ES2581916T5 - Method for washing fabrics at low temperature - Google Patents

Description

DESCRIPTION

Method for washing fabrics at low temperature

field of invention

The present invention relates to a method for washing fabrics. The method exhibits good fabric cleaning performance, good fabric care profile, good fabric freshness profile, and has an excellent environmental profile.

Background of the invention

With the advent of more environmentally friendly and sustainable laundry products, laundry processes, and laundry applications, there is a need to ensure that fabric cleaning, fabric care, and Fabric freshness profiles remain acceptable. At lower wash temperatures, dissolving efficiency is negatively affected, especially in the case of solid laundry detergent products. Furthermore, the reaction kinetics of washing processes are reduced at lower washing temperatures. Tissue deposition efficiency is also affected by lowering the wash temperature. The perfume release profile also changes with the decrease in wash temperature.

The inventors have discovered that certain detergent ingredients, and certain combinations of detergent ingredients, allow fabrics to be washed at low temperatures in a more environmentally friendly and sustainable way, while ensuring good fabric cleaning performance, good profile of fabric care, and good profile of freshness of the fabrics.

All patents US-2006/089284, US-2004/018951, EP-1036840, WO-98/59024, EP-158464, US-4743394, US-5482646, US-6274545, GB-2289687, US-5945394, GB -1013394, FR-1059696, FR-1115755 and EP-890635 are related to methods for washing fabrics at low temperatures.

Summary of the invention

The present invention refers to a method for washing fabrics as defined in the claims.

Detailed description of the invention

Fabric washing method

The method for washing fabrics comprises the step of contacting a laundry detergent composition with water to form a wash solution and washing the fabric in said wash solution, wherein the wash solution has a temperature of more than 0 °C to 20 °C, preferably 19 °C, or 18 °C, or 17 °C, or 16 °C, or 15 °C, or 14 °C, or 13 °C, or 12 °C, or 11°C, or 10°C, or 9°C, or 8°C, or 7°C, or 6°C, or even 5°C. The fabric may be contacted with water before, or after, or simultaneously, prior to contacting the laundry detergent composition with water.

Typically, the wash solution is formed by contacting the laundry detergent with water in an amount such that the concentration of the laundry detergent composition in the wash solution is more than 0 g/l to 5 g. /l, preferably 1 g/l, and preferably 4.5 g/l, or 4.0 g/l, or 3.5 g/l, or 3.0 g/l, or 2.5 g/ l, or even at 2.0 g/l or even at 1.5 g/l.

Most preferably, the fabric laundering method is carried out in a front-loading automatic washing machine. In this embodiment, the wash solution formed and the concentration of the laundry detergent composition in the wash solution refer to those of the main wash cycle. Any ingress of water during the optional rinse stage(s) that typically occur when a fabric is washed in a front-loading automatic washing machine have not been included in determining the volume of wash solution. Of course, any suitable automatic washing machine may be used, although it is highly preferred that a front-loading automatic washing machine be used.

It is highly preferred that the wash solution comprises 40 liters or less of water, preferably 35 liters or less, preferably 30 liters or less, preferably 25 liters or less, preferably 20 liters or less, preferably 15 liters or less, preferably 12 liters or less. less, preferably 10 liters or less, preferably 8 liters or less, or even 6 liters or less of water. Preferably, the wash solution comprises from more than 0 to 15 liters, or 1 liter, or 2 liters, or 3 liters, and preferably up to 12 liters, or 10 liters, or even 8 liters of water. Most preferably, the wash solution comprises 1 litre, or 2 litres, or 3 litres, or 4 litres, or even 5 liters of water.

Typically, 0.01 kg to 2 kg of fabric per liter of wash solution is dosed into said wash solution. Typically, it is dosed at 0.01 kg, or 0.02 kg, or 0.03 kg, or 0.05 kg, or 0.07 kg, or 0.10 kg, or 0 .12 kg, or 0.15 kg, or 0.18 kg, or 0.20 kg, or 0.22 kg, or 0.25 kg of fabric per liter of wash solution to said wash solution.

Preferably 50g or less, more preferably 45g or less, or 40g or less, or 35g or less, or 30g or less, or 25g or less, or 20g or less, or even 15g or less, or even 10g or less of composition laundry detergent is contacted with water to form the wash solution.

Preferably, the laundry detergent composition is contacted with more than 0 litres, preferably more than 1 litre, and preferably 70 liters or less of water to form the wash solution, or preferably 40 liters or less of water , or preferably 35 liters or less, or preferably 30 liters or less, or preferably 25 liters or less, or preferably 20 liters or less, or preferably 15 liters or less, or preferably 12 liters or less, or preferably 10 liters or less, or preferably 8 liters or less, or even 6 liters or less of water to form the wash solution.

Especially preferred, catalytic ingredients are used to improve the cleaning performance of the laundry detergent composition during the process of the present invention. Catalytic ingredients are also preferably used to improve the hygiene profile of the laundry detergent composition during the method of the present invention.

Detergent composition for laundry

The laundry detergent composition comprises, and wherein the laundry detergent composition comprises more than 1% by weight of detersive surfactant and other detergent ingredients.

The composition may be in any form, for example, a solid or tablet powder form, or a liquid including a gel form, or any combination thereof. The composition can be in any unit dose form, for example a tablet or a pouch, or even a detergent sheet. However, it is highly preferred that the composition is in solid form, and it is especially preferred that the composition is in the form of free-flowing particles, for example such that the composition is in the form of discrete, independent particles.

The laundry detergent composition may comprise from 0% by weight to 40% by weight, or more than 0% by weight, and preferably 30% by weight, or 25% by weight, or 20% by weight, or 15% by weight, or 10% by weight, or 8% by weight, or 6% by weight, or 4% by weight, or 2% by weight of water. This may be preferred if the composition is a liquid including a gel form, and/or a unit dose form such as a unit dose bag.

The composition is a fully finished laundry detergent composition. Typically, if the composition is in the form of free-flowing particles, the composition comprises a plurality of chemically different populations of particles. The composition is not only a component of a laundry detergent composition that can be incorporated into a laundry detergent composition (such as an enzyme pellet, or a surfactant particle, or a bleach particle), it is a composition Completely finished laundry detergent. That said, it is within the scope of the present invention that an additional rinse-additive composition (eg, a fabric conditioner or enhancer) or a main wash-additive composition (eg, bleach additive) is also used in conjunction with the laundry detergent composition during the method of the present invention. Although, it may be preferable not to use any bleach additive composition together with the laundry detergent composition during the method of the present invention.

The laundry detergent composition preferably comprises from 0% by weight to less than 10% by weight of zeolite-type builder, and from 0% by weight to less than 10% by weight of builder phosphate type. The laundry detergent composition may comprise cationic polymer. The laundry detergent composition may preferably comprise perfume microcapsules.

A most preferred laundry detergent composition is a solid laundry detergent composition comprising (a) ethoxylated alkyl sulphate having an average degree of ethoxylation of 0.5 to 3.5, (b) 0% by weight to 10% by weight of zeolite-type builder, (c) from 0% by weight to 10% by weight of phosphate-type builder, (d) enzyme, (e) bleach catalyst having a structure that corresponds to the following general formula

wherein R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl, (f) layered particle, wherein the layered particle comprises a core and a shell, wherein the core comprises a source of hydrogen peroxide, wherein the shell comprises a binder and a bleach activator and wherein the weight ratio of hydrogen peroxide source to bleach activator is from about 5:1 to about 1.1:1, (g) optionally, transition metal bleach catalyst, (h) optionally, shading agent and (i), optionally, from 0% by weight to 10% by weight of sodium carbonate.

bleaching ingredient

Preferably, the laundry detergent composition comprises a bleach ingredient, the bleach ingredient having a logPo/w value of no more than 0, preferably no more than -0.5, preferably no more than -1.0, preferably no more to -1.5, preferably not more than -2.0, preferably not more than -2.5, preferably not more than -3.0, still more preferably not more than -3.5. The method for determining the value of logPo/w is described in more detail below.

Typically, the bleach ingredient can generate a bleach species having an XSO value of from 0.01 to about 0.30, preferably from 0.05 to about 0.25, even more preferably from about 0.10 to 0, twenty. The method for determining the value of Xso is described in more detail below. For example, bleaching ingredients having an isoquinolinium structure can generate a bleach species having an oxaziridinium structure. In this example, the value of X ^so is that of the oxaziridinium bleach species.

Without wishing to be bound by theory, the inventors believe that control of electrophilicity and hydrophobicity in the manner described above allows the bleaching ingredient to be delivered substantially only to those areas of the fabric that are most hydrophobic, and contain electron-rich soils, including visible chromatophores, which are susceptible to bleaching by highly electrophilic oxidants.

Preferably, the bleaching ingredient is catalytic. A highly preferred bleach ingredient is a bleach catalyst that can accept an oxygen atom from a peroxyacid and/or salt thereof, and transfer the oxygen atom to an oxidizable substrate. Suitable bleach catalysts include, but are not limited to, iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonyl imines, N-phosphonyl imines, N-acyl imines, thiadiazole dioxides , perfluoroimines, cyclic sugar ketones and mixtures thereof.

Suitable iminium cations and polyions include, but are not limited to, N-methyl-3,4-dihydroisoquinolinium tetrafluoroborate, prepared as described in Tetrahedron (1992), 49(2), 423-38 (see for example, compound 4, page 433), N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate, prepared as described in US-5,360,569 (see, for example, Column 11, Example 1), and p- N-octyl-3,4-dihydroisoquinolinium toluenesulfonate, prepared as described in US-5,360,568 (see, eg, Column 10, Example 3).

Iminium zwitterions include, but are not limited to, N-(3-sulfopropyl)-3,4-dihydroisoquinolinium, inner salt, prepared as described in US 5,576,282 (see, for example, Column 31, Example II), N-[2-(sulfooxy)dodecyl]-3,4-dihydroisoquinolinium, inner salt, prepared as described in US Pat. No. 5,817,614 (see, eg, Column 32, Example V), 2- [3-[(2-ethylhexyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt, prepared as described in WO-05/047264 (see, for example, page 18, the Example 8), and 2-[3-[(2-butyloctyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt.

Modified amine oxygen transfer catalysts include, but are not limited to, 1,2,3,4-tetrahydro-2-methyl-1-isoquinolinol, which can be made according to the procedures described in Tetrahedron Letters (1987 ), 28(48), 6061-6064. Suitable modified amine oxide oxygen transfer catalysts include, but are not limited to, sodium 1-hydroxy-N-oxy-N-[2-(sulfoxy)decyl]-1,2,3,4-tetrahydroisoquinoline.

Suitable N-sulfonyl imine oxygen transfer catalysts include, but are not limited to, 3-methyl-1,2-benzisothiazole-1,1-dioxide, prepared according to the procedure described in the Journal of Organic Chemistry (1990) , 55(4), 1254-61.

N-phosphonyl imine oxygen transfer catalysts include, but are not limited to, [R-(E)]-N-[(2-chloro-5-nitrophenyl)methylene]-P-phenyl-P-(2 ,4,6-trimethylphenyl)-phosphinicamide, which can be prepared according to procedures described in the Journal of the Chemical Society, Chemical Communications (1994), (22), 2569-70.

N-acyl imine oxide oxygen transfer catalysts include, but are not limited to, [N(E)]-N-(phenylmethylene)acetamide, which can be prepared according to procedures described in the Polish Journal of Chemistry (2003), 77(5), 577-590.

Thiadiazole dioxide oxygen transfer catalysts include, but are not limited to, 3-methyl-4-phenyl-1,2,5-thiadiazole-1,1-dioxide, which can be made according to procedures described in US -5,753,599 (Column 9, Example 2).

Perfluoroimine oxygen transfer catalysts include, but are not limited to, (Z)-2,2,3,3,4,4,4-heptafluoro-N-(nonafluorobutyl)butanimidoyl fluoride, which can be prepared according to procedures described in Tetrahedron Letters (1994), 35(34), 6329-30.

Cyclic ketone sugar oxygen transfer catalysts include, but are not limited to, 1,2:4,5-di-O-isopropylidene-D-erythro-2,3-hexodiide-2,6-pyranose as described prepared in US-6,649,085 (Column 12, Example 1).

Preferably, the bleach catalyst comprises an iminium and/or carbonyl functional group and is typically capable of forming an oxaziridinium and/or dioxirane functional group upon acceptance of an oxygen atom, especially upon acceptance of a carbon atom. oxygen from a peroxyacid and/or salt thereof. Preferably, the bleach catalyst comprises an oxaziridinium functional group and/or can form an oxaziridinium functional group upon acceptance of an oxygen atom, especially upon acceptance of an oxygen atom from a peroxyacid and/or salt thereof. themselves. Preferably, the bleach catalyst comprises a cyclic iminium functional group, preferably wherein the cyclic moiety has a ring size of five to eight atoms (including the nitrogen atom), preferably six atoms. Preferably, the bleach catalyst comprises an aryliminium functional group, preferably a bicyclic aryliminium functional group, preferably a 3,4-dihydroisoquinolinium functional group. Typically, the imine functional group is a quaternary imine functional group and can typically form a quaternary oxaziridinium functional group upon acceptance of an oxygen atom, especially upon acceptance of an oxygen atom from a peroxyacid and / or get out of them.

Preferably, the bleach catalyst has a chemical structure corresponding to the following chemical formula

where n and m are independently from 0 to 4, preferably n and m are both 0, each R1 is selected, independently from one another, from a substituted or unsubstituted radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, fused aryl radicals, heterocyclic ring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxy, and any two substituents on adjacent R1 can combine to form a fused aryl, fused carbocyclic, or fused heterocyclic ring, each R2 is selected , independently from each other, of a substituted or unsubstituted radical selected, independently from each other, from the group consisting of hydrogen, hydroxy, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups, and amide groups, any R2 can be joined together with any other of R2 to form part of a common ring, any Either geminal R2 can combine to form a carbonyl and any two R2 can combine to form a substituted or unsubstituted fused unsaturated moiety, R3 is ^a substituted or unsubstituted C1 to C20 alkyl, R4 is hydrogen or the moiety ^Qt- A, where Q is a branched or unbranched alkylene, t = 0 or 1 and A is an anionic group selected from the group consisting of OSO ³ -, SO ³ -, CO ² -, OCO ² -, OPO ³ 2- , OPO ³ H- and OPO ² -, R5 is hydrogen or the moiety -CR11R12-Y-Gb-Yc-[(CR9R10)yO]k-R8, wherein each Y is independently selected from the group consisting of in O, S, NH, or N-R8, and each R8 is independently selected from the group consisting of alkyl, aryl, and heteroaryl, said moieties being substituted or unsubstituted and said moieties having either substituted or unsubstituted , less than 21 carbons, each G is independently selected from the group consisting of CO, SO ² , SO, PO, and PO ² , R9 and R10 are selected, independently independently of each other, from the group consisting of H and C ¹ -C ⁴ alkyl, R11 and R12 are independently selected from the group consisting of H and alkyl or, when taken together, may be joined to form a carbonyl, b = 0 or 1, c can be = 0 or 1, but c must be = 0 if b = 0, y is an integer from 1 to 6, k is an integer from 0 to 20, R6 is H or an alkyl, aryl or heteroaryl moiety, said moieties being substituted or unsubstituted, and X, if present, is a suitable counterion for charge balancing, preferably X is present when R4 is hydrogen, suitable Xs include, but are not limited to limiting form, chloride, bromide, sulfate, methosulfate, sulfonate, p-toluenesulfonate, boron tetrafluoride, and phosphate.

In one embodiment of the present invention, the laundry detergent composition comprises a bleach catalyst having a structure corresponding to the following general formula.

wherein R13 is a branched alkyl group containing from three to 24 carbon atoms (including branched carbon atoms) or a linear alkyl group containing from one to 24 carbon atoms, preferably R13 is a branched alkyl group containing eight to eighteen carbon atoms or a linear alkyl group containing eight to eighteen carbon atoms, preferably R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl , n-dodecyl, n-tetradecyl, nhexadecyl, n-octadecyl, iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl, preferably R13 is selected from the group consisting of 2-butyloctyl, 2-pentylnonyl, 2- hexyldecyl, iso-tridecyl and iso-pentadecyl.

In another embodiment of the present invention, the bleach catalyst has a structure corresponding to the following general formula or mixtures thereof

wherein G is selected from -O-, -CH ² O-, -(CH ² ) ² -, and -CH ² - each R1 is selected from H or C ¹ -C ⁴ alkyl. Suitable C ¹ -C ⁴ alkyl moieties include, but are not limited to, methyl, ethyl, iso-propyl, and ferc-butyl. Each R2 is independently selected from C4 -C8 alkyl, benzyl, ² -methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 4-ethylbenzyl, 4-iso-propylbenzyl, and ⁴ -ferc-butylbenzyl. Suitable C ⁴ -C ⁸ alkyl moieties include, but are not limited to, n-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, cyclohexylmethyl, n-heptyl, and octyl.

In one aspect of the invention, G is selected from -O- and -CH ² -R1 is selected from H, methyl, ethyl, iso-propyl and ferc-butyl. Each R2 is independently selected from ^{C4 -C6} alkyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4-methylbenzyl.

In another aspect of the invention, G is -CH ² -, R1 is H, and each R2 is independently selected from one of nbutyl, n-pentyl, n-hexyl, benzyl, 2-methylbenzyl, 3-methylbenzyl, and 4- methylbenzyl.

Method to determine the value of logPo/w

The logPo/w value is determined according to the method disclosed in Brooke, D.N., Dobbs, A.J., Williams, N, Ecotoxicology and Environmental Safety (1986) 11(3): 251-260.

Method to determine Xso

The Xso parameter is determined according to the method described in Adam, W., Haas, W., Lohray, B.B. Journal of the American Chemical Society (1991) 113(16) 6202-6208.

Transition Metal Bleach Catalyst

Preferably, the laundry detergent composition comprises a transition metal catalyst. Preferably, the transition metal catalyst can be encapsulated. The transition metal bleach catalyst typically comprises a transition metal ion, preferably selected from transition metals selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V) , Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I) , Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V) , Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV) ), more preferably Mn(II), Mn(III), Mn(IV), Fe(II), Fe(III), Cr(II), Cr(III), Cr(IV), Cr(V), and Cr(VI).

The transition metal bleach catalyst comprises a ligand, preferably a macropolycyclic ligand, more preferably a cross-bridged macropolycyclic ligand. The transition metal ion is preferably coordinated to the ligand. Preferably, the ligand comprises at least four donor atoms, at least two of which are bridgehead-forming donor atoms.

Preferably, the cross-bridged macropolycyclic ligand is coordinated by four or five donor atoms to the same transition metal and comprises

(i) an organic macrocyclic ring containing four or more donor atoms selected from N and, optionally,

O and S, at least two of these donor atoms being N (preferably at least 3, more preferably at least

4, of these donor atoms are N), separated from each other by covalent bonds of 2 or 3 non-donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms being coordinated to the same transition metal In the complex,

(ii) a cross-bridged chain covalently connecting at least 2 non-adjacent N-donor atoms of the organic macrocyclic ring, said non-adjacent N-donor atoms being covalently connected bridgehead-forming N-donor atoms that are coordinated to the same transition metal in the complex, and wherein said cross-bridged chain comprises from 2 to about 10 atoms (preferably, the cross-bridged chain is selected from 2, 3, or 4 non-donor atoms, and 4-6 non-donor atoms with an additional donor atom, preferably N), and

(iii) optionally, one or more non-macropolycyclic ligands, preferably selected from the group consisting of H ² O, ROH, NR ³ , RCN, OH-, OOH-, RS-, RO-, RCOO-, OCN-, SCN- , N ³ -, CN-, F-, Cl-, Br-, NO ² -, SO ⁴ 2-, SO ³ 2-, PO ⁴ 3-, organic phosphates, organic phosphonates, organic sulfates, organic sulfonates and donors of N aromatics, such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, R being H, optionally substituted alkyl, optionally substituted aryl

A transition metal bleach catalyst comprises a complex of a transition metal and a rigid macropolycyclic ligand, preferably a cross-bridged macropolycyclic ligand, wherein

(1) said transition metal is selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co (I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr (III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV),

V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III) and Ru(IV), and

(2) said rigid macropolycyclic ligand is coordinated by at least four, preferably four or five, donor atoms to the same transition metal and comprises

(i) an organic macrocyclic ring containing four or more donor atoms (preferably at least 3, more preferably at least 4, of these donor atoms are N) separated from each other by covalent bonds of at least one, preferably 2 or 3, atoms non-donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms being coordinated to the same transition metal in the complex,

(ii) a linking moiety, preferably a cross-bridged chain, covalently connecting at least 2 (preferably non-adjacent) donor atoms of the organic macrocyclic ring, said donor atoms being covalently connected (preferably non-adjacent) donor atoms forming a head which are coordinated to the same transition metal in the complex, and wherein said linking moiety (preferably a cross-bridged chain) comprises from 2 to about 10 atoms (preferably the cross-bridged chain is selected from 2, 3-4 non-donor atoms, and 4-6 non-donor atoms with one additional donor atom), including, for example, a cross-bridge resulting from a Mannich condensation of ammonia and formaldehyde, and

(iii) optionally, one or more non-macropolycyclic ligands, preferably monodentate ligands, such as those selected from the group consisting of H ² O, ^{rO h} , NR ³ , RCN, OH-, OOH-, RS-, RO-, RCOO-, OCN-, SCN-, N ³ -, CN-,

F-, Cl-, Br-, I-, O ² -, NO ³ -, NO ² -, SO ⁴ 2-, SO ³ 2-, PO ⁴ 3-, organic phosphates, organic phosphonates, organic sulphate sulphonates and donors of aromatic N's, such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, R being H, optionally substituted alkyl, optionally substituted aryl (specific examples of monodentate ligands including phenolate, acetate or the like)

Cross-bridged macropolycyclic ligands include

(i) the cross-bridged macropolycyclic ligand of formula (I) having a denticity of 4 or 5

(ii) the cross-bridged macropolycyclic ligand of formula (II) having a denticity of 5 or 6

(II),

(iii) the cross-bridged macropolycyclic ligand of formula (III) having a denticity of 6 or 7,

(III),

where in these formulas

- each "E" is the moiety (CRn)a-X-(CRn)á, where X is selected from the group consisting of O, S, NR and P, or a covalent bond, and preferably X is a covalent bond and for each E the sum of a to' is selected, independently of each other, from 1 to 5, more preferably 2 and 3,

- each “G” is the remainder (CRn)b,

- each “R” is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkyladl (eg, benzyl), and heteroaryl, or two or more R's are covalently linked to form an aromatic, heteroaromatic ring , cycloalkyl or heterocycloalkyl,

- each “D” is a donor atom selected, independently from one another, from the group consisting of N, O, S, and P and at least two D atoms are bridgehead-forming donor atoms coordinated to the transition metal (in the In preferred embodiments, all donor atoms designated D are donor atoms that coordinate to the transition metal, as opposed to heteroatoms of the framework that are not in D, such as may be present in E, heteroatoms that are not D may not be coordinators, and in fact are not coordinators when present in the preferred embodiment),

- “B” is a carbon atom or a donor atom “D”, or a cycloalkyl or heterocyclic ring,

- each "n" is an integer selected, independently from each other, from 1 and 2, which completes the valence of the carbon atoms to which the R residues are covalently attached,

- each "n'" is an integer selected, independently from one another, from 0 and 1, which completes the valence of the donor atoms D to which the residues R are covalently bonded,

- each "n"" is an integer selected, independently from each other, from 0, 1 and 2, which completes the valency of the B atoms to which the R moieties are covalently attached,

- each “a” and “a'“ are an integer selected, independently from each other, from 0 to 5, preferably aa' is equal to 2 or 3, where the sum of all values “a” plus “a' ” in the ligand of formula (I) is within the range of about 6 (preferably 8) to about 12, the sum of all values “a” plus “a'” in the ligand of formula (II) is within the range from about 8 (preferably 10) to about 15 and the sum of all values "a" plus "a'" in the ligand of formula (III) is within the range of about 10 (preferably 12) to about 18,

- each "b" is an integer selected, independently from each other, from 0 to 9, preferably from 0 to 5 (where when b = 0, (CRn)ü represents a covalent bond), or, in any of the formulas above, one or more of the covalently bonded (CRn)b moieties of any D to atom B is absent provided that at least two CRn)b covalently bond two of the D donor atoms to atom B in the formula and the sum of all “b” values are within the range of about 1 to about 5.

A cross-bridged macropolycyclic ligand is selected from the group consisting of

where in these formulas

- each “R” is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl (eg benzyl) and heteroaryl or two or more R's are covalently linked to form an aromatic, heteroaromatic ring, cycloalkyl or heterocycloalkyl,

- each "n" is an integer selected, independently from one another, from 0, 1 and 2, which completes the valency of the carbon atoms to which the R residues are covalently attached,

- each “b” is an integer selected, independently of each other, from 2 and 3, and

- each “a” is an integer selected, independently from each other, from 2 and 3.

Transition metal bleach catalysts include: Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-4,10-dimethyl-1,4, 7,10-Tetraazabicyclo[5.5.2]tetradecane Manganese(II), Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Hexafluorophosphate, Aqua- hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III), Diaquo-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5. 2]tetradecane Manganese(II), Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Tetrafluoroborate, Diaquo-4,10-dimethyl-1 Tetrafluoroborate, 4,7,10-Tetraazabicyclo[5.5.2]tetradecane Manganese(II), Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III) Hexafluorophosphate, Dichloro- 5,12-di-n-butyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II), Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[ 6.6.2]hexadecane Manganese(II), Dichloro-5-n-buty l-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II), Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraazabicyclo[ 6.6.2]hexadecane Manganese(II), Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane Manganese(II), Dichloro-5,12- Dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Iron(II), Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II), Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Copper(II), Dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo[5.5.2] tetradecane Copper(II), Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Cobalt(II), Dichloro-4,10-dimethyl-1,4,7,10- tetraazabicyclo[5.5.2]tetradecane Cobalt(II), Dichloro 5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-4,10-dimethyl -3-phenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II), Dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12-tetraazabicyclo[6.6 .2]hexadecane Manganese(II), Dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tet Raazabicyclo[5.5.2]tetradecane Manganese(II), Dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-4, 10-Dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II), Dichloro-2,4,5,9,11,12-hexamethyl-1,5, 8,12-Tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II ), Dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-2,2,4, 5,9,11,11,12-octamethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-3,3,5,10,10,12-hexamethyl-1, 5,8,12-Tetraazabicyclo[6.6.2]hexadecane Manganese(II) Dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Dichloro- 3-Butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Dichloro-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese( II), Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II), Dichloro-1,5, 8,12-Tetraazabicyclo[6.6.2]hexadecane Iron(II), Dichloro-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Iron(II), Aqua-chloro-2-(2-hydroxyphenyl)- 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Aqua-chloro-10-(2-hydroxybenzyl)-4,10-dimethyl-1,4,7, 10-tetraazabicyclo[5.5.2]tetradecane Manganese(II), Chloro-2-(2-hydroxybenzyl)-5-methyl1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Chloro-10-(2-hydroxybenzyl)-4-methyl-1,4,7 ,10-Tetraazabicyclo[5.5.2]tetradecane Manganese(II), Chloro-5-methyl-12-(2-picolyl)-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II) Chloride , Chloro-4-methyl-10-(2-picolyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane Manganese(II) Chloride, Dichloro-5-(2-sulfato)dodecyl-12- methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III), Acuo-chloro-5-(2-sulfato)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6 .2]hexadecane Manganese(II), Aqua-chloro-5-(3-sulfonopropyl)-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Dichloro-5 Chloride -(Trimethylammoniopropyl)dodecyl-12-methyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(III), Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo[ 8.5.2]heptadecane Manganese(II) Dichloro-14,20-dimethyl-1,10,14,20-tetraazatricyclo[8.6.6]docosa-3(8),4,6-triene Manganese(II), Dichloro- 4,11-dimethyl-1,4,7,11-tetraazab icyclo[6.5.2]pentadecane Manganese(II), Dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo[7.6.2]heptadecane Manganese(II), Dichloro-5,13-dimethyl-1, 5,9,13-Tetraazabicyclo[7.7.2]heptadecane Manganese(II), Dichloro-3,10-bis(butylcarboxy)-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Diaquo-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecane Manganese(II), Chloro-20-methyl-1,9-hexafluorophosphate ,20,24,25-pentaazatetracyclo[7.7.7.13'7.111,15.]pentacose-3,5,7(24),11,13,15(25)-hexaene Manganese(II), Trifluoromethanesulfono-20-Trifluoromethanesulfonate methyl-1,9,20,24,25-pentaaza-tetracyclo[7.7.7.13'7.111,15.]pentacose-3,5,7(24),11,13,15(25)-hexaene ManganeseQI), Trifluoromethanesulfonate of Trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaazatetracyclo[7.7.7.13,7.111,1 .]pentacose-3,5,7(24),11,13,15(25)-hexaene Iron (II), Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo[6.6.5]nonadecane Manganese(II) Hexafluorophosphate, Chloro-4,10 Hexafluorophosphate ,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II), Chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo Chloride [6.6.5]nonadecane Manganese(II), Chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo[5.5.5]heptadecane Manganese(II) Chloride, Dichloro-5,12 -diethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecanemanganese and mixtures thereof.

Other suitable transition metal bleach catalysts are described in US-5,580,485, US-4,430,243, US-4,728,455, US-5,246,621, US-5,244,594, US-5,284,944, US- 5,194,416, US-5,246,612, US-5,256,779, US-5,280,117, US-5,274,147, US-5,153,161, US-5,227,084, US-5,114,606, US-5,114. 611, US-549,271 A1, EP 544,490 A1, EP 549,272 A1 and EP 544,440 A2.

A suitable transition metal bleach catalyst is a manganese-based catalyst, for example, described in US-5,576,282.

Suitable cobalt bleach catalysts are described, for example, in US 5,597,936 and US 5,595,967. These cobalt-type catalysts are readily prepared by known procedures as described, for example, in US-5,597,936 and US-5,595,967.

A suitable transition metal bleach catalyst is a ligand transition metal complex, such as the bispidones described in WO-05/042532 A1.

The inventors have discovered that the transition metal bleach catalysts provide robust cleaning profiles, especially under dilute wash liquor conditions, and especially against unsaturated beta-carotene, squalene and triglyceride soils, especially at low wash temperatures.

preformed peracid

The laundry detergent composition may comprise a preformed peracid. The pre-peroxyacid or salt thereof is typically either a peroxycarboxylic acid or salt thereof, or a peroxysulfonic acid or salt thereof.

The preformed peroxyacid or salt thereof is preferably a peroxycarboxylic acid or salt thereof, typically having a chemical structure corresponding to the following general formula

wherein R14 is selected from alkyl, aralkyl, cycloalkyl, aryl, or heterocyclic groups, the R14 group may be linear or branched, substituted or unsubstituted, and Y is any suitable counterion that achieves electrical charge neutrality, preferably Y is selected hydrogen, sodium or potassium. Preferably R14 is a substituted or unsubstituted straight or branched C ^6-9 alkyl. Preferably, the peroxyacid or salt thereof is selected from peroxyhexanoic acid, peroxyheptanoic acid, peroxyoctanoic acid, peroxynonanoic acid, peroxydecanoic acid, any salt thereof, or any combination thereof. Preferably, the peroxyacid or salt thereof has a melting point in the range of 30°C to 60°C.

The preformed peroxyacid or salt thereof may also be a peroxysulfonic acid or salt thereof, typically having a chemical structure corresponding to the following general formula

EITHER

R 15— S ------- O -------- O Z

EITHER

wherein R15 is selected from alkyl, aralkyl, cycloalkyl, aryl, or heterocyclic groups, the R15 group may be linear or branched, substituted or unsubstituted, and Z is any suitable counterion that achieves electrical charge neutrality, preferably Z is selected from hydrogen, sodium or potassium. Preferably R15 is a substituted or unsubstituted straight or branched C ^6-9 alkyl.

The preformed peroxyacid or salt thereof may be in an encapsulated form, preferably molecularly encapsulated. Typically, the preformed peroxyacid molecules are individually separated from one another by any means of molecular encapsulation.

Preferably, the preformed peroxyacid is a guest molecule in a guest-host complex. Typically, the host molecule of the host-host complex comprises, or is capable of forming (eg, through its intermolecular configuration) a cavity into which the preformed peroxyacid can be located. The host molecule is typically in the form of a relatively open structure that provides a cavity that can be occupied by a preformed peroxyacid molecule thereby forming the host-guest complex. The preformed peroxyacid molecule can be trapped by one or more host molecules, for example by formation of a clathrate-type compound, also typically known as an inclusion compound, cage compound, intercalation compound, or adduct.

The host molecule is usually capable of forming hydrogen bonds such as intramolecular hydrogen bonds or intermolecular hydrogen bonds. Preferably, the host molecule is capable of forming intermolecular hydrogen bonds.

Suitable host molecules include urea, cyclodextrins, particularly beta-cyclodextrins, thiourea, hydroquinone, perhydrotriphenylene, deoxycholic acid, triphenylcarbinol, calixarene, zeolites, particularly wide pore zeolites, and any combinations thereof. Host molecules are most preferably water soluble; this is desirable to allow efficient release and dispersion of the preformed peroxyacid upon introduction of the host-guest complex into an aqueous environment, such as a wash solution. Preferably the host molecule is urea or thiourea, especially preferably the host molecule is urea.

The host-guest complex is preferably at least partially, preferably essentially completely, coated by a coating ingredient; this is desirable to further improve the stability of the preformed peroxyacid. Typically, the coating ingredient is essentially incapable of hydrogen bonding; this helps to ensure the optimal intermolecular configuration of the host molecules, especially when the host-guest complex is a clathrate compound, and furthermore improves the stability of the preformed peroxyacid. Typically, the coating ingredient is chemically compatible with the host-guest complex and has a suitable release profile, especially a suitable melting point range. The coating ingredient melting point range is preferably from 35°C to 60°C, more preferably 40°C to 50°C, or 46°C to 68°C. Suitable coating ingredients include paraffin waxes, semicrystalline waxes (also typically known as intermediate microcrystalline waxes), microcrystalline waxes, and natural waxes. Preferred paraffin waxes include Merck® 7150 and Merck® 7151 supplied by E. Merck of Darmstadt, Germany, Boler® 1397, Boler® 1538 and Bole® 1092 supplied by Boler of Wayne, Pa, Ross® 115 fully refined paraffin wax /120 supplied by Frank D. Ross Co., Inc. of Jersey City, NJ, Tholle® 1397 and Tholle® 1538 supplied by Tholler of Wayne, Pennsylvania, Paramelt® 4608 supplied by Terhell Paraffin of Hamburg, Germany, and Paraffin® R7214 supplied by Moore & Munger of Shelton, Conn. Preferred paraffin waxes typically have a melting point in the range of 46 °C to 680°C and typically have a number average molecular weight in the range of 350 Da to 420 Da. Natural waxes, such as Myrica cerifera natural wax, having a melting point in the range of 42 °C to 480°C, supplied by Frank D. Ross Co., Inc., and synthetic wax substitutes are also suitable. natural waxes, such as synthetic spermaceti wax, having a melting point in the range of 42 °C to 50°C, supplied by Frank D. Ross Co., Inc., synthetic beeswax (BD4) and synthetic glyceryl behenate (HRC) wax. Other suitable coating ingredients include fatty acids, especially hydrogenated fatty acids. However, most preferably, the coating ingredient is a paraffin wax.

Typically, the host-guest complex is an intimate mixture with a source of acid. Typically, the host-guest complex and the acid source are in particulate form, preferably being in a mixture of one particle with another, typically both are present on the same particle. Preferred sources of acid include fatty acids, especially hydrogenated fatty acids, which may also be suitable coating ingredients and have been described above, carboxylic acids, including monocarboxylic acids, and polycarboxylic acids, such as dicarboxylic acids and tricarboxylic acids. Preferably the acid source is a bicarboxylic acid.

It may be preferred that the host-guest complex be an intimate mixture with a free radical scavenger. A suitable free radical scavenger is butylated hydroxytoluene.

Without wishing to be bound by theory, the inventors believe that the preformed peroxyacid has the ability to bleach even in the absence of a source of alkalinity or hydrogen peroxide. The preformed peroxyacid is not susceptible to the effects of catalase. This means that, on a weight basis, the preformed peroxyacid provides good bleaching performance when compacted in alkalinity/buffer systems and the pH of the wash solution is lowered.

hydrogen peroxide source

The composition preferably comprises a source of hydrogen peroxide, preferably more than 0% by weight to 15% by weight, preferably 1% by weight, or 2% by weight, or 3% by weight, or 4% by weight. weight, or from 5% by weight, and preferably to 12% by weight, or preferably from 0% by weight to 10% by weight of hydrogen peroxide source. Preferably the source of hydrogen peroxide is coated, preferred coatings include sulfate salts, silicate salts, carbonate salts, burkeite, borosilicate, and any mixtures thereof including any double salts thereof. Preferably, the wash solution comprises more than 0 g/l to 0.5 g/l hydrogen peroxide, preferably 0.01 g/l, and preferably 0.4 g/l, or even 0.3 g/l, or even 0.2 g/l or even 0.1 g/l. Preferably, the laundry detergent composition comprises a source of hydrogen peroxide in an amount such that, during the method of the present invention, more than 0 g to 1.5 g, or 1.0 g, or 0.8 g , or 0.6 g, or 0.5 g, or 0.4 g of hydrogen peroxide source per liter of water is contacted with said water when the wash solution is formed.

Typically, the hydrogen peroxide source comprises from 10% to 100%, by weight of the hydrogen peroxide source, hydrogen peroxide.

Preferred sources of hydrogen peroxide include sodium perborate in, preferably in the form of monohydrate or tetrahydrate or mixtures thereof, sodium percarbonate. Especially preferred is sodium percarbonate. The bleach activator at least partially, preferably completely, surrounds the source of hydrogen peroxide.

bleach activator

Preferably, the composition comprises a bleach activator. Suitable bleach activators are compounds which, when used in conjunction with a source of hydrogen peroxide, produce the peracid corresponding to the bleach activator in situ. Various non-limiting examples of bleach activators are described in US 4,915,854, issued April 10, 1990 to Mao et al., and US 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and mixtures thereof can also be used. See also US patent no. 4,634,551 for other typical bleaches and activators useful in the present invention. Another suitable bleach activator is decanoyloxybenzenecarboxylic acid (DOBA).

Highly preferred amide derivative bleach activators are those of the formulations

R1N(R5)C(O)R2C(O)L

either

R1C(O)N(R5)R2C(O)L

wherein as used for these compounds, R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable leaving group. A leaving group is any group that has been displaced from the bleach activator as a result of the nucleophilic attack of the hydroperoxide anion on the bleach activator. A preferred leaving group is oxybenzenesulfonate.

Preferred examples of bleach activators of the above formulas include (6-octanamidocaproyl)oxybenzenesulfonate, (6-nonanamido-caproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof, as described in US-4,634. 551, incorporated by reference herein.

Another class of bleach activators comprises the benzoxazine type activators described by Hodge et al. in US Patent 4,966,723, issued October 30, 1990. A highly preferred activator of the benzoxazine type is

Yet another class of preferred whitening activators are acyl-lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas

wherein as used for these compounds, R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam-type activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl 3,5-valerola ,5-tri-methylhexanoyl valerolactam and mixtures thereof. See also US Patent 4,545,784, issued to Sanderson on October 8, 1985, which discloses acylcaprolactams, including benzoylcaprolactam, adsorbed on sodium perborate. Highly preferred bleach activators are nonanoyloxybenzenesulfonate (NOBS) and/or tetraacetylethylenediamine (TAED).

layered particle

In the present invention, the laundry detergent composition comprises a layered particle. The layered particle comprises a core and a shell. The core comprises a source of hydrogen peroxide. The layer comprises a binder and a bleach activator. The weight ratio of said source of hydrogen peroxide to said bleach activator present in the layered particle is preferably from about 5:1 to about 1.1:1, or from about 4:1 to about 1.5:1, or about 2: 1.

Preferably, the layered particle may have an average diameter of from about 600 pm to about 2,000 pm or from about 800 pm to about 1,000 pm. In one aspect, the layer can have a thickness of from about 25 pm to about 150 pm, or from about 40 pm to about 100 pm.

Preferably, the binder may comprise, based on the total weight of the layered particle, from about 2% to about 20%, or from about 4% to about 15%, or from about 6% to about 10%, or from about 7%. % to about 8% of said layered particle. The binder may comprise, based on the total weight of the layered particle, from about 0.001% to about 5%, or from about 0.5% to about 3%, or from about 1% to about 2% water. In one aspect, the binder can be substantially free of water. In one aspect, the binder may be capable of absorbing from about 0.1% to about 20%, or from about 1% to about 15%, or from about 2% to about 10% of water by weight of said binder on a 80% relative humidity at 32°C. In one aspect, the binder may have a viscosity of from about 200 to about 20,000, or from about 500 to about 7,000, or from about 1,000 to about 2,000 mPa.s (centipoise) at a shear rate of 25 s-1 to 25 °C

The binder may comprise, based on the total weight of binder, from about 40% to 100%, or from about 50% to about 99%, of a surfactant material selected from the group consisting of anionic surfactant, nonionic surfactant, and combinations of the same, more preferably alcohol ethoxylate and linear alkyl benzene sulfonate. In one aspect, the binder may comprise, based on the total weight of binder, from about 60% to about 100%, or from about 70% to about 90%, of a non-surfactant material comprising a hydrocarbon material selected from the group consisting of fats, triglycerides, lipids, fatty acids, soft paraffin waxes, and combinations thereof.

The binder may have a pH of from about 3 to about 9, or about 5 to about 8, or about 7, measured in a 10% solution in water. In one aspect, the binder may comprise a solvent.

The layered particle may comprise a dusting powder which may comprise a material selected from the group consisting of silicas, zeolites, amorphous aluminosilicates, clays, starches, celluloses, water-soluble salts, such as an inorganic salt selected from the group consisting of chloride sodium, sodium sulfate, magnesium sulfate, and salts and mixtures thereof, polysaccharides, including sugars, and combinations thereof.

The layer may comprise an additive selected from the group consisting of acid materials, moisture scavengers, gelling agents, antioxidants, organic catalysts, and combinations thereof.

In one aspect, the additive may comprise an acidic material having a pKa of from about 3 to about 7, or from about 5. In one aspect, the acidic material may be ascorbic acid.

In one aspect, the additive may comprise a moisture scavenger which may be selected from the group consisting of crosslinked polyacrylates, sodium maleic/acrylic copolymers, magnesium sulfate, and combinations thereof.

In one aspect, the additive may comprise a gelling agent which may be selected from the group consisting of a cellulose, including methyl cellulose and CMC, alginate and derivatives thereof, starches, polyvinyl alcohols, polyethylene oxide, polyvinylpyrrolidone, polysaccharides , including chitosan and/or natural gums, including carrageenan, xanthan gum, guar gum, locust bean gum, and combinations thereof, polyacrylates, including cross-linked polyacrylates, alcohol ethoxylates, lignosulfonates, surfactants and mixtures thereof, surfactants powdered anionics and combinations thereof.

In one aspect, the additive may comprise an antioxidant which may be selected from the group consisting of phenolic antioxidants, amine antioxidants, alkylated phenols, hindered phenolics, benzofuran or benzopyran, alpha-tocopherol, beta-tocopherol, gamma-tocopherol, delta -tocopherol and derivatives thereof, 6-hydroxy-2,5,7,8-tetra-methylchroman-2-carboxylic acid, ascorbic acid and its salts, butylated hydroxybenzoic acids and their salts, gallic acid and its alkyl esters, acid uric acid and its salts and alkyl esters, sorbic acid and its salts, amines, sulfhydryl compounds, dihydroxyfumaric acid and its salts, and combinations thereof, 2,6-di-ferc-butylphenol, 2,6-di-ferc- butyl-4-methylphenol, mixtures of 2 and 3-ferc-butyl-4-methoxyphenol, propyl gallate, ferrc-butylhydroquinone, benzoic acid derivatives such as methoxybenzoic acid, methylbenzoic acid, dichlorobenzoic acid, dimethylbenzoic acid, 5-hydroxy -2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzo furan-3-one, 5-hydroxy-3-methylene-2,2,4,6,7-pentamethyl-2.3-dihydro-benzofuran, 5-benzyloxy-3-hydroxymethyl-2,2,4,6,7- pentamethyl-2,3-dihydro-1-benzofuran, 3-hydroxymethyl-5-methoxy-2,2,4,6,7-pentamethyl-2,3-dihydro-1-benzofuran, ascorbic acid, 1,2-dihydro -6-ethoxy-2,2,4-trimethylquinoline and combinations thereof, 2,6-di-tert-butylhydroxytoluene, alpha-tocopherol, hydroquinone, 2,2,4-trimethyl-1,2-dihydroquinoline, 2, 6-di-ferc-butylhydroquinone, 2-ferc-butylhydroquinone, ferrc-butyl-hydroxyanisole, lignosulfonic acid and salts thereof, benzoic acid and derivatives thereof, trimethoxybenzoic acid, toluic acid, catechol, f-butyl catechol, benzylamine, amino alcohols , 1,1,3-tris(2-methyl-4-hydroxy-5-f-butylphenyl)butane, N-propyl gallate or mixtures thereof, or di-ferc-butylhydroxytoluene.

In one aspect, the additive may comprise an organic catalyst which may be selected from the group consisting of iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonyl imines, N-phosphonyl imines, N -acyl imines, thiadiazole dioxides, perfluoroimines, cyclic sugar ketones, and combinations thereof, or an organic catalyst selected from the group consisting of 2-[3-[(2-hexyldodecyl)oxy]-2-(sulfooxy)propyl ]-3,4-dihydroisoquinolinium, inner salt, 3,4-dihydro-2-[3-[(2-pentylundecyl)oxy]-2-(sulfooxy)propyl]isoquinolinium, inner salt, 2-[3-[( 2-butyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium inner salt, 3,4-dihydro-2-[3-(octadecyloxy)-2-(sulfooxy)propyl]isoquinolinium inner salt , 2-[3-(hexadecyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt, 3,4-dihydro-2-[2-(sulfooxy)-3-(tetradecyloxy)propyl]isoquinolinium , inner salt, 2-[3-(dodecyloxy)-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium , inner salt, 2-[3-[(3-hexyldecyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt, 3,4-dihydro-2-[3-[(2- pentylnonyl)oxy]-2-(sulfooxy)propyl]isoquinolinium, inner salt, 3,4-dihydro-2-[3-[(2-propylheptyl)oxy]-2-(sulfooxy)propyl]isoquinolinium, inner salt, 2 -[3-[(2-butyloctyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt, 2-[3-(decyloxy)-2-(sulfooxy)propyl]-3,4 -dihydroisoquinolinium, inner salt, 3,4-dihydro-2-[3-(octyloxy)-2-(sulfooxy)propyl]isoquinolinium, inner salt, 2-[3-[(2-ethylhexyl)oxy]-2-( sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt, or mixtures thereof, or 2-[3-[(2-butyloctyl)oxy]-2-(sulfooxy)propyl]-3,4-dihydroisoquinolinium, inner salt.

In one aspect, the layered particle may be substantially free of fatty acids, polyol fatty acid esters, polyglycols, and fatty alcohol oxalkylates.

chelating

The composition may comprise a chelant. Suitable chelants include diethylene-triamine-pentaacetate, diethylene-triamine-penta(methylenephosphonic) acid, ethylenediamine-N'N'-disuccinic acid, ethylenediamine-tetraacetate, ethylenediaminetetra(methylenephosphonic) acid, and hydroxyethane di(methylenephosphonic) acid. A preferred chelator is ethylenediamine-N'N'-disuccinic acid (EDDS) and/or hydroxyethane diphosphonic acid (HEDP). The laundry detergent composition preferably comprises ethylenediamine-N'N'-disuccinic acid, or salts thereof. Preferably, the ethylenediamine-N'N'-disuccinic acid is in the enantiomeric S'S' form. Preferably, the composition comprises the disodium salt of 4,5-dihydroxy-m-benzenedisulfonic acid.

Fabric Matting Agent

Suitable fabric shading agents include dyes, dye-clay conjugates, and pigments which preferably meet the needs of Test Method 1 described hereinafter. Suitable dyes include small dye molecules and polymeric molecules. Suitable small molecule dyes include small molecule dyes selected from the group consisting of dyes that fall within the color index (C.I.) classifications of Direct Blue, Direct Red, Direct Violet, Acid Blue, Acid Red, Acid Violet, Basic Blue, Basic Violet and Basic Red, or mixtures thereof, for example

(1) Direct blue dyes of the tris-azo type of formula

where at least two of the naphthyl rings A, B and C are substituted by a sulfonate group, ring C may be substituted in the 5-position by an NH ² or NHPh group, X is a benzyl or naphthyl ring substituted with up to 2 sulfonate groups and may be substituted at position 2 with an OH group and may also be substituted with an NH ² or NHPh group.

(2) Violet direct dyes of the bis-azo type of formula

where Z is H or phenyl, ring A is preferably substituted by a methyl and methoxy group at the positions indicated by arrows, ring A can also be a naphthyl-type ring, group Y is a benzyl ring or naphthyl ring, which is substituted by a sulfate group and can be mono- or di-substituted by methyl groups.

(3) Blue or red acid dyes of formula

where X and Y must be, at least one of the two, an aromatic group. In one aspect, both the aromatic groups can be a substituted benzyl or naphthyl group which can be substituted with non-water soluble groups, such as alkyl or alkoxy or aryloxy groups, X and Y can be unsubstituted with water soluble groups. such as sulfonates or carboxylates. In another aspect, X is a benzyl group substituted with a nitro group and Y is a benzyl group.

(4) Red acid structure dyes

where B is a naphthyl or benzyl group which may be substituted with water-insoluble groups such as alkyl or alkyloxy or aryloxy groups, B may be unsubstituted with water-soluble groups such as sulfonates or carboxylates.

(5) Dis-azo type dyes of the structure

wherein X and Y, independently of ^one another, are each hydrogen, C1- ^C4 alkyl or C1- ^{C4 alkoxy} , Ra is hydrogen or aryl, Z is C1- ^C4 alkyl, ^C1 - ^{C4 alkoxy} , halogen, hydroxyl or carboxyl, n is 1 or 2, and m is 0, 1 or 2, as well as the corresponding salts thereof and mixtures thereof.

(6) Triphenylmethane dyes of the following structures

and mixtures thereof. In another aspect, suitable small molecule dyes include small molecule dyes selected from the group consisting of number dyes, according to the Color Index (Society of Dyers and Colourists, Bradford, UK) Direct Violet 9, Direct Violet 35, Direct Violet 48, Direct Violet 51, Direct Violet 66, Direct Blue 1, Direct Blue 71, Direct Blue 80, Direct Blue 279, Acid Red 17, Acid Red 73, Acid Red 88, Acid Red 150, Acid Violet 15, Acid Violet 17 , Acid Violet 24, Acid Violet 43, Acid Red 52, Acid Violet 49, Acid Blue 15, Acid Blue 17, Acid Blue 25, Acid Blue 29, Acid Blue 40, Acid Blue 45, Acid Blue 75, Acid Blue 80, Acid Blue 83, Acid Blue 90 and Acid Blue 113, Acid Black 1, Basic Violet 1, Basic Violet 3, Basic Violet 4, Basic Violet 10, Basic Violet 35, Basic Blue 3, Basic Blue 16, Basic Blue 22, Basic Blue 47 , Basic Blue 66, Basic Blue 75, Basic Blue 159 and mixtures thereof. In another aspect, suitable small molecule dyes include suitable small molecule dyes selected from the group consisting of numbers, according to Color Index (Society of Dyers and Colourists, Bradford, UK) Acid Violet 17, Acid Violet 43, Acid Red 52, Acid Red 73, Acid Red 88, Acid Red 150, Acid Blue 25, Acid Blue 29, Acid Blue 45, Acid Blue 113, Acid Black 1, Direct Blue 1, Direct Blue 71, Direct Violet 51 and mixtures thereof . In another aspect, suitable small molecule dyes include suitable small molecule dyes selected from the group consisting of numbers, according to Color Index (Society of Dyers and Colourists, Bradford, UK) Acid Violet 17, Direct Blue 71, Direct Violet 51, Direct Blue 1, Acid Red 88, Acid Red 150, Acid Blue 29, Acid Blue 113 or mixtures thereof.

Suitable polymeric dyes include polymeric dyes selected from the group consisting of polymers containing conjugated chromogens (polymeric dye conjugates) and polymers with chromogens copolymerized in the polymer backbone and mixtures thereof.

In another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of high affinity tissue dyes sold under the name Liquitint® (Milliken, Spartanburg, South Carolina, USA), polymeric dye conjugates formed from from at least one reactive dye and a polymer selected from the group consisting of a hydroxyl moiety, a primary amine moiety, a secondary amine moiety, a thiol moiety, and mixtures thereof. In yet another aspect, suitable polymeric dyes include polymeric dyes selected from the group consisting of Liquitint® (Milliken, Spartanburg, South Carolina, USA) Violet CT, carboxymethyl cellulose (CMC) conjugated to a dye Reactive Blue, Reactive Violet or Reactive Red as, for example, CMC conjugated with the name dyes, according to the C.I. Reactive Blue 19, available from Megazyme, Wicklow, Ireland, under the product name AZO-CM-CELLULOSE, product code S-ACMC, alkoxylated triphenylmethane polymeric dyes, alkoxylated thiophene polymeric dyes, and mixtures thereof.

Suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of at least one cationic/basic dye and a smectite-type clay, and mixtures thereof. In another aspect, suitable dye-clay conjugates include dye-clay conjugates selected from the group consisting of a cationic/basic dye selected from the group consisting of CI Basic Yellow, 1 to 108, CI Basic Orange, 1 to 69, CI Basic Red, from 1 to 118, CI Basic Violet, from 1 to 51, CI Basic Blue, from 1 to 164, CI Basic Green, from 1 to 14, CI Basic Brown, from 1 to 23; CI Basic Black, from 1 to 11; and a clay selected from the group consisting of montmorillonite-type clay, hectorite-type clay, saponite-type clay, and mixtures thereof. In yet another aspect, suitable clay-dye conjugates include clay-dye conjugates selected from the group consisting of Basic Blue B7 Montmorillonite Conjugate CI 42595, Basic Blue B9 Montmorillonite Conjugate CI 52015, Basic Violet V3 Montmorillonite Conjugate CI 42555 , Montmorillonite conjugate Basic Green G1 CI 42040, Montmorillonite conjugate Basic Red R1 CI 45160, Montmorillonite conjugate CI Basic Black 2, Hectorite conjugate Basic Blue B7 CI 42595, Hectorite conjugate Basic Blue B9 CI 52015, Hectorite conjugate Basic Violet V3 CI 42555, conjugate of hectorite Basic Green G1 CI 42040, conjugate of hectorite Basic Red R1 CI 45160, conjugate of hectorite CI Basic Black 2, conjugate of saponite Basic Blue B7 CI 42595, conjugate of saponite Basic Blue B9 CI 52015, conjugate of Basic Violet V3 Saponite CI 42555, Basic Green G1 Saponite Conjugate CI 42040, Basic Red R1 Saponite Conjugate CI 45160, CI Basic Saponite Conjugate Black 2 conjugate and mixtures thereof.

Suitable pigments include pigments selected from the group consisting of flavantrone, indantrone, chlorinated indantrone containing 1 to 4 chlorine atoms, pyrantrone, dichloropyrantrone, monobromodichloropyrantrone, dibromodichloropyrantrone, tetrabromopyrantrone, perylene-3,4,9,10-acid diimide tetracarboxylic, where the imide groups can be unsubstituted or substituted by C1-C3 alkyl or a phenyl or heterocyclic radical, and where the phenyl and heterocyclic radicals can additionally bear substituents that do not confer water solubility, amides of the anthrapyrimidinecarboxylic acid, violanthrone, isoviolanthrone, dioxazine-type pigments, copper phthalocyanine, which may contain up to 2 chlorine atoms per molecule, polychloro-copper phthalocyanine or polybromochloro-copper phthalocyanine, which contains up to 14 bromine atoms per molecule, and mixtures of the same. In another aspect, suitable pigments include pigments selected from the group consisting of Ultramarine Blue (name C.I. Pigment Blue 29), Ultramarine Violet (C.I. Pigment Violet 15) and mixtures thereof.

The aforementioned fabric shading agents can be used in combination (any mixture of fabric shading agents can be used). Suitable fabric shading agents are available from Aldrich, Milwaukee, Wisconsin, USA, Ciba Specialty Chemicals, Basel, Switzerland, BASF, Ludwigshafen, Germany, Dayglo Color Corporation, Mumbai, India, Organic Dyestuffs Corp. , East Providence, Rhode Island, USA, Dystar, Frankfurt, Germany, Lanxess, Leverkusen, Germany, Megazyme, Wicklow, Ireland, Clariant, Muttenz, Switzerland, Avecia, Manchester, UK, and/or made according to the examples contained in this report.

Suitable shading agents are described in US 7,208,459 B2.

test method 1

The following is a protocol for defining whether a dye or pigment material is a fabric shading agent for the purpose of the present invention.

1.) Fill two Tergotometer vessels with 800ml of Newcastle upon Tyne, UK mains water (~12 grains per US gallon total hardness, supplied by Northumbrian Water, Pity Me, Durham, Co. Durham, United Kingdom).

2) Insert the containers in the tergotometer-type apparatus, with the water temperature controlled at 30 0C and the agitation set at 40 rpm for the duration of the experiment.

3) Add 4.8 g of IEC-B detergent (Type B detergent for IEC 60456 base reference washing machine), supplied by wfk, Brüggen-Bracht, Germany, to each container.

4) After two minutes, add 2.0 mg of active dye to the first container.

5) After one minute, add 50g plain cotton T-shirt (supplied by Warwick Equest, Consett, County Durham, UK), cut into 5cm x 5cm swatches, to each container.

6) After 10 minutes, empty the containers and refill them with cold water (16°C) with a hardness of 14.4 English Clark degrees with a calcium to magnesium molar ratio of 3:1.

7) After 2 minutes of rinsing, remove the fabrics.

8) Repeat steps 3-7 for three more cycles using the same treatments.

9) Collect and hang the fabrics in a closed area for 12 hours to dry.

10) Analyze samples using a Hunter Miniscan spectrometer equipped with D65 illuminant and UVA filter to obtain Hunter a (red-green axis) and Hunter b (yellow-blue axis) values.

11) Average the Hunter a and Hunter b values for each set of tissues. If the dye-treated fabrics under assessment show an average hue difference greater than 0.2 units on either the a-axis or the b-axis, it is considered to be a fabric-shaping agent for the purpose of the invention.

Enzyme

Most preferably, the laundry detergent composition comprises enzymes. Suitable enzymes include

1. Enzymes derived from EC 1.1.3.x (oxidoreductases that act on CH-OH as donors and with oxygen as acceptor). Examples of suitable oxidoreductases classified as EC 1.1.3.x are glucose oxidase, aryl alcohol oxidase and galactose oxidase. A suitable hexose oxidase is OxyGo® 1500 (Danisco).

2. Enzymes derived from E.C. 1.11.x.x (oxidoreductases that act on peroxide as an acceptor). An example of a suitable oxidoreductase that acts on peroxide as an acceptor is Guardzyme® (Novozymes).

3. Enzymes derived from E.C. 2.3.x.x (acyl transferases).

4. Enzymes derived from E.C. 2.4.x.x (glycosyl transferases).

5. Enzymes derived from E.C. 3.1.1.1 (carboxyl esterase).

6. Enzymes derived from EC 3.1.1.3 (triacylglycerol lipase). Lipases having the EC classification 3.1.1.3, as defined by the EC classification, IUPAC-IUBMB. Suitable lipases include both the wild type and their genetically modified variants that have at least about 90%, at least about 95%, at least about 98%, or at least about 99%, or 100% identity to said lipase. In one aspect, the lipase is a variant of the natural lipase from Thermomyces lanuginosus comprising the T231R and N233R mutations. The natural sequence is 269 amino acids (amino acids 23-291) of Swissprot Swiss-Prot accession number O59952 (derived from Thermomyces lanuginosus ( Humicola lanuginosa). Suitable commercially available lipases include Lipolase®, Lipolase Ultra®, Lipex ® and Lipolex®, all available from Novozymes A/S.

7. Enzymes derived from E.C. 3.1.1.20 (tannase). Suitable tannases are described in WO 06/002955A2.

8. Enzymes derived from E.C. 3.1.1.42 (chlorogenate hydrolase).

9. Enzymes derived from EC 3.1.1.73 (feruloil esterase). Suitable ferulic acid esterases are derived from Aspergillus awamori, Aspergillus tubingensis, Aspergillus niger, Talaromyces stipatus, Piromyces equiv. Cellvibrio japonicus, Talaromyces stipatus and Clostridium japonicus. Other ferulic acid esterases are described in Acta Biochimica et Biophysica Sinica, 2007, 39(11):811-828, which has been incorporated by reference herein.

10. Enzymes derived from EC 3.1.1.74 (cutinase). In one aspect, the enzyme may comprise a cutinase as defined in EC Class 3.1.1.73. The enzyme may have at least about 90%, or about 95%, or about 98% identity to a native one from one of Fusarium solani, Pseudomonas mendocina, or Humicola insolens.

11. Enzymes derived from EC 3.2.1.1 (α-amylase). Alpha amylases belong to EC Class 3.2.1.1. Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified mutants (variants) are included. A preferred alkaline alpha-amylase is derived from a Bacillus strain, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp., such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, DSM 9375 (USP 7,153,818) DSM 12368, DSMZ #12649, KSM AP1378 (WO-97/00324), KSM K36 or KSM K38 (EP 1,022,334). Preferred amylases include

(a) Variants described in WO 94/02597, WO 94/18314, WO 96/23874 and WO 97/43424, especially variants with substitutions at one or more of the following positions to the enzyme listed as Id. sec. No. 2 in WO 96/23874. 15, 23, 105, 106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243, 264, 304, 305, 391,408 and 444,

(b) the variants described in USP 5,856,164 and WO99/23211, WO96/23873, WO00/60060 and WO06/002643, especially variants with one or more substitutions at the following positions with respect to the AA560 enzyme listed as Id. sec. #12 in WO06/002643 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441,444, 445, 446, 447, 450, 461, 471, 482, 484, preferably also containing the D183* and G184* deletions, and

(c) variants that have at least 90% identity with seq. No. 4 in WO-06/002643, the natural enzyme from Bacillus SP722, especially the variants with deletions at positions 183 and 184 and the variants described in WO-00/60060, which have been incorporated by reference herein memory. Suitable commercial alpha-amylases are DURAMYL®, LIQUEZYME® TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL® and BAN® (Novozymes A/S), BIOAMYLASE-D(G), BIOAMYLASE ® L (Biocon India Ltd.), KEMZYM® AT 9000 (Biozym Ges. mbH, Austria), RAPIDASE®, PURASTAR®, OPTISIZE HT PLUS® and PURASTAR OXAM® (Genencor International Inc.) and KAM® (KAO, Japan) . In one aspect, the preferred amylases are NATALASE®, STAINZYME® and STAINZYME PLUS®.

12. Enzymes derived from EC 3.2.1.2 (p-amylase).

13. Enzymes derived from EC 3.2.1.4 (cellulase), EC 3.2.1.21 (p-glucosidase) and EC 3.2.1.91 (cellulose 1,4-pcellobiosidase). Suitable cellulases include cellulases from the genera Bacillus , Pseudomonas , Humicola , Fusarium , Thielavia , Acremonium , e.g. eg, the fungal cellulases produced from Humicola insolens , Myceliophthora thermophila , Fusarium oxysporum described in US-4,435,3077, US-5,648,263, US-5,691,178, US-5,776,757 and WO-89/09259. Other suitable cellulases are alkaline or neutral cellulases which have color care benefits. Examples of these cellulases are the cellulases described in EP-0495 257, EP-0 531 372, WO 96/11262, WO 96/29397, Wo 98/08940. Other examples are cellulase variants such as those described in WO 94/07998, EP-0531 315, US-5,457,046, US-5,686,593, US-5,763,254, WO 95/24471, WO 98/12307 and WO 99/01544, and WO 01/062903. Commercially available cellulases include Celluclean®, Celluzyme®, Renozyme® and Carezyme®, (Novozymes A/S), Clazinase® and Puradax HA®, (Genencor International Inc.) and KAC® 500, (Kao Corporation) and the sold under the trade names Biotouch® and Ecostone® (AB Enzymes). Especially suitable cellulases are variants of Family 44 cellulases showing xyloglucanase activity described in WO 2001/062903 (Novozymes).

14. Enzymes derived from E.C. 3.2.1.20 (a-glucosidase).

15. Enzymes derived from E.C. 3.2.1.25 (p-mannosidase) and E.C. 3.2.1.78 (mannan endo-1,4-p-mannosidase). Mannan endo-1,4-p-mannosidases are described in WO 99/09126, WO99/64573 and WO99/09128. Preferred mannanases are available under the trade names Mannaway® (Novozymes A/S) and Purabrite® (Genencor International).

16. Enzymes derived from E.C. 3.2.1.151 (xyloglucan-specific endo-p-1,4-glucanase).

17. Enzymes derived from E.C. 3.2.1.155 (xyloglucan-specific exo-p-1,4-glucanase).

18. Enzymes derived from E.C. 3.4.x.x (peptidases). Suitable proteases include those of animal, vegetable or microbial origin. Those of microbial origin are preferred. Chemically or genetically modified mutants are included. The protease may be a serine protease, preferably a microbial alkaline protease or a trypsin-like protease. Examples of neutral or alkaline proteases include

(a) subtilisins (EC 3.4.21.62), especially those derived from Bacillus, such as Bacillus lentus, B. alkalilophilus, B. subtilis, B. amyloliquefaciens, Bacillus pumilus and Bacillus gibsonii, and Cellumonas, described in US-6,312,936 B1, US-5,679,630, US-4,760,025, US-5,030,378, WO-05/052146, DEA6022216A1 and DEA 6022224A1,

(b) trypsin-like proteases which are trypsin (eg, of porcine or bovine origin) and the Fusarium protease described in WO-89/06270, and

(c) metalloproteases, especially those derived from Bacillus amyloliquefaciens described in WO-07/044993A2. Preferred proteases are those derived from the BPN' and Carlsberg families, especially the subtilisin BPN' protease derived from Bacillus amyloliquefaciens. In one aspect, the protease is a variant of the native Bacillus amyloliquefaciens -derived subtilisin BPN' enzyme containing the Y217L mutation. The natural BPN' subtilisin enzyme sequence is 275 amino acids (amino acids 108-382) from Swissprot accession number P00782 (derived from Bacillus amyloliquefaciens ). Suitable commercial preferred protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Ovozyme®, Neutrase®, Everlase® and Esperase® from Novozymes A/S (Denmark), those marketed under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase® and Purafect OXP® from Genencor International, and sold under the trade names Opticlean® and Optimase® by Solvay Enzymes. In one aspect, the preferred protease is that sold under the tradename Purafect Prime®, supplied by Genencor International.

19. Enzymes derived from E.C. 4.2.2.2 (pectate lyase). In one aspect, the enzyme may comprise a pectate lyase. Suitable pectate lyases are described in WO 00/42151 and WO 00/42147. Suitable pectate lyases are available under the trade names Pectawash® and Pectaway® by Novozymes A/S.

20. Enzymes derived from E.C. 4.2.2.10 (pectin lyase).

detersive surfactant

The composition comprises more than 1% by weight of detersive surfactant, preferably from 10% by weight to 40% by weight, preferably 12% by weight, or 15% by weight, or even 18% by weight of detersive surfactant. Preferably, the surfactant comprises alkylbenzene sulfonate and one or more detersive cosurfactants. The surfactant preferably comprises a C ¹⁰ -C ¹³ alkylbenzene sulfonate and one or more cosurfactants. The cosurfactants are preferably selected from the group consisting of ethoxylated C ¹² -C ¹⁸ alkyl alcohols, preferably having an average degree of ethoxylation of 1 to 7, ethoxylated C ¹² -C ¹⁸ alkyl sulfates, preferably having an average degree of ethoxylation of 1 to 5, and mixtures thereof. However, other surfactant systems may be suitable for use in the present invention.

Suitable detergent surfactants include anionic detergent surfactants, nonionic detergent surfactants, cationic detergent surfactants, zwitterionic detergent surfactants, amphoteric detergent surfactants, and mixtures thereof.

Suitable anionic detersive surfactants include: alkyl sulfates, alkyl sulfonates, alkyl phosphates, alkyl phosphonates, alkyl carboxylates, and mixtures thereof. The anionic surfactant may be selected from the group consisting of ^C10 - ^C18 alkylbenzene sulfonates (LAS), preferably C10-C13 alkylbenzene sulfonates, primary, branched-chain, straight-chain, and ^C10 - ^{C20 alkylsulfonates} ( ^AS ). random string, typically having the following formula

CH3(CH2)xCH2-OSO3-M+

where M is hydrogen or a cation providing charge neutrality, preferred cations are sodium and ammonium cations, where x is an integer of at least 7, preferably at least 9, C ¹⁰ -C ¹⁸ alkyl sulphates secondary (2,3), which typically have the following formulas

OS03“M+ ^bear 3' ^m +

CH3(CH2) ^x ÍCH)CH ^j OR CH3(CH2)y¿H)CH2CH3

where, M is hydrogen or a cation providing charge neutrality, preferred cations include sodium and ammonium cations, where x is an integer of at least 7, preferably at least 9, y is an integer of at least 8, preferably at least 9, C ¹⁰ -C ¹⁸ alkylalkoxycarboxylates, medium chain branched alkyl sulphates, as described, in greater detail, in US 6,020,303 and US 6,060,443, Modified Alkylbenzene Sulfonate (MLAS), as is described in more detail in WO-99/05243, WO-99/05242, WO-99/05244, WO-99/05082, WO-99/05084, WO-99/05241, WO-99/07656, WO-00/23549 and WO-00/23548, Methyl ester sulfonate (MES), alpha-olefin sulfonate and mixtures thereof.

Preferred anionic detersive surfactants include: substituted or unsubstituted, linear or branched alkylbenzene sulfonate detersive surfactants, preferably C ⁸ -C ¹⁸ linear alkylbenzene sulfonate detersive surfactants, substituted or unsubstituted linear or branched alkylbenzene sulfonate detersive surfactants, detersive surfactants substituted or unsubstituted, linear or branched alkyl sulfate, including C ⁸ -C ¹⁸ linear alkyl sulfate detersive surfactants, C ⁸ -C ¹⁸ alkyl branched C ¹ -C ³ alkyl sulfate detersive surfactants, C ⁸ -alkyl sulfate detersive surfactants C ¹⁸ alkoxylated, linear or branched, and mixtures thereof, linear or branched, substituted or unsubstituted alkyl sulfonate detersive surfactants, and mixtures thereof.

Preferred alkyl alkoxylated sulphate detersive surfactants are substituted or unsubstituted linear or branched C ^8-18 alkyl alkoxylated detersive surfactants having an average degree of alkoxylation of 1 to 30, preferably 1 to 10. Preferably, the alkyl sulphate detersive surfactant alkoxylated is a substituted or unsubstituted, linear or branched, ethoxylated C ^8-18 alkyl sulfate having an average degree of ethoxylation of from 1 to 10. Most preferably, the alkoxylated alkyl sulfate detersive surfactant is a linear, ethoxylated C ^8-18 alkyl ^sulfate . unsubstituted, having an average degree of ethoxylation of 3 to 7. Preferably, the laundry detergent composition comprises an ethoxylated alkyl sulfate having an average degree of ethoxylation of 0.5 to 3.5, preferably 1.0 to 3.0, and preferably 1.0 or 3.0.

Preferred anionic detersive surfactants are selected from the group consisting of substituted or unsubstituted C ^12-18 linear or branched alkyl sulfates, substituted or unsubstituted C ^10-13 linear or branched alkylbenzene sulfonates, preferably C ^10-13 linear alkylbenzene sulfonates, and mixtures thereof. Linear C ^10-13 alkylbenzene sulfonates are highly preferred. Highly preferred are linear C ^10-13 alkylbenzene sulfonates obtainable, preferably obtainable, by sulfonation of commercially available linear alkylbenzenes (LAB); suitable LABs include short chain 2-phenyl LABs, such as those supplied by Sasol under the tradename Isochem® or those supplied by Petresa under the tradename Petrelab®; Other suitable LABs include long chain 2-phenyl LABs, such as those supplied by Sasol under the tradename Hyblene®. An anionic detersive surfactant is an alkylbenzene sulfonate that is obtained by the DETAL catalyzed process, although other synthetic routes, such as HF, may also be suitable. Preferably, the laundry detergent composition predominantly comprises a C12 alkyl sulphate.

Suitable cationic detersive surfactants include alkylpyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl ternary sulfonium compounds, and mixtures thereof. The cationic detersive surfactant may be selected from the group consisting of alkoxylated quaternary ammonium (AQA) surfactants, as described in greater detail in US-6,136,769, dimethyl hydroxyethyl quaternary ammonium surfactants, as described in greater detail , in US-6,004,922, cationic polyamine surfactants, as described, in greater detail, in WO-98/35002, WO-98/35003, WO-98/35004, WO-98/35005 and WO-98/ 35006, cationic ester surfactants, as described, in greater detail, in US-4,228,042, US-4,239,660, US-4,260,529, and US-6,022,844, amino surfactants, as described, in more detail, in US-6,221,825 and WO-00/47708, specifically amidopropyl dimethylamine, and mixtures thereof. Preferred cationic detersive surfactants are quaternary ammonium compounds having the general formula

(R)(R1)(R2)(R3)N+ X-

wherein R is a substituted or unsubstituted straight or branched C ^6-18 alkyl or alkenyl moiety, R ¹ and R ² are independently selected from methyl or ethyl moieties, R ³ is a hydroxyl, hydroxymethyl or hydroxyethyl, X is an anion providing charge neutrality; preferred anions include halides (such as chloride), sulfate, and sulfonate. Preferred cationic detersive surfactants are C ^6-18 monoalkyl mono-hydroxyethyl dimethyl quaternary ammonium chlorides. Highly preferred cationic detersive surfactants are mono-C ^8-10 alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride, mono-C ^10-12 alkyl monohydroxyethyl dimethyl quaternary ammonium chloride and mono-C ¹⁰ alkyl mono-hydroxyethyl dimethyl quaternary ammonium chloride.

Suitable nonionic detersive surfactant may be selected from the group consisting of: C ⁸ -C ¹⁸ alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell, C ⁶ -C ¹² alkylphenol alkoxylates, wherein the alkoxylate units are ethyleneoxy units, propyleneoxy units or a mixture thereof, C ¹² -C ¹⁸ alcohol and C ⁶ -C ¹² alkylphenol condensates with ethylene oxide/propylene oxide block polymers, such as BASF's Pluronic®, C medium chain branched alcohols ¹⁴ -C ²² , ^BA , as described, in greater detail, in US ^Pat . in greater detail, in US-6,153,577, US-6,020,303 and US-6,093,856, alkyl polysaccharides, as described, in greater detail, in US-4,565,647, specifically alkyl polyglucosides, as described, in greater detail , in US-4,483,780 and US-4,483,779, polyhydroxy fatty acid amides, as described, in greater d detail, in US-5,332,528, WO-92/06162, WO-93/19146, WO-93/19038 and WO-94/09099, ether-capped poly(oxyalkylated) alcohol surfactants, as described, in greater detail, in US-6,482,994 and WO-01/42408, and mixtures thereof.

The nonionic detersive surfactant could be an alkyl polyglucoside and/or an alkoxylated alkyl alcohol. Preferably the nonionic detersive surfactant is a substituted or unsubstituted linear or branched C ^8-18 alkyl ethoxylated alcohol having an average degree of ethoxylation from 1 to 10, more preferably 3 to 7.

amphiphilic graft copolymer

The laundry detergent composition preferably comprises an amphiphilic graft copolymer, preferably the amphiphilic graft copolymer comprises (i) a polyethylene glycol backbone and (ii) and at least one pendant moiety selected from polyvinyl acetate, polyvinyl alcohol ) and mixtures thereof. A preferred amphiphilic graft copolymer is Sokalan HP22, supplied by BASF.

cellulosic type polymer

Preferably, the laundry detergent composition comprises a cellulosic-type polymer. The cellulosic polymer can be any polymer that is, or is derived from, cellulose. Suitable cellulosic-type polymers include anionically modified celluloses, nonionically modified celluloses, cationically modified celluloses, zwitterionically modified celluloses, and any mixtures thereof. Suitable cellulosic-type polymers can be both ionically modified and non-ionically modified, such as a cellulose that is modified by the incorporation of both an alkyl and a carboxymethyl substituent moiety.

The cellulosic polymer is typically a cellulose or a modified cellulose. Suitable cellulosic-type polymers include cellulose, cellulose ethers, cellulose esters, cellulose amides, and mixtures thereof. Suitable cellulosic-type polymers include anionically modified cellulose, nonionically modified cellulose, cationically modified cellulose, zwitterionically modified cellulose, and mixtures thereof. Cellulosic-type polymers include methyl cellulose, carboxymethyl cellulose, ethyl cellulose, hydroxyl ethyl cellulose, hydroxyl propyl methyl cellulose, carboxymethyl cellulose ester, and mixtures thereof.

Other suitable cellulosic-type polymers include cationic cellulose and derivatives thereof. Suitable cationic cellulose is available from Amerchol Corp. (Edison, NJ, USA) in its JR™ and LR™ series of polymers. Another suitable cationic cellulose is in the form of a hydroxyethylcellulose salt which is reacted with a trimethylammonium substituted epoxide, such as that supplied by Amerchol Corp. under the trade name Polyquaternium 10™. Another suitable type of cationic cellulose includes the quaternary ammonium salts of hydroxyethylcellulose which has been reacted with a lauryl dimethyl ammonium substituted epoxide, such as that supplied by Amerchol Corp. under the trade name Polyquaternium 24™. Suitable cellulosic polymers are supplied by Amerchol Corp. under the trade name Polymer LM-200™. Other suitable cellulosic-based polymers include TYLOSE MH50™ methylhydroxyethylcellulose and METHOCEL F4M™ hydroxypropylmethylcellulose. Other suitable cellulosic-based polymers include quaternary nitrogen-containing cellulose ethers, such as those described, in more detail, in US-3,962,418, and copolymers of etherified cellulose and starch, such as those described, in greater detail, in US-3,958,581.

Most preferably, the cellulosic polymer is carboxymethyl cellulose, typically with the following general formula

and wherein at least one R moiety is CH ² COO-.

Preferred cellulosic-based polymers are selected from the group consisting of cellulose, carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, alkyl cellulose, mixed alkyl and carboxy methyl cellulose, and mixtures thereof. Highly preferred are carboxymethyl cellulose and/or methyl cellulose. The most preferred cellulosic type polymers are carboxymethyl cellulose.

polymeric carboxylate

The composition preferably comprises a polymeric carboxylate. It may be preferred that the composition comprises at least 5%, or at least 6%, or at least 7%, or at least 8%, or even at least 9%, by weight of the composition, of polymeric carboxylate. The polymeric carboxylate can sequester free calcium ions in the wash solution. The carboxylate polymer can also act as a soil dispersant and can provide a particulate stain removal cleaning benefit. Preferred polymeric carboxylates include polyacrylates, preferably having a weight average molecular weight of 1,000 Da to 20,000 Da, copolymers of maleic acid and acrylic acid, preferably having a molar ratio of maleic acid monomers to acrylic acid monomers of 1 :1 to 1:10 and a weight average molecular weight of 10,000 Da to 200,000 Da or preferably having a molar ratio of maleic acid monomers to acrylic acid monomers of 0.3:1 to 3:1 and a weight weight average molecular weight from 1,000 Da to 50,000 Da.

Zeolite-type detergent builder

Preferably, the composition comprises 0% by weight to 10% by weight of builder, preferably 8% by weight, or 6% by weight, or 4% by weight, or even 2% by weight of builder. detergent builder. The composition may even be substantially free of builder, "substantially free" means "not deliberately added". Detergency builders are Zeolite A, Zeolite P and Zeolite MAP.

Phosphate-type builder

Preferably, the composition comprises 0% by weight to 10% by weight of phosphate builder, preferably 8% by weight, or 6% by weight, or 4% by weight or even 2% by weight. of phosphate-type builder. The composition may even be substantially free of phosphate builder, substantially free means "not deliberately added". A typical phosphate builder is sodium tri-polyphosphate.

carbonate source

The composition may comprise a carbonate source. Preferred carbonate sources include sodium carbonate and/or sodium bicarbonate. A highly preferred source of carbonate is sodium carbonate. Sodium percarbonate can also be used as the carbonate source. Preferably, the composition comprises from 0% by weight to 10% by weight of sodium carbonate.

Other detergent ingredients

The composition typically comprises other detergent ingredients. Suitable detergent ingredients include transition metal catalysts, enzymes, such as amylases, carbohydrases, cellulases, laccases, lipases, bleach enzymes, such as oxidases and peroxidases, proteases, pectatolyases, and mannanases, suds suppressor systems, such as silicone-based suds, rinse aids, shading agents, photobleachers, fabric softening agents, such as clay, silicone, and/or quaternary ammonium compounds, flocculants, such as polyethylene oxide, dye transfer inhibitors, such as polyvinylpyrrolidone, poly 4-N-oxide vinylpyridine and/or copolymer of vinylpyrrolidone and vinylimidazole, components for fabric integrity, such as oligomers produced by the condensation of imidazole and epichlorohydrin, soil dispersants and soil redeposition aids, such as alkoxylated polyamines and ethoxylated ethyleneimine polymers , anti-redeposition components, such as polyesters, perfumes, such as perfume microcapsules, soap rings, aesthetic particles, dyes, fillers, such as sodium sulfate, although it is preferred that the composition be substantially free of fillers, silicate salt, such as sodium silicate, including 1.6R and 2.0R sodium silicate, or sodium metasilicate, copolyesters of dicarboxylic acids and diols, cellulosic polymers, such as methyl cellulose, carboxymethyl cellulose, hydroxyethoxy cellulose, or other alkyl or alkylalkoxy cellulose and any combination thereof.

reserve alkalinity

Typically, the laundry detergent composition has a reserve alkalinity of at least 5.0, preferably at least 5.5, or at least 6.0, or at least 6.5, or at least 7.0. , or at least 7.5, or at least 8.0, or at least 8.5, or at least 9.0, or at least 9.5, or at least 10.0, or at least 10.5, or at least 11.0, or at least 11.5, or at least 12.0, or at least 13, or at least 14, or at least 15, or at least 16, or at least 17, or at least 18 , or at least 19 or at least 20. Preferably, the reserve alkalinity will not exceed 100.

As used herein, the term "reserve alkalinity" is a measure of the buffering capacity of the laundry detergent composition (g/NaOH/100g detergent composition) determined by titrating a 1% (w/v) solution of detergent composition with hydrochloric acid at pH 7.5, i.e. to calculate reserve alkalinity as defined below

Reserve alkalinity (up to pH 7.5) as % alkali in g NaOH/100 g product = T x M x 40 x Vol.

10 x weight x aliquot

T = Volumetric titration (ml) up to pH 7.5

M = Molarity of HCl = 0.2

40 = Molecular weight of NaOH

Vol = Total volume (ie 1000 ml)

W = Weight of product (10 g)

Aliquot = (100 mL)

Obtain a sample of 10 g weighed with an accuracy of two decimal places, of a fully formulated detergent composition. The sample should be obtained using a Pascall sampler in a dust-tight compartment. Add the 10 g sample to a plastic beaker and add 200 ml of carbon dioxide-free deionized water. Shake using a magnetic stirrer on a stir plate at 150 rpm until completely dissolved and for at least 15 minutes. Transfer the contents of the beaker to a 1-liter volumetric flask and adjust the volume to 1 liter with deionized water. Mix well and immediately take a 100 ml ± 1 ml aliquot using a 100 ml pipet. Measure and record the pH and temperature of the sample using a pH-meter capable of reading to ±0.01 pH units, with stirring, ensuring that the temperature is 21 °C /- 2 °C. Titrate volumetrically while stirring with 0.2 M hydrochloric acid until the pH is exactly 7.5. Record the milliliters of hydrochloric acid used. Take the average title of three identical repetitions. Perform the calculations described above to calculate RA at pH 7.5.

Preferably, the reserve alkalinity of the detergent composition will be greater than 7.5 and preferably greater than 8. The reserve alkalinity may be greater than 9 or even greater than 9.5 or 10, or greater. The AR can be up to 20 or higher.

A suitable reserve of alkalinity can be provided, at least in part, for example, by one or more of the alkali metal silicates (excluding crystalline layered silicate), typically amorphous silicate salts; generally sodium salts in a 1.0 to 2.2 ratio, alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates, persalts such as perborates and percarbonates also contribute to alkalinity . Sodium percarbonate can also be used. Most preferably, the laundry detergent composition comprises a source of alkalinity selected from sodium metasilicate, sodium hydroxide, and mixtures thereof.

pH

Preferably, the laundry detergent composition has a pH of less than 11.0 at a concentration of 1 g/l in deionized water at a temperature of 20°C. Preferably, the laundry detergent composition has a pH below 10.5, or below 10.0 or even below 9.5 at a concentration of 1 g/l in deionized water at a temperature of 20°C.

However, the laundry detergent can have a pH of at least 11.0 at a concentration of 1 g/L in deionized water at a temperature of 20 °C. If the laundry detergent composition has such high pH profiles, then preferably, the laundry detergent composition comprises more than 10% by weight, preferably more than 12% by weight, or more than 15% by weight, or more than 17% by weight, or more than 20% by weight, or more than 22% by weight, or more than 25% by weight of source of alkalinity.

Preferred sources of alkalinity include alkali metal silicates (excluding crystalline layered silicate), typically amorphous silicate salts; generally sodium salts in a 1.0 to 2.2 ratio, alkali metal typically sodium carbonate, bicarbonate and/or sesquicarbonates, persalts such as perborates and percarbonates also contribute to alkalinity . Sodium percarbonate can also be used. Most preferably, the laundry detergent composition comprises a source of alkalinity selected from sodium metasilicate, sodium hydroxide, and mixtures thereof.

The pH can be determined by dissolving or diluting the laundry detergent composition to a concentration of 1 g/l at a temperature of 20°C and the pH can be determined by any suitable method, such as the use of a pH meter.

Examples (not according to the invention)

30 g of the following free-flow laundry detergent compositions were used to wash 3.0 kg of fabric in a front-loading Miele 3622 automatic washing machine (13 L wash solution volume, short wash cycle (1 h). , 25 min), 12 °C wash temperature).

Claims (14)

Yo. A method for washing fabrics comprising the step of contacting a laundry detergent composition with water to form a wash solution and washing the fabric in said wash solution, wherein the wash solution has a temperature of more than from 0°C to 20°C and wherein the laundry detergent composition comprises more than 1% by weight of detersive surfactant and other detergent ingredients, including a layered particle, wherein the layered particle comprises a core and a layer, in wherein the core comprises a source of hydrogen peroxide, wherein the layer comprises a binder and a bleach activator, and wherein the weight ratio of the source of hydrogen peroxide to the bleach activator present in the layered particle is in the range from about 5:1 to about 1.1:1. A method according to claim 1, wherein the laundry detergent composition further comprises a perfume microcapsule. A method according to claim 1 or 2, wherein the laundry detergent composition comprises a bleaching ingredient selected from. (a) bleaching ingredient having a logPo/w value of no greater than about 0, wherein the bleaching ingredient is capable of generating species having an Xso value of from about 0.01 to about 0.30 and preferably having a structure that corresponds to the following general formula:

wherein R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, isodecyl, iso-tridecyl and iso-pentadecyl; I (b) transition metal bleach catalyst; I (c) preformed peracid; I (d) source of coated hydrogen peroxide, preferably the bleach ingredient is encapsulated or coated, and preferably the laundry detergent composition comprises from greater than 0% by weight to 10% by weight of hydrogen peroxide source A method according to any preceding claim, wherein the laundry detergent composition comprises a chelator selected from.

ethylenediamine-N'N'-disuccinic acid or salt thereof (EDDS), and/or (b) 4,5-dihydroxy-m-benzenedisulfonic acid disodium salt. A method according to any preceding claim, wherein the laundry detergent composition comprises a shading agent. A method according to any preceding claim, wherein the laundry detergent composition comprises an enzyme. A method according to any preceding claim, wherein the laundry detergent composition has one of the following characteristics: (a) a reserve alkalinity of 5 or higher; I (b) a pH less than 11.0 at a concentration of 1 g/l in deionized water at a temperature of 20 °C; either (c) comprises more than 10.0% by weight of alkalinity source, and has a pH of at least 11.0 at a concentration of 1 g/l in deionized water at a temperature of 20°C. A method according to any preceding claim, wherein the laundry detergent composition comprises: (a) from 0% by weight to less than 10% by weight of zeolite-type builder. Y (b) from 0% by weight to less than 10% by weight of phosphate builder. A method according to any preceding claim, wherein the laundry detergent composition comprises a detersive surfactant selected from: (a)

ethoxylated alkyl sulfate having an average degree of ethoxylation of 0.5 to 3.5; and/or (b) predominantly, C ¹² alkyl sulfate. A method according to any preceding claim, wherein the laundry detergent composition comprises a polymer selected from: (a) an amphiphilic graft polymer, preferably the amphiphilic graft polymer comprises: (i) a polyethylene glycol backbone; Y (ii) at least one pendant moiety selected from poly(vinyl acetate), poly(vinyl alcohol) and mixtures thereof; I (b)

cellulosic type polymer, preferably carboxymethyl cellulose; I (c) polymeric carboxylate; I (d) cationic polymer. A method according to any preceding claim, wherein the laundry detergent composition is in a form selected from: (a) solid; I (b)

liquid; I (c) unit dose. A method according to any preceding claim, wherein the laundry detergent composition comprises from 0% by weight to 40% by weight of water, preferably from 0% by weight to 20% by weight of water, more preferably from 0 % by weight to 10% by weight of water. A method according to any preceding claim, wherein the wash solution has a temperature of more than 0 0C to 15 0C, preferably 0 0C to 10 0C. 14. A method for washing fabrics comprising the step of contacting a solid laundry detergent composition with water to form a wash solution and washing the fabric in said wash solution, wherein the wash solution has a temperature of greater than 00C to 20 °C and wherein the solid laundry detergent composition comprises: (a)

ethoxylated alkyl sulfate having an average degree of ethoxylation of 0.5 to 3.5; (b) from 0% by weight to 10% by weight of zeolite-type builder; (c) from 0% by weight to 10% by weight of phosphate builder; (d) enzyme; (e) bleach catalyst having a structure corresponding to the following general formula:

wherein R13 is selected from the group consisting of 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, iso-nonyl, isodecyl, iso-tridecyl and iso-pentadecyl, (f) layered particle, wherein the layered particle comprises a core and a layer, wherein the core comprises a source of hydrogen peroxide, wherein the layer comprises a binder and a bleach activator, and wherein the weight ratio of hydrogen peroxide source to bleach activator is from about 5:1 to about 1.1:1, (g) optionally, transition metal bleach catalyst; (h) optionally, shading agent; Y (i) optionally from 0% by weight to 10% by weight of sodium carbonate.