WO2023030951A1

WO2023030951A1 - Bleach catalysts, bleach systems and cleaning compositions

Info

Publication number: WO2023030951A1
Application number: PCT/EP2022/073355
Authority: WO
Inventors: Katherine Mary Thompson
Original assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Current assignee: Unilever Global IP Ltd; Unilever IP Holdings BV; Conopco Inc
Priority date: 2021-09-01
Filing date: 2022-08-22
Publication date: 2023-03-09
Anticipated expiration: 2024-03-01

Abstract

A bleach catalyst comprising an organic acid-metal complex comprising an organic acid-metal datively bonded to at least one metal cations. A bleach system comprising the bleach catalyst in combination with a bleach. A cleaning composition comprising the bleach catalyst, a bleach and a detersive surfactant.

Description

BLEACH CATALYSTS, BLEACH SYSTEMS AND CLEANING COMPOSITIONS

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a novel bleach catalyst comprising aminopolycarboxylic acid metal complexes comprising a non-aromatic organic acid and one or more datively bound metal cations, a bleach system comprising said catalyst, and further, cleaning compositions comprising the bleach catalyst I system.

BACKGROUND OF THE INVENTION

Cleaning compositions comprise bleach to remove stains by oxidizing the stain components. Bleach systems tackle difficult to remove colored stains, such as teastains. Bleach systems, beside a source of bleach, may contain bleach activator and bleach catalyst to provide effective bleaching also at low wash temperatures. One known effective bleach catalyst is based on a manganese complex of the formula [L_nMn_mXp]^zYq, as described in EP0458397A2.

However, such bleach catalysts have poor biodegradability.

Despite the prior art there remains a need to provide an improved bleach catalyst.

SUMMARY OF THE INVENTION

Accordingly, in a first aspect the invention provides a bleach catalyst comprising an non-aromatic organic acid -metal complex comprising an aminopolycarboxylate datively bonded to one or more metal cations.

In a second aspect the invention provides a bleach system including a bleach catalyst a bleach catalyst comprising:

(i) an organic acid-metal complex comprising an organic acid datively bound to one or more metal cations; and

(ii) including a bleach.

The bleach catalyst and bleach system have particular application in cleaning formulations to form a new and improved bleach composition. Accordingly in a further aspect the invention provides a cleaning composition comprising:

(i) a cleaning component;

(ii) a bleach catalyst comprising an organic acid-metal comprising an organic acid datively bonded to at least one metal cation: and

(ii) optionally including a bleach.

The cleaning component may comprise a detersive surfactant.

In a further aspect the invention provides use of a bleach catalyst comprising a organic acid-metal complex comprising an non-aromatic organic acid datively bonded to at least one metal cation.

The organic acid is preferably selected from non-aromatic or aromatic acids.

Suitably, the metal cation comprises Fe²⁺, Fe³⁺, Mn²⁺, Mn³⁺, Mn⁴⁺, Mn⁵⁺, Mn⁶⁺, Mn⁷⁺ and Co²⁺, Co³⁺ or mixtures thereof, preferably comprises Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Co²⁺, Co³⁺ or mixtures thereof and even more preferably comprises Mn²⁺, Mn⁴⁺ or mixtures thereof.

Most preferably, the metal cation comprises iron- (Fe), Manganese- (Mn) cobalt- (Co) cations or any combination thereof.

Preferably, the cleaning composition/bleach s comprises at most 1 wt. % of phosphonate (based on total weight of the composition.

Preferably the pH of a solution of 1 wt. % of the cleaning composition in water as measured at 25 degrees Celsius is from 7.0 to 12.0.

Unless otherwise made clear from the context, where the terms ‘aminopolycarboxylic acid’ or ‘organic acid’ are used these encompass their corresponding salts (and vice versa). Surprisingly it was observed that organic acid-metal cation complexes of the invention can be effective in promoting bleaching of dyes in solution by having bleach catalyst activity.

In another aspect the invention relates to the use of a composition comprising an nonaromatic organic acid-metal cation complex comprising an non-aromatic organic acid datively bound to one or more metal cations for cleaning, especially bleaching a substrate.

Non-aromatic organic acid complexes

Non-aromatic organic complexes or sequestrants as such are known and include poly(hydroxy-acids), for example citric acid, isocitric acid, gluconic acid and malic acid; poly(carboxylic acids) such as propane-1 , 2, 3-tricarboxylic acid, 1 ,2, 3, 4 butanetetracarboxylic acid, malonic acid, succinic acid. Other sequestrant include mono and poly-hydroxamates, for example alkylhydroxamates, malonic dihydroxamic acid, deferoxamine B, deferoxmine E.

Preferably the non-aromatic acid is an aliphatic acid.

Of these, gluconic acid, such as D-gluconic acid and citric acid are more preferred and citric acid is even more preferred.

The preferred complexes have the following formulae: [M_mL_n]^pY^q.rH2O where, M is iron, manganese or cobalt, L is an aminocarboxylic ligand, m = 1-3, n = 1-3, p = 0-3, q = 0-3, r = 0-3. If p <1 >, Y is a counterion.

General methods to prepare organic ligand-metal ion complexes are known in the art (e.g. V. Springer et. al. Preparation and study of the solid complexes of the racemic ethylenediamine-N,N'-disuccinic acid with iron(lll), cobalt(lll), and bismuth(lll) ions. Chem. Zvesti 34(2), pages 184-189, 1980; US5,559,261 and W. Wang et al, Homo- and hetero-metallic manganese citrate complexes: Syntheses, crystal structures and magnetic properties, Polyhedron, 25, 1656-1668, 2005. The preferred method of manufacture the non-aromatic organic acid sequestrant comprising one or more datively bound metal cations preferably iron- (Fe), Manganese- (Mn) and/or cobalt- (Co) cations comprises the following steps: a) providing an aqueous solution comprising non-aromatic organic acid sequestrant and metal cations preferably Fe, Mn and/or Co cations, wherein the molar ratio of the non-aromatic organic acid sequestrant and the cations is from 100:1 to 1 :6; and b) optionally adjusting the pH of the aqueous solution to the range of from 6 to 11 ; and c) removing water from the aqueous solution to provide a composition comprising non-aromatic organic acid sequestrant comprising datively bound metal cations, preferably Fe, Mn and/or Co cations, and the composition having water content of at most 60 wt.% and/or precipitating the complexes from aqueous solution by adding a non-aqueous solvent (preferably an organic solvent such as ethanol).

Preferably at step c) water is removed until a solid is provided or a precipitated solid formed on addition of an organic solvent is separated from the supernatant solution by filtration and then air dried. This is especially advantageous when the non-aromatic organic acid sequestrant comprising one or more datively bound metal cations preferably iron- (Fe), Manganese- (Mn) and/or cobalt- (Co) cations is part of the ingredients to make a tablet or powder detergent.

Suitable examples of such water-soluble salts are the chloride, sulphate or carbonate salts of Fe, Mn and/or Co. The Fe²⁺, Fe³⁺, Mn²⁺, Mn³⁺, Mn⁴⁺, Mn⁵⁺, Mn⁶⁺, Mn⁷⁺ and Co²⁺, Co³⁺ are the preferred cations. Advantageously the cation is a Fe²⁺, Fe³⁺, Mn²⁺ and/or Mn⁴⁺ cation and particularly preferred are the Fe³⁺, Fe²⁺ and Mn²⁺ oxidation states.

As indicated in the method, the molar ratio of non-aromatic organic acid sequestrant and the cations can be from 100:1 to 1 :6. Lower ratios will lead to only a part of the non-aromatic organic acid sequestrant comprising datively bound Fe, Mn and/or Co ions. This can be beneficial since such a non-aromatic organic acid sequestrant mixture can both contribute to effective bleaching as well as providing strong builder and chelating functionality in one go. Higher ratios are beneficial to provide a more targeted bleach catalyst activity and can allow for more than one Fe, Mn and/or Co cation to be datively bound to the non-aromatic organic acid sequestrant. In this respect it is noted that many non-aromatic organic acid sequestrant are capable of datively binding more than one Fe, Mn and/or Co cations.

Preferred compounds include [Mn"(Hcitrate)]^_, [Mn"(H2Citrate)2]²', [Mn"(H2Citrate)] polymer, [Mn'^Hcitrate^]²', [Mn"₃(Hcitrate)]2, [Mn^IH(citrate)2]⁵', [Fe^IH(citrate)]', [Fe'"(Hcitrate)], [Fe^IH(citrate)2]⁵', [Fe^IH2(citrate)2]²' , [Co"(H2Citrate)], [Co'"(Hcitrate)], where H₄citrate is citric acid; [Mn"(GH₄)₂], [Mn"(GH₃)₂]²-, [Mn"₂(GH₃)₄]⁴-, [Mn"(GH₃)]³', [Mn^l"₂(GH₃)₄ (OH)₂]⁴-, Mn^IV2(GH₃)₄O)₂(OH)₂]⁶-, [Fe" GH₄]⁺, [Fe^IH GH₃]⁺ , [Fe^IH GH]; [Fe^IH G]²-, [Fe^lll2(GH₃)₂(OH₄)(H₂O)2]²- , [Co" (GH₃)], [Co¹¹¹ (GH₂)] where HGH₄ is D-gluconic acid, GH₄' is the gluconate mono-anion and GH₃ ^2- is the gluconate di-anion.

The cleaning composition I bleach system comprises from 0.002 to 20 wt. % of free acid equivalent of one or more non-aromatic organic acid sequestrant comprising one or more datively bound metal cations preferably Fe, Mn and/or Co cations. A further beneficial amount is from 0.1 to 20 wt. %, more preferably from 0.2 to 10 wt. %, even more preferably from 0.3 to 5 wt. % and still even more preferably from 0.4 to 4 wt. %

Besides the non-aromatic organic acid sequestrant datively bound to one or more metal cations preferably Fe, Mn and/or Co cations, further organic acid may be present which does not comprise such datively bound Fe, Mn and/or Co cations.

An optimal balance of non-aromatic organic acid sequestrant comprising one or more datively bound metal cations preferably Fe, Mn or Co cations versus non-aromatic organic acid sequestrant not comprising such, is considered to be from 1 :4000 to 100:1 , more preferably from 1 :100 to 20:1 , even more preferably from 1 :50 to 1 :1 and still even more preferably from 1 :20 to 1 :10. Such ratios provide a balanced bleach catalyst activity and a sequestrant activity. Preferably the cleaning composition I bleach system of the invention does not comprise further poorly biodegradable bleach catalyst and beneficially comprises essentially no further bleach catalyst (biodegradable or not).

In particular it is preferred that the non-aromatic organic acid sequestrant has an average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the organic acid is not a polymer-based acid as these tend to be less biodegradable. The organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.

The non-aromatic organic acid sequestrant of the invention does not contain any covalently bound N or P atoms to reduce any eutrophication issues. Further preferred is that it does not contain any S atoms. In fact, the most preferred non-aromatic organic acid sequestrant of the invention (as considered from the free-acid equivalent structure) contains no other covalently bound atoms than C, H and O atoms.

Aromatic Organic Acid-Metal Complexes

Pyridine is a heterocyclic organic compound with the chemical formula C5H5N. Acid derivatives of pyridine acid derivatives are defined as pyridine compounds in which at least one or more of the H-atoms is replaced with and acid moiety, such as carboxylic acid moiety and/or a sulfonic acid moiety.

Preferably, at least one carboxylate is in a 2 or 3--position relative to the nitrogen atom, and most preferably in the 2-position.

Preferred are carboxylic acid moieties and especially those based on formic acid (i.e. - COOH), acetic acid (i.e. CH2COOH), propionic acid (e.g. -CH2CH2COOH), of these those based on formic acid are even more preferred. Examples of such acid derivatives of pyridine with one or more carboxylic acid moieties based on formic acid are picolinic acid and dipicolinic acid. At least one of the hydrogen atoms of the pyridine is replaced with an acid moiety. A such 1 , 2, 3, 4 or all of the hydrogen atoms of a pyridine can be replaced with an acid moiety. Best results were found when at least 2 of the hydrogen atoms were replaced with an acid moiety. Hence advantageously 2 or 3 hydrogen atoms are replaced with an acid moiety and more beneficially 2 are replaced with an acid moiety. Preferentially, the pyridine ring is substituted with at least one carboxylic acid moiety at the 2- or 3- positions, more preferably at the 2-position.

Apart from replacement of at least one hydrogen atoms of a pyridine with an acid moiety, the acid derivatives of pyridine can include those compounds in which further hydrogen atoms are replaced by non-acid moieties. Examples are acid derivatives of pyridine which can be considered acid derivatives of bromo-pyridine and bipyridine. However preferably the acid derivative of pyridine invention is based on the chemical formula C5H5N in which one or more H-atoms are replaced acid moieties only.

The preferred complexes have the following formulae: [M_mL_n]^pY^q.rH2O where, M is iron, manganese or cobalt, L is an acid derivative of pyridine ligand, m = 1-3, n = 1-3, p = 0- 3, q = 0-3, r = 0-3. If p <1 >, Y is counterion.

General methods to prepare organic ligand-metal ion complexes are known in the art (e.g. V. Springer et. al. Preparation and study of the solid complexes of the racemic ethylenediamine-N,N'-disuccinic acid with iron(lll), cobalt(lll), and bismuth(lll) ions. Chem. Zvesti 34(2), pages 184-189, 1980; US5,559,261).

The preferred method of manufacture the acid derivative of pyridine comprising one or more datively bound metal cation, preferably iron- (Fe), Manganese- (Mn) and/or cobalt- (Co) cations comprises the following steps: a) providing an aqueous solution comprising acid derivative of pyridine and said metal cation (e.g. Fe, Mn and/or Co cations), wherein the molar ratio of the acid derivative of pyridine and the cations is from 100:1 to 1 :6; and b) optionally adjusting the pH of the aqueous solution to the range of from 6 to 11 ; and; c) removing water from the aqueous solution to provide a composition comprising acid derivative of pyridine comprising datively covalent bound Fe, Mn and/or Co cations and the composition having water content of at most 60 wt.% and/or precipitating the complexes from aqueous solution by adding a non-aqueous solvent (preferably an organic solvent such as ethanol).

Preferably at step c) water is removed until a solid is provided or a precipitated solid formed on addition of an organic solvent is separated from the supernatant solution by filtration and then air dried. This is especially advantageous when the acid derivative of pyridine comprising one or more datively covalent bound metal cation, preferably iron- (Fe), Manganese- (Mn) and/or cobalt- (Co) cations is part of the ingredients to make a tablet or powder detergent.

As indicated in the method, the molar ratio of acid derivative of pyridine and the cations can be from 100:1 to 1 :6. Lower ratios will lead to only a part of the acid derivative of pyridine comprising datively covalent bound metal cations e.g. Fe, Mn and/or Co ions. This can be beneficial since such an acid derivative of pyridine mixture can both contribute to effective bleaching as well aiding builder and chelating functionality in one go. Higher ratios are beneficial to provide a more targeted bleach catalyst activity and can allow for more than one metal e.g. Fe, Mn and/or Co cation to be datively bound to the acid derivative of pyridine. In this respect it is noted that some acid derivative of pyridine can be capable of datively binding more than one metal e.g. Fe, Mn and/or Co cations.

Preferred compounds include:

[Fe^lll(pic)₃], [Fe(pic)₂(H₂O)]-, [Fe'"(pic)₂OH]₂, [Fe^lll ₂(OH)₂(pic)₄], [Mn"(pic)(OH)₂]„, [Mn"CI(pic)(H₂O)₂]_n, [Mn" (pic)₂]„, [Mn"CI(pic)]_n, [Mn"(pic)₂ (H₂O)₂], [Mn"(pic)₂ (OH)₂]²; [Mn" Cl₂(pic)₂]²-, [Mn^l"(pic)₃], [Mn'"(pic)₂(OH)], [Mn"^lCI(pic)₂(H₂O)], [Mn^lv ₂O₂(pic)₄], [Co" (pic)₂], [Co'^pic)^, [Fe"(dipic)(H₂O)₃], [Fe"(dipic)₂]²-, [Fe"₂(dipic)₂(H₂O)₆], [Fe^lll(dipic)(OH)]_J [Fe^lll(dipic)₂]-, [Mn"(dipic)(H₂O)₃], [Mn"(dipic)₂(H₂O)]²-, [Mn"₂(dipic)₂(H₂O)6], [Mn^IH(dpic)₂]', [Co"(dipic)₂]’, [Co^IH(dipic)₂] where Hpic is picolinic acid and H₂dipic is dipicolinic acid.

The ‘n’ indicates chain/polymeric compounds. These may break up into monomers with pH changes I reacting with bleach.

Bleach systems/ cleaning compositions of the invention comprise from 0.002 to 20 wt. % of acid derivative, of pyridine comprising one or more datively bound metal e.g. Fe, Mn and/or Co cations. A further beneficial amount is from 0.1 to 20 wt. %, more preferably from 0.2 to 10 wt. %, even more preferably from 0.3 to 5 wt. % and still even more preferably from 0.4 to 4 wt. %

Besides the acid derivative of pyridine non-covalently bound to one or more metal e..g Fe, Mn and/or Co cations, further organic acid may be present which does not comprise such datively bound metal e.g. Fe, Mn and/or Co cations.

An optimal balance of acid derivative of pyridine comprising one or more datively bound metal e.g. Fe, Mn or Co cations versus non-aromatic organic acid not comprising such, is considered to be from 1 :4000 to 100:1 , more preferably from 1 :100 to 20:1 , even more preferably from 1 :50 to 1 :1 and still even more preferably from 1 :20 to 1 :10. Such ratios provide a balanced bleach catalyst activity and a sequestrant activity.

Preferably bleach systems/ cleaning compositions of the invention do not comprise further poorly biodegradable bleach catalyst and beneficially comprises essentially no further bleach catalyst (biodegradable or not).

In particular it is preferred that the acid derivative of pyridine has an average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the acid derivative of pyridine is not a polymer-based acid as these tend to be less biodegradable. The acid derivative of pyridine employed in accordance with the invention preferably comprises 6 to 25 carbon atoms, more preferably 7 to 10 carbon atoms.

The acid derivative of pyridine of the invention preferably does not contain any covalently bound P atoms to reduce any eutrophication issues. Further preferred is that it does not contain any S atoms. In fact, the most preferred acid derivative of pyridine of the invention contains no other covalently bound atoms than C, H, O and N atoms.

Organic Acid

Inclusion of further organic acids and/or their corresponding salts (not comprising dative bonds with metal cations preferably Fe, Mn and/or Co cation and not being aminopolycarboxylates) is beneficial in providing improved detergency whilst capable of being made from renewable materials (e.g. plant-based) and readily biodegradable.

Said further organic acid used in the detergent composition of the invention can be any organic acid. Particularly good results were achieved with organic acids being polyacids (i.e. acids having more than one carboxylic acid group), and more particularly with di- or tricarboxylic organic acids. The organic acids used in the invention have an average molecular mass of at most 500 Dalton, more preferably of at most 400 Dalton and most preferably of at most 300 Dalton, the molecular mass being based on the free acid equivalent. In any case, preferably the organic acid is not a polymer-based acid. The organic acid employed in accordance with the invention preferably comprises 3 to 25 carbon atoms, more preferably 4 to 15 carbon atoms.

In view of consumer acceptance and reducing environmental impact, the organic acids preferably are those which are also found naturally occurring, such as in plants. As such, organic acids of note are acetic acid, citric acid, aspartic acid, lactic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, saccharic acids, their salts, or mixtures thereof. Of these, of particular interest are citric acid, aspartic acid, acetic acid, lactic acid, succinic acid, glutaric acid, adipic acid, gluconic acid, their salts, or mixtures thereof. Citric acid was found highly advantageous. Citric acid is naturally occurring, highly biodegradable as well as providing added builder activity and disintegration properties.

Advantageously the detergent composition of the invention comprises a free acid equivalent of organic acid not comprising datively bound metal cations preferably Fe, Mn and/or Co cations of from 1 to 30 wt. %, more preferably of from 5 to 20 wt. % and even more preferably from 8.0 to 15 wt.%. Preferred salt forms of the further organic acid are alkali metal salts and beneficially their sodium salts.

Aminopolycarboxylate

Aminopolycarboxylates are well known in the detergent industry and sometimes referred to as aminopolycarboxylic acids chelants. They are generally appreciated as being strong builders. Suitable aminopolycarboxylic acids include glutamic acid N,N- diacetic acid (GLDA), methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDS), iminodimalic acid (IDM), ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA) aspartic acid diethoxysuccinic acid (AES) aspartic acid-N,N-diacetic acid (ASDA) , hydroxyethylene-diaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA) , iminodifumaric (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), ethylenediaminedifumaric acid (EDDF), ethylenediaminedimalic acid (EDDM), ethylenediamineditartaric acid (EDDT), ethylenediaminedimaleic acid and (EDDMAL).

Preferred aminopolycarboxylates are GLDA, MGDA, EDDS, IDS, IDM or a mixture thereof, more preferred are GLDA, MGDA, EDDS or a mixture thereof and even more preferred are GLDA and MGDA or a mixture thereof. Of these GLDA is especially preferred as it can be made from bio-based materials (e.g. monosodium glutamate, which itself can be made as by-product from corn fermentation). Also, GLDA itself is highly biodegradable. MGDA is more preferred in view of it being somewhat less hygroscopic, which improves detergent stability during storage. The cleaning composition I bleach system according to the invention preferably comprises from 0.5 to 40 wt. % free acid equivalent of total aminopolycarboxylate. A particularly preferred amount of free acid equivalent of aminopolycarboxylate is from 0.5 to 20 wt. %, more preferably from 1.0 to 15 wt. %, even more preferably from 2.0 to 10 wt. % and still even more preferably from 3.0 to 8 wt.%.

Preferred salts are alkali-based salts and more preferred are sodium-based salts. pH profile

The cleaning composition I bleach system provides a pH of a solution of 1 wt.% of the cleaning composition I bleach system in water as measured at 25 degrees Celsius of from 7.0 to 12.0, preferably of from 8.5 to 11.0 and even more preferably of from 9.0 to 10.5.

Bleach

The cleaning composition I bleach system preferably comprises from 0.1 to 25 wt. % of bleach. Inorganic and/or organic bleaches can be used. Bleach may be selected from peroxides, organic peracids, salts of organic peracids and combinations thereof. Advantageously the bleach is selected from peroxides (including peroxide salts such as sodium percarbonate), organic peracids, salts of organic peracids and combinations thereof. More preferably, the bleach is a peroxide. Most preferably, the bleach is a hydrogen peroxide or a percarbonate. Further preferred, the bleach is a coated percarbonate. Tetraacetylethylenediamine (TAED) may be included as a peracetic acid precursor. More preferred amounts of bleach are from 1.0 to 25 wt.%, even more preferably at from 2.0 to 20 wt. % and still even more preferably from 5 to 15 wt.%.

The improved bleaching composition has particular application in detergent formulations to form a new and improved detergent bleach composition within the purview of the invention, comprising the bleach catalyst, the bleach, a surface-active material, and usually also detergency builders and other known ingredients of such formulations, as well as in the industrial bleaching of yarns, textiles, paper, woodpulp and the like. These are discussed in more detail below. Bleach Activators

The detergent composition of the invention preferably comprises one or more bleach activators such as peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N, N, N', N '-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sul phonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4, 751,015. A beneficial amount of bleach activator is from 0.1 to 10 wt.%, more preferably from 0.5 to 5 wt.% and even more preferably from 1.0 to 4 wt. %.

Further ingredients

The cleaning composition I bleach system may comprise further ingredients, such as further detergent active components.

Definitions

The following terms, as used herein, are defined below:

Articles such as "a" and "an" when used in a claim, are understood to mean one or more of what is claimed or described.

“Alkyl” means an unsubstituted or substituted saturated hydrocarbon chain having from 1 to 18 carbon atoms. The chain may be linear or branched.

“Dative bond” is used interchangeably with co-ordinate bond, co-ordinate covalent, and dative covalent bond. It is a covalent bond (a shared pair of electrons) in which both electrons come (are donated) from the same atom.

"include", "includes" and "including" are meant to be non-limiting.

Concentrations expressed in wt. % of “free acid equivalent" refer to the concentration of the compound expressed as wt. %, assuming it would be in fully protonated from. The following table shows how the free acid equivalent concentrations can be calculated for some (anhydrous) aminopolycarboxylates and (anhydrous) acid salts.

“M⁺” “M1 ⁺” or “M2⁺ denote metal ions with unspecified positive charge and for the sake of clarity the “+” sign does not imply only monovalent ions- but also divalent, trivalent, tetravalent etc., and other multiply charged metal cations (whether free ions e.g. in solution or a bound ion a complex). Conversely where the ion is specified such as Ca²⁺ this implies a specific charge, here +2 (divalent ion).

“Textiles” can include woven fabrics, non-woven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends.

"substantially free of” or "substantially free from" refers to either the complete absence of an ingredient or a minimal amount thereof merely as impurity or unintended byproduct of another ingredient. A composition that is "substantially free" of/from a component means that the composition comprises less than 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, by weight of the composition, of the component.

"Substrate” preferably is any suitable substrate and includes but is not limited to fabric substrates and dishes. Fabric substrates includes clothing, linens and other household textiles etc. In the context of fabrics, wherein the term “linen” is used to describe certain types of laundry items including bed sheets, pillow cases, towels, tablecloths, table napkins and uniforms and the term “textiles” can include woven fabrics, nonwoven fabrics, and knitted fabrics; and can include natural or synthetic fibres such as silk fibres, linen fibres, cotton fibres, polyester fibres, polyamide fibres such as nylon, acrylic fibres, acetate fibres, and blends thereof including cotton and polyester blends. “Dishes” is meant generically and encompasses essentially any items which may be found in a dishwashing load, including crockery chinaware, glassware, plasticware, hollowware and cutlery, including silverware. Substrate may also include any inanimate “household surface”, “household hard surface”, it is meant herein any kind of surface typically found in and around houses like kitchens, bathrooms, e.g., floors, walls, tiles, tile grouting windows, cupboards, sinks, showers, shower plastified curtains, wash basins, WCs, fixtures and fittings and the like made of different materials like ceramic, vinyl, no-wax vinyl, linoleum, melamine, glass, Inox®, Formica®, vitroceramic, any plastics, plastified wood, metal or any painted or varnished or sealed surface and the like. Household hard surfaces also include household appliances including, but not limited to refrigerators, freezers, washing machines, automatic dryers, ovens, microwave ovens, dishwashers and so on. Such hard surfaces may be found both in private households as well as in commercial, institutional and industrial environments.

“Cleaning” includes any of washing, soaking, soil removal, stain removal, mould removal, and any combination thereof and may comprise pretreatment or direct treatment of substrates, and may utilise a detersive surfactant.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition unless otherwise indicated. It should be understood that every maximum numerical limitation given throughout this specification includes every lower numerical limitation, as if such lower numerical limitations were expressly written herein. Every minimum numerical limitation given throughout this specification will include every higher numerical limitation, as if such higher numerical limitations were expressly written herein. Every numerical range given throughout this specification will include every narrower numerical range that falls within such broader numerical range, as if such narrower numerical ranges were all expressly written herein Product Form

The cleaning composition I bleach system may be may be suitable for cleaning a substrate as defined herein.

The cleaning composition I bleach system may be in particulate form. The term "particulate” in this context means free-flowing or compacted solid forms such as powders, granules, ribbon, noodle, pellets, flakes, pastille bars, briquettes or tablets. Preferably the composition is in the form of powder, granules or a tablet. The composition may be in the form of a unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet.

The composition according to the present invention may be made via a variety of conventional methods known in the art and those which includes but is not limited to the mixing of ingredients, including dry-mixing, compaction such as agglomerating, extrusion, tableting, or spray-drying of the various compounds comprised in the detergent component, or mixtures of these techniques, whereby the components herein also can be made by for example compaction, including extrusion and agglomerating, or spray-drying. The cleaning composition I bleach system may be made by any of the conventional processes, especially preferred is the technique of slurry making and spray drying.

The compositions preferably have a density of more than 350 grams/litre, more preferably more than 450 grams/litre or even more than 570 grams/litre.

Solid e.g. particulate compositions may also incorporate non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers, fillers.

Alternatively, the cleaning composition I bleach system may be a liquid or a gel. The term “liquid” in the context of this invention denotes that a continuous phase or predominant part of the composition is liquid and that the composition is flowable at 15°C and above. Accordingly, the term “liquid” may encompass emulsions, suspensions, and compositions having flowable yet stiffer consistency, known as gels or pastes. The viscosity of the composition may suitably range from about 200 to about 10,000 mPa.s at 25°C at a shear rate of 21 sec¹. This shear rate is the shear rate that is usually exerted on the liquid when poured from a bottle. Pourable liquid compositions generally have a viscosity of from 100 to 2,500 mPa.s, preferably from 100 to 1500 mPa.s. Liquid compositions which are pourable gels generally have a viscosity of from 1 ,500 mPa.s to 6,000 mPa.s, preferably from 1 ,500 mPa.s to 2,000 mPa.s.

The cleaning composition may be a laundry cleaning composition.

The cleaning composition may be a liquid and may generally comprise from 5 to 95%, preferably from 10 to 90%, more preferably from 15 to 85% water (by weight based on the total weight of the composition). The composition may also incorporate from 0.1 to 15% (by weight based on the total weight of the composition) of non-aqueous carriers such as hydrotropes, co-solvents and phase stabilizers.

In the case of compositions comprising a bleach catalyst together with a bleach, where such compositions comprise water, it is preferred that the bleach is segregated from the bleach catalyst for example using separate containers or encapsulation or other segregation means.

Surfactants

Cleaning composition I bleach systems if utilized, may comprise a surfactant. The surfactant may be present at 5 to 40%, preferably 15 to 35% (by weight based on the total weight of the composition). Alternatively, the surfactant may be present up to 60% (by weight based on the total weight of the composition).

Preferably the surfactant is a detersive surfactant. Preferred detersive surfactants may be selected from non-soap anionic surfactants, nonionic surfactants and mixtures thereof.

Suitable non-soap anionic surfactants include salts of organic sulfates and sulfonates having alkyl radicals containing from about 8 -22, preferably 10 - 18, carbon atoms; e.g. alkyl sulfates, alkyl ether sulfates, alkaryl sulfonates, alpha-olefin sulfonates and mixtures thereof. The alkyl radicals may be saturated. The alkyl ether sulfates may contain from one to ten ethylene oxide or propylene oxide units per molecule, and preferably contain one to three ethylene oxide units per molecule. The counterion for anionic surfactants is generally an alkali metal such as sodium or potassium; or an ammoniacal counterion such as monoethanolamine, (MEA) diethanolamine (DEA) or triethanolamine (TEA). Mixtures of such counterions may also be employed.

A preferred class of non-soap anionic surfactant for use in the invention includes alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) with an alkyl chain length of from 10 to 18 carbon atoms. Commercial LAS is a mixture of closely related isomers and homologues alkyl chain homologues, each containing an aromatic ring sulfonated at the “para" position and attached to a linear alkyl chain at any position except the terminal carbons. The linear alkyl chain typically has a chain length of from 11 to 15 carbon atoms, preferably about C12. Each alkyl chain homologue consists of a mixture of all the possible sulfophenyl isomers except for the 1 -phenyl isomer. LAS is normally formulated into compositions in acid (i.e. HLAS) form and then at least partially neutralized in-situ.

Also suitable are alkyl ether sulfates having a straight or branched chain alkyl group having 10 to 18, more preferably 12 to 14 carbon atoms and containing an average of 1 to 3EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES) in which the predominantly C12 lauryl alkyl group has been ethoxylated with an average of 3EO units per molecule.

Some alkyl sulfate surfactant (PAS) may be used, such as non-ethoxylated primary and secondary alkyl sulfates with an alkyl chain length of from 10 to 18.

Mixtures of any of the above described materials may also be used. A preferred mixture of non-soap anionic surfactants for use in the invention comprises linear alkylbenzene sulfonate (preferably Cn to C15 linear alkyl benzene sulfonate) and sodium lauryl ether sulfate (preferably C10 to C18 alkyl sulfate ethoxylated with an average of 1 to 3 EO). The total level of non-soap anionic surfactant may suitably range from 5 to 30% (by weight based on the total weight of the composition).

Nonionic surfactants may be present, polyoxyalkylene compounds, i.e. the reaction product of alkylene oxides (such as ethylene oxide or propylene oxide or mixtures thereof) with starter molecules having a hydrophobic group and a reactive hydrogen atom which is reactive with the alkylene oxide. Such starter molecules include alcohols, acids, amides or alkyl phenols. Where the starter molecule is an alcohol, the reaction product is known as an alcohol alkoxylate. The polyoxyalkylene compounds can have a variety of block and heteric (random) structures. For example, they can comprise a single block of alkylene oxide, or they can be diblock alkoxylates or triblock alkoxylates. Within the block structures, the blocks can be all ethylene oxide or all propylene oxide, or the blocks can contain a heteric mixture of alkylene oxides. Examples of such materials include aliphatic alcohol ethoxylates such as Cs to Cis primary or secondary linear or branched alcohol ethoxylates with an average of from 2 to 40 moles of ethylene oxide per mole of alcohol.

Preferred nonionics are aliphatic Cs to Cis, more preferably C12 to C15 primary linear alcohol ethoxylates with an average of from 3 to 20, more preferably from 5 to 10 moles of ethylene oxide per mole of alcohol.

The nonionic may be present at 0 to 25% (by weight based on the total weight of the composition).

One or more cosurfactants (such as amphoteric (zwitterionic) and/or cationic surfactants) may be used in addition to the surfactants described above.

Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two of the methyl groups, and mixtures thereof. Cationic surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition). Specific amphoteric (zwitterionic) surfactants include alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, having alkyl radicals containing from about 8 to about 22 carbon atoms, the term “alkyl” being used to include the alkyl portion of higher acyl radicals. Amphoteric (zwitterionic) surfactant, when included, may be present in an amount ranging from 0.1 to 5% (by weight based on the total weight of the composition).

Polymeric Cleaning Boosters

The cleaning composition I bleach system may comprise polymeric cleaning boosters, such as antiredeposition polymers, soil release polymers and mixtures thereof.

Anti-redeposition polymers stabilise the soil in the wash solution thus preventing redeposition of the soil. Suitable anti-redeposition polymers for use in the invention include alkoxylated polyethyleneimines. Polyethyleneimines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. Preferred alkoxylated polyethylenimines for use in the invention have a polyethyleneimine backbone of about 300 to about 10000 weight average molecular weight (M_w). The polyethyleneimine backbone may be linear or branched. It may be branched to the extent that it is a dendrimer. The alkoxylation may typically be ethoxylation or propoxylation, or a mixture of both. Where a nitrogen atom is alkoxylated, a preferred average degree of alkoxylation is from 10 to 30, preferably from 15 to 25 alkoxy groups per modification. A preferred material is ethoxylated polyethyleneimine, with an average degree of ethoxylation being from 10 to 30, preferably from 15 to 25 ethoxy groups per ethoxylated nitrogen atom in the polyethyleneimine backbone.

Preferably, the polyamine is a soil release agent comprising a polyamine backbone corresponding to the formula: i

(HN-Rh+KN-RlTrlN-RlrlH having a modified polyamine formula V(n⁺1)WmYnZ, or a polyamine backbone corresponding to the formula:

having a modified polyamine formula V(nk⁺1)WmYnY'kZ, wherein k is less than or equal to n,

Preferably, the polyamine backbone prior to modification has a molecular weight greater than about 200 daltons.

Preferably, i) V units are terminal units having the formula:

ii) W units are backbone units having the formula

Y units are branching units having the formula: and

IV) Z units are terminal units having the formula:

Preferably, backbone linking R units are selected from the group consisting of C2-C12 alkylene, -(R1O)xR3 (OR1)x-, -(CH2CH(OR2)CH₂O)z(R1O)yR1(OCH₂CH(OR2)CH2)w-, -CH2CH(OR2)CH2- and mixtures thereof, provided that when R comprises C1-C12 alkylene R also comprises at least one - (R1O)xR3(OR1)x-, -(CH₂CH(OR2)CH₂O)z(R1O)yR1- (OCH₂CH(OR2)CH₂)w-, or - CH₂CH(OR2)CH₂-unit;

Preferably, R1 is C2-C6 alkylene and mixtures thereof;

Preferably, R2 is hydrogen, (R1O)XB, and mixtures thereof;

Preferably, R3 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -C(O)-, -C(O)NHR5NHC(O)-, C(O)(R4)rC(O)-, - CH2CH(OH)CH₂O(R1O)yR1O-CH₂CH(OH)CH2-, and mixtures thereof;

Preferably, R4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof;

Preferably, R5 is C2-C12 alkylene or C6 C12 arylene;

Preferably, E units are selected from the group consisting of (CH2)p-CO2M, - (CH₂)qSO₃M, -CH(CH₂CO2M)CO2l\/l, (CH₂)pPO₃M, -(R1O)xB, and mixtures thereof,

Preferably, B is hydrogen, -(CH₂)qSO₃M, -(CH₂)pCO₂M, -(CH₂)q CH(SO₃M)CH₂SO₃M, - (CH₂)qCH(SO₂M)CH₂SO₃M, - (CH2)pPO₃M, -PO₃M, and mixtures thereof, Preferably, M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance;

Preferably X is a water soluble anion;

Preferably k has the value from 0 to about 20;

Preferably m has the value from 4 to about 400;

Preferably n has the value from 0 to about 200;

Preferably p has the value from 1 to 6,

Preferably q has the value from 0 to 6;

Preferably r has the value 0 or 1;

Preferably w has the value 0 or 1 ;

Preferably x has the value from 1 to 100;

Preferably y has the value from 0 to 100; and

Preferably z has the value 0 or 1.

The overall level of anti-redeposition polymer, when included, may range from 0.05 to 6%, more preferably from 0.1 to 5% (by weight based on the total weight of the composition).

Another type of suitable anti-redeposition polymer for use in the invention includes cellulose esters and ethers, for example sodium carboxymethyl cellulose.

Mixtures of any of the above described materials may also be used.

Soil release polymers help to improve the detachment of soils from fabric by modifying the fabric surface during washing. The adsorption of an SRP over the fabric surface is promoted by an affinity between the chemical structure of the SRP and the target fibre.

SRPs for use in the invention may include a variety of charged (e.g. anionic) as well as non-charged monomer units and structures may be linear, branched or star-shaped. The SRP structure may also include capping groups to control molecular weight or to alter polymer properties such as surface activity. The weight average molecular weight (M_w) of the SRP may suitably range from about 1000 to about 20,000 and preferably ranges from about 1500 to about 10,000.

SRPs for use in the invention may suitably be selected from copolyesters of dicarboxylic acids (for example adipic acid, phthalic acid or terephthalic acid), diols (for example ethylene glycol or propylene glycol) and polydiols (for example polyethylene glycol or polypropylene glycol). The copolyester may also include monomeric units substituted with anionic groups, such as for example sulfonated isophthaloyl units. Examples of such materials include oligomeric esters produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, dimethyl terephthalate (“DMT”), propylene glycol (“PG”) and poly(ethyleneglycol) (“PEG”); partly- and fully-anionic-end-capped oligomeric esters such as oligomers from ethylene glycol (“EG”), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; nonionic-capped block polyester oligomeric compounds such as those produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na- dimethyl-5-sulfoisophthalate, and copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate

Other types of SRP for use in the invention include cellulosic derivatives such as hydroxyether cellulosic polymers, C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; polymers with poly(vinyl ester) hydrophobic segments such as graft copolymers of poly(vinyl ester), for example Ci-Ce vinyl esters (such as poly(vinyl acetate)) grafted onto polyalkylene oxide backbones; poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate; and polyester-polyamide polymers prepared by condensing adipic acid, caprolactam, and polyethylene glycol.

Preferred SRPs for use in the invention include copolyesters formed by condensation of terephthalic acid ester and diol, preferably 1 ,2 propanediol, and further comprising an end cap formed from repeat units of alkylene oxide capped with an alkyl group. Examples of such materials have a structure corresponding to general formula (II):

in which R¹ and R² independently of one another are X-(OC2H4)n-(OC3H6)_{m ;} in which X is C1-4 alkyl and preferably methyl; n is a number from 12 to 120, preferably from 40 to 50; m is a number from 1 to 10, preferably from 1 to 7; and a is a number from 4 to 9.

Because they are averages, m, n and a are not necessarily whole numbers for the polymer in bulk.

Mixtures of any of the above described materials may also be used.

The overall level of SRP, when included, may range from 0.1 to 10%, preferably from 0.3 to 7%, more preferably from 0.5 to 5% (by weight based on the total weight of the composition).

Fatty Acid

Detergent may in some cases contain one or more fatty acids and/or salts thereof.

Suitable fatty acids in the context of this invention include aliphatic carboxylic acids of formula RCOOH, where R is a linear or branched alkyl or alkenyl chain containing from 6 to 24, more preferably 10 to 22, most preferably from 12 to 18 carbon atoms and 0 or 1 double bond. Preferred examples of such materials include saturated C12-18 fatty acids such as lauric acid, myristic acid, palmitic acid or stearic acid; and fatty acid mixtures in which 50 to 100% (by weight based on the total weight of the mixture) consists of saturated C12-18 fatty acids. Such mixtures may typically be derived from natural fats and/or optionally hydrogenated natural oils (such as coconut oil, palm kernel oil or tallow). The fatty acids may be present in the form of their sodium, potassium or ammonium salts and/or in the form of soluble salts of organic bases, such as mono-, di- or triethanolamine.

Mixtures of any of the above described materials may also be used.

Fatty acids and/or their salts, when included, may be present in an amount ranging from about 0.25 to 5%, more preferably from 0.5 to 5%, most preferably from 0.75 to 4% (by weight based on the total weight of the composition).

For formula accounting purposes, in the formulation, fatty acids and/or their salts (as defined above) are not included in the level of surfactant or in the level of builder.

Enzymes

The cleaning composition I bleach system may comprise an effective amount of one or more enzymes selected from the group comprising, pectate lyase, protease, amylase, cellulase, lipase, mannanase and mixtures thereof. The enzymes are preferably present with corresponding enzyme stabilizers.

The level of each enzyme in the composition is from 0.0001 wt.% to 1 wt.% (of the composition). Total enzyme levels may be from 0.0001 to 5%.

Levels of enzyme present in the composition preferably relate to the level of enzyme as pure protein.

Preferred enzymes include those in the group consisting of: proteases, cellulases, alpha-amylases, peroxidases/oxidases, pectate lyases, and/or mannanases. Said preferred enzymes include a mixture of two or more of these enzymes.

Preferably the enzyme is selected from: proteases, cellulases, and/or alpha-amylases.

Preferred proteases are selected from the following group, serine, acidic, metallo- and cysteine proteases. More preferably the protease is a serine and/or acidic protease. Preferably the protease is a serine protease. More preferably the serine protease is subtilisin type serine protease.

Any enzyme present in the composition may be stabilized using conventional stabilizing agents, e.g., a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid, or a boric acid derivative, e.g., an aromatic borate ester, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition may be formulated as described in e.g. WO 92/19709 and WO 92/19708.

The cleaning composition I bleach system preferably has a pH in the range of 7 - 12 more preferably 6 to 8, when measured on dilution of the composition to 1% (by weight based on the total weight of the composition) using demineralised water.

Other Ingredients

The cleaning composition I bleach system may contain further optional ingredients to enhance performance and/or consumer acceptability. Examples of such ingredients include fragrance oils, foam boosting agents, preservatives (e.g. bactericides), antioxidants, sunscreens, anticorrosion agents, colorants, pearlisers and/or opacifiers, and shading dye. Each of these ingredients will be present in an amount effective to accomplish its purpose. Generally, these optional ingredients are included individually at an amount of up to 5% (by weight based on the total weight of the composition).

The cleaning composition I bleach system generally contains no more than 0.2%, preferably from 0 to 0.1%, more preferably from 0 to 0.01% and most preferably 0% (by weight based on the total weight of the composition) of transition metal ions selected from Fe(ll), Fe (III), Cr(ll - VI), Cu(ll), Co (II), Co (III), Mn (II), Mn (III), Ni(ll), Ce (III), Ce (IV) and Zn (II) and mixtures thereof.

The cleaning composition I bleach system generally contains no more than 0.2%, preferably no more than 0.1%, more preferably no more than 0.01% and most preferably 0% (by weight based on the total weight of the composition) of oxidising agents selected from halogen-based bleaches (e.g. alkali metal hypochlorites and alkali metal salts of di- and tri-chloro and di- and tri-bromo cyanuric acids

Packaging and dosing

The cleaning composition I bleach system may be packaged in any suitable form.

It may be packaging as unit doses in polymeric film soluble in the wash water. Alternatively, the cleaning composition I bleach system may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.

Detergent methods may suitably be carried out in a top-loading or front-loading automatic washing machine or can be carried out by hand.

In automatic washing machines, the dose of cleaning composition I bleach system is typically put into a dispenser and from there it is flushed into the machine by the water flowing into the machine, thereby forming the wash liquor.

A subsequent aqueous rinse step and drying the substrate is preferred. Any input of water during any optional rinsing step(s) is not included when determining the volume of the wash liquor. Drying can take place either in an automatic dryer or in the open air.

A typical solid cleaning composition / (powder) includes the following:

Unless stated otherwise or is apparent from the context of the description, preferred embodiments mentioned for one aspect of the invention applies mutated mutandis to the other aspects of the invention as well. The below examples are meant to be illustrative and not limiting.

EXAMPLES

Example 1 - Citrates

A base solution was made by dissolving 0.02% of naphthol blue black dye (available from Sigma-Aldrich) in water and adjusting the pH to 10 (using 0.1 M bicarbonate). To 1 ml of this solution was added 1 ml water, 1 ml of 80 mM hydrogen peroxide and optionally 1 ml of a 100 ppm stock solution of bleach catalyst (or water in the case of a catalyst free control).

The final composition of the reaction mixtures were 0.005 wt. % of naphthol blue black dye, hydrogen peroxide at a level of 20 mM and optionally 25ppm of bleach catalyst according to the invention, or (not according to the invention) bare Mn²⁺ (as water soluble MnSOt) bare ferrous or ferric iron (as water soluble ferrous sulphate or ferric chloride) as controls. The final solution was incubated at 20 degrees Celsius for 20 hours after which the light absorbance was measured at 629nm using a UV-VIS spectrophotometer. The results are given in the Table 1 below.

Table 1: dye-bleaching results at pH 10.

The experiment was repeated, at pH of 7.0 by adjusting the pH with phosphate in place of the bicarbonate. The results are shown in Table 2 below. Table 2: dye-bleaching results at pH 7.0.

The results show that organic sequestrant complexes of Mn²⁺, Fe²⁺, Fe³⁺ improve dye bleaching at 20 degrees Celsius and a pH of 10 or 7 compared to the use of these metal ions alone. Citric acid and D-gluconic acid complexes of iron are more efficacious versus complexes of manganese. These conditions are relevant for machine dishwash wash liquor conditions when operating at low temperatures.

Example 2 - Picolinic, dipicolinic acids

A base solution was made by dissolving 0.02% of naphthol blue black dye (available from Sigma-Aldrich) in water and adjusting the pH to 10 (using 0.1 M bicarbonate). To 1 ml of this solution was added 1 ml water, 1 ml of 80 mM hydrogen peroxide and optionally 1 ml of a 100ppm stock solution of bleach catalyst (or water in the case of a catalyst free control). The final composition of the reaction mixtures contained 0.005 wt. % of naphthol blue black dye, hydrogen peroxide at a level of 20 mM and optionally 25ppm of bleach catalyst according to the invention, or (not according to the invention) bare Mn²⁺ (as water soluble MnSOt) as control. The final solution was incubated at 20 degrees Celsius for 20 hours after which the light absorbance was measured at 629nm using a LIV-VIS spectrophotometer. The results are given in the Table 1 below. Tablet dye-bleaching results at pH 10.

The experiment was repeated, at pH of 7.0 by adjusting the pH with phosphate in place of the bicarbonate. The results are shown in Table 2 below.

Table 2: dye-bleaching results at pH 7.0.

The results show that acid derivative of pyridine complexes of Mn²⁺, Fe²⁺, Fe³⁺ improve dye bleaching at 20 degrees Celsius and a pH of 10 or 7 compared to the use of these metal ions alone. These conditions are relevant for machine dishwash wash liquor conditions when operating at low temperatures.

Claims

33 Claims

1 . A bleach catalyst comprising an organic acid-metal complex comprising an organic acid datively bonded to at least one metal cations.

2. A bleach catalyst according to claim 1 wherein the organic acid comprises a nonaromatic acid.

3. A bleach catalyst according to claim 1 or claim 2 wherein the non-aromatic organic acid comprises citric acid, gluconic acid, hydroxamic acid and 1 ,2, 3, 4 butanetetracarboxylic acid, preferably citric acid and D-gluconic acid and more preferably citric acid.

4. A bleach catalyst according to any preceding claim, wherein the organic acid comprises an aromatic organic acid.

5. A bleach catalyst according to claim 4 wherein the aromatic organic acid comprises an acid derivative of pyridine.

6. A bleach catalyst according to any of claims 4 -5 wherein wherein the acid derivative of pyridine comprises picolinic acid, dipicolinic acid and more preferably dipicolinic acid.

7. A bleach catalyst according to any preceding claim, wherein the metal cation comprises Fe²⁺, Fe³⁺, Mn²⁺, Mn³⁺, Mn⁴⁺, Mn⁵⁺, Mn⁶⁺, Mn⁷⁺ and Co²⁺, Co³⁺ or mixtures thereof, preferably comprises Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Co²⁺, Co³⁺ or mixtures thereof and even more preferably comprises Mn²⁺, Mn⁴⁺ or mixtures thereof.

8. A bleach catalyst according to claim 7 as dependent on any of claims 2-3, wherein the non-aromatic organic acid comprises any of [Mn"(Hcitrate)]', [Mn"(H2Citrate)2]²', [Mn"(H2Citrate)] polymer, [Mn'^Hcitrate^]²', [Mn"₃(Hcitrate)]2, [Mn^IH(citrate)2]⁵', [Fe^IH(citrate)]', [Fe^IH(Hcitrate)], [Fe^IH(citrate)2]⁵', [Fe^IH2(citrate)2]²'-, [Co"(H2Citrate)], [Co^IH(Hcitrate)], where H₄citrate is citric acid; [Mn"(GH4)2], [Mn"(GH₃)2]²', [Mn"₂(GH₃)₄]⁴', [Mn"(GH₃)]³', [Mn^lll ₂(GH₃)₄ (OH)₂]⁴-, Mn^IV2(GH₃)₄O)2(OH)₂]⁶-, [Fe" 34

GH₄]⁺, [Fe^IH GH₃]⁺ , [Fe^IH GH]; [Fe^IH G]²; [Fe^lll ₂(GH₃)₂(OH₄)(H₂O)₂]²- , [Co" (GH₃)], [Co^IH (GH₂)] where HGH₄ is D-gluconic acid, GH₄' is the gluconate mono-anion and GH₃ ²' is the gluconate di-anion or any combination thereof.

9. A bleach catalyst according to claim 7 as dependent on any of claims 4-6 wherein the aromatic organic acid comprises , [Fel I l(pic)3], [Fe(pic)2(H2O)]-, [Felll(pic)2OH]2, [Felll2(OH)2(pic)4], [Mnll(pic)(OH)2]n, [MnllCI(pic)(H2O)2]n, [Mnll (pic)2]n, [MnllCI(pic)]n, [Mnll(pic)2 (H2O)2], [Mnll(pic)2 (OH)2]2-, [Mnll CI2(pic)2]2-, [Mnlll(pic)3], [Mnlll(pic)2(OH)], [Mnl IICI(pic)2(H2O)], [MnlV2O2(pic)4], [Coll (pic)2], [Colll(pic)3], [Fell(dipic)(H2O)3], [Fell(dipic)2]2-, [Fel l2(dipic)2(H2O)6], [Felll(dipic)(OH)], [Felll(dipic)2]-, [Mnl l(dipic)(H2O)3], [Mnl l(dipic)2(H2O)]2-,

[Mnl l2(dipic)2(H2O)6], [Mnlll(dpic)2]-, [Coll(dipic)2]-, [Colll(dipic)2] where Hpic is picolinic acid and H2dipic is dipicolinic acid or any combination thereof

10. A bleach system comprising a bleach catalyst of any preceding claim in combination with a bleach.

11 . A cleaning composition comprising a bleach catalyst according to any of claims 1 - 5.

12. A cleaning composition according to claim 11 further comprising an anionic surfactant.

13. A cleaning composition according to claim 11 or 12 further comprising a bleach activator in an amount of from 0.1 to 10 wt. %, preferably from 0.5 to 5 wt. % and more preferably from 1.0 to 4 wt. %. and optionally including a bleach.

14. Use of a bleach catalyst comprising an organic acid-metal complex comprising an organic acid datively bonded to at least one metal cation for cleaning a substrate.

15. Use of a cleaning composition comprising an organic acid-metal complex comprising an organic acid datively bonded to at least one metal cation for cleaning a substrate.