particles having beneficial properties in a bleaching formulation of the application, e.g. a solid detergent formulation.

[0149] Thus, the bleaching formulation of the application can be in the form of non-friable particles comprising the composition of the first or second aspect of the application, optionally with additional inert solids, bleach precursors, fillers and salts and with coating agents. The definition and description of each of the necessary and optional ingredients classes are given above in the detailed description section.

[0150] The particles of the first or second aspect of the application (optionally in the form of non-friable particles as described above) are typically subjected to compaction, milling, pulverisation, etc. to provide a dry composition having the desired particle size. As is well known in the art, when such compositions are incorporated into a solid bleaching formulation, e.g. a granule for use in laundry, the agglomerated particles comprising the bleach-activating catalyst desirably have approximately the same size and bulk density as the other components of the solid bleaching formulation, to avoid separation by percolation or flotation.

[0151] The present application also relates to a process for preparing the particles of the first aspect of the application, wherein the process comprises the steps of:

[0152] (a) mixing a solution comprising a salt, manganese (II) oxalate, a polysaccharide absorbent processing additive, optionally a filler, optionally a water-soluble polymer, optionally a salt and optionally a bleach-activating agent, of the following composition: [HL] + (X i- ) 1 / i ,[H2L] 2+ (X i- ) 2 / i ,H3L] 3+ (X i- ) 3 / i ,[(HL-BG-LH)] 2+ (X i- ) 2 / i ,[(HL-BG-LH2)] 3+ (X i- )3 / i , [(H2L-BG-LH2)] 4+ (X i- ) 4 / i , [(H3L-BG-LH2)] 5+ (X i- ) 5 / i , and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i wherein L, BG, i and X i- are as defined above;

[0153] (b) compacting the mixture of step (a); and

[0154] (c) coating the compacted material of step (b) with a coating agent.

[0155] The present application also relates to a process for preparing the granules of the second aspect of the present application, wherein the process comprises the steps of:

[0156] (a) mixing a solution comprising a salt, a polysaccharide absorbent processing additive, optionally a water-soluble polymer, optionally a filler, optionally an inorganic salt and optionally a bleach activator of the following composition: [HL] + (X i- ) 1 / i , [H2L] 2+ (X i- ) 2 / i , H3L] 3+ (X i- ) 3 / i , [(HL-BG-LH)] 2+ (X i- ) 2 / i , [(HL-BG-LH2)] 3+ (X i- ) 3 / i , [(H2L-BG-LH2)] 4+ (X i- ) 4 / i , [(H3L-BG-LH2)] 5+ (X i- ) 5 / i , and / or [(H3L-BG-LH3)] 6+ (X i- ) 6 / i wherein L, BG, i and X i- are as defined above;

[0157] (b) compacting the mixture of step (a); and

[0158] (c) Optionally, the compacted material of step (b) is coated with a coating agent, wherein the mixture of step (a) contains no or less than 0.01 wt% Mn.

[0159] In a preferred embodiment of these methods, the mixture from step (a) is extruded as an extrudate.

[0160] The particles of the first or second aspect of this invention are typically present in the bleaching formulation of the third aspect in solid (typically granular) form (e.g., granules), with an average particle size typically of 50-2500 μm, for example 100-1600 μm. The particle size can be measured using a laser diffraction particle size analyzer, such as a Malvern HP equipped with a 100 mm lens.

[0161] The bulk density and size of the particles can be controlled by compositions, process conditions, or both known in the art.

[0162] Those skilled in the art are familiar with suitable particle size and density (and / or suitable size and density can be determined through routine experiments), as well as suitable techniques for achieving suitable particle size and density, such as conventional granulation techniques. For example, according to a third aspect of the invention, suitable particles can be prepared by any conventional and / or known granulation technique, such as using a disc granulator, fluidized bed, Schugi mixer, etc. Plowshare mixers, rotary drums, and other low-energy mixers; compaction (including extrusion and pelletizing), optionally followed by crushing and grinding; granulation and pelletizing using Sandvik Roto molding machines when using melt binders; and high-shear energy processes using high-speed mixers / granulators with high-energy stirring and cutting actions. An example of a suitable compactor is Hosokawa equipment, such as the Bepex L200 / 30. An example of such high-speed mixing / granulating equipment is Fukae. TM The FS-G mixer was manufactured by Fukae Powtech Kogyo Co., Ltd. of Japan. Other mixers that can be used in the methods of this invention include Diosna. TM Manufactured by TKFielder Ltd., UK; Fuji TM VG-C series, manufactured by Fuji Sangyo Co., Ltd. of Japan; and Roto TM Manufactured by Zanchete & Co Srl, Italy. In addition to intermittent equipment, high-speed mixers / granulators can also be used, such as... Recycler.

[0163] The particles of the first aspect of the application (i.e. particles comprising manganese (II) oxalate, a polysaccharide absorbent and a salt of compound L or L-BG-L as described herein) have particular use in a bleaching formulation. The particles are used to catalyse the oxidative activity of a peroxygen compound which can be included in the bleaching formulation of the application or which can be generated in situ from the bleaching formulation.

[0164] The particles of the second aspect of the application (i.e. particles comprising a polysaccharide absorbent, a salt of compound L or L-BG-L as described herein but not comprising manganese (II) oxalate) can be used in a bleaching formulation without the addition of any manganese source. As described above, in the presence of a peroxygen compound, the salt of compound L or L-BG-L is believed to bind to Mn ions present in certain stains.

[0165] Alternatively, the particles of the second aspect of the application can be used in a bleaching formulation which comprises a separate composition comprising a Mn salt or Mn complex. Without being bound by theory, when the particles of the second aspect of the application comprising a salt of compound L or L-BG-L and the particles comprising a Mn salt or Mn complex are dissolved in water for contact with a substrate, a Mn ligand species is formed in situ according to the fifth aspect of the application, resulting in enhanced stain (colouring) bleaching activity.

[0166] Various commercially available Mn salts can be used for this purpose, such as manganese (II) oxalate, dimanganese (III) trioxalate, manganese (II) diacetate, manganese (III) triacetate, manganese (II) dichloride, manganese (II) sulphate, manganese (II) dinitrate and manganese (III) trisacetylacetonate. Of these manganese (II) oxalates, manganese (II) diacetate, manganese (II) diacetate, manganese (II) dichloride, manganese (II) sulphate, manganese (II) dinitrate are typically used. More typically, manganese (II) oxalate, manganese (II) diacetate and manganese (II) sulphate are used. Most typically, particles comprising manganese (II) oxalate are used when added separately to a bleaching formulation comprising the particles of the second aspect of the application comprising a salt of compound L or L-BG-L. The use of manganese (II) oxalate in dishwasher formulations is described in WO2016 / 012080 (Weylchem Wiesbaden GmbH) including those formulations containing particles comprising manganese (II) oxalate.

[0167] If the composition applied contains a Mn complex, the Mn complex can contain a ligand L or L-BG-L, preferably wherein L is a ligand L or L-BG-L of a compound according to formula (I), or it can contain a ligand that is not a ligand L or L-BG-L. For the avoidance of any doubt, when L or L-BG-L is bound to a transition metal ion, each triamine ring bound to the metal ion will be fully deprotonated. The definition of the latter type of manganese complex can be found in WO2017 / 134463 (Catexel Ltd.). More typical are compositions containing a manganese complex comprising a ligand L or L-BG-L, wherein L is a compound according to formula (I). More typical are compositions comprising a dinuclear Mn complex L-BG-L, wherein L is a compound according to formula (I). Even more typical are compositions containing a Mn complex comprising 1,4,7-trimethyl-1,4,4-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)-ethane (Me4-DTNE). More typical are compositions comprising a complex selected from the group consisting of: [Mn IV 2(μ-O)3(Me3TACN)2](PF6)2, [Mn IV 2(μ-O)3(Me3TACN)2]Cl2, [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)](PF6)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.

[0168] Even more typical are compositions comprising [Mn IIIMn IV (Mn(μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2or [Mn IV 2(μ-O)3(Me3TACN)2](PF6)2. Most typically compositions comprising [Mn IV 2(μ-O)3(Me3TACN)2](PF6)2.

[0169] Suitable examples of particles containing dinuclear Mn(IV) complexes comprising a ligand of formula (I) can be found in WO 94 / 21777 (Unilever PLC and Unilever N.V.), WO 95 / 06710 (Unilever PLC and Unilever N.V.), WO 2014 / 198368 (Weylchem Wiesbaden GmbH), WO 2014 / 198369 (Weylchem Wiesbaden GmbH), WO 2016 / 177439 (Novozymes A / S), WO 2017 / 118542 (Dalli-Werke GmbH), WO 2017 / 153612 (Novozymes A / S and Unilever N.V.), WO 2018 / 011596 (Itaconix Ltd.) and WO 2018 / 210442 (Weylchem Wiesbaden GmbH).

[0170] Without being bound by theory, when a mixture of a ligand of compound L or L-BG-L (wherein L is as defined above and preferably a compound of formula (I)) and a Mn complex comprising a ligand different from the ligand of compound L or L-BG-L is applied in a bleaching solution, the ligand of compound L or L-BG-L displaces the ligand originally bound to the Mn complex, forming a MnL or MnL-BG-L species that activates the peroxygen compound in the bleaching solution, thus improving the bleaching of stains (coloration).

[0171] If the ligand L or L-BG-L is protonated, upon binding to the metal ion, the ligand L or L-BG-L will lose its proton. If a Mn complex comprising a ligand L or L-BG-L, e.g. a ligand L or L-BG-L wherein L is a compound according to formula (I), is used in the granule, said substitution of the ligand bound to the Mn complex will not occur. However, in a bleaching process, some ligands can degrade in the bleaching process, and by adding a granule comprising a ligand according to the second aspect of the application, the ligand species from the degradation of the Mn complex can be replaced by the ligand L or L-BG-L, e.g. a ligand L or L-BG-L wherein L is a compound of formula (I), leading to a re-establishment of bleaching activity. Thus, the amount of Mn complex in the granule used in a detergent product can be significantly reduced compared to a detergent product not comprising a granule of the second aspect of the application. Thus, the colour of the granule is lighter than the colour of a similar granule containing a Mn complex comprising a ligand L or L-BG-L, e.g. a ligand L or L-BG-L wherein L is a compound of formula (I).

[0172] When a peroxygen compound is present in the bleaching formulation comprising the granule of the application, it can be and typically is a compound capable of generating hydrogen peroxide in aqueous solution. Suitable amounts of peroxygen compound included in the bleaching formulation can be determined by the person skilled in the art, but typical amounts are in the range of 1-35 wt%, e.g. 5-25 wt%, based on the solid content of the bleaching formulation. The person skilled in the art will understand that in case the bleaching formulation contains a bleaching system comprising a peroxygen compound and so-called bleach precursors (discussed below), lower amounts of peroxygen compound can be used.

[0173] Suitable sources of hydrogen peroxide are well known in the art. Examples include alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic perhydrate salts such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Typical peroxygen compounds included in the bleaching formulation are per salts, such as sodium perborate, e.g. sodium perborate monohydrate and sodium perborate tetrahydrate, and sodium percarbonate. According to some specific embodiments, the bleaching formulation comprises sodium perborate monohydrate or sodium perborate tetrahydrate. The inclusion of sodium perborate monohydrate is advantageous as it has a high active oxygen content. For environmental reasons, the use of sodium percarbonate is most advantageous.

[0174] Organic peroxy acids can also be used as the peroxygen compound. These can be monoperoxy acids or diperoxy acids. Typical monoperoxy acids or diperoxy acids have the general formula HOO-(C=0)-R-Z, wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having a lactam linkage or a phenylene or substituted phenylene group; Z is hydrogen, halogen, alkyl, aryl, imido aromatic or non-aromatic group, COOH or (C=0)OOH group or quaternary ammonium group.

[0175] Typical monoperoxy acids include peroxybenzoic acid, peroxy lauric acid, N,N-phtalimido peroxyhexanoic acid (PAP) and 6-octylamino-6-oxo-peroxyhexanoic acid. Typical diperoxy acids include, for example, 1,12-diperoxydodecanoic acid (DPDA) and 1,9-diperoxyazelaic acid.

[0176] In addition to organic peroxy acids, inorganic peroxy acids are also suitable, for example potassium monopersulfate (MPS).

[0177] If organic or inorganic peroxy acids are included in the bleach formulation, they are typically included in the bleach formulation in an amount in the range of about 2-10 wt%, for example 4-8 wt%.

[0178] However, the bleach formulation need not comprise a peroxygen compound: alternatively, the bleach formulation of the present application can comprise a bleach system which is constituted by components which are suitable to generate hydrogen peroxide in situ (but which are not themselves peroxygen compounds). An example of this is the use of C 1-4 alcohol oxidase and C 1-4 alcohol, for example a combination of methanol oxidase and ethanol. Such combinations are described in WO 95 / 07972 Al (Unilever N.V. and Unilever pic).

[0179] Typically, the bleaching species is generated in situ. For example, organic peroxy acids are typically generated in situ, rather than being included in the bleach formulation, as the peroxy acids themselves tend to be unstable. For this reason, the bleach formulation typically comprises a bleach system which comprises a peracid salt (for example sodium perborate (optionally hydrated) or sodium percarbonate) which generates hydrogen peroxide in water, and a so-called peroxygen bleach precursor which is capable of reacting with the hydrogen peroxide to generate the organic peroxy acid.

[0180] The use of bleach systems comprising peroxygen bleach precursors is very familiar to the person skilled in the art, and the peroxygen bleach precursors are well known to the person skilled in the art and are described in the literature. For example, references in this regard are UK patents BP 836988, 864798, 907356, 1003310 and 1519351; European patents EP 0185522A, EP 0174132A, EP 0120591A; and US patents US 1246339, 3332882, 4128494, 4412934 and 4675393. Suitable bleach precursors have been listed above.

[0181] Where used, the peroxygen bleach precursor compound is typically present in the bleach formulation in an amount of up to 12 wt%, for example 2-10 wt%, of the composition, based on the solid content of the bleach formulation.

[0182] The peroxygen compounds or bleach systems described herein can be stabilized in the bleach formulation by providing a protective coating (e.g., a coating comprising sodium metaborate and sodium silicate) to the peroxygen compounds or bleach systems.

[0183] For automatic dishwasher cleaning, the corrosion of glassware during the rinse phase can be inhibited by the use of glass corrosion inhibitors. These are, for example, crystalline phyllosilicates and / or zinc salts. Crystalline phyllosilicates are, for example, commercially available under the trade name SKS-6 (delta-Na2Si205) from Weyl Chem. Other known crystalline phyllosilicates are, for example, Na-SKS-1 (Na2Si 22 O 45 • xH2O, kenyaite), Na-SKS-2 (Na2Si 14 O 29 • xH2O, makite), Na-SKS-3 (Na2Si8O 17 • xH2O), Na-SKS-4 (Na2Si4O9 • xH2O, kenyaite), Na-SKS-5 (alpha-Na2Si205), Na-SKS-7 (beta-Na2Si205, cancrinite), Na-SKS-9 (NaHSi205 • H2O), Na-SKS-10 (NaHSi205 • 3H2O, sturmanite), Na-SKS-11 (t-Na2Si205) and Na-SKS-13 (NaHSi205). An overview of crystalline phyllosilicates can be found, for example, in the article published in "Seifen- Fette-Wachse, Volume 116, Issue 20 / 1990", pages 805-808.

[0184] In another preferred embodiment of the present application, the detersive and cleaning compositions of the present application, in particular the dishwasher detergents, comprise preferably from 0.1 to 20 wt.%, more preferably from 0.2 to 15 wt.% and even more preferably from 0.4 to 10 wt.% of a crystalline phyllosilicate, relative to the total weight of the composition.

[0185] For the control of glass corrosion, the detersive and cleaning compositions of the present application, in particular the dishwasher detergents, can comprise at least one zinc or bismuth salt, preferably selected from the group consisting of organic zinc salts, more preferably selected from the group consisting of soluble organic zinc salts, still more preferably selected from the group consisting of soluble zinc salts of monomeric or polymeric organic acids, and even more preferably selected from the group consisting of zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluene sulfonate. Bismuth salts such as bismuth acetate can be used as a substitute or in combination with these zinc salts.

[0186] In the context of the present application, preference is given to washing and cleaning compositions, in particular dishwasher detergents, wherein the amount of zinc salt is 0.1 to 10 wt.%, preferably 0.2 to 7 wt.%, more preferably 0.4 to 4 wt.%, relative to the total weight of the composition, irrespective of the zinc salt used, in particular irrespective of whether an organic or inorganic zinc salt, a soluble or insoluble zinc salt or mixtures thereof is used.

[0187] The cleaning agents of the present application can also contain silver corrosion inhibitors for controlling the corrosion of silver. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, 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.

[0188] According to some particular embodiments, the bleaching formulation can be used for bleaching and / or modifying (e.g. degrading) a polysaccharide (e.g. cellulose or starch) or a polysaccharide-containing (e.g. cellulose-containing, herein also referred to as cellulose) substrate. Cellulose substrates are widely present in the home, industrial and institutional laundry, wood pulp, cotton processing, etc. industries. For example, raw cotton (ginned output) is dark brown in color due to natural pigments in the plant. The cotton and textile industry recognizes the need to bleach cotton before it is used in textiles and other areas. The purpose of bleaching such cotton fibers is to remove natural and extraneous impurities while producing a significantly whiter material.

[0189] Regardless of the properties of the substrate treated according to the method of the fourth aspect of the present application, this is done objectively to bleach, i.e. to remove unwanted chromophores (be it stains (dyeing) or solids on cloth in e.g. laundry or dishwashing applications, residual lignin in wood pulp or polyphenolic substances in raw cotton, wood pulp and paper) and / or to degrade substances, e.g. starch or polyphenolic substances in dishwashing. Thus, according to some particular embodiments, the substrate can be a soiled dish or a polysaccharide or polysaccharide-containing substrate, e.g. wherein the polysaccharide is a cellulose substrate, e.g. cotton, wood pulp, paper or starch.

[0190] Thus, the bleaching formulation of the present application can be used in a dishwashing method. Such a method generally involves cleaning tableware in a mechanical dishwashing machine, typically to remove starch and polyphenolic components from the surface of the tableware. The term "tableware" herein includes within its scope cookware as well as plates, crockery and other eating (e.g. cutlery) and table utensils, e.g. made of ceramic, metal or plastic material. Thus, embodiments of the fourth aspect of the present application include a method of cleaning tableware in a mechanical dishwashing machine, which comprises contacting the tableware with water and the bleaching formulation of the third aspect of the present application.

[0191] While it will be appreciated that the application should not be considered as so limited, in the case where the bleaching formulation is for use in hard surface cleaning applications, the bleaching formulation will typically include other components well known to those of ordinary skill in the art, such as bleaching stabilizers (also known as chelating agents), for example organic chelating agents such as aminophosphonate or carboxylate chelating agents; one or more surfactants, for example cationic, anionic or non-anionic (amphiphilic) surfactants; and other components including, but not limited to, detersive adjuncts, enzymes and perfumes.

[0192] The bleaching formulation of the third aspect of the application will preferably contain from 0.1 to 50 wt% of one or more surfactants. The bleaching formulation can comprise one or more anionic surfactants and one or more non-ionic surfactants. Typically, the anionic and non-ionic surfactants of the surfactant system can be selected from those described in "Surfactant Active Agents", Vol. 1, Schwartz & Perry, Interscience 1949, Vol. 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 non-ionic surfactants can be found, for example, in WO 03 / 072690 Al (Unilever N.V. et al), WO 02 / 068574 Al (Unilever N.V. et al) and WO 2012 / 048951 Al (Unilever PLC et al).

[0193] Those skilled in the art of bleaching formulations will be familiar with the use of enzymes in this regard. Enzymes can provide cleaning performance, fabric care and / or hygiene benefits. The enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Members of these enzyme classes are described in the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, Recommendations on Biochemical Nomenclature: Enzyme Nomenclature (1992, ISBN 0-1202271 16-5-3, Academic Press). Detergent enzymes are described in more detail, for example, in US patent US6579839 (Price et al).

[0194] Suitable detersive adjuncts as optional ingredients can also be present, for example as described in WO 00 / 34427 Al. The adjuncts can include aluminosilicates, in particular zeolites, such as A, B, C, X and Y type zeolites, and MAP zeolites as described in EP 0 384 070 A; and precipitation aids such as sodium carbonate. Such adjuncts are typically present in amounts of from about 5 to 80 wt%, more preferably from about 10 to 50 wt%, based on the solid content of the bleach formulation.

[0195] The person skilled in the art will be readily able to formulate suitable bleach formulations for use in the cleaning of tableware or laundry, in accordance with his normal skill. Likewise, the person skilled in the art will be readily able to formulate bleach formulations suitable for use in the other applications described herein. Such formulations may, for example, comprise additional metal ion-based bleach catalysts or organic bleach catalysts suitable for catalysing the activity of the peroxygen compounds described herein. Non-limiting examples of transition metal-based bleach catalysts can be found in, for example, EP 2 228 429 Al (Unilever PLC and Unilever N.V.), with references cited therein and examples of organic catalysts can be found in WO 2012 / 071 153 Al (The Procter & Gamble Company).

[0196] The present application also relates to a cleaning method, said method comprising contacting a substrate to be cleaned with water and a bleach formulation as defined above.

[0197] Preferably, the cleaning method is a method of cleaning tableware, in particular by use of a mechanical dishwasher, said method comprising contacting tableware to be cleaned with water and a bleach formulation as described above.

[0198] Also preferred is a method of cleaning a textile or non-woven fabric, the method comprising contacting a textile or non-woven fabric to be cleaned with water and a bleach formulation as defined above.

[0199] The following non-limiting examples serve to more fully demonstrate embodiments of the application. Example

[0200] Chemicals used

[0201] Manganese oxalate dihydrate was obtained from Weylchem Performance Products.

[0202] Mn(II)CI2tetrahydrate, Mn(CH3COO)2tetrahydrate and sodium carbonate were obtained from Sigma-Aldrich.

[0203] Corn starch was obtained from Roth.

[0204] TAED P) is derived from Weylchem ​​Performance Products.

[0205] Polyvinyl alcohol as a trade name 6-88 is from Kuraray.

[0206] Trisodium citrate is derived from Jungbunzlauer.

[0207] Sodium percarbonate is derived from Solvay.

[0208] SKS-6 silicate ( SKS-6) from Weylchem ​​Performance Products.

[0209] PEG 1500 and PEG 6000 powders were obtained from Clariant.

[0210] PA25Cl and Lutensol T07 were obtained from BASF.

[0211] The protease Blaze Evity 150T and the amylase Stainzyme Plus Evity 24T are derived from Novozymes.

[0212] All other chemicals were obtained from Sigma-Aldrich.

[0213] Synthesis of protonated ligand salts

[0214] General Procedure

[0215] In a 2-liter three-necked flask equipped with a reflux condenser, temperature control, and stirrer, add 750 mL of water and 200 g of Me3TACN. Cool the amine-Me3TACN aqueous solution to approximately 5–10 °C in an ice bath with stirring. Carefully add a calculated amount of hydrochloric acid (2 molar equivalents of 37 wt% concentrated hydrochloric acid) or sulfuric acid (2 molar equivalents of 96 wt% concentrated sulfuric acid) to the amine solution using a dropping funnel and ice cooling. Similarly, slowly add 1 molar equivalent of solid oxalic acid (98 wt%) in solid form to the solution containing Me3TACN. In all cases, maintain the temperature inside the flask below 20 °C using ice cooling. After the acid addition is complete, stir the mixture for one hour.

[0216] Water is removed under vacuum in a rotary evaporator. All products formed are pale yellow to grayish-white solids.

[0217] Recrystallization from ethanol yielded a white to off-white powder that was dried under vacuum at 70 °C overnight. The solid was isolated from ethanol and then the ethanol was evaporated using a rotary evaporator, after which a dark brown oil was recovered (which was discarded).

[0218] Yields of [H2(Me3TACN)]Cl2, [H2(Me3TACN)](HSO4)2, and [H2(Me3TACN)](oxalic acid)2were 92%, 89%, and 68%, respectively (based on the amount of Me3TACN).

[0219] Analysis

[0220] Elemental Analysis

[0221] [H2(Me3TACN)]Cl2.1 / 2H2O (Mw = 253.21)

[0222] C9H 23 N3Cl2 Calc: C 42.69, H 9.55, N 16.59;

[0223] Found: C 42.49 / 42.60, H 9.71 / 9.73, N 16.64 / 16.56.

[0224] The chloride content was determined gravimetrically as AgCl, which gave 28.27% Cl (calc. 28.06%).

[0225] [H2(Me3TACN)](oxalic acid)2(MW = 351.35)

[0226] C 13 H 25 N3O8 Calc: C 44.44, H 7.17, N 11.96;

[0227] Found: C 44.29 / 44.38, H 7.22 / 7.29, N 11.89 / 11.89.

[0228] [H2(Me3TACN)](HSO4)2(MW = 367.43)

[0229] C9H 27 N3S2O8 Calc: C 29.43, H 6.86, N 11.44, S 17.45;

[0230] Found: C 29.27 / 29.27, H 6.89 / 6.94, N 11.34 / 11.33; S 17.39 / 17.21.

[0231] Infrared and Raman Spectra

[0232] [H2(Me3TACN)](oxalate)2

[0233] 1612 and 713 cm -1 The IR bands at 1612 and 713 cm-1 are assigned to oxalate vibrations, in agreement with the literature (K.I. Peterson and D.P. Pullmann, J. Chem. Ed., 93, 1130, 2016).

[0234] 1463 and 885 cm -1 The Raman bands at 1463 and 885 cm-1 are assigned to oxalate vibrations, in agreement with the literature (K.I. Peterson and D.P. Pullmann, J. Chem. Ed., 93, 1130, 2016).

[0235] [H2(Me3TACN)](HSO4)2

[0236] 3400 cm -1 The IR band at 3400 cm-1 is assigned to OH stretching of the bisulfate anion, 1700 cm -1 The IR band at 1700 cm-1 is assigned to asymmetric vibration of the bisulfate anion. Also at 1074, 1027, 820, 624 cm -1 The peaks at 1074, 1027, 820, 624 cm-1 originate from the same anion, as listed in the literature: A. Periasamy et al., Rasayan J. Chem., 2, 981 (2009).

[0237] In Raman at 975 and 624 cm -1 The Raman peaks at 975 and 624 cm-1 are assigned to sulfate anion, as published in the same literature.

[0238] NMR spectra

[0239] [H2(Me3TACN)](HSO4)2 in D2O: 2.89 ppm (3H, CH3) and 3.91 ppm (4H, CH2CH2).

[0240] [H2(Me3TACN)](HSO4)2 in d 6 -DMSO: 2.72 ppm (3H, CH3) and 3.36 ppm (4H, CH2CH2), 8.12 ppm, broad (1.2H, broad - sulfate).

[0241] [H2(Me3TACN)](oxalate)2 in d 6 -DMSO: 2.51 ppm (3H, CH3), 2.91 ppm (4H, CH2CH2), and 11.05 ppm (1.4, broad - oxalate).

[0242] [H2(Me3TACN)]Cl2in D2O: 2.83 ppm (3H, CH3) and 3.29 ppm (4H, CH2CH2).

[0243] Preparation of granules and ADW tablets

[0244] A typical formulation for the preparation of granules according to the table below is as follows (example given for granule 3).

[0245] In an Eirich lab mixer (type R02), 30 g of [H2Me3TACN](HSO4)2, 30 g of manganese (II) oxalate, 180 g of corn starch and 960 g of TAED were added and mixed thoroughly at room temperature (2 minutes at 23.3-24.6 °C). Subsequently, the mixture was put into a Hosokawa Bepex L200 / 30 compactor and compacted at 3.8 N / mm 2 The compacted mixture was compacted twice (15 minutes at a capacity of 9.9 kg / h the first time and 6 minutes at a capacity of 4.86 kg / h the second time). After the compaction step, the material was milled to obtain a granule size of 1.5 mm using a Frewitt type GLA.ORV.0215 mill. The granules thus obtained were then sieved and pressed to obtain granules of size < 1.5 mm. The granules were then filtered over a metal mesh (< 0.2 mm) to separate the granules smaller than 0.2 mm. The granules that were too large (> 1.5 mm) or too small (< 0.2 mm) were compacted again as described above.

[0246] The overall yield was 83% (the remaining 17% were fine granules (< 0.2 mm) which were used again for compaction as described above. The granules were then coated with 3 wt% PVOH using a fluid bed Glatt coater (GPCG 1.1). Visual inspection revealed almost colourless (off-white) granules.

[0247] In a similar way, granules 1 and 2 were prepared using the hydrochloride salt of the ligand (abbreviated as [H2L]Cl2in the table) and using the oxalate salt of the ligand (abbreviated as [H2L](oxalate)2([H2L](Hoxalate)2) in the table).

[0248] Two other comparative granules were prepared using MnCl2instead of manganese (II) oxalate (granule 5) and manganese (II) diacetate (granule 6).

[0249] Also as a comparison, the same granule 3 was prepared, but now without the PVOH coating step (granule 4).

[0250] Table 1 : Particles of the invention (particles 1-3) and comparative particles (particle 4 is identical to particle 3 but without coating, particle 5 is identical to particle 3 but using MnCI2 instead of manganese oxalate, particle 6 is identical to particle 3 but using manganese (II) diacetate

[0251] instead of manganese oxalate)

[0252]

[0253] L represents Me3TACN or 1,4,7-trimethyl-1,4,7-triazacyclononane.

[0254] Furthermore, particles comprising [H2Me3TACN](HSO4)2 but without manganese (II) oxalate catalyst were prepared according to the following procedure: in an Eirich lab blender (type R02), 25.1 g of [H2Me3TACN](HSO4)2, 180 g of corn starch and 800 g of TAED were added and mixed thoroughly at room temperature (2 minutes at 23.3-24.6 °C). Subsequently, the mixture was put into a Hosokawa Bepex L200 / 30 compactor and compacted at 24.7-29.9 °C with 24-34 N / mm 2 The compacted mixture.

[0255] After the compaction step, the material was milled with a Frewitt type GLA.ORV.0215 mill to obtain a particle size of 1.5 mm. The particles thus obtained were then sieved and pressed to obtain particles with a size < 1.5 mm. Then, the particles were filtered over a metal mesh (size < 0.2 mm), whereby particles larger than 0.2 mm were separated. Then, the particles were coated with 3 wt% PVOH using a fluid bed Glatt coater (GPCG 1.1 ). Visual inspection showed almost colourless (off-white) particles.

[0256] The composition of this particle is:

[0257]

[0258] L represents Me3TACN or 1,4,7-trimethyl-1,4,7-triazacyclononane.

[0259] The composition of the ADW formulation to which particles comprising manganese and ligand salt were added is given in the table below.

[0260] Subsequently, various granules as shown in Table 1 were treated as follows. Each granule (5.95 g) was placed into a container containing the ADW ingredients (950 g in total) as shown in Table 2 below and the ADW ingredients and granule material were mixed thoroughly. Tablets of 20 g each were prepared by using a Carver Handtablettenpresse Model 4332 using a pressure of 1.5 tons.

[0261] Tablets containing granules with PVOH coating (granules 1, 2, 3, 5, 6) remained white / off-white, while tablets containing granule 4 (without PVOH coating) showed brownish spots immediately after compression and were therefore discarded.

[0262] Table 2: Composition of Automatic Dishwasher (ADW) formulations

[0263]

[0264]

[0265] Cleaning test

[0266] In an automatic dishwasher (Miele G 1223 SC GSL2), the tea stain removal of various tablets containing granules with Mn and ligand salt were tested using the described ADW formulation containing the granules (45°C, standard program R-time 2, 21° DH water hardness, 50 g IKW soil - scenario). The cleaning performance evaluation was based on visual inspection, where 0% means no cleaning of the tea stains and 100% means complete removal of the tea stains.

[0267] All formulations containing granules 1-6 showed very good cleaning performance under these conditions (tea cups were completely clean, scored 10 on a scale of 1 to 10). On the same scoring scale, the blank (absence of ligand and Mn salt in the formulation) showed a performance of 4.8.

[0268] Storage stability test

[0269] Tablets were stored in an oven at 50°C and then tested for their cleaning performance and visually evaluated (change in color of the tablets).

[0270] ADW tablets containing granules 1-3 (Manganese (II) oxalate and each ligand salt) did not show a color change during this storage.

[0271] Granules 4, 5 and 6 showed brownish spots, indicating that the Mn(II) salt had been oxidized to Mn(IV)02species during the storage conditions.

[0272] The tea stain bleaching performance of granules 1, 2 and 3 was 10 (thus the same as freshly prepared tablets). Granules 4, 5 and 6 showed much poorer tea stain bleaching performance after storage: 6, 7 and 6.5 respectively.

[0273] These data clearly show that the combination of manganese (II) oxalate and the Me3TACN ligand salt is highly preferred over other Mn(II) salts in combination with the same ligand salt (1-3 vs. 5 and 6).

[0274] Furthermore, the comparison of granule ADW tablets with granules 3 and 4 shows that the PVOH coating is necessary to obtain storage stable tablets that retain high bleaching activity.

[0275] Finally, the experiments detailed above clearly show that it is possible to obtain storage stable granules comprising manganese (II) oxalate and a ligand salt, corn starch as absorbent and TAED and coated with PVOH that are colourless or off-white and that provide very good cleaning ability in a dishwashing cleaning test compared to orange, pink or red granules comprising dinuclear Mn(III) or Mn(IV) complexes with the same ligand as disclosed in the prior art.

[0276] White granules comprising [H2(Me3TACN)](HSO4)2 and corn starch as absorbent and TAED and coated with PVOH that can be used in laundry or dishwashing detergent formulations have also been successfully prepared.

Claims

1. A granule comprising: salts of the following composition: [HL] + (X i- ) 1 / i , [H2L] 2+ (X i- ) 2 / i and / or [H3L] 3+ (X i- ) 3 / i wherein L is a monocyclic triamine, i is 1 or 2, and X i- is a monovalent or divalent anion; wherein the granule comprises: a coating agent, a polysaccharide absorbent, 0.02-25 wt% of manganese (II) oxalate, and 0.1-25 wt% of the salt.

2. The granule according to claim 1, wherein L is a ring of formula (I): wherein: p is 3; R is independently selected from the group consisting of hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH; R1, R2, R3, and R4 are independently selected from H, C1-C4 alkyl, and C1-C4 alkylhydroxy; and wherein X i- selected from the group consisting of Cl - , Br - , I - , NO3 - , ClO4 - , PF6 - , BF4 - , OCN - , SCN - , SO4 2- , R'SO4 - , R'COO - , R"C2O4 - , C2O4 2- , CF3SO3 - and R'SO3 - , wherein R' is selected from the group consisting of hydrogen, C1-C8 alkyl, phenyl and methyl substituted phenyl, and R" is selected from the group consisting of H, Na, K and Li.

3. The granule according to claim 2, wherein L is 1,4,7-triazacyclononane, 1,4,7- trimethyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,4-dimethyl-1,4,7- triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triazacyclononane, and 1,2,2,4,7- pentamethyl-1,4,7-triazacyclononane.

4. The granule according to claim 3, wherein L is 1,4,7-trimethyl-1,4,7-triazacyclononane.

5. The granule according to any one of claims 1-4, wherein X - is selected from the group consisting of CI - , HC2O4 - and HSO4 - .

6. The granule according to claim 1, wherein the granule contains at least one additional ingredient selected from the group consisting of a water-soluble polymer, a filler, an inorganic salt, and a bleach activator, and wherein these additional ingredients are present in an amount of: 0-20 wt% of a water-soluble polymer, 0-85 wt% of a filler, 0-85 wt% of an inorganic salt, 0-90 wt% of a bleach activator; wherein the percentages are based on the total amount of the granule.

7. The granule according to claim 6, comprising 0.5-25 wt% of a coating agent and 0.02-25 wt% of a salt of the formula: [HL] + (X i- ) 1 / i and / or [H2L] 2+ (X i- ) 2 / i .

8. The granule according to claim 6, wherein the polysaccharide absorbent is selected from the group consisting of starch, modified starch, cellulose, alginate, or a combination thereof.

9. The granule of claim 6, wherein the polysaccharide absorbent is selected from natural gums.

10. The granule according to claim 8, wherein the polysaccharide absorbent is starch.

11. The granule according to claim 10, wherein the polysaccharide absorbent is corn starch.

12. The granule according to any one of the preceding claims 6-11, wherein the water- soluble polymer is selected from polyvinyl alcohol or a polyvinyl alcohol derivative.

13. The granule according to any one of the preceding claims 6-11, wherein the filler is selected from organic fillers and inorganic fillers that are not absorbents.

14. The granule according to any one of the preceding claims 6-11, wherein the bleach activator is tetraacetyl ethylene diamine.

15. The granule according to any one of claims 1-4, wherein the granule comprises a coating, the coating comprising a water-soluble polymer.

16. The granule according to claim 15, wherein the coating comprises a water-soluble polymer selected from polyvinyl alcohol or a polyvinyl alcohol derivative.

17. A bleaching formulation comprising the granule of any one of claims 1-16 and a peroxygen compound or a precursor of a peroxygen compound.

18. The bleaching formulation according to claim 17, further comprising a Mn complex.

19. A cleaning agent comprising the bleaching formulation of any one of claims 17-18.

20. The cleaning agent according to claim 19, wherein the cleaning agent is a dishwashing agent.

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