Liquid formulation comprising alcohol and highly water-soluble manganese complex salt catalyst, bleaching formulation and cleaning agent comprising formulation

Abstract

Liquid formulations comprising an alcohol and a highly water-soluble manganese complex root catalyst, bleaching formulations and cleaning agents comprising the same, disclosed are liquid compositions comprising a solvent, the solvent is selected from the group consisting of monoaliphatic alcohols having 2 to 6 carbon atoms, mono-, di-, tri-or tetraalkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol or glycerol wherein each OH group may be optionally and independently substituted by an OR group wherein R is an alkyl group having 1 to 4 carbon atoms, and wherein the solvent optionally comprises 0.01-10 wt% of an inorganic or organic acid and in which there is dissolved a mononuclear or binuclear Mn (III) and / or Mn (IV) complex salt having selected non-coordinating counterions, having a water solubility of at least 30 g / L at 20 DEG C, and wherein the solvent optionally comprises 0.01-10 wt% of an inorganic or organic acid and in which there is dissolved a mononuclear or binuclear Mn (III) and / or Mn (IV) complex salt having selected non-coordinating counterions, and wherein the mononuclear or binuclear Mn (III) and / or Mn (IV) complex comprises at least one cyclic triamine ligand. The liquid composition and formulations comprising the same are suitable for use in catalytic oxidation, for example as a component of dishwasher bleaching compositions. The present invention also relates to cleaning agents comprising the liquid compositions described herein.

Description

Technical Field

[0001] The present invention relates to a liquid composition comprising a selected non-aqueous solvent and a manganese complex salt of selected water solubility.

[0002] The invention also relates to a bleaching formulation comprising the liquid composition and a peroxy compound or a precursor thereof.The liquid composition and formulations comprising the composition are suitable for use in catalytic oxidation or bleaching, for example as a component of an automatic dishwasher (ADW) bleaching composition. Background Art

[0003] Manganese catalysts based on triazacyclononane ligands are known to be active catalysts in bleaching stains in laundry detergent products and dishwashing products, and are used to treat cellulosic substrates such as wood pulp or raw cotton (see for example EP 0 458 397 A2 (Unilever NV and Unilever plc) and WO 2006 / 125517 A1 (Unilever plc et al.)).

[0004] Because these catalysts are so effective, only small amounts of catalyst need be used in bleaching detergents or dishwashing formulations, typically at levels below 0.1 wt% in the detergent or dishwashing formulation. The difficulty associated with using such low dosages is achieving accurate dosage of the catalyst and uniform distribution throughout the formulation. When the catalyst is not uniformly distributed in the formulation, use of such detergent formulations in washing machines or hand washing can result in either underdosing (i.e. having poor bleaching performance) or overdosing of the catalyst (i.e. causing excessive decomposition of the hydrogen peroxide and possible appearance of brown spots). A well-known method of circumventing this potential problem is to include a solid catalyst on a solid support in the bleaching formulation, or alternatively to use a catalyst solution.

[0005] At present, only binuclear tri-μ-oxo bridged manganese (IV) complex catalysts of the ligand 1,4,7-trimethyl-1,4,7-triazacyclononane-bis-hexafluorophosphate (hereinafter referred to as MnTACN-PF6) are used in particles (see, for example, WO 2018 / 210442, Weylchem ​​Wiesbaden GmbH). Recently, a patent application for particles containing highly water-soluble MnTACN catalysts was also published (compare WO 2022 / 058039 A1, Weylchem ​​Performance Products GmbH).

[0006] WO 2022 / 189535 A1 (Reckitt Benckiser Finish BV) discloses a liquid detergent composition comprising manganese 1,4,7-triazacyclononane (MnTACN) and its derivatives, a selected hydrotrope and a nonionic surfactant. The composition is contained in a water-soluble film. The composition may additionally contain an organic solvent, such as dipropylene glycol. The claimed liquid composition is stable, compatible with polyvinyl alcohol (PVOH), and overcomes the stability and aesthetic limitations of currently known MnTACN-containing compositions. It was found that the claimed composition is able to dissolve MnTACN to obtain a transparent liquid while remaining suitable for PVOH containers. The liquid composition is recommended for ADW formulations. In this document, the anion of the MnTACN-complex is not disclosed. In addition, the main part of the composition is the presence of a hydrotrope and a nonionic surfactant. According to this reference, the inclusion of a nonionic surfactant and a hydrotrope in a solvent (such as dipropylene glycol) is necessary for the dissolution of the manganese complex salt. This document does not suggest providing a liquid composition by omitting nonionic surfactants and hydrotropes and by using selected solvents and Mn-complexes with selected counterions.

[0007] US2012 / 053109A1 discloses a stable liquid bleaching composition comprising a peroxygen component such as H2O2, a polyol such as glycerol, water and a metal-containing bleaching catalyst. In addition to the peroxygen compound, the preparation also contains a large amount of water. In this document, many different types of metal-containing bleaching catalysts are mentioned. However, in the embodiments, only a Mn-complex without any counter ions is disclosed. There is no guidance in this document to use a metal-containing bleaching catalyst with a selected counter ion, resulting in high solubility of these catalysts. This document does not suggest providing a liquid composition by omitting peroxide and water and by using a selected solvent and a manganese complex with a selected counter ion.

[0008] WO 2022 / 106276A1 (Reckitt Benckiser Finish BV) discloses a liquid detergent composition for ADW formulations comprising MnTACN and its derivatives and a polar solvent. The composition is contained in a water-soluble film and preferably contains an aprotic polar solvent. A variety of such solvents are listed, such as propylene carbonate, acetonitrile, dimethyl sulfoxide, ethylene carbonate, N-methylpyrrolidone, cyclopentane sulfone, nitromethane and N-acetylpiperidine. According to the disclosure, the liquid composition is stable, compatible with PVOH, and overcomes the stability and aesthetic limitations of currently known MnTACN-containing compositions. In this document, the anions of the MnTACN complex are not disclosed.

[0009] In most tablets used for ADW cleaning, the bleach catalyst is contained in the tablet as solid particles in the required dosage.Currently, only MnTACN-PF6 catalyst in particles is used in ADW tablets.

[0010] Some ADW tablets also contain a compartment with a liquid, which often contains a dye as a consumer cue. It is interesting to be able to include a manganese complex (e.g., MnTACN) in such a compartment with a liquid to be able to eliminate the need to include solid particles containing the manganese complex in the solid portion of the formulation, thereby resulting in further compression of the automatic dishwashing formulation.

[0011] Experiments show that it is difficult to dissolve the MnTACN-PF6 catalyst in many non-aqueous solvents. The non-aqueous solvents that can be used are DMF or CH3CN. However, these solvents appear to be harmful and should be avoided in ADW preparations for home use. Manganese complexes with other anions show a high degree of water solubility and may have a wider solubility curve than PF6 salts. However, these compounds are obtained by evaporating a water / ethanol solvent mixture or a pure water solvent for synthesizing these compounds (see, for example, EP2753627B1 (Catexel Technologies Ltd.)). Therefore, all impurities derived from the synthesis of these compounds (if present) are retained in the dry material, which may cause further instability (as explained in WO 2006 / 125517A1, Unilever PLC and Hindustan Lever Ltd.). So while good solubility may be more feasible, high storage stability may become a greater problem than expected for the MnTACN-PF6 catalyst, which is obtained from the same water or water / ethanol mixture as described before, but has been additionally precipitated / crystallized during the synthesis (leading to the removal of impurities if originally present).

[0012] Although the technology of bleaching formulations is constantly improving, there is still a need to develop further formulations of bleach catalysts that exhibit good storage stability and high bleaching activity. In particular, there is a need for liquid compositions that can be manufactured by simple processes. The present invention aims to address these needs. SUMMARY OF THE INVENTION

[0014] We have surprisingly found that selected manganese complexes can be dissolved and remain stable in selected solvents, including those that also contain small amounts of acid. It has been found that these liquid compositions are also stable to PVOH, which is typically used as the membrane material for the compartment containing the liquid composition. It has been found that these liquid compositions are suitable for use in ADW formulations having a liquid compartment.

[0015] Thus, in a first aspect, the present invention provides a liquid composition comprising: a solvent selected from the group consisting of a monoaliphatic alcohol having 2 to 6 carbon atoms, a mono-, di-, tri- or tetra-alkylene glycol having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol and / or glycerol, wherein each OH group may be optionally and independently substituted by an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms; the solvent optionally containing 0.01 to 10 wt % of an inorganic or organic acid; and a mononuclear or binuclear Mn(III) and / or Mn(IV) complex salt dissolved therein, the complex salt having a non-coordinating counterion and having a water solubility of at least 30 g / L at 20° C., wherein the mononuclear or binuclear Mn(III) and / or Mn(IV) complex salt comprises at least one ligand of the following formula (I):

[0016]

[0017] in:

[0018]

[0019] p is 3,

[0020] R is independently selected from hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH, or one R through a C2-C6 alkylene bridge, C6-C 10 The arylene bridge may contain one or two C1-C3 alkylene units and one C6-C 10 The bridge of the arylene unit is connected to the nitrogen atom of another Q of another ring of formula (I), and the bridge may be optionally independently selected C1-C 24 Alkyl substituted one or more times, and

[0021] R1, R2, R3 and R4 are independently selected from H, C1-C4-alkyl and C1-C4-alkylhydroxy.

[0022] The ligand of formula (I) is preferably a monocyclic triamine, or preferably two monocyclic triamines are linked via a divalent organic bridging group as defined above.

[0023] The most preferred ligand is one ring of formula (I) or two rings of formula (I) linked by an organic divalent group R:

[0024]

[0025] in:

[0026]

[0027] p is 3,

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

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

[0030] In a second aspect, the present invention provides a bleaching formulation comprising a liquid composition according to the first aspect of the present invention.

[0031] In a third aspect, the present invention provides a cleaning agent comprising the liquid composition according to the first aspect of the present invention, or comprising the bleaching preparation according to the second aspect of the present invention.

[0032] Further aspects and embodiments of the invention will become apparent from the following discussion. DETAILED DESCRIPTION OF THE INVENTION

[0034] As noted above, the present invention is based in part on the discovery that selected manganese complexes are soluble in selected solvents to produce stable liquid compositions that are colored due to the inclusion of the manganese complex, exhibit high bleaching activity in bleaching formulations containing peroxygen compounds, and exhibit high stability upon storage.

[0035] The liquid composition of the first aspect of the present invention comprises: a solvent selected from the group consisting of a monoaliphatic alcohol having 2 to 6 carbon atoms, a mono-, di-, tri- or tetra-alkylene glycol having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol and / or glycerol, wherein each OH group may be optionally and independently substituted by an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms, and wherein the solvent optionally contains 0.01 to 10 wt % of an inorganic or organic acid; and a mononuclear or binuclear Mn(III) and / or Mn(IV) complex salt dissolved therein, which has a non-coordinating counterion selected from the group consisting of a halide (ion, chloride, bromide or iodide), a nitrate, a nitrite, a thiocyanate, a cyanate cyanide, a cyanide), sulfate, bisulfate, sulfate monoester, sulfonate, monocarboxylate, dicarboxylate and dicarboxylic acid monoester, and having a water solubility of at least 30 g / L at 20° C., and wherein the mononuclear or binuclear Mn(III) and / or Mn(IV) complex comprises at least one ligand of formula (I) as disclosed above.

[0036] The term "water-soluble" as used herein is meant to describe a compound that is soluble in water at 20°C at a concentration of at least 30 g / L, preferably greater than 50 g / L, more preferably greater than 100 g / L, most preferably greater than 200 g / L.

[0037] The term "liquid composition" used in the present specification refers to a composition that is in a liquid state at 25°C.

[0038] The nature of the non-coordinating counterion of the manganese complex is an essential feature of the present invention. The non-coordinating counterion is selected from the anions of halides, nitrates, nitrites, thiocyanates, cyanates, sulfates, bisulfates, sulfate monoesters, sulfonates, monocarboxylates, dicarboxylates and dicarboxylates. Preferred non-coordinating counterions are selected from the group consisting of Cl - Br - ,I - 、NO3 - 、ClO4 - 、OCN - 、SCN - 、SO4 2- 、R'SO4 - 、R'COO - , R” oxalate - , oxalate 2- CF3SO3 - and R'SO3 - , wherein R' is selected from hydrogen, C1-C4-alkyl and phenyl or C1-C4-alkyl-substituted phenyl, preferably methyl-substituted phenyl, wherein R" is selected from H, Na, K and Li.

[0039] R” Oxalate - is a singly charged counterion, where R" can be hydrogen (i.e. HOOC-COO - , hydrogen oxalate), or selected from Li + 、Na + and K + Alkali metal ions. If R” oxalate - If present, there will be an equal amount of positive charge in the manganese complex.

[0040] Oxalate can also exist as a divalent anion, i.e. (COO)2 2- There may be two or more positive charges in the manganese complex, or there may be two or more manganese complexes with a charge of +1.

[0041] When present as the counterion of the manganese complex used in the present invention, the divalent anion oxalate is represented by oxalate 2- .

[0042] Hydrogen oxalate is the most typical oxalate used as the counter ion of the manganese complex of the present invention.

[0043] Similarly, the sulfate divalent anion is represented by SO4 2- , for the same reason as the above mentioned oxalate divalent anion.

[0044] Typically, the counterion is selected from Cl - 、NO3 - , hydrogen oxalate, HSO4 - 、SO4 2- 、R'COO - and R'SO3 - , wherein R' is selected from alkyl and aryl, preferably selected from methyl, phenyl, 4-methylphenyl, 4-ethylphenyl and 4-isopropylphenyl.

[0045] More typically, the counterion is selected from Cl - 、SO4 2- 、NO3 - , acetate, benzoate and tosylate.

[0046] In particular, the counterion will be selected from SO4 2- and NO3 - , most preferably NO3 - .

[0047] According to some specific embodiments, each R of the ring of formula (I) is independently selected from hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH, or one R is linked to the nitrogen atom of another Q of another ring of formula (I) via an ethylene or propylene bridge.

[0048] According to some other embodiments, each R is independently selected from hydrogen, C1-C 6- 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.

[0049] According to some other preferred embodiments, each R is independently selected from CH3, C2H5, CH2CH2OH and CH2COOH.

[0050] In the case where one R is connected to the nitrogen atom of another Q of another ring of formula (I), this is typically via an ethylene bridge. In this embodiment, the other R groups are the same, including those in the other rings of formula (I), and the R groups are typically C1-C 6- Alkyl, especially methyl.

[0051] According to some further preferred embodiments, R1, R2, R3 and R4 are independently selected from hydrogen and methyl, and in some particular embodiments, wherein R1, R2, R3 and R4 are each hydrogen.

[0052] When a compound of formula (I) comprises a group R connected via a bridge to a nitrogen atom (i.e. N) of another Q of another ring of formula (I), it is understood that, in particular embodiments, such a compound of formula (I) comprising an ethylene bridge may alternatively be represented by the following structure:

[0053]

[0054] wherein R, R1, R2, R3 and R4 are as defined herein, including the various specific embodiments listed.

[0055] The bridge connecting the two Q moieties is preferably a C2-C6 alkylene bridge connecting the two monocyclic polyamines of formula (I). 10 In the case of an arylene bridge, this may be, for example, phenylene or the corresponding arylene formed by abstracting two hydrogen atoms from naphthalene.

[0056] Examples of preferred triamine ligands 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. These compounds may carry further substituents on the nitrogen atom and / or the CH-group.

[0057] 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-triaza-cyclononane (2-MeTACN), 1,4-dimethyl-1,4,7-triazacyclononane, 1,2,4,7-tetramethyl-1,4,7-triaza-cyclononane (1,2,4,7-Me4TACN), 1,2,2,4,7-pentamethyl-1,4,7-triazacyclononane (1,2,2,4,7-Me5TACN), 2-phenyl-1,4,7-trimethyl-1,4,7-triazacyclononane and 2-decyl-1,4,7-trimethyl-1,4,7-triazacyclononane.

[0058] These cyclic triamines can be synthesized in the manner described, for example, by K. Wieghardt et al. in Inorganic Chemistry 1982, 21, 3086ff. or in B. Dietrich, P. Viout, J.-M. Lehn in "Macrocyclic Chemistry", Weinheim 1993.

[0059] According to some particular embodiments of the present invention, the ligand of formula (I) is 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononane-1-yl)-ethane (Me4-DTNE). According to still more particular embodiments of the present invention, the compound of formula (I) is Me3-TACN.

[0060] Typically, the liquid composition comprises 0.05-10 wt% of the manganese complex salt. More preferably, the liquid composition comprises 0.1-5 wt% of the manganese complex salt.

[0061] The solvent used in the liquid composition of the present invention is selected from monoaliphatic alcohols having 2 to 6 carbon atoms, mono-, di-, tri- or tetraalkylene glycols having 2, 3 or 4 carbon atoms in the alkylene part, cyclohexanol, benzyl alcohol and / or glycerol. One or more hydroxyl groups of the alcohol can be etherified with an alkanol having 1 to 4 carbon atoms. This results in the corresponding OH group being replaced by an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms.

[0062] Examples of monoaliphatic alcohols having 2 to 6 carbon atoms are ethanol, 1- or 2-propanol, and 1-, 2- or 3-butanol.

[0063] Examples of mono-, di-, tri- or tetraalkylene glycols are ethylene glycol (ethylene glycol), propylene glycol (propylene glycol) and butanediol (butylene glycol) and their di-, tri- and tetraalkylene glycol homologues.

[0064] Alkylene glycols and the corresponding mono- or dimethyl ethers are preferred, and alkylene glycols having 3 or 4 carbon atoms in the alkylene moiety are most preferred.

[0065] Also preferred are di-, tri- or tetra-alkylene glycols and the corresponding mono- or dimethyl ethers, most preferably di-, tri- or tetra-alkylene glycols having 3 or 4 carbon atoms in the alkylene moiety.

[0066] The solvent may optionally contain 0.01-10 wt% of an inorganic acid or an organic acid. This further improves the stability of the liquid composition.

[0067] The inorganic acid may be a mineral acid such as hydrochloric acid, sulfuric acid, phosphorous acid, perchloric acid and nitric acid. Sulfuric acid and nitric acid are preferred.

[0068] The organic acid may be a mono- or dicarboxylic acid or a monosulfonic acid. Examples are formic acid, acetic acid, propionic acid, butyric acid, maleic acid, oxalic acid, citric acid and ascorbic acid, preferably citric acid.

[0069] In addition to the above-mentioned manganese complex salt and solvent, the liquid composition of the present invention may also contain a small amount (eg 5 wt % or less, preferably 3 wt % or less) of an additional polar solvent, such as water.

[0070] Examples of polar solvents are N-acetylcaprolactam, propylene carbonate, valerolactone, acetonitrile, ε-caprolactone, ε-caprolactam, dimethyl sulfoxide, ethylene carbonate, γ-butyrolactone, N-methylpyrrolidone, methyl sulfolane, sulfolane, 2,3-butylene carbonate, nitromethane, 2-pyrrolidone, dibutylene sulfone, cyclobutanone, cyclopentanone, ethylene glycol sulfite, glycerol carbonate acetate, N-acetylpiperidine and / or N-acetylpyrrolidone.

[0071] The preferred polar solvent content of the liquid composition of the present invention is less than 3 wt%. Most preferably, the liquid composition of the present invention contains no polar solvent, preferably no water.

[0072] In addition to the manganese complex salt, alkylene glycol solvent and optional additional polar solvent and / or acid, the liquid composition of the present invention may also contain small amounts (e.g. 20 wt % or less, preferably 10 wt % or less, more preferably 5 wt % or less) of additional ingredients.

[0073] Examples of additional ingredients are surfactants, preferably nonionic surfactants, hydrotropes, redox-active substances, paraffin oils, benzotriazoles, dyes and / or material care agents.

[0074] Examples of material care agents are silver or copper protectants. Preferred silver / copper protectants are benzotriazole (BTA) or bis-benzotriazole and substituted derivatives thereof. Preferred BTA is tolyltriazole (TTA).

[0075] Without wishing to be bound by theory, it is believed that the addition of a nitrogen donating ligand such as BTA helps stabilize the manganese complex salt from degradation in solution.

[0076] In a preferred embodiment, the liquid composition comprises a manganese complex salt wherein the ligand is 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)ethane (Me4-DTNE).

[0077] In another preferred embodiment, the liquid composition comprises a manganese complex salt wherein the non-coordinating counterion is an anion selected from the group consisting of: Cl -Br - ,I - 、NO3 - 、ClO4 - 、OCN - 、SCN - 、SO4 2- 、R'SO4 - 、R'COO - , R” oxalate - , oxalate 2- CF3SO3 - and R'SO3 - , wherein R' is selected from hydrogen, C1-C4 alkyl and optionally methyl-substituted phenyl, wherein R" is selected from H, Na, K and Li. R" oxalate - is a singly charged counterion, where R" can be hydrogen, i.e. HOOC-COO - (hydrogen oxalate), or is selected from Li + 、Na + and K + of alkali metal ions.

[0078] In a more preferred embodiment, the liquid composition comprises a non-coordinating counterion selected from the group consisting of: NO3 - 、SO4 2- 、HSO4 - , Cl - , acetate, tosylate or benzoate.

[0079] In another preferred embodiment, the liquid composition comprises an ion-containing bleach catalyst selected from the group consisting of: [Mn IV 2(μ-O)3(Me3TACN)2]SO4, [Mn IV 2(μ-O)3(Me3TACN)2](NO3)2,[Mn IV 2(μ-O)3(Me3TACN)2](toluenesulfonate)2, [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)]-SO4, [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)](NO3)2, , [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 and [Mn IV 2(μ-O)3(Me3TACN)2]Cl2, more preferably selected from [Mn IV 2(μ-O)3(Me3TACN)2]SO4, [MnIV 2(μ-O)3(Me3TACN)2](NO3)2 and [Mn IV 2(μ-O)3(Me3TACN)2](Toluenesulfonate)2.

[0080] In preferred compositions, the solvent is selected from monoaliphatic alcohols having 3 to 6 carbon atoms, monoalkylene glycols having 3 or 4 carbon atoms in the alkylene moiety, di-, tri- or tetraalkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol and / or glycerol, wherein each OH group may be optionally and independently substituted with an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms.

[0081] In a more preferred composition, the solvent is selected from monoalkylene glycols having 3 or 4 carbon atoms in the alkylene moiety, and / or di-, tri- or tetra-alkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, wherein each glycol OH group may be optionally and independently substituted with an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms, with the proviso that the solvent is not ethylene glycol.

[0082] In still another preferred embodiment, the liquid composition comprises a solvent selected from the group consisting of propylene glycol (propylene glycol), butylene glycol (butylene glycol), diethylene glycol (diethylene glycol), dipropylene glycol (dipropylene glycol), dipropylene glycol, dibutylene glycol (dibutylene glycol), triethylene glycol (triethylene glycol), tripropylene glycol (tripropylene glycol), tributylene glycol (tributylene glycol), and tetraethylene glycol (tetraethylene glycol), wherein each glycol OH group may be optionally and independently substituted with an OR group, wherein R is an alkyl group having 1-4 carbon atoms.

[0083] In a still more preferred embodiment, the liquid composition comprises a solvent wherein R is methyl.

[0084] Very preferred solvents are those in which the propylene group is selected from 1,2-propylene or 1,3-propylene and in which the butylene group is selected from 1,2-butylene, 1,3-butylene or 1,4-butylene.

[0085] Still more preferred solvents are selected from propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether and dipropylene glycol methyl ether.

[0086] The most preferred solvent is selected from propylene glycol, propylene glycol monomethyl ether and dipropylene glycol methyl ether.

[0087] The most preferred acid is selected from sulfuric acid, nitric acid and citric acid.

[0088] In a very preferred embodiment of the liquid composition of the invention, the amount of mononuclear or binuclear Mn(III) and / or Mn(IV) complex is 0.1-5 wt % relative to the total amount of complex and solvent.

[0089] The liquid composition may also contain a bleach activator. As bleach activators, the composition according to the invention may contain compounds generally known in the prior art. These compounds are preferably polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluril, in particular tetraacetyl glycoluril (TAGU), triacetin (triacetin), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyloxybenzenesulfonate or n-lauroyloxybenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxybenzenesulfonate or n-lauroyloxybenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxybenzenesulfonate, and acylated phenolcarboxylic acids. Benzoic acid or lauroyloxybenzoic acid (NOBA or DOBA, respectively), carboxylic anhydrides, in particular phthalic anhydride, acylated polyvalent alcohols, preferably triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyxylose and octaacetyllactose, and acetylated and optionally N-alkylated glucosamine and gluconolactone, and / or N-acylated lactams, such as N-benzoyl-caprolactam. It is also possible to preferably use hydrophilically substituted acyl acetals and acyl lactams. In addition, nitrile derivatives such as n-methylmorpholine acetonitrile methylsulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of bleach activators can also be used.

[0090] Suitably, the liquid composition may comprise TAED, NOBS, triacetin and DOBA. More suitably, the liquid composition may comprise TAED.

[0091] In one embodiment, the liquid composition comprises 0.5-30 wt% of a bleach activator. Suitably, the liquid composition comprises 1-20 wt% of a bleach activator. Liquid compositions which do not contain any bleach activator are preferred.

[0092] The production of the liquid composition of the present invention can be carried out according to methods known per se.

[0093] In a first preferred process variant, the dissolution of the solid components in the solvent takes place in a mixing device. The components are processed in conventional mixing devices, which are operated batchwise or continuously and are usually equipped with a rotating mixing mechanism. When mixing, all mixing variants are possible, which ensures a thorough mixing of the components.

[0094] In a preferred embodiment, all components are mixed simultaneously. However, multi-stage mixing processes are also conceivable, in which the individual components enter the overall mixture individually or in different combinations together with other additives.

[0095] The solvent is thoroughly mixed with the powdered active substance and other optional additives to form a liquid composition. During the mixing step, the contents of the mixture may be heated to accelerate the dissolution of the solid components.

[0096] Preferred liquid compositions of the present invention are also characterized in that, based on the total amount of the composition, the water content is less than 3 wt% (measured by Karl Fischer), particularly preferably 0-2 wt%. Most preferably, the liquid compositions of the present invention are free of water or almost free of water, which means that their water content is less than 1 wt%.

[0097] As will be appreciated by those skilled in the art, it may be desirable to further process the liquid compositions of the first aspect of the invention, for example to include these compositions in bleach formulations or cleaning formulations (e.g., ADW formulations). Although the compositions of the first aspect of the invention may be included in bleach formulations and cleaning formulations as such due to their excellent storage stability, the formulator may wish to combine the ingredients of the bleach or cleaning formulation with a liquid composition stored in a container having a wall made of a water-soluble polymer (e.g., PVOH).

[0098] Liquid compositions of the first aspect of the invention are particularly useful when used in bleaching formulations. The bleach catalyst present in the liquid composition serves to catalyse the oxidative activity of a peroxygen compound which may be contained in a bleaching formulation according to the invention or which may be generated in situ from such a bleaching formulation.

[0099] When a peroxygen compound is present in a bleaching formulation comprising a liquid composition of the invention, it may be, and typically is, a compound capable of generating hydrogen peroxide in aqueous solution. Suitable amounts of peroxygen compounds to be included in the bleaching formulation may be determined by the skilled person, but typical amounts are 1 to 35 wt%, e.g. 5 to 25 wt%, based on the solids content of the bleaching formulation. It will be appreciated by those skilled in the art that lower amounts of peroxygen compounds may be used when the bleaching formulation comprises a bleaching system comprising a peroxygen compound and a so-called bleach precursor (discussed below).

[0100] Suitable hydrogen peroxide sources are widely known in the art. Examples include alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts, such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Typical peroxy compounds included in bleaching formulations are persalts, such as optionally hydrated sodium perborate (e.g. sodium perborate monohydrate and sodium perborate tetrahydrate) and sodium percarbonate. According to a particular embodiment, the bleaching formulation comprises sodium perborate monohydrate or sodium perborate tetrahydrate. Due to its high active oxygen content, it is advantageous to include sodium perborate monohydrate. For environmental reasons, it is most advantageous to use sodium percarbonate.

[0101] Organic peroxyacids can also be used as peroxy compounds. These can be monoperoxyacids or diperoxyacids. Typical monoperoxyacids or diperoxyacids have the general formula HOO-(C=O)-RZ, wherein R is an alkylene or substituted alkylene group containing 1 to about 20 carbon atoms, optionally with an internal amide bond, or a phenylene or substituted phenylene group; and Z is hydrogen, a halogen, an alkyl, an aryl, an imino-aromatic or non-aromatic group, a COOH or (C=O)OOH group or a quaternary ammonium group.

[0102] Typical monoperoxyacids include peroxybenzoic acid, peroxylauric acid, N,N-phthalyliminoperoxycaproic acid (PAP) and 6-octylamino-6-oxo-peroxycaproic acid. Typical diperoxyacids include, for example, 1,12-diperoxydodecanoic acid (DPDA) and 1,9-diperoxyazelaic acid.

[0103] Besides organic peroxyacids, inorganic peroxyacids are also suitable, for example potassium monopersulfate (MPS).

[0104] If organic or inorganic peroxyacids are included in the bleaching formulation, they are typically incorporated into the bleaching formulation in an amount of about 2 to 10% by weight, for example 4 to 8% by weight.

[0105] However, it is not necessary for bleaching preparations to comprise peroxygen compounds; instead, bleaching preparations according to the invention may comprise a bleaching system consisting of components suitable for the in situ generation of hydrogen peroxide (but which are not themselves peroxygen compounds).

[0106] Typically, bleaching substances are generated in situ. For example, organic peroxyacids are usually generated in situ rather than being included in the bleaching formulation, the peroxyacids themselves usually being insufficiently stable. For this reason, bleaching formulations usually comprise: a bleaching system containing a persalt (e.g. sodium perborate (optionally hydrated) or sodium percarbonate), which generates hydrogen peroxide in water; and a so-called peroxy bleaching precursor capable of reacting with hydrogen peroxide to generate the organic peroxyacid.

[0107] When used, the bleach precursor compound is typically present in the bleach formulation in an amount of up to 12% by weight of the composition, based on the solids content of the bleach formulation, for example from 2 to 10% by weight.

[0108] The peroxygen compounds or bleaching systems described herein may be stabilized in bleaching formulations by providing them with a protective coating, for example a coating comprising sodium metaborate and sodium silicate.

[0109] For automatic dishwasher cleaning, corrosion of glassware during the rinse phase can be inhibited by using glass corrosion inhibitors. These inhibitors are, for example, crystalline layered silicates and / or zinc salts. Crystalline layered silicates are available, for example, from WeylChem under the trade name SKS-6 (δ-Na2Si2O5). Other known crystalline layered silicates are, for example, Na-SKS-1 (Na2Si 22 O 45 ·xH2O, sodium silicate), Na-SKS-2 (Na2Si 14 O 29 xH2O, sodium hydroxide silica), Na-SKS-3 (Na2Si8O 17 ·xH2O), Na-SKS-4 (Na2Si4O9·xH2O, nadalite), Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (β-Na2Si2O5, sodium nadalite), Na-SKS-9 (NaHSi2O5·H2O), Na-SKS-10 (NaHSi2O5·3H2O, nadalite), Na-SKS-11 (t-Na2Si2O5) and Na-SKS-13 (NaHSi2O5). For example, in “Seifen- An overview of crystalline sheet silicates can be found in the article published in "Fette-Wachse, volume 116, No. 20 / 1990", pages 805-808.

[0110] In a further preferred embodiment of the present invention, the cleaning compositions of the present invention, in particular dishwasher detergents, preferably incorporate crystalline layered silicates at 0.1-20 wt%, more preferably 0.2-15 wt%, more preferably 0.4-10 wt%, all relative to the total weight of the composition.

[0111] To control glass corrosion, the cleaning compositions of the present invention, in particular dishwasher detergents, can incorporate at least one zinc or bismuth salt, preferably selected from organic zinc salts, more preferably selected from soluble organic zinc salts, still more preferably selected from soluble zinc salts of monomeric or polymeric organic acids, still more preferably selected from zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc rosinate, zinc valerate and zinc p-toluenesulfonate. Bismuth salts (e.g. bismuth acetate) can be used as a substitute for these zinc salts or in combination with these zinc salts.

[0112] In the context of the present invention, it is preferred that the amount of zinc salt in the cleaning composition, in particular the dishwasher detergent, 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, independently of which zinc salt is used, in particular independently of whether an organic or inorganic zinc salt, a soluble or insoluble zinc salt or a mixture thereof is used.

[0113] The cleaning agents of the invention may also contain silver corrosion inhibitors for controlling silver corrosion. Preferred silver corrosion inhibitors are organic sulfides, such as cystine and cysteine, dihydric or trihydric phenols, optionally alkyl- or aryl-substituted triazoles, such as benzotriazole, isocyanuric acid, salts and / or complexes of titanium, zirconium, hafnium, cobalt or cerium, wherein the metal mentioned is present in one of the oxidation states II, III, IV, V or VI, depending on the metal.

[0114] According to a particular embodiment, bleaching formulations can be used to bleach and / or modify (e.g., degrade) polysaccharides (e.g., cellulose or starch) or substrates containing polysaccharides (e.g., containing cellulose, also referred to herein as cellulose). Cellulosic substrates are widely found in domestic, industrial, and institutional laundry, wood pulp, cotton processing industries, and the like. For example, raw cotton (output from the cotton gin) is dark brown in color due to natural pigments in the plant. The cotton and textile industries recognize the need to bleach cotton before using it in textile and other fields. The purpose of bleaching such cotton fibers is to remove natural and extraneous impurities while producing a whiter material.

[0115] Regardless of the nature of the substrate treated by the method of the fourth aspect of the invention, the purpose of doing so is to achieve bleaching, i.e., to remove unwanted chromophores (e.g., in laundry or dishwashing applications, these are stains or solids on cloth, residual lignin in wood pulp or polyphenolic substances present in raw cotton, wood pulp and paper) and / or to degrade materials (e.g., starch or polyphenolic substances in dishwashing). Thus, according to some particular embodiments, the substrate may be dirty dishware or a polysaccharide substrate or a polysaccharide-containing substrate, e.g., wherein the polysaccharide is a cellulosic substrate, such as cotton, wood pulp, paper or starch.

[0116] Thus, the bleaching formulations of the present invention can be used in a dishwashing method. Such methods typically involve cleaning tableware in a mechanical dishwasher, 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 tableware (e.g., cutlery) and serving utensils, such as items made of ceramic, metal or plastic materials. Thus, an embodiment of the fourth aspect of the present invention includes a method for cleaning tableware in a mechanical dishwasher, the method comprising contacting the tableware with water and the bleaching product of the third aspect of the present invention.

[0117] Although it should be understood that the present invention should not be considered as so limited, when the bleaching formulation is intended for hard surface cleaning applications, the bleaching formulation will generally contain other components well known to those of ordinary skill in the art, such as bleach stabilizers (also known as sequestrants), for example organic sequestrants such as aminophosphonates or carboxylate sequestrants; one or more surfactants, such as cationic, anionic or non-anionic (amphiphilic) surfactants; and other components including (but not limited to) detergency builders, enzymes and fragrances.

[0118] The bleaching formulation of the third aspect of the invention will contain preferably 0.1 to 50 wt% of one or more surfactants.Such bleaching formulations may comprise one or more anionic surfactants and one or more nonionic surfactants. Typically, the anionic and nonionic surfactants of the surfactant system can be selected from the surfactants described in: "Surfactant Active Agents, Vol 1, Interscience 1949 by Schwartz & Perry, vol 2, Interscience 1958 by Schwartz, Perry & Berch; the current edition of "McCutcheon's Emulsifiers and Detergents" published by Manufacturing Confectioners Company; or in Tenside Taschenbuch, H. Stache, Carl Hauser Verlag, 1981. Description examples of suitable anionic and nonionic surfactants can be found, for example, in WO 03 / 072690 A1 (Unilever NV et al.), WO 02 / 068574 A1 (Unilever N.V. et al.) and WO 2012 / 048951 A1 (Unilever PLC et al.).

[0119] Those familiar with bleaching formulations will be familiar with the use of enzymes in this article. Enzymes can provide cleaning performance, fabric care and / or hygiene benefits. The enzymes include oxidoreductases, transferases, hydrolases, lyases, isomerases and ligases. Members of these enzymes are described in Enzyme Nomenclature 1992: Recommendations of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology on the Nomenclature and Classification of Enzymes, 1992, ISBN 0-1202271165-3, Academic Press. Decontamination enzymes are described in more detail in, for example, U.S. Patent No. 6579839 (Price et al.).

[0120] Suitable detergent builders may also be present as optional ingredients, for example as described in WO 00 / 34427 A1. Builders may include aluminosilicates, in particular zeolites, for example zeolite A, B, C, X and Y types, and zeolite MAP as described in EP 0384070 A, and precipitated builders, for example sodium carbonate. Such builders are typically present in an amount of about 5 to about 80 wt%, more preferably about 10 to 50 wt%, based on the solids content of the bleach formulation.

[0121] Those skilled in the art will be able to easily formulate bleaching formulations suitable for dishwashing or laundry cleaning according to their routine skills. Similarly, the technician will be able to easily formulate bleaching formulations suitable for other applications described herein. Such formulations may include, for example, additional bleaching catalysts based on metal ions or organic bleaching catalysts suitable for catalyzing the activity of peroxy compounds described herein. Non-limiting examples of bleaching catalysts based on transition metals can be found in, for example, EP2228429A1 (Unilever PLC and Unilever NV) and the references cited therein, and examples of organic catalysts can be found in WO 2012 / 071153A1 (The Procter & Gamble Company).

[0122] The invention also relates to a method of cleaning, which method comprises contacting a substrate to be cleaned with water and a bleaching preparation as defined above.

[0123] Preferably, the cleaning method is a method for cleaning dishes, in particular by using a mechanical dishwasher, which method comprises contacting the dishes to be cleaned with water and a bleaching product as defined above.

[0124] The following non-limiting examples more fully illustrate embodiments of the present invention. Example

[0125] Chemicals used

[0126] Dipropylene glycol was obtained from Sigma Aldrich.

[0127] Sulfuric acid (98%) was obtained from Merck.

[0128] Nitric acid (68%), obtained from Merck.

[0129] Citric acid, obtained from VWR Chemicals.

[0130] Dowanol PM and Dowanol DPM were obtained from Merck.

[0131] [Mn IV 2(μ-O)3(Me3-TACN)2](PF6)2*H2O (Me3-TACN=1,4,7-trimethyl-1,4,7-triazacyclononane), abbreviated as MnTACN-PF6, obtained according to the description in EP0458397 B (Unilever NV and Unilever PLC). Solubility in water is 10.8 g / L (20°C)

[0132] [Mn IV 2(μ-O)3(Me3-TACN)2]SO4*4H2O, abbreviated as MnTACN-SO4, was obtained as described in EP2753627B (Catexel Technologies Ltd). The solubility in water was determined to be greater than 735 g / L, which is equivalent to >73.5 wt%.

[0133] [Mn IV 2(μ-O)3(Me3-TACN)2](NO3)2, abbreviated as MnTACN-NO3, is obtained in a similar manner as described in EP2753627B for MnTACN-SO4 salt, except that the synthesis is carried out starting from Mn(NO3)2. The solubility in water at 20°C is determined to be greater than 283 g / L, which is equivalent to >28.3 wt%.

[0134] [Mn IV 2(μ-O)3(Me3-TACN)2]Cl2*3H2O, abbreviated as MnTACN-Cl2, which was obtained according to the description in EP275362B (Catexel Technologies Ltd), and [Mn IV2(μ-O)3(Me3-TACN)2](toluenesulfonate)2, abbreviated as MnTACN-Ts2, was obtained according to the description in WO2011 / 066934 (Clariant International Ltd.). [Mn IV The solubility of 2(μ-O)3(Me3-TACN)2]Cl2*3H2O in water at 20°C is greater than 182 g / L, equivalent to >18.2% wt%. [Mn IV The solubility of 2(μ-O)3(Me3-TACN)2](toluenesulfonate)2 in water at 20°C is greater than 100 g / L, equivalent to >10 wt%.

[0135] The following experiments show the benefit of the MnTACN catalyst having high water solubility relative to MnTACN-PF6.

[0136] [Mn IV 2(μ-O)3(Me3-TACN)2](benzoate)2*4H2O is abbreviated as MnTACN-benzoate, which is as described in EP2753627B (Catexel Technologies Ltd) for [Mn IV 2(μ-O)3(Me3-TACN)2]SO4, except that now 1 molar equivalent of sodium benzoate is added in the complexation step together with MnSO4, and after the oxidation / neutralization step, an additional 1.5 molar equivalents of sodium benzoate are added. IV 2(μ-O)3(Me3-TACN)2]SO4 was isolated and worked up as described.

[0137] The analysis of the product isolated in 80% yield was as follows:

[0138] C 32 H 60 Mn2N6O 11 Analysis and calculation: C 47.17, H 7.42, N 10.32;

[0139] Results: C 47.27, H 7.57, N 11.07%.

[0140] IR (KBr pellets): 3458br, 2961w, 2925w, 1595s, 1510vs, 1452m, 1397s, 1051m, 1024w, 1004m, 790m, 705m, 660m, 593m cm -1 .

[0141] 1H NMR (D2O, 400MHz) (ppm): 2.25 (br, 42H, NCH3+NCH2), 7.44 (t, J=7.2, 4H, Ph-H), 7.53 (t, J=7.2, 2H, Ph-H), 7.86 (d, J=7.2, 4H, Ph-H).

[0142] UV / Vis (ε: M-1.cm-1, in water): 224nm (40237), 278nm (21132), 315nm (13143), 392nm (1240), 482nm (510).

[0143] [Mn IV The solubility of 2(μ-O)3(Me3-TACN)2](benzoate)2*4H2O in water at 20°C is greater than 1000g / L.

[0144] A) Experiments showing that the solvents used in the present invention do not interact with PVOH bags

[0145] Different solvents (1 mL) were added to small bags made of standard PVOH film and sealed using a hot plate (150°C). The bags containing solvents were stored at 40°C for 26 weeks and then at room temperature for 26 weeks. When the bags did not change in appearance or leak solvent, they were considered stable.

[0146] The following solvents showed good stability of PVOH bags when contained in the solvents listed below:

[0147] ·Dipropylene glycol

[0148] Dipropylene glycol with 3wt% H2SO4

[0149] ·Dipropylene glycol with 3wt% HNO3

[0150] Dipropylene glycol and 3wt% citric acid

[0151] ·Dowanol DPM (dipropylene glycol methyl ether)

[0152] ·Dowanol PM *) (Dipropylene glycol methyl ether) with 3wt% HNO3

[0153] *) Dowanol PM is unstable in the absence of acid, or in the presence of H2SO4 or citric acid.

[0154] When any of the above solvents (without or with acid) were mixed with water to obtain 5.7 wt% of water, simulating the addition of 15% MnTACN-SO4 solution to the solvent, poor stability of the PVOH film was observed.

[0155] Therefore, the MnTACN salt could not be metered in as an aqueous solution, which is the solvent used to prepare the MnTACN compound, and therefore no additional dissolution and stability tests were performed on the MnTACN salt pre-dissolved in water and then mixed with the above mentioned solvent.

[0156] B) Experiments showing that the water-soluble MnTACN catalyst dissolves in the solvent used in the present invention and exhibits good storage stability, whereas the MnTACN-PF6 salt exhibits poor solubility.

[0157] B1) Comparative Experiment

[0158] Dissolution of MnTACN-PF6 catalyst in various solvents: First, the solvents in which the PF6 salt of the MnTACN catalyst can be dissolved are screened.

[0159] This compound is easily soluble in formic acid, but turns brown. It can also be dissolved in ethylene glycol after heating. Finally, MnTACN-PF6 dissolves very well in acetonitrile.

[0160] Poor solubility was observed in 1,3-propanol-diol, 1-hexanol, 1-propanol, 2-ethyl-1-hexanol, 2-propanol, dipropylene glycol, Dowanol PM, Dowanol DPM, ethanol (anhydrous), and ethyl acetate (the solvent remained colorless).

[0161] These results indicate that PF6 salts can only be dissolved in a selected group of solvents, typically those that are not suitable for use in consumer products due to toxicity reasons (e.g. acetonitrile) or poor stability observed (e.g. formic acid). The only relevant solvent identified was ethylene glycol, which, however, showed poor compatibility with PVOH membranes. All other solvents tested and used according to the present invention were unsuitable for dissolving MnTACN-PF6.

[0162] B2) MnTACN-SO4 was then tested in various solvents.

[0163] In dipropylene glycol, good solubility and stability were observed.

[0164] The same phenomenon was found in the presence of 3 wt% citric acid. However, in the presence of 3 wt% sulfuric acid and 3 wt% nitric acid, precipitation was observed after 2 weeks of storage.

[0165] • Good solubility and stability were observed in Dowanol PM without or with 3 wt% citric acid. Poor solubility was observed when sulfuric acid or nitric acid was used.

[0166] - In propylene glycol, good solubility and stability were observed (added acids were not tested).

[0167] Therefore, these results indicate that MnTACN-SO4 can be dissolved and remain stable in more solvents (or in combination with acids) than MnTACN-PF6.

[0168] B3) MnTACN-NO3 was then tested in various solvents.

[0169] In dipropylene glycol, good solubility and stability were observed. The same was found in the presence of 3 wt% sulfuric acid and 3 wt% nitric acid.

[0170] Good solubility and stability were observed in Dowanol PM without or with 3 wt% citric acid or 3 wt% sulfuric acid.

[0171] - In propylene glycol, good solubility and stability were observed (added acids were not tested).

[0172] These results therefore indicate that MnTACN-NO3 can be dissolved and remain stable in more solvents (or combinations with acids) than MnTACN-PF6.

[0173] B4) Finally, some other water-soluble MnTACN salts were tested for dissolution in dipropylene glycol and kept there for 4 weeks. MnTACN-toluenesulfonate and MnTACN-Cl2 also dissolved in this solvent, although the chloride salt had to be heated. The latter looked a bit brown, probably because a less pure sample was used.

[0174] MnTACN-benzoate also dissolves well in dipropylene glycol and shows very high stability upon storage (at least 7 months at room temperature).

[0175] C. Dishwasher tea stain cleaning experiment.

[0176] Standard dishwasher tablets were prepared using the same ingredients as disclosed in WO2022 / 058039 (Weylchem ​​Performance Products GmbH). With each tablet (14 g) (or without catalyst (blank)) 100 mg of FDO X (uncoated particles containing 2 wt% MnTACN-PF6 (comparative)), or 82 mg of dipropylene glycol containing 1.64 mg dissolved MnTACN-SO4 (Example low MnTACN-SO4) or 100 mg of dipropylene glycol containing 2 mg dissolved MnTACN-SO4 (Example high MnTACN-SO4).

[0177] The cleaning test showed the following results for cleaning a tea stain on a teacup (0 means no cleaning and 100 means complete removal of the tea stain):

[0178] -Blank: 55 points

[0179] -Comparison: 72 points

[0180] -Example Low MnTACN-SO4: 80 points

[0181] -Example High MnTACN-SO4: 85 points

[0182] These results indicate that MnTACN-SO4 dissolved in dipropylene glycol cleans tea stains better than MnTACN-PF6-based particles on an equimolar level (Example low MnTACN-SO4) and on an equal weight basis of MnTACN-SO4 and MnTACN-PF6 (Example high MnTACN-SO4).

[0183] These results are particularly surprising since the anion of the MnTACN complex does not alter the bleaching activity (or enhance hydrogen peroxide). Therefore, these results suggest that the dissolution of MnTACN-PF6 (added as particles) may not be optimal compared to the MnTACN-SO4 catalyst pre-dissolved in dipropylene glycol.

Claims

1. A liquid composition comprising: a solvent selected from the group consisting of monoaliphatic alcohols having 2 to 6 carbon atoms, mono-, di-, tri- or tetraalkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol and / or glycerol, wherein each OH group may optionally and independently be substituted with an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms; wherein the solvent optionally contains 0.01-10 wt % of an inorganic acid or an organic acid; and A mononuclear or binuclear Mn(III) and / or Mn(IV) complex salt dissolved in a solvent, the mononuclear or binuclear Mn(III) and / or Mn(IV) complex salt having an aqueous solubility of at least 30 g / L at 20° C. and a non-coordinating counterion selected from the group consisting of halides, nitrates, nitrites, thiocyanates, cyanates, sulfates, bisulfates, sulfate monoesters, sulfonates, monocarboxylates, dicarboxylates and dicarboxylic acid monoesters, and the mononuclear or binuclear Mn(III) and / or Mn(IV) complex comprises at least one ligand of formula (I): in: p is 3, R is independently selected from hydrogen, C1-C 24 alkyl, CH2CH2OH and CH2COOH, or one R through a C2-C6 alkylene bridge, C6-C 10 The arylene bridge may contain one or two C1-C3 alkylene units and one C6-C 10 The bridge of the arylene unit is connected to the nitrogen atom of another Q of another ring of formula (I), wherein the bridge may be optionally independently selected C1-C 24 Alkyl substituted one or more times, and R1, R2, R3 and R4 are independently selected from H, C1-C4-alkyl and C1-C4-alkylhydroxy.

2. The composition according to claim 1, wherein the solvent is selected from monoaliphatic alcohols having 3 to 6 carbon atoms, monoalkylene glycols having 3 or 4 carbon atoms in the alkylene moiety, di-, tri- or tetraalkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, cyclohexanol, benzyl alcohol and / or glycerol, wherein each OH group may be optionally and independently substituted by an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms.

3. The composition according to claim 2, wherein the solvent is selected from monoalkylene glycols having 3 or 4 carbon atoms in the alkylene moiety, and / or di-, tri- or tetra-alkylene glycols having 2, 3 or 4 carbon atoms in the alkylene moiety, wherein each glycol OH group may be optionally and independently substituted with an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms, with the proviso that the solvent is not ethylene glycol.

4. A composition according to any one of claims 1 to 3, wherein the ligand of formula (I) is 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3-TACN) or 1,2-bis(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)ethane (Me4-DTNE).

5. The composition according to any one of claims 1 to 4, wherein the non-coordinating counterion is an anion selected from the group consisting of: Cl - Br - ,I - 、NO3 - 、ClO4 - 、OCN - 、SCN - 、SO4 2- 、HSO4 - 、R'SO4 - 、R'COO - , R” oxalate - , oxalate 2- CF3SO3 - and R'SO3 - , wherein R' is selected from hydrogen, C1-C4 alkyl and optionally methyl-substituted phenyl, wherein R" is selected from H, Na, K and Li, R" is oxalate - is a singly charged counterion, R" can be hydrogen (i.e. HOOC-COO - , hydrogen oxalate) or selected from Li + 、Na + and K + of alkali metal ions.

6. The composition according to claim 5, wherein the non-coordinating counterion is selected from NO3 - 、SO4 2- 、HSO4 - , Cl - , acetate, tosylate or benzoate.

7. The composition according to any one of claims 1 to 6, wherein the bleach catalyst containing a water-soluble transition metal ion is selected from [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](toluenesulfonate)2, [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)]-SO4, [Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)](NO3)2,[Mn III Mn IV (μ-O)2(μ-CH3COO)(Me4DTNE)]Cl2 and [Mn IV 2(μ-O)3(Me3TACN)2]Cl2.

8. The composition according to claim 7, wherein the bleaching catalyst containing a water-soluble transition metal ion is selected from [Mn IV 2(μ-O)3(Me3TACN)2]SO4, [Mn IV 2(μ-O)3(Me3TACN)2](NO3)2 and [Mn IV 2(μ-O)3(Me3TACN)2](Toluenesulfonate)2.

9. The composition according to at least one of claims 1 to 8, wherein the solvent is selected from trimethylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, triethylene glycol, tripropylene glycol, tributylene glycol, tetraethylene glycol, wherein each glycol OH group may be optionally and independently substituted with an OR group, wherein R is an alkyl group having 1 to 4 carbon atoms.

10. The composition of claim 9, wherein R is methyl. 11 . The composition according to claim 9 , wherein the propylene group is selected from 1,2-propylene or 1,3-propylene, and the butylene group is selected from 1,2-butylene, 1,3-butylene or 1,4-butylene.

12. The composition according to any one of claims 1 to 11, wherein the solvent is selected from propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl ether and dipropylene glycol methyl ether.

13. The composition of claim 12, wherein the solvent is selected from propylene glycol, propylene glycol monomethyl ether and dipropylene glycol methyl ether.

14. The composition of any one of claims 1-13, wherein the acid is selected from sulfuric acid, nitric acid and citric acid.

15. The composition according to any one of claims 1 to 14, wherein the amount of the mononuclear or binuclear Mn(III) and / or Mn(IV) complex is 0.1 to 5 wt% relative to the total amount of the complex and the solvent.

16. A bleaching formulation comprising a composition as claimed in any one of claims 1 to 15 and a peroxy compound and / or a precursor thereof.

17. A cleaning agent comprising the composition of any one of claims 1 to 15 or the bleaching preparation of claim 16, wherein the cleaning agent is preferably a dishwashing agent.

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