WO1998000501A1

WO1998000501A1 - Detergent composition comprising dianionic cleaning agent and an enzyme

Info

Publication number: WO1998000501A1
Application number: PCT/US1997/010751
Authority: WO
Inventors: Jean-Luc Bettiol; Peter Robert Foley; Alison Lesley Main; Barry Thomas Ingram; Stephen Wayne Heinzman
Original assignee: The Procter & Gamble Company
Priority date: 1996-06-28
Filing date: 1997-06-20
Publication date: 1998-01-08
Also published as: MA24230A1; ZA975699B; AU3496597A

Abstract

According to the present invention there is provided a detergent composition comprising a dianionic cleaning agent and an enzyme.

Description

DETERGENT COMPOSITION COMPRISING DIANIONIC CLEANING AGENT AND AN ENZYME

Technical Field

The present invention relates to a detergent composition comprising a dianionic cleaning agent in combination with an enzyme exhibiting improved cleaning benefits.

Background to the Invention

Various laundry detergent compositions which are designed not only to clean fabrics, but also to provide care benefits, have been described in the literature and have entered the marketplace with very substantial commercial success. Enzyme components have been described for incorporation into such compositions to provide specific cleaning benefits. For example amylase is particularly useful with respect to soils containing carbohydrate, lipase is useful for the removal of mainly fat-containing soils and protease is useful for the removal of mainly proteinaceous soils. However, enzyme compatibility and stability with other detergent ingredients can be a major concern.

Most conventional detergent compositions also contain mixtures of various detersive surfactants. Examples include various anionic surfactants, especially the alkyl benzene sulfonates and alkyl sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates. Surfactants can be useful in the removal of a wide variety of soils and stains from a variety of surfaces.

A problem common to detergent compositions comprising either an enzyme or a surfactant is in-wash soil fragment redeposition. Enzymatic action during the wash removes soils from a soiled substrate surface. It is believed that further in-wash enzymatic action on soils causes said soils to break-up into fragments; it is these fragments that may then redeposit onto the substrate surface. Soil fragment redeposition is believed to be the cause of a variety of problems associated with laundry and dishwashing detergent composition. For example, the off-white appearance of some fabrics can be caused by the redeposition of soil fragments after laundering. Redeposition of soils onto fabrics after laundering may also result in fabric harshness. With respect to automatic dishwashing, a problem commonly associated with redeposited soil fragments is the appearance of spot and films on the surface of washed substrates.

It is the surprising finding of the present invention that detergent compositions comprising a dianionic cleaning agent in combination with an enzyme, provide reduced soil redeposition benefits, in addition to improved cleaning performance, especially of greasy soils.

US-A-3, 832,408 describes detergent compositions comprising 2- hydrocarbyl-l ,4-butanediol ethoxylate disulfate in combination with high levels of phosphate builder. US-A-3, 860,625 and US-A-3,634,269 describe 2-hydrocarbyl-l,4-butanediol ethoxylate disulfate as components of phosphate-free detergent compositions.

Additionally, US-A-3,959,334 and US- A-4, 000,081 describe 2- hydrocarbyl-l ,4-butanediol disulfates said to be suitable as lime soap dispersants and a method for synthesizing these disulfates.

DE-A- 2,845,905 describes a process for continuous manufacture of butanediol-1 ,4 by catalytic hydrogenation of maleic anhydride.

Summary of the Invention

According to the present invention there is provided a detergent composition comprising

a) a dianionic cleaning agent comprising a structural skeleton of at least five carbon atoms to which two anionic substituent groups spaced at least three atoms apart, are attached, wherein at least one anionic substituent group is a sulfate group and the other is selected from the group consisting of sulfate and sulfonate groups; and

b) an enzyme.

Detailed description of the invention

Dianionic cleaning agent

A first essential component of the cleaning compositions of the present invention is a dianionic cleaning agent. The dianionic cleaning agent comprises a structural skeleton of at least five carbon atoms, to which two anionic substituent groups spaced at least three atoms apart, are attached. At least one of said anionic substituent groups is a sulfate group; the other is a sulfate or sulfonate group, preferably a sulfate group. Said structural skeleton can for example comprise any of the groups consisting of alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine and amide groups.

The structural skeleton preferably comprises from 5 to 32, preferably 7 to 28, most preferably 12 to 24 atoms. Preferably the structural skeleton comprises only carbon-containing groups and more preferably comprises only hydrocarbyl groups. Most preferably the structural skeleton comprises only straight or branched chain alkyl groups.

The structural skeleton is preferably branched. Preferably at least 10 % by weight of the structural skeleton is branched and the branches are preferably from 1 to 5, more preferably from 1 to 3, most preferably from 1 to 2 atoms in length (not including the sulfate or sulfonate group attached to the branching).

Again, the anionic substituent groups present in the dianionic cleaning agents useful herein are spaced at a distance of at least three atoms from each other. For example, where one anionic substituent group is attached to a carbon (the first carbon), said first carbon is attached to a second carbon, which is in turn, attached to a third carbon and the third carbon is attached to the second anionic substituent group to give a spacing of three carbon atoms.

In a preferred aspect of the present invention, at least one anionic substituent group is substituted at a primary position on the structural skeleton. The anionic substituent groups are preferably spaced 1-3, 1-4, 1- 5, 1-6 or greater apart; a 1-4 substitution for disulfated compounds is most preferred, and 1-4 and 1-5 substitution for sulfated/sulfonated compounds is most preferred. For full clarity, the term 1-n substitution is to be interpreted such that 1 indicates an anionic substituent group located at a given position on the structural skeleton and n indicates the number of atoms spaced between the first and second anionic substituent groups.

A preferred dianionic cleaning agent has the formula

A— X ^" M ⁺

R

B— Y ^' M

where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Ci to C28» preferably C3 to C24, most preferably Cg to C20_» ^or hydrogen; A and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length C\ to C28_» preferably C\ to C5, most preferably C\ or C2, or a covalent bond, A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.

The most preferred dianionic cleaning agent has the formula as above where R is an alkyl group of chain length from C\Q to Ci8, A and B are independently C\ or C2, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

Preferred dianionic cleaning agents herein include: (a) 1 ,3 disulfate compounds, preferably 1,3 C7-C23 (i.e. , the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from C4 to C20;

(b) 1 ,4 disulfate compounds, preferably 1 ,4 C8-C22 straight or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from C4 to Cjg; preferred R are selected from octanyl, nonanyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, and mixtures thereof; and

(c) 1 ,5 disulfate compounds, preferably 1 ,5 C9-C23 straight or branched chain alkyl or alkenyl disulfates, more preferably having the formula:

wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about C\g.

The dianionic cleaning agent is typically present at levels of incorporation of from about 0.1 % to about 40% , preferably from about 0.1 % to about 35% , most preferably from about 0.5% to about 15 % by weight of the detergent composition. The dianionic cleaning agent may also be present as a componen of a surfactant system wherein the dianionic clenaing agent is present at levels of from 0.1 % to 99.9% , preferably from 1 % to 60% , most preferably from 5 % to 40% by weight of the surfactant system.

As will be appreciated more fully from the following discussion of preferred synthesis methods, the present invention compositions may also comprise some amount of sulfated alcohols and/or sulfonated alcohols which may comprise (to differing degrees depending on the reaction conditions used) a portion of the dianionic cleaning agent raw material used to manufacture the present invention compositions. Such alcohols are typically compatible with the present invention compositions and may be present as long as the requisite amount of dianionic cleaning agent is present in the final composition.

Synthesis Methods:

Known syntheses of certain disulfated surfactants, in general, use an alkyl or alkenyl succinic anhydride as the principal starting material. This is initially subjected to a reduction step from which a diol is obtained. Subsequently the diol is subjected to a sulfation step to give the disulfated product. As an example, US-A-3,634,269 describes 2-alkyl or alkenyl- 1 ,4-butanediol disulfates prepared by the reduction of alkenyl succinic anhydrides with lithium aluminium hydride to produce either alkenyl or alkyl diols which are then sulfated. In addition, US-A-3,959,334 and US- A-4, 000,081 describe 2-hydrocarby 1- 1 ,4-butanediol disulfates also prepared using a method involving the reduction of alkenyl succinic anhydrides with lithium aluminium hydride to produce either alkenyl or alkyl diols which are then sulfated.

See also US-A-3, 832,408 and US-A-3, 860,625 which describe 2- alkyl or alkenyl- 1 ,4-butanediol ethoxylate disulfates prepared by the reduction of alkenyl succinic anhydrides with lithium aluminium hydride to produce either alkenyl or alkyl diols which are then ethoxylated prior to sulfation.

These compounds may also be made by a method involving synthesis of the disulfated cleaning agent from a substituted cyclic anhydride having one or more carbon chain substituents having in total at least 5 carbon atoms comprising the following steps:

(i) reduction of said substituted cyclic anhydride to form a diol; and (ii) sulfation of said diol to form a disulfate wherein said reduction step comprises hydrogenation under pressure in the presence of a transition metal-containing hydrogenation catalyst.

The cyclic anhydride starting material has a ring structure and comprises an acid anhydride linkage. Cyclic anhydrides are generally formed by a ring forming condensation reaction of a single organic compound having a first carboxylic acid (-COOH) functional group and a second -COY functional group separated from the carboxylic acid functional group by at least two carbon atoms, wherein Y is usually an OH, or halogen functionality.

A specific example of an organic compound which may be condensed to form a cyclic anhydride is maleic acid which on self- condensation provides maleic anhydride. Maleic anhydride is readily available commercially. The ring structure of the cyclic anhydride starting material contains from 4 to 7 carbon atoms, preferably from 4 to 6 carbon atoms in the ring structure. Most preferably the cyclic anhydride starting material is based on succinic anhydride which has a 5-membered ring structure containing 4 carbon atoms in the ring.

The cyclic anhydride starting material is substituted by one or more carbon containing substituents, such that in total, these substitutents contain at least 5 carbon atoms, preferably from 5 to 25 carbon atoms, more preferably from 7 to 21 carbon atoms. Preferably, all of the carbon chain substituent(s) comprise either alkyl or alkenyl chains, which may be branched or unbranched. In one preferred aspect they are essentially unbranched. In another preferred aspect the chains are primarily monobranched, that is more than 50% by weight of the chains are monobranched. In one preferred aspect the substituted cyclic anhydride has a single carbon chain substituent. In another preferred aspect the substituted cyclic anhydride has two carbon chain substituents each having different points of attachment to the ring structure.

Substituted alkenylsuccinic and alkylsuccinic anhydrides are suitable starting materials herein. Preferred anhydrides of this type have the following structures: ^R2 o ^R O

R R

Alkyisuccinic O Alkenylsuccinic O

Anhydride - Anhydride

O O

where R and R2 are either H or an alkyl group. In one preferred aspect R2 is H.

Linear alkenylsuccinic anhydrides may be obtained in high yield from the single stage 'ene reaction' of maleic anhydride with an alpha- olefm. Branched alkenylsuccinic anhydrides may be obtained from the single stage 'ene reaction' of maleic anhydride with an internal olefin, such as those obtainable from the familiar SHOP (tradename of the Shell Corporation) olefin making process.

Alkyisuccinic anhydride starting materials can be made by reducing alkenylsuccinic anhydrides. This reduction can be achieved under the conditions of the catalytic hydrogenation reduction step as described herein.

The first step is the reduction of the substituted cyclic anhydride to form a diol. The reduction step comprises hydrogenation under pressure in the presence of a transition metal-containing hydrogenation catalyst.

It is an advantage of this method that under the conditions of the catalytic hydrogenation reduction step any alkene linkages are also reduced to alkyl linkages. Thus, if an alkenylsuccinic anhydride is used as the starting material it is reduced via a (single) reduction step to the diol having alkyl chain substituents, as are desired. This contrasts with the situation where UAIH4, which does not reduce alkene linkages, is used in the reduction step, wherein an extra step involving the reduction of the alkenyl succinic anhydride to the alkyl succinic anhydride (via e.g. Pd/hydrogen) must be employed to obtain the desired diol product.

The hydrogenation catalyst acts functionally to enhance the efficiency of the reductive hydrogenation process. For use on a commercial scale it is desirable that the catalyst is easy to regenerate. Preferably the catalyst contains a transition metal selected from the group consisting of the group VIA (particularly Cr), VIIA (particularly Mn), VIII (particularly Fe, Co, Ni, Ru, Rh, Pd. Pt) and IB (particularly Cu) elements. Catalysts containing mixtures of any of these transition metals are envisaged as are catalysts containing other metals including the alkali and alkaline earth metals. Copper-containing catalysts, particularly copper chromite (which is commercially available and relatively easy to regenerate) are most preferred.

The hydrogenation catalyst may advantageously be supported on an inert support material. The support material can generally comprise an oxide salt comprising a metal selected from the group consisting of aluminium, silicon and any mixtures thereof. Supports comprising aluminium oxide or silicon dioxide are especially preferred. Carbon and clay materials are also suitable supports.

The reductive hydrogenation step is carried out under pressure, and generally at elevated temperature. Usually a solvent is employed. This step can be carried out by a batch, continuous or vapor-phase process. A continuous process is preferred. The pressure is typically from 1 x 10^ to 1 x 10? Pa, more preferably from 1 x 10^ to 5 x 10^ Pa. The temperature is generally from 150 to 350°C, more preferably from 200 to 300°C. The time of reaction is generally from 30 minutes to 10 hours. Suitable solvents include alcohols, particularly methanol, ethanol, propanol and butanol .

It is to appreciated that the exact process conditions used for any particular synthesis will be varied to achieve optimum results in accord with the usual process optimization steps which will be within the remit of the skilled person. In particular the process conditions will be adjusted to minimize the occurence of any competing side-reactions.

One possible problem derives from the incomplete reduction of the cyclic anhydride, such that lactones are formed. These are however, convertible to diols by further catalytic hydrogenation. It may be advantageous to carry out the hydrogenation in two steps, preferably as part of a continuous step- wise process, such that a lactone is formed in the first step followed by a second step in which the lactone is reduced to the diol. Conditions which favour lactone formation are high temperature ( -300 °C) and low pressures ( ~ 1 x 10$ Pa). Any water formed during the hydrogenation will primarily be in the vapour phase, so that the anhydride is unlikely to be converted to a carboxylic acid which can inhibit the catalyst. The best conditions for diol formation from the lactone are lower temperatures ( -220 °C) and high pressures ( — 1 x 10? Pa), both of which conditions minimize the production of furan by-product.

Furans can be formed by a ring closure reaction of the diol product. The tendency for such furans to form is greater at higher reaction temperatures and can be promoted by the transition-metal containing catalysts employed in the reduction step. The formation of furans may therefore be minimzed by the use of lower reaction temperatures and by designing the process such that once formed the diol is removed from the catalytic environment. The latter objective is met by the use of a continuous process whereby the reactants contact a high level of catalyst for a relatively short time and are then removed from the catalytic environment. By optimization of the time of contact with the catalyst the formation of the desired diol is maximized and that of the furan by-product minimized.

The presence of acids promotes furan formation. In particular, carboxylic acids which may be formed by certain ring-opening reactions of the cyclic anhydrides under the conditions of the reduction step can promote furan formation. This problem can be alleviated by first forming the lactone in a separate step as mentioned above or by the use of an additional esterification step in which the cyclic anhydride is first treated with an alcohol, particularly methanol, in the presence of an esterification catalyst to form a diester. The diester is then converted to the diol via the reduction step.

The sulfation step may be carried out using any of the sulfation steps known in the art, including for example those described in US-A- 3,634,269, US- A-3, 959,334 and US-A-4,000,081. In particular the sulfation may be carried out in two stages where the first stage involves treatment of the diol with a sulfation agent, generally selected from the group consisting of chlorosulfonic acid, sulfur trioxide, adducts of sulfur trioxide with amines and any mixtures thereof. The second stage involves neutralization, which is generally carried out using NaOH. Synthesis Example I - C14 alkyl-1.4-disulfate

Decyl succinic anhydride as shown in the reaction scheme below (R = a heptyl group) is employed as the starting material. This material is obtained by hydrogenation in the presence of a Pd catalyst of the alkenyl succinic anhydride product obtained from the 'ene' reaction of maleic (acid) anhydride with dec- 1 -ene.

The general reaction scheme for the reduction step is as outlined below:

O

R Cu Chromite (cat)

R = C7 O

Alcohol solvent ROH

Alkyisuccinic Anhydride O

OH ₊ R

Alkyl 1 ,4-Diol Alkylfuran O OH

C0₂R'

R Half-ester

CQ₂H

It should be noted from the above that both furan and half ester byproducts can also be formed in the reaction.

The reactor utilized is an electrically heated 500 ml (39 mm internal diameter x 432 mm internal length) Autoclave Engineers type 316 (tradename) stainless steel rocking autoclave fitted with an internal thermocouple and valving for periodic sampling of reaction mixtures. The reactor is charged with 50 ml of alcohol solvent and 5 grams of copper chromite catalyst, as sold by Engelhardt under the tradename CU-1885P, that had been washed several times with high purity water then several times with alcohol solvent. The reactor and contents are then heated to 250°C at a hydrogen pressure of 2.4 x 10^ Pa and held for 1 hour. The reactor is then cooled and charged (without exposing the catalyst to air) with 20 grams of the cyclic anhydride starting material and an additional 50 ml of alcohol solvent. The process is carried out under different conditions of pressure and temperature, and with varying reaction times. Details of different reaction conditions are summarized in the table below:

Example No. Pressure Temp. Time Solvent (lOόPa) (°C)

1 2.8 235 2.1 hr 1-butanol

2 2.1 210 48 hr 1-butanol

3 2.85 250 2.5 hr 1-butanol

4 2.1 250 15 hr methanol

5 2.1 300 15 hr methanol

6 2.1 200 15 hr 1-octanol

7 2.1 192 4.5 days isobutanol

8 2.1 187 2.5 days ethylene glycol

The sulfation step is carried out, in each case, on the 1 ,4-alkyl diol product obtained from the reduction step. Chlorosulfonic acid is used which results in a high yield (typically > 90%) of the required C14 alkyl 1 ,4 disulfate end-product as shown below:

R-

OS0₃Na OS0₃Na

R2 = H R = C7

Synthesis Example II - C14 alkyl-1.4-disulfate The alkenyl succinic anhydride product obtained from the 'ene' reaction of maleic (acid) anhydride with dec-1-ene (i.e. R = a heptyl group) is used directly as the cyclic anhydride starting material. The need for the additional 'pre-step' of reduction of the alkenyl succinic anhydride to an alkyl succinic anhydride is thus avoided. All other method steps are as in Synthesis Example I.

The reaction scheme for the reduction step is thus as shown below:

O

R Copper Chromite, H2

O

1-Butanol Solvent

Alkenylsuccinic Anhydride O OButyl

OH ^R O

+

Alkyl-1 ,4-Diol OH Half esters

OH

R

Alkylfuran O

Synthesis Example III - Preparation of Alkyl 1.4-Sulfate/Sulfonates

1 ,4-dialcohol starting materials are first prepared as described hereinbefore by reduction of alkenyl succinic anhydrides. The desired compounds are then prepared following the reaction sequence as follows (wherein R can be alkyl or alkenyl, C% to C20):

Step 1

Step 2

KMnO₄

Step 3

Ns&SCfc or NaHSg⁾

This reaction scheme is described in part in greater detail in Berridge, et. al. , (J. Org. Chem. 1990, 55, 1211). This paper illustrates Steps 1 and 2 for several 1 ,2-, 1,3-, and 1 ,4-dialcohols, and also illustrates the opening of cyclic sulfates with phenoxide and fluoride anions. Thus, this reaction sequence is not limited to the preparation of 1 ,4-sulfate/sulfonates, but may also be followed for the preparation of 1.3-sulfate/sulfonates from the corresponding 1 ,3-dialcohols.

Enzyme

A second essential component of the detergent compositions is an enzyme.

Suitable enzymatic materials include the commercially available upases, cutinases, amylases, neutral and alkaline proteases, esterases, cellulases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Preferred enzymes are discussed in US Patents 3,519,570 and 3,533, 139.

Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount" . The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, whitening, deodorizing, or freshness improving effect on substrates. In practical terms for current commercial preparations, typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5 % , preferably from 0.01 % to 1 % by weight of a commercial enzyme preparation. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. As well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble. When desired, a protease having decreased absorption and increased hydrolysis is available as described in WO 9507791 to Procter and Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of 4-99, + 101, + 103, + 104, + 107, + 123, +27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, +204, +206, +210, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A. Baeck, et al, entitled "Protease-Containing Cleaning Compositions" having US Serial No. 08/322,676, and C Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994.

Protease enzyme may be incorporated into the compositions in accordance with the invention at a level of from 0.0001 % to 4% active enzyme by weight of the composition. Preferred amylases include, for example, α-amylases obtained from a special strain of B licheniformis, described in more detail in GB-1 ,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl fungamyl and BAN by Novo Industries A/S.

Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem. , Vol. 260, No. 11 , June 1985, pp. 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL ® in commercial use in 1993. These preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g. , to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g. , at a pH from about 8 to about 11 , measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability- enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amy lases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the detergent compositions of the present invention include α-amylases characterized by having a specific activity at least 25 % higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. (Such Phadebas® α-amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are α-amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. Amylase enzyme may be incorporated into the composition in accordance with the invention at a level of from 0.0001 % to 2% active enzyme by weight of the composition.

Lipolytic enzyme may be present at levels of active lipolytic enzyme of from 0.0001 % to 2% by weight, preferably 0.001 % to 1 % by weight, most preferably from 0.001 % to 0.5% by weight of the compositions.

The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomvces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes. which is described in Granted European Patent, EP-B-0218272.

Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza. as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Patent 4,810,414, Huge-Jensen et al, issued March 7, 1989.

Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. The weight ratio of dianionic cleaning agent to an enzyme (on an active enzyme by weight basis) is preferably from 300: 1 to 1 : 10, more preferably from 100: 1 to 1 :8, most preferably from 50: 1 to 1 :5.

Additional detergent components

The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical form of the composition, and the precise nature of the washing operation for which it is to be used.

The compositions of the invention preferably contain one or more additional detergent components selected from surfactants, bleaches, builders, alkalinity system, organic polymeric compounds, enzyme stabilising system, suds suppressors, lime soap dispersants, soil suspension and anti-redeposition agents and corrosion inhibitors.

Enzyme Stabilizing System

A preferred component of the compositions herein may comprise from about 0.001 % to about 10% , preferably from about 0.005 % to about 8% , most preferably from about 0.01 % to about 6% , by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof. Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.

Surfactant

The detergent compositions of the invention preferably contain one or more surfactants selected from anionic, nonionic, non-ester cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof. The surfactant is preferably present as a component of a surfactant system at a level of from 0.1 % to 50%, more preferably from 1 % to 40% by weight, most preferably from 5% to 30% by weight of the surfactant system.

A typical listing of anionic, nonionic, ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S. P. 3,929,678 issued to Laughlin and Heuring on December 30, 1975. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A list of suitable cationic surfactants is given in U.S. P. 4,259,217 issued to Murphy on March 31, 1981.

Where present, ampholytic, amphoteric and zwitteronic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants.

Anionic surfactant

Essentially any anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C^-C, monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C^-C^ diesters), N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.

Anionic mono-sulfate surfactant Anionic mono-sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl mono-sulfates, alkyl ethoxymono-sulfates, fatty oleoyl glycerol mono-sulfates, alkyl phenol ethylene oxide ether mono-sulfates, the C5-C17 acyl-N-(C ι-C4 alkyl) and -N-(Cι-C2 hydroxyalkyl) glucamine mono-sulfates, and mono-sulfates of alkylpolysaccharides such as the mono-sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl mono-sulfate surfactants are preferably selected from the linear and branched primary C 10-C18 alkyl mono-sulfates, more preferably the C I J - C 15 branched chain alkyl mono-sulfates and the C12-C14 linear chain alkyl mono-sulfates.

Alkyl ethoxymono-sulfate surfactants are preferably selected from the group consisting of the C10-CI8 alkyl mono-sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxymono-sulfate surfactant is a Cπ-Cig, most preferably C11-C15 alkyl mono-sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl mono-sulfate and alkyl ethoxymonosulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO

93/18124.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Anionic carboxylate surfactant it

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl poly ethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2θ)_x CH2COO-M+ wherein R is a C^ to Ci alkyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation. Suitable alkyl poly ethoxy polycarboxylate surfactants include those having the formula RO-(CHRι-CHR2-0)-R3 wherein R is a C6 to Ci alkyl group, x is from 1 to 25, Ri and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-l - undecanoic acid, 2-ethyl-l-decanoic acid, 2-propyl-l-nonanoic acid, 2- butyl-1-octanoic acid and 2-pentyl-l-heptanoic acid. Certain soaps may also be included as suds suppressors.

Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of formula R-CON (Rl) CH2 COOM, wherein R is a C5-C17 linear or branched alkyl or alkenyl group, R^l is a C1-C4 alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.

Alkoxylated nonionic surfactant Essentially any alkoxylated nonionic surfactants are suitable herein. The ethoxylated and propoxylated nonionic surfactants are preferred.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxy late/propoxylate condensates with propylene glycol , and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxylated alcohol surfactant

The condensation products of aliphatic alcohols with from 1 to 25 moles of alkylene oxide, particularly ethylene oxide and/or propylene oxide, are suitable for use herein. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fattv acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R^CONR^Z wherein : Rl is H, C 1-C4 hydrocarbyl, 2- hydroxy ethyl, 2-hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable C1-C4 alkyl, more preferably C\ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight-chain C5-C19 alkyl or alkenyl, more preferably straight-chain C9- C17 alkyl or alkenyl, most preferably straight-chain C\ \-C \ alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6C0N(R7)2 wherein R6 is an alkyl group containing from 7 to 21 , preferably from 9 to 17 carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, and - (C2H4θ)_xH, where x is in the range of from 1 to 3.

Nonionic alkylpolysaccharide surfactant

Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysaccharide, e.g. , a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula

R2θ(C_nH₂nO)t(glycosyl)_x

wherein R2 is selected from the group consisting of alkyl, alky Iphenyl, hydroxyalkyl, hydroxy alky Iphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

End-capped nonionic surfactants

End-capped nonionic surfactants include essentially any nonionic surfactant comprising a branched chain alkyl or substituted alkyl group. Suitable end- capped nonionics include end-capped Butyl-polypropylene glycol ethyl ether described in GB l,221 ,217and end-capped polyethylene glycol ether describes in US 5,205,959.

Preferred end-capped nonionic surfactants include the alkoxylated and alkoxylated alcohol nonionic end-capped surfactants. A preferred embodiment of the present invention is a mixed surfactant system comprising an end-capped nonionic and a polyhydroxy fatty acid amide. The resulting mixed surfactant systems surprisingly exhibit low sudsing benefits.

Amphoteric surfactant

Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula R3(OR4)_XNO(R5)2 wherein R^ is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R^ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3 ; and each R^ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. Preferred are C ifj-C ig alkyl dimethylamine oxide, and C O-lg acylamido alkyl dimethylamine oxide.

A suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc. , Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(R')2N +R2C00^" wherein R is a C6-Cιg hydrocarbyl group, each R¹ is typically C 1-C3 alkyl, and R² is a C1-C5 hydrocarbyl group. Preferred betaines are Ci2-lg dimethyl-ammonio hexanoate and the C iO-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Cationic surfactants

Suitable cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Other suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C6-C16, preferably C6-C10 N-alkyl or alkenyl ammomum surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Water-soluble builder compound

The detergent compositions of the present invention preferably contain a detergency builder compound. Suitable builder compound include water- soluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition.

Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, borates, phosphates, and mixtures of any of the foregoing.

The carboxylate or polycarboxylate builder can be momomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates. Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1 ,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-l , l ,3-propane tricarboxylates described in British Patent No. 1 ,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261 ,829, 1 , 1,2,2-ethane tetracarboxylates, 1 , 1 , 3, 3 -propane tetracarboxylates and 1 , 1, 2, 3 -propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

The parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.

Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions are useful water-soluble builders herein.

Suitable examples of water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammomum pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 21 , and salts of phytic acid.

Partially soluble or insoluble builder compound

The detergent compositions of the invention may optionally contain a partially soluble or insoluble builder compound, typically present at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% weight of the composition.

Examples of largely water insoluble builders include the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na_z[(Alθ2)z(Siθ2)y]. H2θ wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28% , more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula

Na 12 [AIO2) 12 (Si0₂)l2J. H2O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na 6 [(Alθ2)86(Siθ2)l06L ²⁷⁶ H2O. Zeolite MAP, as disclosed in EP-B- 384,070 is a preferred zeolite builder herein.

Organic peroxyacid bleaching system

A preferred feature of detergent compositions of the invention is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches

Inorgamc perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a level of from 1 % to 40 % by weight, more preferably from 2 % to 30% by weight and most preferably from 5 % to 25% by weight of the compositions.

Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The inorganic perhydrate salts are normally the alkali metal salts. The inorganic perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product. Suitable coatings comprise inorganic salts such as alkali metal silicate, carbonate or borate salts or mixtures thereof, or organic materials such as waxes, oils, or fatty soaps.

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaBθ2H2θ2 or the tetrahydrate NaBθ2H2θ2-3H2θ.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2Cθ3.3H2θ2, and is available commercially as a crystalline solid.

Potassium peroxymonopersulfate is another inorganic perhydrate salt of use in the detergent compositions herein.

Peroxyacid bleach precursor

Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as

O X - C -L

where L is a leaving group and X is essentially any functionality, such that on perhydroloysis the structure of the peroxyacid produced is

O X - C - OOH

Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1 % to 15% by weight, most preferably from 1.5% to 10% by weight of the detergent compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A-0170386.

Leaving groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

Preferred L groups are selected from the group consisting of:

O

•N— C— R¹ — N Λ N __N_ ?_C__CH__R4

Y

R³ Y

I I

-O-CH=C— CH=CH₂ -O— CH=C— CH=CH₂

R³ O II Y I

-O— C=CHR⁴ . and -N-S- -CH- -R⁴ R³ O

and mixtures thereof, wherein R is an alkyl, aryl, or alkaryl group containing from 1 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is H or R , and Y is H or a solubilizing group. Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammomum or alkyl ammmonium groups

-CO2 wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammomum or substituted ammomum cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Alkyl percarboxylic acid bleach precursors

Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis. Preferred precursors of this type provide peracetic acid on perhydrolysis.

Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

Other preferred alkyl percarboxylic acid precursors include sodium 3,5,5- tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxy benzene sulfonate (ABS) and pentaacetyl glucose.

Amide substituted alkyl peroxyacid precursors

Amide substituted alkyl peroxyacid precursor compounds are suitable herein, including those of the following general formulae:

R¹ — C — N — R² — C — L R¹ — N — C — R² — C — L

O R⁵ O or R⁵ O O wherein Rl is an alkyl group with from 1 to 14 carbon atoms, R² is an alkylene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N- benzoyl imidazole and N-benzoyl benzimidazole. Other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic peroxyacid precursors

Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

Typically, cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammmonium group, preferably an ethyl or methyl ammomum group. Cationic peroxyacid precursors are typically present in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451; 4,397,757; 5,269,962; 5, 127,852; 5,093,022; 5,106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.

Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, 08/298904 and 08/298906.

Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N- acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammomum methylene benzoyl caprolactams and the trialkyl ammomum methylene alkyl caprolactams.

Benzoxazin organic peroxyacid precursors

Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

wherein R_j is H, alkyl, alkaryl, aryl, or arylalkyl.

Preformed organic peroxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.

A preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:

R — C — N — R² — C — OOH R — N — C - R² — C - OOH

O R⁵ O or R⁵ O O

wherein Rl is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R^ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxicaproic acid are also suitable herein.

Bleach catalyst

The compositions optionally contain a transition metal containing bleach catalyst. One suitable type of bleach catalyst is a catalyst system comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron, cobalt or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetre (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Pat. 4,430,243. Other types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include MnϊV2(u-0)3(l ,4,7-trimethyl-l ,4,7- triazacyclononane)2-(PF6)2, MnIH2(^u-0)l(^u-OAc)2(l,4,7-trimethyl- 1 ,4,7-triazacyclononane)2-(Clθ4)2, MτJ^4( -0)^(l ,^→ - triazacyclononane)4-(C104)2, Mn^IIIMn^IV4(u-0) i (u-OAc)2-( 1 ,4,7- trimethyl-l ,4,7-triazacyclononane)2-(C104)3, and mixtures thereof. Others are described in European patent application publication no. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl- 1 ,5,9-triazacyclododecane, 2-methyl- 1 ,4,7-triazacyclononane, 2-methyl- 1 ,4,7-triazacyclononane, l,2,4,7-tetramethyl-l ,4,7-triazacyclononane, and mixtures thereof.

For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5, 194,416 which teaches mononuclear manganese (IV) complexes such as Mn(l,4,7-trimethyl- l ,4,7-triazacyclononane)(OCH3)3_(PF6). Still another type of bleach catalyst, as disclosed in U.S. Pat. 5, 114,606, is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups. Other examples include binuclear Mn complexed with tetra-N-dentate and bi-N-dentate ligands, including N4MnH (u-0)2MnIVN4) ⁺ and [Bipy2MnM(u-0)2MnI^vbipy2]-(C104)3.

Further suitable bleach catalysts are described, for example, in European patent application No. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601 ,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/1 igand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866, 191 (transition metal-containing salts), U.S. 4,430,243 (chelants with manganese cations and non-catalytic metal cations), and U.S. 4,728,455 (manganese gluconate catalysts).

Alkalinity system

An optional component of the detergent compositions is from 1.5% to 95%, preferably from 5% to 60%, most preferably from 10% to 40% by weight of the composition of an alkalinity system comprising components capable of providing alkalinity species in solution. By alkalinity species it is meant for the purposes of this invention: carbonate, bicarbonate, hydroxide and the various silicate anions. Such alkalinity species can be formed for example, when alkaline salts selected from alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and any mixtures thereof are dissolved in water. Alkali metal percarbonate and persilicate salts are also suitable sources of alkalinity species.

Heavy metal ion sequestrant

The detergent compositions of the invention preferably contain as an optional component a heavy metal ion sequestrant. By heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.

Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5 % by weight of the compositions.

Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1 -hydroxy disphosphonates and nitrilo trimethylene phosphonates. Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy- ethylene 1 , 1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2- hydroxypropylenediamine disuccinic acid or any salts thereof. Especially preferred is ethylenediamine-N,N' -disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammomum salts thereof, or mixtures thereof.

Other suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyl diacetic acid or glyceryl imino diacetic acid, described in EP-A-317,542 and EP-A- 399, 133. The iminodiacetic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516, 102 are also suitable herein. The β- alanine-N,N' -diacetic acid, aspartic acid-N,N' -diacetic acid, aspartic acid- N-monoacetic acid and iminodisuccinic acid sequestrants described in EP- A-509,382 are also suitable.

EP-A-476,257 describes suitable amino based sequestrants. EP-A-510,331 describes suitable sequestrants derived from collagen, keratin or casein. EP-A-528,859 describes a suitable alkyl iminodiacetic acid sequestrant. Dipicolinic acid and 2-phosphonobutane-l,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N^* -disuccinic acid (GADS), ethylenediamine-N- N' -diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N-N'- disuccinic acid (HPDDS) are also suitable.

Organic polymeric compound Organic polymeric compounds are preferred additional components of the detergent compositions in accord with the invention, and are preferably present as components of any particulate components where they may act such as to bind the particulate component together. By organic polymeric compound it is meant herein essentially any polymeric organic compound commonly used as dispersants, and anti-redeposition and soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30% , preferably from 0.5 % to 15 % , most preferably from 1 % to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A- 1,596, 756. Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 100,000, especially 40,000 to 80,000.

The polyamino compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A-305283 and EP-A-351629.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, particularly those having an average molecular weight of from 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.

Further useful organic polymeric compounds are the polyethylene glycols, particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000.

Suds suppressing system

The detergent compositions of the invention, when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05% to 10% , most preferably from 0.1 % to 5 % by weight of the composition.

Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds and 2-alkyl alcanol antifoam compounds.

By antifoam compound it is meant herein any compound or mixtures of compounds which act such as to depress the foaming or sudsing produced by a solution of a detergent composition, particularly in the presence of agitation of that solution.

Particularly preferred antifoam compounds for use herein are silicone antifoam compounds defined herein as any antifoam compound including a silicone component. Such silicone antifoam compounds also typically contain a silica component. The term "silicone" as used herein, and in general throughout the industry, encompasses a variety of relatively high molecular weight polymers containing siloxaπe units and hydrocarbyl group of various types. Preferred silicone antifoam compounds are the siloxanes, particularly the polydimethylsiloxanes having trimethylsilyl end blocking units.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble salts thereof. These materials are described in US Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C g-C40 ketones (e.g. stearone) N- alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, bis stearic acid amide and monostearyl di- alkali metal (e.g. sodium, potassium, lithium) phosphates and phosphate esters.

A preferred suds suppressing system comprises

(a) antifoam compound, preferably silicone antifoam compound, most preferably a silicone antifoam compound comprising in combination

(i) polydimethyl siloxane, at a level of from 50% to 99% , preferably 75 % to 95 % by weight of the silicone antifoam compound; and

(ii) silica, at a level of from 1 % to 50%, preferably 5 % to 25 % by weight of the silicone/silica antifoam compound;

wherein said silica/silicone antifoam compound is incorporated at a level of from 5 % to 50% , preferably 10% to 40% by weight;

(b) a dispersant compound, most preferably comprising a silicone glycol rake copolymer with a polyoxyalkylene content of 72-78 % and an ethylene oxide to propylene oxide ratio of from 1 : 0.9 to 1 : 1.1, at a level of from 0.5% to 10% , preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544;

(c) an inert carrier fluid compound, most preferably comprising a Ci6- Cjg ethoxylated alcohol with a degree of ethoxylation of from 5 to 50, preferably 8 to 15, at a level of from 5% to 80% , preferably 10% to 70% , by weight;

A highly preferred particulate suds suppressing system is described in EP- A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range 50°C to 85 °C, wherein the organic carrier material comprises a monoester of glycerol and a fatty acid having a carbon chain containing from 12 to 20 carbon atoms. EP-A- 0210721 discloses other preferred particulate suds suppressing systems wherein the organic carrier material is a fatty acid or alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof, with a melting point of from 45 °C to 80 °C.

Clay softening system

The detergent compositions may contain a clay softening system comprising a clay mineral compound and optionally a clay flocculating agent.

The clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647. European Patents No.s EP-A- 299,575 and EP-A-313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.

Polymeric dye transfer inhibiting agents

The detergent compositions herein may also comprise from 0.01 % to 10% , preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.

a) Polyamine N-oxide polymers

Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula :

(I₎ Ax

R

wherein P is a polymerisable unit, and

O O O

A is NC, CO, C, -O-, -S-, -N-; x is O or 1 ;

R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or any combination thereof whereto the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group is part of these groups.

The N-O group can be represented by the following general structures :

O

O (R^ x -N R^y

(R₃)_{z or} = N-(R₁)x

wherein Rl , R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations thereof, x or/and y or/and z is 0 or 1 and wherein the nitrogen of the N-O group can be attached or wherein the nitrogen of the N-O group forms part of these groups. The N-O group can be part of the polymerisable unit (P) or can be attached to the polymeric backbone or a combination of both.

Suitable polyamine N-oxides wherein the N-O group forms part of the polymerisable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-O group forms part of the R-group. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N-O group is attached to the polymerisable unit. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups wherein the nitrogen of the N-O functional group is part of said R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The polyamine N-oxides can be obtained in almost any degree of polymerisation. The degree of polymerisation is not critical provided the material has the desired water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are coploymers of N-vinylimidazole and N- vinylpyrrolidone having an average molecular weight range of from 5,000 to 50,000. The preferred copolymers have a molar ratio of N- vinylimidazole to N-vinylpyrrolidone from 1 to 0.2. c) Polyvinylpyrrolidone

The detergent compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). PVP K-15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12.

d) Polvvinyloxazolidone

The detergent compositions herein may also utilize polyvinyloxazolidones as polymeric dye transfer inhibiting agents. Said polyvinyloxazolidones have an average molecular weight of from 2,500 to 400,000.

e) Polyvinylimidazole

The detergent compositions herein may also utilize polyvinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylimidazoles preferably have an average molecular weight of from 2,500 to 400,000.

Optical brightener

The detergent compositions herein also optionally contain from about 0.005% to 5 % by weight of certain types of hydrophilic optical brighteners.

Hydrophilic optical brighteners useful herein include those having the structural formula:

wherein Ri is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2- hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4' ,-bis[(4-anilino-6-(N-2- bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When in the above formula, Ri is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'- bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, Ri is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s- triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

Cationic fabric softening agents

Cationic fabric softening agents can also be incoφorated into compositions in accordance with the present invention. Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 Oi l 340.

Catiomc fabric softening agents are typically incoφorated at total levels of from 0.5 % to 15% by weight, normally from 1 % to 5% by weight.

Other optional ingredients

Other optional ingredients suitable for inclusion in the compositions of the invention include perfumes, colours and filler salts, with sodium sulfate being a preferred filler salt.

pH of the compositions

The present compositions preferably have a pH measured as a 1 % solution in distilled water of at least 10.0, preferably from 10.0 to 12.5, most preferably from 10.5 to 12.0.

Form of the compositions

The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms. The compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.

The mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.

The bulk density of granular detergent compositions in accordance with the present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel moulded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the funnel. The funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base. The cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.

To carry out a measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup. The filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement eg; a knife, across its upper edge. The filled cup is then weighed and the value obtained for the weight of powder doubled to provide a bulk density in g/litre. Replicate measurements are made as required.

Dianionic cleaning agent agglomerate particles

The dianionic cleaning agent herein is preferably present in granular compositions in the form of dianionic cleaning agent agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules. The most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active dianionic cleaning agent pastes and to control the particle size of the resultant agglomerates within specified limits. Such a process involves mixing an effective amount of powder with a high active dianionic cleaning agent paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D- 4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used, such as a Lodige CB (Trade Name).

A high active dianionic cleaning agent paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of surfactant is typically used. The paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the dianionic cleaning agent used. An operating temperature of the paste of 50°C to 80°C is typical.

Laundry washing method

Machine laundry methods herein typically comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry detergent composition in accord with the invention. By an effective amount of the detergent composition it is meant from 40g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.

In a preferred use aspect a dispensing device is employed in the washing method. The dispensing device is charged with the detergent product, and is used to introduce the product directly into the drum of the washing machine before the commencement of the wash cycle. Its volume capacity should be such as to be able to contain sufficient detergent product as would normally be used in the washing method.

Once the washing machine has been loaded with laundry the dispensing device containing the detergent product is placed inside the drum. At the commencement of the wash cycle of the washing machine water is introduced into the drum and the drum periodically rotates. The design of the dispensing device should be such that it permits containment of the dry detergent product but then allows release of this product during the wash cycle in response to its agitation as the drum rotates and also as a result of its contact with the wash water.

To allow for release of the detergent product during the wash the device may possess a number of openings through which the product may pass. Alternatively, the device may be made of a material which is permeable to liquid but impermeable to the solid product, which will allow release of dissolved product. Preferably, the detergent product will be rapidly released at the start of the wash cycle thereby providing transient localised high concentrations of product in the drum of the washing machine at this stage of the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that container integrity is maintained in both the dry state and during the wash cycle. Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157, 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette" . Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/ 11562.

Especially preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 & 0343070. The latter Application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice, the orifice being adapted to admit to the bag sufficient product for one washing cycle in a washing process. A portion of the washing medium flows through the orifice into the bag, dissolves the product, and the solution then passes outwardly through the orifice into the washing medium. The support ring is provided with a masking arrangemnt to prevent egress of wetted, undissolved, product, this arrangement typically comprising radially extending walls extending from a central boss in a spoked wheel configuration, or a similar structure in which the walls have a helical form.

Alternatively, the dispensing device may be a flexible container, such as a bag or pouch. The bag may be of fibrous construction coated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may be formed of a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501 , 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water impermeable polymeric film such as polyethylene or polypropylene.

Packaging for the compositions

Commercially marketed executions of the bleaching compositions can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials and any suitable laminates. A preferred packaging execution is described in European Application No. 94921505.7.

Abbreviations used in Examples

In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS Sodium linear Cj2 alkyl benzene sulfonate

TAS Sodium tallow alkyl sulfate

C_x SADS Sodium C_x alkyl disulfate of formula

R-CH(CH2Sθ4")CH2CH2S0₄- where R = Cirj-

Ci8, C45AS Sodium C14- 5 linear alkyl sulfate

CxyEzS Sodium Ciχ-Ciy branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 A C 14- 15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide

C25E3 A C 12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide

C25E5 A C 12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide Nonionic C13-C15 mixed ethoxylated/propoxylated fatty alcohol with an average degree of ethoxylation of

3.8 and an average degree of propoxylation of 4.5 sold under the tradename Plurafac LF404 by

BASF GmbH (low foaming)

QAS R2.N+(CH₃)2(C₂H4θH) with R₂ = C_i2 - C14 Soap Sodium linear alkyl carboxylate derived from an

80/20 mixture of tallow and coconut oils.

TFAA C 16-Cl 8 alkyl N-methyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula

Nai2(A102Siθ2)l2- 27H20 having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6 Crystalline layered silicate of formula δ -Na2Si2θ5

Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous Sodium Silicate (Siθ2:Na2θ; 2.0 ratio)

Metasilicate Sodium metasilicate (Siθ2:Na2θ ratio = 1.0) Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425μm and 850 μm

MA/AA Copolymer of 1 :4 maleic/acrylic acid, average molecular weight about 70,000.

CMC Sodium carboxymethyl cellulose Protease Proteolytic enzyme of activity 4KNPU/g sold by

NOVO Industries A/S under the tradename

Savinase

Alcalase Proteolytic enzyme of activity 3AU/g sold by

NOVO Industries A/S Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename

Carezyme

Amylase Amylolytic enzyme of activity 60KNU/g sold by

NOVO Industries A/S under the tradename

Termamyl 60T

BSA Amylotic enzyme sold under the tradename LEI 7 by Novo Industries A/S (approx 1 % enzyme activity)

Lipase Lipolytic enzyme of activity lOOkLU/g sold by

NOVO Industries A/S under the tradename

Lipolase

Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2

PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2

Percarbonate Sodium Percarbonate of nominal formula

2Na2Cθ3.3H2θ2

NaDCC Sodium dichloroisocyanurate NOBS Nonanoyloxybenzene sulfonate in the form of the sodium salt.

TAED Tetraacetylethylenediamine DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the

Trade name Dequest 2060

BTA Benzotriazole BzP Benzoyl Peroxide

Paraffin Paraffin oil sold under the tradename Winog 70 by Winershall

Bismuth nitrate Bismuth nitrate salt PA30 Polyacrylic acid of average molecular weight approximately 8,000

Teφolymer Teφolymer of average molecular weight approx.

7,000, comprising acrylic:maleic:ethylacrylic acid monomer units at a weight ratio of 60:20:20

480N Random copolymer of 3:7 acrylic/methacrylic acid, average molecular weight about 3,500

PAAC Pentaamine acetate cobalt (III) salt

Photoactivated Sulfonated Zinc Phthlocyanine encapsulated in bleach dextrin soluble polymer Brightener 1 Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-l .3.5- triazin-2-y l)amino) stilbene-2 :2 ' -disulfonate .

HEDP 1 , 1-hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide PVPVI Copolymer of polyvinylpyrolidone and vinylimidazole

SRP 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephtaloyl backbone

SRP 2 Diethoxy lated poly (1 , 2 propylene terephtalate) short block polymer

Silicone antifoam Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1.

KOH 100% active solution of Potassium Hydroxide In the following Examples all levels are quoted as % by weight of the composition:

Example 1

The following laundry detergent compositions A to F were prepared in accord with the invention:

A B C D E F

C 14 SADS 8.0 8.0 8.0 8.0 8.0 8.0

C25E3 3.4 3.4 3.4 3.4 3.4 3.4

QAS - 0.8 - - 0.8 -

Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1

Carbonate 13.0 13.0 13.0 27.0 27.0 27.0

Silicate 1.4 1.4 1.4 3.0 3.0 3.0

Sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1

PB4 9.0 9.0 9.0 9.0 9.0 9.0

TAED 1.5 1.5. 1.5 1.5 1.5 1.5

DTPMP 0.25 0.25 0.25 0.25 0.25 0.25

HEDP 0.3 0.3 0.3 0.3 0.3 0.3

Protease 0.26 0.26 0.4 0.16 0.16 0.4

Amylase 0.2 0.1 0.1 0.1 0.3 0.3 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3

CMC 0.2 0.2 0.2 0.2 0.2 0.2

Photoactivated 15 15 15 15 15 15 bleach (ppm) ppm ppm ppm ppm ppm ppm

Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09

Perfume 0.3 0.3 0.3 0.3 0.3 0.3

Silicone antifoam 0.5 0.5 0.5 0.5 0.5 0.5

Misc/minors to 100%

Density in g/litre 850 850 850 850 850 850

Example 2

The following granular laundry detergent compositions G of bulk density 750 g/litre were prepared in accord with the invention:

G

C22 SADS 5.25

C45AS -

C25AE3S -

C45E7 3.25

C25E3 -

QAS 0.8

STPP 10.7

Zeolite A 10.7

Carbonate 6.1

Bicarbonate -

Silicate 6.8

Sodium sulfate 39.8

PB4 5.0

TAED 0.5

DTPMP 0.25

HEDP -

Protease 0.26

Lipase 0.15

Cellulase 0.28

Amylase 0.2 MA/AA 0.8

CMC 0.2

Photoactivated bleach 15 ppm (ppm)

Brightener 1 0.08

Brightener 2 -

Perfume 0.3

Silicone antifoam 0.5

Minors/misc to 100%

Example 3

The following nil bleach-containing detergent formulations of particular use in the washing of colored clothing, according to the present invention were prepared:

Amylase 0.4 0.6 0.6

Cellulase 0.6 0.6 0.3

Silicone antifoam 5.0 2.5 0.5

Dry additives

Sodium sulfate 0.0 9.0 0.0

Balance (Moismre and 100.0 100.0 100.0 Miscellaneous)

Density (g/litre) 700 700 700

Example 4

The following detergent formulations, according to the present invention were prepared:

Example 5

The following high density detergent formulations, according to the present invention were prepared:

Example 6

The following liquid detergent formulations, according to the present invention were prepared:

S T u V W X

C 16 SADS 10.0 3.0 9.0 6.0 3.0 1.5

C25AS 4.0 1.0 - 10.0 13.0 15.0

C25E3S 1.0 - - 3.0 2.0 4.0

C25E7 6.0 8.0 - 2.5 - 4.0

TFAA - - - 4.5 6.0 8.0

QAS - 3.0 - 1.0 -

TPKFA 2.0 - - 2.0 15.0 7.0

Rapeseed fatty - - - 5.0 - 4.0 acids

Citric acid 2.0 3.0 1.0 1.5 1.0 1.0

Dodecenyl/tetrade 12.0 10.0 15. - - - cenyl succinic acid 0

Oleic acid 4.0 2.0 1.0 ~ -

-

Ethanol 4.0 4.0 7.0 2.0 2.0 2.0

1 ,2 Propanediol 4.0 4.0 6.0 7.0 8.0 13.-

Mono Ethanol - - - 5.0 9.0 Amine

Tri Ethanol Amine - - - - - -

NaOH up to pH 8.0 8.0 7.6 7.7 7.5 8.2

Ethoxylated 0.5 0.2 0.3 tetraethylene pentamine

DTPMP 1.0 1.0 2.0 1.0 1.2 -

SRP 2 0.3 - 0.1 - 0.1

PVNO - - - - - 0.10

Protease 0.5 0.5 - 0.25 0.5 0.6

Alcalase - - 1.5 - - -

Lipase - 0.10 - 0.01 0.15

Amylase 0.25 0.25 0.6 0.5 0.9 0.6

Cellulase - - - 0.05 - 0.15 Endolase - - - 0.10 - -

Boric acid 0.1 0.2 1.0 2.0 1.5 2.5

Na formate - - - - - -

Ca chloride - 0.015 - 0.01 - -

Bentonite clay - - 4.0 - 4.0 -

Suspending clay - - 0.6 - 0.3 - SD3

Balance (Moisture 100 100 100 100 100 100 and

Miscellaneous)

Example 7

The following compact high density (0.96Kg/l) dishwashing detergent compositions AA to AC were prepared in accord with the invention. Granular dishwashing detergent compositions examples AD to AF of bulk density 1.02Kg/L were prepared in accord with the invention:

AA AB AC AD AE AF

STPP 24.80 24.80 25.00 30.00 30.00 30.00

Citrate 10.00 10.00 - 8.00 -

Carbonate - - 17.50 30.50 23.50 30.50

Silicate 20.36 20.36 14.81 7.40 7.40 7.40

Metasilicate 2.50 2.50 2.50 2.50 - 2.50

PB1 7.79 - - 4.40 2.40 -

PB4 - 7.79 - - - -

Percarbonate - - 6.70 - - 5.40

Ci8 SADS 0.5 0.4 0.2 1.2 1.3 1.7

Nonionic 1.50 1.50 2.00 0.75 0.75 0.75

TAED 2.39 2.39 2.39 1.00 1.00

HEDP 0.46 0.46 1.00 0.46 0.46 0.46

DTPMP - - 0.65 - - -

BzP - 4.44 - - 1.40 -

Paraffin 0.50 0.50 0.50 0.25 0.25 0.25

Protease 2.20 2.20 2.20 1.10 2.0 1.10

Amylase 1.50 1.50 1.20 0.38 0.38 0.15

BTA 0.30 0.30 0.30 - - 0.15

Bismuth Nitrate - - 0.30 0.30 - -

PA30 - - - - - -

Teφolymer - 4.00 - - - -

480N 2.77 2.77 6.00 - - -

Sulphate 8.44 8.44 20.77 23.90 21.90 21.90

Misc inc moismre to balance pH(l% 10.90 10.90 11.00 10.80 10.80 10.80 solution)

Example 8

The following detergent composition tablets in accord with the present invention of 25g weight were prepared by compression of a granular dishwashing detergent composition at a pressure of 13KN/cm2 using a standard 12 head rotary press:

AG AH Al

STPP 25.00 16.4 30.00

Citrate - - 15.00

Carbonate - 5.00 -

Silicate 26.40 14.80 25.00

Protease 1.76 2.20 0.60

Amylase 1.20 - 0.60

PB1 1.56 7.79 -

PB4 6.92 - 11.40

C20 SADS 1.6 1.3 0.6

Nonionic 1.20 2.00 1.10

TAED 4.33 2.39 0.80

HEDP 0.67 0.67 -

DTPMP 0.65 - -

Paraffin 0.42 0.50 -

BTA 0.24 0.30 -

PA30 3.2 - -

Sulphate 25.05 12.70 1.20

Misc inc moismre to balance pH (1 % solution) 10.60 10.60 11.00 Example 9

The following liquid detergent compositions in accord with the present invention AJ to AK, of density 1.40Kg/L were prepared:

Claims

WHAT IS CLAIMED:

1. A detergent composition comprising

a) a dianionic cleaning agent comprising a structural skeleton of at least five carbon atoms to which two anionic substiment groups spaced at least three atoms apart, are attached wherein at least one anionic substiment group is a sulfate group and die other is selected from the group consisting of sulfate and sulfonate groups; and

b) an enzyme.

2. A detergent composition according to claim 1 wherein said dianionic cleaning agent comprises a structural skeleton of from 5 to 32 atoms.

3. A detergent composition according to either of claims 1 or 2 wherein the structural skeleton comprises only carbon-containing groups.

4. A detergent composition according to claim 3 wherein the structural skeleton comprises only hydrocarbyl groups.

5. A detergent composition according to claim 4 wherein the structural skeleton comprises only saturated alkyl groups.

6. A detergent composition according to any of claims 1 to 5 wherein the structural skeleton is branched.

7. A detergent composition according to any of claims 1 to 6 wherein at least one anionic substiment group is substimted at a primary location on the structural skeleton.

8. A detergent composition according to claim 7 wherein the anionic substiment groups are substimted at the 1 ,4 positions on the structural skeleton.

9. A detergent composition according to any of claims 1 to 8 wherein the second anionic substiment group is a sulfate group.

10. A detergent composition according to any of claims 1 to 9 wherein the dianionic cleaning agent is of the formula

A— X ^" M

*-< . .

B— Y M

where R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length Ci to C28, or hydrogen; A and B are independently selected from alkyl, substimted alkyl, and alkenyl groups of chain length C i to C28, or a covalent bond, and A and B in total contain at least 2 atoms; A, B, and R in total contain from 4 to about 31 carbon atoms; X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and M is a cationic moiety.

11. A detergent composition according to claim 10 wherein R is an alkyl group of chain length C10 to Ci , A and B are independantly of cahin length either Cl or C2 and both X and Y are sulfate groups.

12. A detergent composition according to any of claims 1 to 11 wherein said enzyme is selected from the group consisting of protease, cellulase, amylase, lipase, peroxidase and mixtures thereof.

13. A detergent composition according to claim 12 wherein the enzyme is a lipase enzyme.

14. A detergent composition according to claim 12 wherein the enzyme is a cellulase enzyme.

15. A detergent composition according to claims 12 wherein the enzyme is a protease enzyme.

16. A detergent composition according to any of claims 1 to 15 wherein the weight ratio of dianionic cleaning agent to an enzyme (on an active enzyme by weight basis) is between 300: 1 and 1: 10.

17. A detergent composition according to any of claims 1 to 16 which additionally comprises an enzyme stabilizer.

18. A detergent composition according to any of claims 1 to 17 which additionally comprises at least 1 % by weight of a detergency builder compound.

19. A detergent composition according to any of claims 1 to 18 wherein the dianionic cleaning agent is present as a component of a surfactant system, additionally comprising a nonionic surfactant.

20. A detergent composition according to claim 19 wherein the dianionic cleaning agent is present at a level of from 0.1 to 99.9% of said surfactant system.

21. A detergent composition according to either of claims 19 or 20 wherein the ratio of dianionic cleaning agent to nonionic surfactant is from 1 : 100 and 100: 1.

22. Use of the detergent composition according to any of claims 1 to 21 in a laundry washing method.

23. Use of the detergent composition according to any of claims 1 to 21 in a dishwashing method.