CN109312267B - Pourable detergent suspensions comprising bleach catalyst particles - Google Patents

Abstract

The present invention relates to a pourable detergent suspension comprising: 30-80% by weight of a moisture absorbing component selected from the group consisting of aminocarboxylate chelants, glycerin, and combinations thereof; 8-25 wt% water; 1-30% by weight of a bleaching agent; 0.1-5 wt% of bleach catalyst particles having a diameter of 20-2000 μm, said bleach catalyst particles comprising: 30-90% by weight of one or more core particles; 10-70 wt% of a coating layer covering the one or more core particles, the coating layer consisting of one or more coating layers and comprising: 1-30 wt% of a coating of catalyst particles comprising at least 30 wt% of a manganese bleach catalyst; and 50-99% by weight of a coating of a water-soluble alkali metal sulfate; the bleach catalyst particles are free of enzyme, contain from 0.3 to 20 wt% of the catalyst particles and contain from 30 to 99 wt% of the water-soluble alkali metal sulphate. The pourable detergent suspension is easy to manufacture and exhibits good storage stability despite its containing bleach, bleach catalyst and large amounts of water.

Description

Pourable detergent suspensions comprising bleach catalyst particles

Technical Field

The present invention relates to pourable detergent suspensions comprising a bleaching agent and a bleach catalyst. More specifically, the present invention relates to a pourable detergent suspension comprising:

● a hygroscopic component selected from the group consisting of aminocarboxylate chelants, glycerin, and combinations thereof;

● water;

● a bleaching agent; and

● bleach catalyst particles.

Despite the presence of bleach catalysts, bleaching agents and large amounts of water, the detergent suspensions of the invention combine pourability with high stability.

Background

Detergent formulations typically contain a number of different active ingredients, including surfactants, builders, enzymes and bleaching agents.

Surfactants are used to release stains and soils and to disperse the released components into the cleaning solution. Enzymes help remove stubborn stains of proteins, starches and lipids by hydrolyzing these components. Bleaching agents are used in detergent compositions to remove bleachable stains, such as those associated with tea, coffee, red wine and various fruit and vegetable products, by oxidation of components that make up these stains. Typical bleaching agents for detergent formulations are chlorine and peroxygen based compounds, such as hypochlorite and percarbonate bleaches, respectively. Bleach catalysts are employed in detergent compositions to activate the bleach, especially at lower temperatures.

Builders are incorporated into detergent formulations to complex magnesium and calcium ions and maintain alkaline pH conditions. Phosphorus-based builders, such as phosphates, have been used in a variety of detergent compositions for many years. However, as part of the increasing trend towards environmentally friendly detergent compositions, alternative builders have been developed and these have found their way into commercial detergent products. Aminocarboxylate chelant L-glutamic-N, N-diacetate is an example of an environmentally friendly builder for commercial detergent products. Typically, the aminocarboxylate chelant is present in the detergent formulation in the form of its (fully deprotonated) sodium salt. The aqueous solution of the aminocarboxylate is basic.

Liquid detergent formulations have been developed because these products offer advantages over powder formulations in that they are easy to apply, can contain higher concentrations of active ingredients, are less subject to moisture damage during storage and/or are more easily dispersed into aqueous cleaning solutions. In order to provide liquid detergent compositions that deliver cleaning, spotting and film-forming properties similar to powder formulations, it is necessary to include components in the liquid product matrix that remain undissolved. These undissolved components need to be suspended uniformly throughout the product to ensure constant, optimal cleaning. Although this can be achieved by instructing the user to shake the product prior to use, it is clearly preferred to provide the liquid detergent formulation in the form of a suspension which remains stable during the life cycle of the product. However, this goal is very difficult to achieve, since the suspended particles undergo sedimentation and emulsification/flotation phenomena, causing the suspension to stratify over time.

Bleaching agents are moisture sensitive detergent ingredients that lose their activity over time if the water activity of the detergent composition is too high. Detergent compositions containing a combination of bleach and bleach catalyst are particularly sensitive to moisture.

EP-A1129160 describes liquid aqueous cleaning compositions containing water, glycerol, builder, enzymes and thickeners.

WO2013/092276 describes detergent formulations containing GLDA, water, citric acid, a non-ionic surfactant, a coated spray-dried percarbonate, Mn catalyst particles and other ingredients.

WO2014/107578 describes detergent compositions containing water, glycerol, polyaminocarboxylic acids (chelating agents), nonionic surfactants.

WO2008/064935 describes a method for preparing bleach catalyst particles comprising, relative to the total weight of the particles,

a)0.1 to 30% by weight of a bleach catalyst,

b) from 40 to 95% by weight of a support material,

c)0.1 to 5 wt% of a binder from the group of organic polymers,

wherein the bleaching catalyst, the support material and the binder from the group of organic polymers are brought into contact with one another in a mixer and granulated, characterized in that

a) First introducing a support material into the mixer, wherein the support material contains more than 70 wt% of carbonates and silicates and the weight ratio of carbonates to silicates is in the range of 10:1 to 1:10, and

b) a solution or suspension containing a bleach catalyst and a binder is sprayed.

WO2016/005392 describes particles comprising

● contains a core of the enzyme surrounded by:

● a first coating layer comprising a bleach catalyst comprising manganese and a ligand which is a di-or trimethyl azacyclononane or a derivative thereof, the first coating layer being surrounded by:

● A second coating layer comprising at least 60% by weight of a water soluble salt having a constant humidity at 20 ℃, the constant humidity being higher than 85%.

Disclosure of Invention

The present inventors have developed a pourable detergent suspension which is easy to manufacture and exhibits good storage stability despite containing bleach, bleach catalyst and a large amount of water.

The pourable detergent suspension of the present invention comprises:

● 30-80 wt% of a moisture absorbing component selected from the group consisting of aminocarboxylate chelants, glycerin, and combinations thereof;

● 8-25 wt% water;

● 1-30% by weight of a bleaching agent;

● 0.1.1 to 5 wt% of bleach catalyst particles having a diameter of 20 to 2000 μm, the bleach catalyst particles comprising:

30-90% by weight of one or more core particles;

10-70 wt.% of a coating layer covering the one or more core particles, the coating layer consisting of one or more coating layers and containing:

-1-30 wt% of a coating of catalyst particles comprising at least 30 wt% of a manganese bleach catalyst; and

-50-99% by weight of a coating of a water-soluble alkali metal sulphate;

the bleach catalyst particles are free of enzyme, contain from 0.3 to 20 wt% of the catalyst particles and contain from 30 to 99 wt% of the water-soluble alkali metal sulphate.

Although the inventors do not wish to be bound by theory, it is believed that the hygroscopic component is capable of reducing the water activity of the detergent suspension to a very low level despite the presence of at least 8 wt% water. Thus, although detergent suspensions contain a moisture-sensitive bleaching system (bleach and bleach catalyst), the suspensions are very stable. A further contribution to this stability is the special bleach catalyst particles containing manganese bleach catalyst particles, which are separated from the other components of the pourable detergent suspension by a water-soluble alkali metal sulphate matrix.

The detergent compositions of the present invention also provide the advantage that a wide range of detergent ingredients can be incorporated therein in dispersed or dissolved form. The bleach catalyst particles are uniformly dispersed throughout the detergent suspension.

Detailed Description

The present invention provides a pourable detergent suspension comprising:

● 30-80 wt% of a moisture absorbing component selected from the group consisting of aminocarboxylate chelants, glycerin, and combinations thereof;

● 8-25 wt% water;

● 1-30% by weight of a bleaching agent;

● 0.1.1 to 5 wt% of bleach catalyst particles having a diameter of 20 to 2000 μm, the bleach catalyst particles comprising:

30-90% by weight of one or more core particles;

10-70 wt.% of a coating layer covering the one or more core particles, the coating layer consisting of one or more coating layers and containing:

-1-30 wt% of a coating of catalyst particles comprising at least 30 wt% of a manganese bleach catalyst; and

-50-99% by weight of a coating of a water-soluble alkali metal sulphate;

the bleach catalyst particles are free of enzyme, contain from 0.3 to 20 wt% of the catalyst particles and contain from 30 to 99 wt% of the water-soluble alkali metal sulphate.

The term "pourable" as used herein refers to a composition that is capable of flowing under ambient conditions. Thixotropic compositions which can be made pourable by shear thinning are also considered pourable.

The term "thixotropic" as used herein means that the composition (e.g., gel or fluid) is viscous under static conditions and becomes less viscous when shaken, agitated, or otherwise stressed. In thixotropic compositions, this so-called "shear thinning effect" is reversible, i.e. the composition will return to a more viscous state once it is no longer subjected to shear stress.

The term "aminocarboxylate chelant" as used herein refers to a compound containing one or more nitrogen atoms attached to one or more carboxyl groups through a carbon atom, which forms a strong complex with a metal ion by donating electron pairs from the nitrogen and oxygen atoms to the metal ion to form multiple chelate rings.

The term "water-soluble alkali metal sulphate" refers to alkali metal sulphates having a solubility in distilled water of at least 10g/l, preferably at least 50g/l at 20 ℃.

Unless otherwise indicated, whenever reference is made herein to "particle size" or "particle diameter", it is meant that a system conforming to the requirements set forth in ISO13320:2009 (such as may be obtained from Malvern InstruMastersizer available from nts Ltd^TM2000) Particle diameter determined by laser diffraction.

Unless otherwise indicated, whenever reference is made herein to water content, the water content includes unbound (free) as well as bound water.

Whenever a parameter such as concentration or ratio is said to be less than a certain upper limit, it is understood that the lower limit of the parameter is 0 without specifying the lower limit.

Whenever the amounts or concentrations of components are quantified herein, unless otherwise indicated, the quantified amounts or quantified concentrations refer to the components themselves, even though it is common practice to add such components in solution or as a mixture with one or more other ingredients.

The detergent suspension of the invention is a homogeneous product. Thus, undissolved components, such as bleach catalyst particles, are uniformly dispersed throughout the detergent suspension.

The detergent suspension preferably contains one or more aminocarboxylate chelants. More preferably, the detergent suspension comprises water and one or more aminocarboxylate chelants in a weight ratio of no more than 2:1, preferably no more than 1.5:1, most preferably no more than 1.2: 1. Water and the one or more aminocarboxylate chelants are typically included in the detergent suspension in a weight ratio of at least 1:3, more preferably at least 1:2, most preferably at least 1: 1.8.

The detergent suspension preferably contains glycerol. The glycerol and water are preferably contained in a pourable detergent suspension in a weight ratio in the range of 2:3 to 1:6, more preferably in the range of 1:2 to 1:5, most preferably in the range of 1:2.2 to 1: 4.

The pourable detergent suspension preferably contains 20-75 wt.%, more preferably 30-60 wt.%, most preferably 35-55 wt.% of glycerol.

The water content of the detergent suspension is preferably 10-22 wt.%, more preferably 11-20 wt.%, most preferably 12-18 wt.%.

The water activity of the detergent suspension at 20 ℃ is usually from 0.2 to 0.6. More preferably, the water activity of the detergent suspension at 20 ℃ is in the range of 0.3 to 0.5, most preferably 0.35 to 0.45.

The pourable detergent suspension preferably contains at least 8 wt%, more preferably 10-40 wt%, most preferably 12-30 wt% of one or more aminocarboxylate chelants.

Preferably, the one or more aminocarboxylate chelants are selected from the group consisting of glutamic acid N, N-diacetic acid (GLDA), methylglycinediacetic acid (MGDA), iminodisuccinic acid (IDS), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethyliminodiacetic acid (HEIDA), nitrilotriacetic acid (NTA), aspartic acid diethoxysuccinic Acid (AES), aspartic acid-N, -diacetic acid (ASDA), hydroxyethylethylenediaminetetraacetic acid (HEDTA), hydroxyethylethylenediaminetriacetic acid (HEEDTA), iminodifumaric acid (IDF), iminoditartaric acid (IDT), iminodimaleic acid (IDMAL), iminodimalic acid (IDM), ethylenediamine difumaric acid (EDDF), ethylenediamine dimalic acid (EDDM), ethylenediamine ditartaric acid (EDDT), ethylenediamine disuccinic acid (EDDS), ethylenediamine dimaleic acid (EDDMAL), and dipicolinic acid (dipicolinic acid), and salts thereof.

More preferably, the one or more aminocarboxylate chelants are selected from GLDA, MGDA, IDS, HEIDA, EDDS and NTA and salts thereof. In an even more preferred embodiment, the one or more aminocarboxylate chelants are selected from GLDA, MGDA, IDS and salts thereof. Most preferably, the one or more aminocarboxylate chelants are selected from GLDA and salts thereof.

The GLDA used in the present suspension is preferably an alkali metal salt of glutamic-N, N-diacetic acid. More preferably, the GLDA used is the sodium salt of glutamic-N, N-diacetic acid. Most preferably, the GLDA used is the tetrasodium salt of glutamic-N, N-diacetic acid.

The combination of glycerin, water and one or more aminocarboxylate chelants generally constitutes at least 45 wt%, preferably at least 55 wt%, most preferably at least 60 wt% of the detergent suspension.

Bleaching agent

The detergent suspension of the invention preferably contains at least 1.5 wt%, more preferably 1.8-15 wt%, most preferably 2-12 wt% of bleaching agent.

The bleaching agent is preferably selected from the group consisting of peroxygen compound bleaches, hydrogen peroxide releasing compounds, hydrogen peroxide generating systems, peroxyacids and salts thereof, peroxyacid bleach precursor systems, and combinations thereof. Even more preferably, the bleaching agent is a source of hydrogen peroxide selected from the group consisting of alkali metal peroxides, organic peroxide bleaching compounds and inorganic persalt bleaching compounds and combinations thereof. Even preferably, the bleaching agent is a peroxide.

Examples of peroxides are monopersulfates, perborate monohydrate, perborate tetrahydrate and the acids and corresponding salts of percarbonates. Organic peracids useful herein include alkyl and aryl peroxyacids such as peroxybenzoic acid and cyclo-substituted peroxybenzoic acids (e.g., peroxy-alpha-naphthoic acid), aliphatic and substituted aliphatic monoperoxy acids (e.g., peroxylauric acid and peroxystearic acid), and Phthalimidoperoxycaproic Acid (PAP).

Typical diperoxy acids useful in the present invention include alkyl diperoxy acids and aryl diperoxy acids such as 1, 12-diperoxydodecanedioic acid (DPDA), 1, 9-diperoxyazelaic acid, diperoxycarbazelaic acid, diperoxydecanedioic acid and diperoxyiisophthalic acid, and 2-decyldiperoxybutane-1, 4-diacid.

Most preferably, the bleaching agent is percarbonate.

The detergent suspension of the invention preferably contains a bleaching agent in particulate form. More preferably, the suspension contains 1-15 wt%, more preferably 2-12 wt% of the bleach-containing particles. Preferably, these particles contain at least 10 wt%, more preferably at least 30 wt%, most preferably at least 50 wt% of bleach.

According to a preferred embodiment, the particles of the bleaching agent (e.g. percarbonate) are coated particles comprising one or more core particles containing the bleaching agent, which core particle or particles are surrounded by a water-soluble coating. The water-soluble coating layer advantageously comprises a coating agent selected from alkali metal sulfates, alkali metal carbonates or alkali metal chlorides and combinations thereof.

The diameter of the bleach particles is typically from 10 to 3000 μm, more preferably from 20 to 2000 μm, most preferably from 30 to 1500 μm.

The volume weighted mean particle size of the bleach particles is preferably from 10 to 3000 μm, more preferably from 100 to 1500 μm, most preferably from 200 to 1000 μm.

Bleach catalyst particles

The pourable detergent suspension of the present invention typically contains 0.2-4 wt%, more preferably 0.2-3 wt%, most preferably 0.4-2.5 wt% of bleach catalyst particles.

The bleach catalyst particles typically contain at least 0.5 wt%, more preferably from 0.8 to 10 wt%, most preferably from 1 to 8 wt% of the manganese bleach catalyst.

The bleach catalyst particles typically contain at least 40 wt%, more preferably at least 50 wt%, most preferably at least 60 wt% of a water-soluble salt.

The bleach catalyst particles typically have a diameter of at least 50 μm, more preferably 100-1500 μm, even more preferably 250-1200 μm, most preferably 350-1000 μm. The bleach catalyst particles are preferably spherical particles.

The catalyst particles in the bleach catalyst particles typically contain at least 50 wt%, more preferably at least 80 wt% of the manganese bleach catalyst.

The inventors have unexpectedly found that particles with particularly good stability can be prepared if the diameter of the catalyst particles is very small. Thus, according to another preferred embodiment, at least 90 wt% of the catalyst particles have a diameter in the range of 0.2 to 25 μm, more preferably in the range of 0.4 to 20 μm, even more preferably in the range of 0.5 to 18 μm, most preferably in the range of 0.6 to 15 μm.

Typically, the volume weighted mean diameter of the catalyst particles is from 1 to 12 μm, most preferably from 1.5 to 10 μm.

The water-soluble alkali metal sulphate in the bleach catalyst particles preferably has a constant humidity of more than 85%, in particular more than 90%, at 2 ℃. A specific example of a suitable salt is Na₂SO₄(CH_20℃＝93％)，K₂SO₄(CH_20℃＝98％)，KHSO₄(CH_20℃86%). The water-soluble alkali metal sulfate may be in anhydrous form, or it may be a hydrated salt, i.e., a crystalline salt hydrate with crystalline bound water. Specific examplesIs anhydrous sodium sulfate (Na)₂SO₄)。

The bleach catalyst particles preferably contain at least 35 wt%, more preferably 40-80 wt%, most preferably at least 45-75 wt% of one or more core particles.

According to a particularly preferred embodiment, the bleach catalyst particle comprises a single core particle.

The diameter of the one or more core particles in the bleach catalyst particles is preferably in the range of from 40 to 1500. mu.m, more preferably in the range of from 80 to 1200. mu.m, even more preferably in the range of from 200 to 1000. mu.m, most preferably in the range of from 300 to 900. mu.m.

The core particle may be composed of an inert support material. The core may suitably contain functional detergent ingredients such as builders, bleach activators, dispersing polymers, silicates, scale inhibitors, glass corrosion inhibitors, rust inhibitors, surfactants and combinations thereof. Preferably, the core particle contains at least 50 wt%, more preferably at least 80 wt%, most preferably at least 90 wt% of an inert carrier material selected from the group consisting of water soluble salts (e.g., sulfates and/or carbonates), cellulose fibers, dextrins, disaccharides, and combinations thereof.

The thickness of the coating of the bleach catalyst particles is preferably from 5 to 150 μm, more preferably from 10 to 120 μm, even more preferably from 12 to 80 μm, most preferably from 15 to 50 μm.

The coating typically comprises no more than 65 wt%, more preferably 20-60 wt%, most preferably 25-55 wt% of the bleach catalyst particles.

The coating preferably comprises from 2 to 25%, more preferably from 3 to 20%, most preferably from 3.5 to 15% by weight of the coating of catalyst particles comprising a manganese bleach catalyst.

According to a particularly preferred embodiment, the bleach catalyst particle comprises a single core particle and the size of the core particle, the thickness of the coating and the size of the catalyst particle have been selected to provide the optimum combination of storage stability, suspension stability and delivery of activity of the bleach catalyst during use. Thus, the bleach catalyst particle preferably comprises a core particle having and meeting the following specifications:

● core particle diameter: 200-;

● catalyst particle diameter: 0.4-20 μm;

● coating thickness: 10-150 μm.

Even more preferably, the bleach catalyst particles meet the following specifications:

● core particle diameter: 300-900 μm;

● catalyst particle diameter: 0.5-18 μm;

● coating thickness: 15-50 μm.

Preferably, the thickness of the coating exceeds the volume weighted mean diameter of the catalyst particles by at least 50%, more preferably by at least 100%, most preferably by at least 200%.

The coating of bleach catalyst particles preferably contains from 55 to 90 wt%, more preferably from 60 to 85 wt% of a water soluble salt.

According to a particularly preferred embodiment of the present invention, the coating of bleach catalyst particles comprises at least two coating layers, including (i) a first coating layer comprising from 30 to 90 wt% of catalyst particles and from 10 to 70 wt% of a water-soluble binder, and (ii) a second coating layer surrounding said first coating layer, said second coating layer comprising at least 60 wt%, more preferably at least 70 wt%, even more preferably at least 80 wt%, most preferably at least 90 wt% of a water-soluble salt.

The water soluble binder is preferably selected from the group consisting of monosaccharides, disaccharides, trisaccharides, dextrins, and combinations thereof. Most preferably, the water soluble binder is selected from the group consisting of sucrose, lactose, dextrin and combinations thereof. Most preferably, the water-soluble binder is a dextrin, such as maltodextrin.

The combination of the catalyst particles, water-soluble salt and water-soluble binder typically comprises at least 60 wt%, more preferably at least 70 wt%, most preferably at least 75 wt% of the coating of the bleach catalyst particles.

The average thickness of the above first coating layer is preferably 2 to 50 μm, more preferably 3 to 30 μm, even more preferably 4 to 25 μm, and most preferably 5 to 20 μm.

The first coating layer typically comprises catalyst particles in an amount of from 2 to 15%, more preferably from 3 to 10%, by weight of the core. The first coating layer preferably contains a water-soluble binder in an amount of from 1 to 20%, more preferably from 2 to 10%, by weight of the core.

The second coating layer of bleach catalyst particles typically comprises at least 5%, more preferably at least 10%, most preferably at least 20% by weight of the core. The second coating layer preferably comprises at most 100 wt%, more preferably at most 80 wt%, most preferably at most 75 wt% by weight of the core.

The average thickness of the second coating layer is preferably at least 3 to 100 μm, more preferably 5 to 80 μm, even more preferably 8 to 60 μm, most preferably 10 to 40 μm.

Optionally, the bleach catalyst particles can comprise an additional third coating layer surrounding the second coating layer. The third coating layer preferably contains at least 20 wt%, more preferably at least 25 wt%, most preferably at least 30 wt% of a film forming component selected from the group consisting of polyethylene glycol (PEG), hydroxypropyl methylcellulose (HPMC), polyvinyl alcohol (PVA), and combinations thereof. Preferably, the thickness of the third coating layer is 1 to 50 μm, most preferably 2 to 30 μm.

According to a particularly preferred embodiment, the manganese bleach catalyst in the coating of the bleach catalyst particles is represented by formula (I):

[L_nMn_mX_p]^zY_q(I)

wherein:

-Mn is manganese, each Mn independently having an oxidation state selected from II, III, IV and V;

-n and m are independent integers from 1 to 4;

-X represents a coordinating or bridging species;

-p is an integer from 0 to 12;

-Y is a counter ion, the type of which depends on the charge z of the complex;

-q is the charge of z divided by Y; and

-L is a ligand as a macrocyclic organic molecule of general formula (II)

Wherein:

■R¹and R²Each selected from H, alkylA group and an aryl group;

■ t and t' are each independently integers from 2 to 3;

■ each D is independently selected from N, NR, PR, O or S, wherein R is H, alkyl or aryl; and

■ s is an integer from 2 to 5;

the weight% of the manganese bleach catalyst is expressed as the weight% of the molar equivalent concentration of the complex, wherein L is 1,4, 7-trimethyl-1, 4, 7-triazacyclononane, m is 2, and X is O^2-P is 3, z is 2+, Y is PF₆ ^-And q is 2.

The manganese bleach catalyst is preferably represented by formula (I) wherein both n and m are preferably 1 or 2, more preferably wherein n ═ m ═ 2. The coefficient p is preferably an integer from 3 to 6.

According to another preferred embodiment, each Mn independently has an oxidation state selected from III and IV.

X in formula (I) preferably represents a radical selected from H₂O，OH^-，O^2-，S₂ ^-，HOO^-，O₂ ^2-，O₂ ^1-，R-COO^-Wherein R is H, optionally substituted alkyl, optionally substituted aryl, NR₃Wherein R is H, optionally substituted alkyl, optionally substituted aryl, Cl^-，SCN^-，N₃ ^-And the like, or combinations thereof. Preferably X represents O^2-Or (OAc)^-More preferably O^2-. Herein, Ac represents an acyl group.

Y is a counter ion, the type of which depends on the charge z of the complex, which may be positive, zero or negative. If z is positive, Y is an anion, e.g. Cl^-，Br^-，I^-，NO₃ ^-，ClO₄ ^-，NCS^-，PF₆ ^-，RSO₄ ^-，OAc^-，BPh₄ ^-，CF₃SO₃ ^-，RSO₃ ^-，RSO₄ ^-And the like, wherein R represents an alkyl group, or an aryl group. Preferably, Y is PF₆ ^-Or ClO₄ ^-. If z is negative, Y is a cation, for example an alkali metal, alkaline earth metal or (alkyl) ammonium cation, etc.

L in formula (I) is a ligand in the form of a macrocyclic organic molecule of general formula (II)

Wherein R is¹And R²Each may be zero, H, alkyl or aryl; t and t' are each independently integers from 2 to 3; each D may independently be N, NR, PR, O or S, where R is H, alkyl or aryl.

D in the formula (II) is preferably NR. If D is N, one of the heterocarbon bonds connected thereto may be unsaturated, for example yielding-N ═ CR¹-fragment, R²Is 0.

The coefficient s in formula (II) is preferably 2, 3 or 4, even more preferably s is 2.

Preferred ligands L are those wherein each D is independently selected from NH or NR, t and t' are 2 or 3, s ═ 2 and R¹＝R²Those where at least one D is NCH, more preferably where at least one D is NCH₃And t ═ 2. Other preferred ligands L are those wherein each D is NCH₃(ii) a t ═ 2; s is 2 and R¹And R²Each of which may be H or alkyl. Examples of such preferred ligands are provided in EP-A-0458397.

Particularly preferred ligands are 1,4, 7-trimethyl-1, 4, 7-triazacyclononane, coded as Me-TACN, 1,4, 7-triazacyclononane, coded as TACN, 1,5, 9-trimethyl-1, 5, 9-triazacyclododecane, coded as Me-TACD; 2-methyl-1, 4, 7-trimethyl-1, 4, 7-triazacyclononane, coded as Me/Me-TACN and 2-methyl-1, 4, 7-triazacyclononane, coded as Me/TACN. Of these ligands, Me-TACN and Me/Me-TACN are most preferred.

Examples of suitable manganese bleach catalysts are provided in EP-A-0458397.

It is preferred that the manganese bleach catalyst comprises one or more of the following

[Mn^III ₂(μ-O)₁(μ-OAc)₂(Me-TACN)₂](ClO₄)₂，

[Mn^IIIMn^IV(μ-O)₁(μ-OAc)₂(Me-TACN)₂](ClO₄)₃，

[Mn^III ₂(μ-O)₁(μ-OAc)₂(Me-TACN)₂](PF₆)₂，

[Mn^III ₂(μ-O)₁(μ-OAc)₂(Me/Me-TACN)₂](PF₆)₂，

[Mn^IV ₂(μ-O)₃(Me-TACN)₂](PF₆)₂And are and

[Mn^IV ₂(μ-O)₃(Me/Me-TACN)₂](PF₆)₂。

even more preferably the manganese bleach catalyst comprises one or more of: [ Mn ]^IV ₂(μ-O)₃(Me-TACN)₂](PF₆)₂And [ Mn^IV ₂(μ-O)₃(Me/Me-TACN)₂](PF₆)₂. Even more preferably the manganese bleach catalyst is [ Mn ]^IV ₂(μ-O)₃(Me-TACN)₂](PF₆)₂。

The bleach catalyst particles of the present invention may suitably be prepared by fluidised bed coating. According to a particularly preferred embodiment, the first coating layer is applied by spraying an aqueous suspension of catalyst particles containing dissolved binder onto a fluidized bed of core particles. Next, the coated particles thus obtained were coated with a second coating layer by fluidized bed coating by spraying a brine solution onto the fluidized bed of the coated particles.

Bleach activators

The detergent composition may contain one or more bleach activators, for example peroxyacid bleach precursors. Peroxyacid bleach precursors are well known in the art. As non-limiting examples, mention may be made of N, N, N ', N' -Tetraacetylethylenediamine (TAED), Sodium Nonanoyloxybenzenesulfonate (SNOBS), sodium benzoyloxybenzenesulfonate (SBOBS) and cationic peroxyacid precursors (SPCC), as described in U.S. Pat. No. 4,751,015.

Surface active agent

The present detergent suspension preferably contains one or more surfactants. The surfactants in the present invention are, for example, "Surfactant Science Series", Vol.82, Handbook of detergents, Part A: properties, chapters 2(Surfactants, classification), g.brown (editorial). Typically, the detergent composition contains from 0.5 to 30 wt%, preferably from 1 to 20 wt%, more preferably from 1.3 to 10 wt% of one or more surfactants. In a preferred embodiment, the surfactant is selected from one or more nonionic surfactants.

According to a particularly preferred embodiment, the composition contains 0.1 to 15 wt.%, more preferably 0.5 to 10 wt.%, most preferably 1 to 5 wt.% of a nonionic surfactant or a mixture of two or more nonionic surfactants. Examples of nonionic surfactants useful in the compositions of the present invention include condensation products of hydrophobic alkyl, alkenyl or alkylaromatic compounds bearing functional groups having free reactive hydrogens useful for condensation with hydrophilic alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, polyethylene oxide or polyethylene glycol, to form nonionic surfactants. Examples of such functional groups include hydroxyl, carboxyl, mercapto, amino or amide groups.

Examples of useful hydrophobes for commercial nonionic surfactants include C8-C18 alkyl fatty alcohols, C8-C14 alkylphenols, C8-C18 alkyl fatty acids, C8-C18 alkyl mercaptans, C8-C18 alkyl fatty amines, C8-C18 alkyl amides and C8-C18 alkyl fatty alkanolamides. Thus, suitable ethoxylated fatty alcohols may be selected from ethoxylated cetyl alcohol, ethoxylated ketostearyl alcohol, ethoxylated isotridecyl alcohol, ethoxylated lauryl alcohol, ethoxylated oleyl alcohol and mixtures thereof. Examples of suitable nonionic surfactants for use in the present invention can be found in Plurafac, supplied by BASF^TMLF series and Synperonic supplied by Croda^TMLow to non-foaming ethoxy of NCA seriesAlkylated/propoxylated straight chain alcohols. Also of interest are the capped ethoxylated alcohols available from BASF as the SLF18 series, and from Lutensol supplied by BASF^TMAlkyl polyglycol ethers prepared from linear saturated C16-C18 fatty alcohols of the AT series. Other nonionic agents suitable for use in the compositions of the present invention are available from BASF/Cognis as Dehypon^TM3697GRA or Dehypon^TMModified fatty alcohol polyglycol ether available from Wet. Also suitable for use in the present invention are Lutensol from BASF^TMThe TO series of nonionic agents are alkyl polyglycol ethers prepared from saturated iso C13 alcohols. Amine oxide surfactants may also be used as anti-redeposition surfactants in the present invention. Examples of suitable amine oxide surfactants are C10-C15 alkyl dimethyl amine oxides and C10-C15 amidoalkyl dimethyl amine oxides. The present inventors have found that detergent compositions which are not only chemically but also physically very stable can be produced if the nonionic surfactant used is a solid at ambient temperature. Thus, advantageously, the composition of the invention contains from 0.1 to 30 wt%, more preferably from 0.5 to 20 wt%, even more preferably from 1 to 10 wt%, most preferably from 1 to 5 wt% of a nonionic surfactant which is solid at 25 ℃.

If anionic surfactants are used, the total amount present is preferably less than 5 wt%, more preferably no more than 2 wt%. Further, if an anionic surfactant is present, it is preferable that a defoaming agent that suppresses foaming be present. Examples of suitable anionic surfactants are methyl ester sulfonates (methyl ester sulfonates) or sodium lauryl sulfate. Preferably no anionic surfactant is present in the composition of the present invention.

Silicates of acid or alkali

Silicates may be added to the formulation. Silicates may be used as builders, buffers or article care agents. Preferred silicates are sodium silicates such as sodium disilicate, sodium metasilicate and crystalline phyllosilicates and mixtures thereof. The silicate is preferably used in the detergent suspension in a concentration of 0.5 to 8 wt%, more preferably 0.8 to 6 wt% of the suspension.

Enzyme

Examples of enzymes suitable for use in the cleaning suspensions of the present invention include lipases, cellulases, peroxidases, proteases (proteolytic enzymes), amylases (amylolytic enzymes) and others, which degrade, alter or promote the degradation or alteration of biochemical soils and stains encountered in cleaning situations, thereby making it easier to remove soils or stains from the substrate to be cleaned, so that the soils or stains are more easily removed in subsequent cleaning steps. Both degradation and alteration can improve soil removal.

Preferably, the one or more active enzymes comprised in the suspension of the invention are selected from the group consisting of proteases, amylases, cellulases, peroxidases, mannanases, pectate lyases and lipases. Most preferably, the active enzyme is selected from the group consisting of proteases, amylases, and combinations thereof.

The suspension of the invention will generally contain at least 10mg/kg, more preferably at least 20mg/kg, even more preferably at least 50mg/kg, most preferably at least 100mg/kg of active enzyme. The concentration of active enzyme is preferably not more than 50g/kg, more preferably not more than 40g/kg, most preferably not more than 30 g/kg.

According to a particularly preferred embodiment, the suspension contains at least 10mg/kg, more preferably at least 20mg/kg, most preferably at least 50mg/kg of active amylase.

According to another particularly preferred embodiment, the suspension contains at least 100mg/kg, more preferably at least 200mg/kg, most preferably at least 400mg/kg of active protease.

The enzyme may be added in liquid or encapsulated form. Examples of encapsulated enzymes are enzyme granules of the D, E and HS types of Genencor and T, GT, TXT and Evity of Novozymes^TMAnd (4) forming granules.

Proteolytic enzymes in the context of the present invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisin (EC 3.4.21.62). The proteolytic enzymes used in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred proteolytic enzymes are those derived from: bacillus, e.g. Bacillus lentus, Bacillus gibsonii, Bacillus subtilis, Bacillus licheniformis, Bacillus alkalophilus, Bacillus amyloliquefaciens and Bacillus pumilus, whichBacillus lentus and Bacillus gibsonii are most preferred. An example of such a proteolytic enzyme is excelase from Genencor^TM，Properase^TM，Purafect^TM，Purafect^TMPrime，Purafect^TMOx; and Novozymes under the trade name Blaze^TM，Ovozyme^TM，Savinase^TM，Alcalase^TM，Everlase^TM，Esperase^TM，Relase^TM，Polarzyme^TM，Liquinase^TMAnd Coronase^TMThose that are sold.

The starch hydrolyzing enzymes used in the present invention may be those derived from bacteria or fungi. Chemically or genetically modified mutants (variants) are included. Preferred starch hydrolyzing enzymes are alpha-amylases derived from a strain of Bacillus, such as Bacillus subtilis, Bacillus licheniformis, Bacillus amyloliquefaciens or Bacillus stearothermophilus. An example of such a starch hydrolyzing enzyme is the Stainzyme from Novozymes under the trade name Stainzyme^TM，Stainzyme^TMPlus，Termamyl^TM，Natalase^TMAnd Duramyl^TMProduction and distribution; and Powerase of Genencor^TM，Purastar^TM，Purastar^TMOxam。Stainzyme^TM，Stainzyme^TMPlus and Powerase^TMIs a preferred amylase.

According to a particularly preferred embodiment of the invention, the suspension contains an active protease and the protease activity of the freshly prepared suspension does not decrease more than 70%, more preferably not more than 50%, most preferably not more than 20% when stored in a closed container at 20 ℃ for 8 weeks. Well-known enzyme stabilizers such as polyol/borax, calcium, formate or protease inhibitors such as 4-formylphenylboronic acid may also be present in the suspension.

Dispersion polymers

The detergent suspension may suitably contain one or more dispersing polymers. The dispersion polymers mentioned in the present invention are selected from the group consisting of antiplaque agents and/or antifouling agents.

Examples of suitable stain blocking polymeric agents include hydrophobically modified polycarboxylic acids such as Acusol^TM460ND (from Dow) and Alcosp from Akzo Nobelerse^TM747, and synthetic clays, preferably those having a high surface area, are very useful for preventing spotting, particularly those formed when dirt and dispersed residues are present where water accumulates on the glass, and spots formed when water is subsequently evaporated.

Examples of suitable anti-fouling agents include organic phosphonates, amino carboxylates, polyfunctional substituted compounds, and mixtures thereof.

Particularly preferred anti-scaling agents are organic phosphonates such as alpha-hydroxy-2 phenylethyl bisphosphonate, ethylene diphosphonate, hydroxy 1, 1-hexylene (hydroxy 1,1-hexylidene), vinylidene-1, 1-diphosphonate, 1, 2-dihydroxyethane 1, 1-diphosphonate and hydroxy-ethylene 1, 1-diphosphonate. Most preferred are hydroxy-ethylene 1, 1-diphosphonate (EDHP) and 2-phosphonobutane, 1,2, 4-tricarboxylic acid (Baysiit, from Bayer). Suitable anti-fouling agents are water-soluble dispersion polymers prepared from allyloxybenzenesulfonic acid monomers, methallylsulfonic acid monomers, copolymerizable nonionic monomers, and copolymerizable ethylenically unsaturated carboxylic acid monomers, as described in US 5547612, or as acrylic acid sulfonated polymers, as described in EP 851022. Polymers of this type comprise polyacrylates with methyl methacrylate, sodium methallylsulfonate and sulfophenol methallyl ether, for example Alcosperse supplied^TM240(akzo nobel). Also suitable are terpolymers containing polyacrylate and 2-acrylamido-2-methylpropanesulfonic acid, such as Acumer 3100 available from Dow. Alternatively, polymers and copolymers of acrylic acid having a molecular weight between 500 and 20,000, such as homopolycarboxylic acid compounds having acrylic acid as monomer units, may also be used. The average weight of such homopolymers in the acid form is preferably from 1,000 to 100,000, in particular from 3,000 to 10,000, for example Sokolan from BASF^TMPA 25 or Acusol from Dow^TM425。

Also suitable are polycarboxylate copolymers of monomers derived from acrylic acid and maleic acid, such as CP5 from BASF. The average molecular weight of these polymers in the acid form is preferably from 4,000 to 70,000. Modified polycarboxylates such as those from BASF may also be usedSokalan^TMCP42，Sokalan^TMCP50, or Alcoguard from Akzo Nobel^TM4160。

Mixtures of anti-fouling agents may also be used. Particularly useful are mixtures of organic phosphonates and acrylic polymers. Preferably, the content of the dispersion polymer is 0.2 to 10% by weight, preferably 0.5 to 8% by weight, and further preferably 1 to 6% by weight of the total suspension.

The glass corrosion inhibitor can prevent irreversible corrosion and iridescence of glass surfaces in machine dishwashing detergents. The claimed suspension may suitably contain a glass corrosion inhibitor. Suitable glass etchants can be selected from the group consisting of salts of zinc, bismuth, aluminum, tin, magnesium, calcium, strontium, titanium, zirconium, manganese, lanthanum, mixtures thereof, and precursors thereof. Most preferred are salts of bismuth, magnesium or zinc or combinations thereof. The preferred content of glass corrosion inhibitor in the present suspension is 0.01-2 wt.%, more preferably 0.01-0.5 wt.%.

Rust inhibitors can prevent or reduce the staining, corrosion or oxidation of metals such as silver, copper, aluminum and stainless steel. Rust inhibitors such as benzotriazole or bis-benzotriazole and substituted or substituted derivatives thereof and those described in EP 723577 (Unilever) may also be included in the suspension. Other rust inhibitors which may be included in the detergent suspension are mentioned in WO 94/26860 and WO 94/26859. Suitable redox activators are, for example, complexes selected from cerium, cobalt, hafnium, gallium, manganese, titanium, vanadium, zinc or zirconium, wherein the metal is in the oxidation state II, IV, V or VI.

Optionally, other components may be added to the formulation, such as perfumes, colorants or preservatives. The desired viscosity properties (profile) of the detergent suspension depend on the end use of the product. Depending on the application, it may be a liquid, gel or paste. Another aspect of the invention relates to a water-soluble pouch (sachet) filled with a suspension as defined hereinbefore.

Rheology of

According to a particularly preferred embodiment of the invention, the detergent suspension is a thixotropic suspension.

The term "thixotropic" is that the product is viscous under static conditions and becomes less viscous when shaken, stirred or otherwise stressed. In thixotropic compositions, this so-called "shear thinning effect" is reversible, i.e. the composition will return to a more viscous state once it is no longer subjected to shear stress. This thixotropic behaviour of the detergent suspension can be demonstrated by measuring the storage modulus (G') and loss modulus (G ") of the product as a function of the angular frequency (ω) on a rheometer in oscillatory mode. Both G 'and G "of the fluid product increase as a function of angular frequency (ω), since G" increases at a faster rate than G'. At very low angular frequencies (ω), G "of the fluid product is below G ', but at ω in the range of 0.05-50rad/s G" exceeds G'.

Using plate-plate geometry, spindle PP50/S (grit blast) and 3mm gap size, using Anton

The MCR 302 rheometer measures both the storage modulus (G') and the loss modulus (G ") of the fluid product at 20 ℃. The program settings of the application are as follows:

● the strain gamma was chosen in the linear visco-elastic range of the product (LVER determined from amplitude sweep). The strain was kept constant at 0.1%.

● starting at 0.01rad/s, the log of the increasing slope of the angular frequency ω is set on the sample from low to high frequency. The end ω is 100rad/s unless the sample is very hard.

● the setting for collecting the measurement points is a "no time setting". In this mode, the device waits for a steady state condition before it acquires its measurement point.

● take six measurement points every ten.

Using oscillatory rheology, both viscous-like and elastic-like properties of a material can be quantified on different time scales. The basic principle of an oscillatory rheometer is to induce sinusoidal shear deformation in a sample and measure the resultant stress response; the time scale of the detection is determined by the oscillation frequency ω of the shear deformation. The sample was placed between the two plates. While the top plate is held stationary, the motor rotates the bottom plate, thereby applying a time-dependent strain γ (t) γ · sin (ω t) on the sample. At the same time, the time-dependent stress σ (t) was quantified by measuring the torque exerted by the sample on the top plate.

Measuring this time-dependent stress response at a single frequency immediately reveals the critical differences between the materials. If the material is an ideal elastic solid, the sample stress is proportional to the strain deformation and the proportionality constant is the shear modulus of the material. The stress is always exactly in phase with the applied sinusoidal strain deformation.

Conversely, if the material is a purely viscous fluid, the stress in the sample is proportional to the strain deformation rate, where the proportionality constant is the viscosity of the fluid. The applied strain and the measured stress are out of phase, with a phase angle δ π/2.

Viscoelastic materials exhibit responses that contain both in-phase and out-of-phase contributions. These contributions reveal the extent of solid-like and liquid-like behavior. As a result, the overall stress response shows a phase shift δ relative to the applied strain deformation, which is between solid and liquid, 0< δ < π/2. The viscoelastic behavior of the system at ω is characterized by a storage modulus G' (ω) and a loss modulus G "(ω), which characterize the solid-like and fluid-like contributions to the measured stress response, respectively. For sinusoidal strain deformation γ (T) ═ γ 0sin (ω T), the stress response of the viscoelastic material is given by σ (T) ═ G' (ω) γ 0sin (ω T) + G "(ω) γ 0cos (ω T).

Whether the product behaves more like a solid or more like a liquid depends on the time scale when it is deformed. At the lowest achievable frequency, the detergent suspensions of the invention have a loss modulus below the storage modulus, indicating solid-like behavior, while at the highest achievable frequency the loss modulus dominates the response, indicating viscous-like behavior.

According to a particularly advantageous embodiment of the invention, the detergent suspension is a thixotropic composition having a storage modulus (G' (ω)) at 20 ℃ and a loss modulus (G "(ω)) at 20 ℃, both moduli being measured as a function of the angular frequency (ω) on a rheometer of the oscillation mode operating at 0.1% strain, wherein:

● at an angular frequency (ω) in the range of 50 to 100rad/s, G "(ω) > G' (ω), and

● G '(omega) < G' (omega) at an angular frequency (omega) in the range of 0.01 to 0.05 rad/s.

Especially preferred are detergent suspensions having a storage modulus (G') and a loss modulus (G ") which satisfy at least one of the following conditions:

● at an angular frequency (ω) in the range of 30 to 100rad/s, more preferably in the range of 10 to 100rad/s, G "(ω) > G' (ω), and

● G '< G' (ω) at an angular frequency (ω) in the range of 0.01 to 0.2rad/s, more preferably in the range of 0.01 to 0.5 rad/s.

The pourable detergent suspension typically has a storage modulus (G') at 0.2rad/s of 1 to 100Pa, more preferably 8 to 30Pa, most preferably 10 to 20 Pa.

The loss modulus (G') at 0.2rad/s of the pourable detergent suspension is preferably from 1 to 100Pa, more preferably from 3 to 60Pa, most preferably from 8 to 30 Pa.

The invention is further illustrated by the following non-limiting examples.

Examples

Example 1

Pourable thixotropic machine dishwashing products were prepared based on the formulations shown in table 1.

TABLE 1

Composition (I)	By weight%
		Glycerol	48.67
Citric acid (50%)	1.43
		DissolvineTMGL 47-S1	9.40
DissolvineTMPD-S 22	18.40
		Process water	7.99
Xanthan gum	0.21
		Light carbonate ash (carbonate ash light)	12.05
Percarbonate salts3	1.10
		Bleach catalyst particles	1.2
LutensolTMAT80 (nonionic surfactant)	1.87

¹Contains about 48 wt.% GLDA and 45 wt.% water

²Contains about 85 wt% GLDA and 9 wt% water

³Coated percarbonate, 98% by weight, 0.2 mm to 1.4 mm

The bleach catalyst particles were prepared as follows:

● core particles having a volume weighted mean diameter of about 600 μm were prepared by high shear granulation

● the core particles were coated with three layers of coating by fluidized bed coating. The core particles were coated sequentially with an aqueous suspension of catalyst particles additionally containing a binder (dextrin), an aqueous suspension of sodium sulfate and titanium oxide, and an aqueous suspension of PEG 4000, titanium dioxide and kaolin. The volume weighted mean diameter of the bleach catalyst particles thus obtained is about 700 μm.

The composition of the bleach catalyst particles is summarized in table 2.

TABLE 2

¹Particles of a bleach catalyst (manganese trimethyl-1, 4, 7-triazacyclononane; CAS No. 116633-52.4); d₉₉<25μm，D₁₀≥1μm；D₅₀In the range of 5-10 μm.

Machine dishwashing products were prepared as follows. The liquid premix was prepared by mixing glycerol and xanthan gum into a homogeneous suspension. Subsequently, water was added with constant stirring. Thereafter, Dissolvine is administered at ambient temperature^TMGL 47-S and citric acid. Next, Dissolvine^TMPD-S is mixed in. Finally, the remaining ingredients were added to the mixture with stirring. All ingredients were mixed under vacuum to minimize bubble formation.

The detergent product thus obtained is a stable suspension which does not phase separate or settle when stored at ambient conditions. The bleaching activity of the product was not significantly reduced during normal storage. The product was very viscous but could be poured out of the bottle without problems.

Example 2

The pourable detergent suspensions according to the invention were compared with the same pourable detergent composition but using different bleach catalyst particles. The bleach catalyst particles a were prepared based on the formulations shown in table 3.

TABLE 3

	By weight%
		ManCat (MN-TACN crystal) Mncat 1033	4
Sodium carbonate (light monohydrate ash)	46.5
		Sodium silicate (Britesil H20)	46.5
Polyacrylate (adhesive) (50% solution Pa 25 CL pH)>8)	3

Bleach catalyst particles a were prepared as follows:

the carbonate and silicate were placed in a ploughshare mixer (ploughhare mixer) together with the ManCat crystals. While mixing, 3% of the binder was sprayed onto the powder bed with a single-phase nozzle within 3 minutes. Mixing was continued for 10 minutes after spraying was complete. Next, the particles were discharged and sieved on a sieve plate of 710-. The fractions >255 μm and <710 μm were used for the experiments.

Pourable detergent suspensions were prepared based on the formulations shown in table 4 (bleach catalyst particle 1 was the bleach catalyst particle described in example 1). Detergent suspension 1 is a detergent suspension according to the invention, detergent suspension a is not.

TABLE 4

The detergent suspension was prepared in 3kg batches in a Unimix (from Haagen & Rinau) mixer, which was operated under vacuum at 70rpm while maintaining the temperature of the mixer contents at 20 ℃. The mixing procedure used was as follows:

introducing glycerol and xanthan gum and mixing for 20 minutes;

adding process water, and continuing stirring for 20 minutes;

addition of citric acid solution and Dissolvine^TMGL 47-S, continue mixing for 5 minutes;

addition of Dissolvine^TMPD-S2, continue mixing for 40 minutes;

addition of Lutensol^TMAT80 and carbonate, and stirring for 30 minutes;

percarbonate and bleach catalyst particles were added and mixing continued for 35 minutes.

The characteristics of the two detergent suspensions are summarized in table 5.

TABLE 5

¹The normalized heat (J/g) generated by a sample of the suspension when held at 50 ℃ for 40 hours was measured using an ATAM III system (from TA Instruments)

The above results indicate that suspension a contains oxidized catalyst particles and that the percarbonate in suspension a decomposes prematurely, possibly due to interaction with the manganese catalyst.

Claims (14)

1. A pourable detergent suspension comprising:

● 30-80 wt% of a moisture absorbing component selected from the group consisting of aminocarboxylate chelants, glycerin, and combinations thereof;

● 8-25 wt% water;

● 0.5.5-30% by weight of a bleaching agent;

● 0.1.1 to 5 wt% of bleach catalyst particles having a diameter of 20 to 2000 μm, the bleach catalyst particles comprising:

30-90% by weight of one or more core particles;

10-70 wt.% of a coating layer covering the one or more core particles, the coating layer consisting of one or more coating layers and containing:

-1-30 wt% of a coating of catalyst particles comprising at least 30 wt% of a manganese bleach catalyst; and

-50-99% by weight of a coating of a water-soluble alkali metal sulphate;

the bleach catalyst particles are free of enzyme, contain from 0.3 to 20 wt% of the catalyst particles and contain from 30 to 99 wt% of the water-soluble alkali metal sulphate.

2. The detergent suspension according to claim 1, wherein at least 90 wt% of the catalyst particles have a diameter of 0.2-25 μm.

3. The detergent suspension according to claim 1 or 2, wherein the bleach catalyst particles comprise a core particle and meet the following specifications:

● diameter of the core particle: 200-;

● volume weighted mean diameter of the catalyst particles: 1-12 μm;

● thickness of the coating: 10-150 μm.

4. The detergent suspension of claim 3, wherein the coating of bleach catalyst particles comprises at least two coating layers comprising (i) a first coating layer comprising 30-90 wt% of the catalyst particles and 10-70 wt% of a water-soluble binder, and (ii) a second coating layer surrounding the first coating layer, the second coating layer comprising at least 60 wt% of a water-soluble salt.

5. The detergent suspension according to claim 4, wherein the water-soluble binder is selected from the group consisting of monosaccharides, disaccharides, trisaccharides, dextrins, and combinations thereof.

6. The detergent suspension according to claim 1 or 2, wherein the water-soluble alkali metal sulfate is sodium sulfate.

7. The detergent suspension according to claim 1 or 2, wherein the suspension comprises 8-40 wt% aminocarboxylate chelant.

8. The detergent suspension according to claim 1 or 2, wherein the suspension comprises 20-75 wt% glycerol.

9. The detergent suspension according to claim 1 or 2, wherein the combination of glycerol, water and aminocarboxylate chelant comprises at least 45 wt% of the suspension.

10. The detergent suspension according to claim 1 or 2, wherein the suspension contains 10-22 wt% water.

11. The detergent suspension according to claim 1 or 2, wherein the suspension has a water activity of 0.2 to 0.6 at 20 ℃.

12. The detergent suspension according to claim 1 or 2, wherein the suspension contains at least 0.1% by weight of water of a structuring biopolymer.

13. The detergent suspension according to claim 12, wherein the structured biopolymer is selected from the group consisting of xanthan gum, locust bean gum, guar gum, gum arabic, gellan gum, carrageenan, carboxymethyl cellulose, microcrystalline cellulose, microfibrillar cellulose, and combinations thereof.

14. The detergent suspension according to claim 1 or 2, wherein the suspension is a thixotropic suspension having a storage modulus (G' (ω)) at 20 ℃ and a loss modulus (G "(ω)) at 20 ℃, both moduli being measured as a function of angular frequency (ω) on a rheometer of oscillatory mode operating at 0.1% strain, wherein:

● at an angular frequency (ω) in the range of 50 to 100rad/s, G "(ω) > G' (ω), and

● G '(omega) < G' (omega) at an angular frequency (omega) in the range of 0.01 to 0.05 rad/s.