GB2332444A - A cleaning composition - Google Patents

Abstract

A cleaning composition or component thereof, comprising a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group, and a oxygen releasing bleach system, in particular systems comprising a hydrophobic peroxyacid bleaching component are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and bleachable stain removal.

Description

A Cleaning ComMsition 2332444

Technical Field

The present invention relates to a cleaning composition or component thereof, comprising a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group, and a oxygen releasing bleach system, in particular systems comprising a hydrophobic peroxyacid bleaching component. The compositions or components of the invention are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and bleachable stain removal.

Backeround to the Invention Amongst consumers there is a need for detergents which provide improved cleaning and stain removal. Different stains can have different properties. Therefore. there is a need to provide detergent compositions which contain various components which together can ensure the removal of all the different stains. Thus, in the last few years detergents have been developed which contain various ty pes of surfactants.

It is known to use cationic surfactants in detergent compositions. For example, GB 2040990A describes granular detergent compositions comprising cationic surfactants.

Furthermore. since certain stains are bleachable, detergent manufacturers have developed bleaches, which can act on the bleachable stains selectively, thus removing the bleachable stains whilst not damaging the fabrics. One type of bleach 3 which is particularly useful therefor is a hydrophobic bleach.

However, many detergent ingredients are not compatible with bleach. Thus, when seeking improved cleaning of both bleachable and non-bleachable stains by combining bleaches and surfactants, it is important that the surfactants are bleach compatible to get the maximum cleaning benefits.

2 1 The Applicants have now found that certain cationic surfactants, containing at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group are very good surfactants for use in cleaning or detergent compositions, which comprise bleach. These compounds are found to be very surface active, in particular under aWAine washing conditions, and they are found to give excellent cleaning performance benefits. This is believed to be due to the compounds containing both a positively charged group and a neutral, more hydrophobic group. Furthermore, several examples of these surfactants are found to be more biodegradable and to have a very low aquatic toxicity, relative to most quaternary amine compounds. It has also been found that the stability of the cationic surfactants is not affected by changes of the pH. The Applicants have found that these surfactants are bleach compatible and they have found that an improved nonbleachable stain removal can be achieved, whilst also an excellent bleachable stainremoval is obtained. In particular, compositions or components, comprising the cationic surfactant and a hydrophobic bleach system, have been found to provide an excellent bleachable and non-bleachable stain removal All documents cited in the present description are, in relevant part incorporated herein by reference.

1 Summary of the invention

The present invention provides a detergent or cleaning composition or component thereof comprising:

(a) at least 0. 0 1 % by. weight of the composition or component, one or more cationic surfactants. comprising a quatemized animoniurri group and a primary arnine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

(b) at least 0.05% by weight of the composition or component, an oxygen releasina bleach system.

3 Detailed descriLtion of the invention Cationic surfactant The compositions or components of the invention comprise at least 0.01% by weight of the composition or the component thereof, a cationic surfactant, which contains at least a quaternized ammonium group and a primary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

Preferred cationic surfactant of the present invention are polyamine cationic 10 surfactants of the general formula (I):

A-L- B-L c X L IVI - D (1) wherein L is a linking unit, and each L is independently selected from the group consisting Of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aral-ky-lene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene: L can be substituted by one or more A, B, C or D units; x is a number from 0 to I O y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from R, R.? - N R3 ffi M_ and ---- N R6 --B-= -N R7 R4 R5 E) M_ and 4 -C- -N 1 R8 wherein R I, R2, R3, R4, R5, R6, R7 and R8 are independently selected from the group consisting Of C I -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of RI, R2, R3, R4, R5, R6, R7 or R8 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or RI and R2, Rland R2 and R3, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure; or R3 is not present and RI or R2 is double bonded to the nitrogen; or R7 is not present and R6 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, R, or R2 or R3 and R4 or R5 form together with the nitrogen atoms of A and D part of a ring structure; M- is one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of R I, R-) or R- is hydrogen, or at least one B is present in which neither R6 nor R7 i 1 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group, or at least one C is present.

The units B-1- and C-L are linked when both are present (i.e. when x and y do not equal 0), and they can be randomly present along the chain between the end units AL and D.

Preferably, the value of x+y is from 1 to 4. Preferably. when x+y is greater than 1, at least one of present 2 1 roups A, B, C or D is a secondary or primary ammonium group.

Highly preferred cationic surfactant of the present invention are cationic surfactants of the general formula (1) r- A-L B- x-D (1) L 1 wherein L is a linking unit, and each L is independently selected from the group consisting Of C2-C30 linear or branched atkylene, alkenylene, alkarylene, aralkylene, arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B or D units; x is a number from 0 to 10; and wherein the unit A is R, ED R2-NM_ R3 R,6 E) -B- -N i M_ R7 and -D comprises a primary amine group and wherein RI, R2, R3, R4 or R5 are independently selected from the group consisting of C I -C-,o linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of RI, R2, R3, R4 or R5 can be a linear or branched polyoxyalkylene group,,,vith from 2 to 26 oxyalkylene units or RI and R2, Rland R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R I or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M- is one or more counterions.

1 c i 1 A----L- B-L j - L X J D (1) Yi wherein L is a linking unit, and each L is independently selected from the group consisting Of C2-C-3,0 linear or branched alkylene, alkenylene, alkarylene, aralkylene. arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L can be substituted by one or more A, B or D units; x is a number from 0 to 10; and wherein the unit A is 6 1 11 R 14 E) R2-N and -N M_ R3 R, R6 ED -B- = N M_ R7 and -D comprises a primary and wherein R I, R2, R3, R4 or R5 are independently selected from the group consisting Of C I -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of R I, R2, R3, R4 or R5 can be a linear or branched polyoxyalkylene _group with from 2 to 26 oxyalkylene units or R I and R2, R I and R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R I or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M- is one or more counterions.

Preferably, the value of x is from 1 to 4. More preferably, x is 0.

Preferably, R I is a C6-C 14 alkyl, (poly) hydroxyalkyl or alkoxy group or an aralk-.,-l group. most preferably a 2-ethythexyl group, R-) and R- are each independently C I C6, more preferably C I -C- alkyl or hydroxyallcyl groups and preferably R4 and R5 are each independently C I -C6. more preferably C I -C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups.

In a further preferred alternative, R4 is preferably a C6-C 14 alkyl, (poly) hydroxyalkyl, alkoxy group or an aralkyl group, most preferably a 2-ethylhexyl group R5 is preferably a C I -C6, more preferably a C I -C3 alkyl, (poly) hydroxyalkyl group and R 1, R2 and R3 are each independently preferably C I -C6, more preferably C I -C -, alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or aral-kyl groups.

7 When RI and R2, RI, R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.

L groups are independently preferably a C2-C8, more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x is 0, the L group is preferably a C2 alkyl group. If group L comprises more than 2 carbon atoms, the surfactant preferably comprises at least one primary or secondary A, B, C or D group.

Examples of preferred cationic surfactants of the present invention are:

R2 RI-N,-L-NH, (11) M_ R3 R2 CH3 R,-N-L-N-L-NH E) ED R3 M_ R6 M_ 2 (111) R2 RIO-N-L-N-H,) (1v) ED M_ R3 wherein RI and R, are as described above; R2, R3 are independently selected from the group consisting of methyl, ethyl, hydroxyethyl, hydroxypropyl, polyhydroxy 8 propyl, ethoxy, propoxy or 2,3,4,5,6-penta hydroxy hexyl, and are most preferably methyl or hydroxyethyl groups; R 10 is a methyl or hydroxyethyl group; L is as described above; RI and/or R2 are most preferably a 2-ethylhexyl group. A highly preferred cationic polyamine surfactant is of formula IV, as defined above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and R 10 are methyl groups, L is C2-C3 alkyl group.

Highly preferred cationic surfactant are those of the formulas:

Nf CH3 Nf CH3 1 NH2 E) R,-N-CH2-0h-NH2 or CH3-N-CH2-CH2-CH C113 CH3 R, 1 or M_ CH3 R N CR) -- CH, - CH, NIH-) CH3 wherein RI is as described above, preferably a C2-C 14, preferably C6-C 14 linear or branched alkyl, (poly) hydroxy alkyl, alkoxy or aralkyl group; particularly preferred RI groups are hydroxvalkyl groups, where the alkyl groups have 2 to 5 carbon atoms, especially hvdroxyethvl and hvdroxvpropyl are preferred, particularl-, preferred alkyl R I groups have up to 9 carbon atoms. most preferably R I is a 2ethylhexyl group, and RI I is a C2-C 14 alkyl, (poly) hydroxy alkyl. alkoxy or aralkyl group or a A or D unit as described above.

The anion M- is a countenon for the canonically charged surfactant. Therefore, the C number of M- anions present will depend on the catioruc charge of the surfactant, which depends on the groups A, B, C and D. The number of M- anions will be at least 1. A preferred countenon is a halide anion, more preferably a sulphate anion.

9 The cationic surfactant is generally present in the composition or component thereof in an amount no greater than 60% by weight, preferably no greater than 10% by weight, most preferably in an amount no greater than 4.5% or even 3% by weight. The benefits of the invention are found even with very small amounts of the cationic surfactant of the invention. Generally there wil-1 be preferably at least 0.05% or at least 0. 1 % by weight of the cationic surfactant in the detergent compositions of the invention.

0Lcygen releasing bleaching system An essential feature of the composition or components thereof, of the invention is at least 0.05% by weight of the composition or component thereof, an oxygen-releasing bleaching system. The oxygen-releasing bleaching system preferably contains an oxygen bleaching species including for example, inorganic perhydrate bleaches or organic peroxyacids, whereby a hydrophobic peroxyacid bleaching component or system, as described below, can be highly preferred.

In a preferred execution the bleaching system contains a hydrogen peroxide source and a peroxyacid bleach precursor compound. The production of the perox1vacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.

Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.

Inorganic pgrhydrate bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the sodium salt at a level of from 1% to 95% by wei ght, more preferably from 10% to 90% by weight and most preferably from 20% to 80% by weialit of the bleaching compositions. When incorporated in a bleaching composition which is comprised in a detergent composition in accordance with the present invention, the inorganic perhydrate salts are preferably present 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 detergent composition.

Examples of inorganic perhydrate salts include perphosphate, persulfate and persilicate salts. A preferred inorganic perhydrate salt is an alkali or alkaline earth )5 metal. preferably sodium or potassium, perborate salt. Sodium perborate can be in the form of the monohydrate of nominal formula NaBO2H202 or the tetrahydrate NaB02H202.3H20.

Sodium or potassium percarbonate can be a highly preferred percarbonate salt for inclusion in the compositions or components thereof, in accordance with the invention. Sodium percarbonate has a formula corresponding to 2Na2C03. 3H202, and is available commercially as a crystalline solid. The perhydrate salts and in particular percarbonate, is most preferably incorporated into such compositions or components thereof in a coated form which provides in product stability.

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 utilise a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.

A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to 0 Interox on 9th March 1977. The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1: 200 to 1: 4, more preferably from 1: 99 to 1 CI 9. and most preferably from 1: 49 to 1: 19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S04.n. Na2C03 wherein n is form 0. 1 to 33, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.

Other coatings which contain silicate (alone or with borate salts or boric acids or other inorp-anics), waxes. oils. fatty soaps can also be used advantageously within the present invention.

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

11 PeroUacid 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 0 X-C-L where L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is 0 X-C-OOH The group X can be any suitable substituent group. The highly preferred hydrophobic peroxylacid precursors will have a group X which contains at least 6 carbon atoms.

preferably from 8 to 25. more preferably from 9 to 15 carbon atoms.

Peroxyacid bleach precursors are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight and most preferably from 1.5% to 10% by weight of the composition or at a level of from 1 % to 50% by 2 0 weight, more preferably from 2% to 30% by weight, most preferably from 5% to 20% by weight of the components of the compositions.

Suitable peroxyacid bleach precursors typically contain one or more N- or 0- acyl erroups. which precursors can be selected from a wide range of classes, whereby it can be preferred that the precursor contains at least one N-acyl group. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871, 2143231 and EP-A0170386.

Leaving groups The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time fi-ame (e.g., a wash cycle).

12 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.

Y -0 3 Y, and -OC R3y 0 0 A\ -N N 3 Li 1 3 1 R R Y 1 Y R 3 1 -u-uti=u-CH=CH2 1 0 0 11 U 1 Y 1 -0-CH=C-CH=CH2 1 R3 0 Y 1 U 1 1 3 11 R 0 1 0 Y -N NR4 c 11 U and mixtures thereof, wherein R' is an alkyl, aryl, or alkaryl group containing from 1 4 to 14 carbon atoms, R is an alkyl chain containing from 1 to 8 carbon atoms, R is 1 3 H or R-, and Y is H or a solubilizing group. Any of R, R and R may be substituted by essentially any ftinctional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, arnide and ammonium or alkyl arrimmonium groups 13 The preferred solubilizing groups are, -SO 4 - M +, -N+(R3)4X- and 0<N(R3)3 and most preferably -SO 3_M+ and -CO 2-M most preferably - SO 3-M CO 2-M wherein R3 is an alkyl chain containing from I 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 allWi metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Cationic pgroLcyacid precursors Cationic peroxyacid precursor compounds are also suitable herein. Typically such cationic peroxyacid precursors are formed by substituting the peroxyacid part With an ammonium or alkyl anunmonium group, preferably an ethyl or methyl ammonium group.

Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4, 751,015; 4,988,45 1; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106, 528; U.K. 1,3 82,594; 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, Nacylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.

A preferred cationically substituted benzoyl oxybenzene sulfonate is the 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:

0 0-DS03- "N + r_ 1 / I Y 14 A preferred cationicaUy substituted alkyl oxybenzene sulfonate is the methyl ammonium derivative of 2,3,3-tri-methyl hexanoyloxybenzene sulfonate.

Preferred cationic peroxyacid precursors of the N-acylated caprolactarn class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:

0 0 N Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.

Alkyl fatty peroxyacid bleach precursors Alkyl fatty peroxyacid bleach precursors form alkyl fatty peroxyacids on perhydrolysis. Preferred precursors of this type give rise to peracetic acid on perhydrolysis.

Preferred alkyl fatty peroxyacid precursor compounds of the imide type include the N-,N,N IN 1 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.

Hydrophobic peroxyacid bleaching component For the purpose of the invention it can be highly preferred that the oxygen-releasing bleach system comprises a hydrophobic peroxyacid bleaching component or system. Namely, it has been found that compositions or components thereof comprising the cationic surfactmt of the invention and a hydrophobic bleaching system. preferably a hydrophobic peroxyacid bleaching system provide an excellent bleachable and non- bleachable stain removal.

Such a hydrophobic peroxyacid bleaching component or system is capable of providing a hydrophobic peroxyacid compound. By hydrophobic organic peroxyacid is compound it is meant herein an organic peroxyacid whose parent carboxylic acid has a critical micelle concentration less than 0.5 moles/litre and wherein said critical micelle concentration is measured in aqueous solution at 2T-50T. Preferably, the hydrophobic peroxyacid compound comprises at least one nitrogen atom.

Preferably the hydrophobic peroxyacid bleaching component or system comprises a hydrogen peroxide source and a hydrophobic peroxyacid bleach precursor compound. Preferably, the hydrophobic peroxyacid bleach precursor compound comprises at least one nitrogen atom. The production of the hydrophobic 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 as described above. In an alternative preferred execution, the hydrophobic peroxyacid bleaching component comprises a preformed hydrophobic peroxyacid, compnsing at least one nitrogen atorn, which is incorporated directly into the composition.

Compositions containing mixtures of a hydrogen peroxide source and hydrophobic peroxyacid precursor, in combination with a preformed hydrophobic peroxyacid are also envisaged.

Preferably, the hydrophobic peroxyacid contains at least 7 carbon atoms, more preferably at least 8 carbon atoms, or even more preferably at least 9 carbon atoms most preferably at least 11 carbon atoms. In a preferred aspect the peroxyacid has an alkyl chain comprising at least 7 carbon atoms, more preferably at least 8 carbon atoms, most preferably at least 9 carbon atoms.

_Amide substituted!Wgl 12eroxyacid precursors Preferred peroxyacid precursors are amide substituted alkyl peroxyacid precursor compounds, including those of the following general formulae:

R' -C-N-R2-C-1- R' --N-C--R2-C-L )o 0 R5 0 or R5 0 0 wherein R 1 is an aryl or 1 group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and lene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group. R 1 preferably contains 16 from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. RI may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R I and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386. It can be preferred that RI and R5 forms together with the nitrogen and carbon atom a ring structure.

Preferred examples of bleach precursors of this type include amide substituted peroxyacid precursor compounds selected from (6-octanamido caproyl)oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzene- suifonate, and the highly preferred (6-nonanamidocaproyl)oxy benzene sulfonate, and mixtures thereof as described in EP-A-0 1703 86.

Berizoxazin organic 1?2roxyacid precursors Also suitable are precursor compounds of the benzoxazin-t.YPe. as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:

0 11 L; 1 0 1 CON //C-Rl 2 5 1,0 wherein R is an alk-,.1, alkarvl. arvl. or arvlalkvl containine at least 5 carbon atoms.

N-acylated lactarn precursors Still another class of hydrophobic bleach activators are the N-acylated precursor compounds of the lactarn class disclosed generally in GB-A-955735. Preferred materials of this class comprise the caprolactams.

Suitable caprolactam bleach precursors are of the formula:

17 0 0 C - CH2 - CH2 1.1 CH2 RI - C - N CH2 - CH2 wherein R I is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. Preferred hydrophobic N-acyl caprolactarn bleach precursor materials are selected from benzoyl caprolactam, octanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, 3,5,5-trimethythexanoyl caprolactam and mixtures thereof A most preferred is nonanoyl caprolactam.

Suitable valero lactams have the formula:

0 R ' -- C - -- N CH2 --- C"2 wherein R I is an alkyl, aryl, alkoxyaryl or alkaryl group containing from 6 to 12 carbon atoms. More preferably, RI is selected from phenyl, heptyl, octyl, nonyl, 2.4,4-trimethylpentyl, decenyl and mixtures thereof Mixtures of any of the peroxyacid bleach precursor, herein before described, may also be used.

Perbenzolc acid precursor Essentially any perbenzoic acid precursors can be suitable herein, including those of the N-acylated lactam class, which are preferred.

Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and 25 unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:

18 1 1 0 00'O-DS03- Also suitable are the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents, including for example:

0Ac 0 AcO 0 0Ac 0Ad 0Bz Ac = COCH3, Bz = Benzoyl Preferred perbenzoic acid precursor compounds of the imide type include 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 berizimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Preferred perbenzoic acid precursors include the benzoyl diacyl peroxides, the berizoyl tetraacyl peroxides, and the compound having the formula:

0 0 0 J 011 OA COOH Plithalic anhydride is another suitable perbenzoic acid precursor compound herein:

19 0 0 (01 0 Perbenzoic acid derivative precursors Suitable perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the perbenzoic group is substituted by essentially any functional group including alkyl groups.

Other preferred precursors include derivatives or benzene sulfonates, preferably sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (isoNOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene suifonate (ABS). Preformed organic Peroxyacid The oxygen releasing bleach system may

contain, in addition to, or as an alternative to a, preferably hydrophobic organic peroxyacid bleach precursor compound, a preformed, preferably hydrophobic organic, peroxyacid Such a preformed peroxyacid is typically present at a level of from 0.05% to 20% by weight, more preferably from 1 % to 10% by weight of the composition.

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

R' ---C -- N-R2-C-OOH 0 R5 0 or R' -N-C-R2-C-00H R5 o 0 wherein R I is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R2 is an alkylene, arylene, and alkarylene group containing from about 1 to 14 carbon atoms, and R5 is H or an alkyl, aryl, or 1 group containing 1 to 10 carbon atoms. R I preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R I may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R2. R2 can include alkyl, aryl, wherein said R2 may also contain halogen, nitrogen, sulphur and other typical substituent groups or organic compounds. R5 is preferably H or methyl. R I and R5 should not contain more than 18 carbon atoms total. Amide substituted bleach activator compounds of this type are described in EP-A-0 1703 86. Suitable examples of this class of agents include (6octylamino)-6-oxo-caproic acid, (6-nonylamino)-6-oxo-caproic acid, (6-decylamino)-6-oxo-caproic acid, magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. 4, 483,781, U.S. 4,634,551, EP 0,133,354, U.S. 4,412,934 and EP 0, 170,3 86. A preferred hydrophobic preformed peroxyacid bleach compound for the purpose of the invention is monononylamido peroxycarboxylic acid.

Other suitable organic peroxyacids include diperoxyalkanedioc acids having more than 7 carbon atoms, such as diperoxydodecanedioc acid (DPDA), diperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. Mono- and diperazelaic acid, mono- and diperbrassylic acid and Nphthaloylaminoperoxicaproic acid (PAP), nonanoylamido peroxo-adipic acid (NAPAA) and hexane sulphenoyl peroxypropionic acid and are also suitable herein.

Other suitable organic peroxyacids include diamino peroxyacids, which are disclosed in WO 95/ 033275, with the following general formula:

r= 0 0 0 0 MOCRRl N)n- C (NR2)n'- R3 - R2N)M-C (NR1)rn- RCOOM wherein:

C5-C12 cYclO )o R is selected ftom the group consisting Of C 1 -C 12 alkylene, alkylene.

C6-C 12 arylene and radical combinations thereof, R 1 and R2 are independently selected from the group consisting of H, Cl - Cl 6 alkyl and C6-C 12 aryl radicals and a radical that can form a C-3-C 12 ring together with R. 1 and both nitrogens; R3 is selected from the group consisting Of C 1 -C 12 alkylene, C 5 21 1 Cl 2 cycloalkylene and C6-C 12 arylene radicals; n and n each are an integer chosen such that the sum thereof is I; m and m' each are an integer chosen such that the sum thereof is 1; and M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.

Other suitable organic peroxyacids are include the amido peroxyacids which are disclosed in WO 95/ 16673, with the following general structure:

X -Ar-CO - NY- R(Z) -CO -OOH in which X represents hydrogen or a compatible substituent, Ar is an aryl group, R represents (CH2)n in which n = 2 or 3, and Y and Z each represent independently a substituent selected from hydrogen or an alkyl or aryl or 1 group or an aryl group substituted by a compatible substituent provided that at least one of Y and Z is not hydrogen if n = 3. The substituent X on the benzene nucleus is preferably a hydrogen or a meta or para substituent, selected from the group comprising halogen. typically chlorine atom, or some other non-released non-interfering species such as an alkyl group, conveniently up to C6 for example a methyl, ethyl or propyl group.

Alternatively, X can represent a second amido-percarboxylic acid substituent of formula:- -CO-NY-R(Z)-CO-OOH in which R, Y, Z and n are as defined above.

MOOC-RICO-NR2-R3-NR4-CO-R5C000M 0 3 wherein RI is selected from the group consisting Of C 1 -C 12 alkylene, C5-C 12 cycloalkylene, C6-C 12 arylene and radical combinations thereof, R It may be found to be particularly useful to mix the pre-formed peroxyacid or the peroxyacid precursor with the cationic surfactant, pnor to incorporation with any 3 3 5 other components of the detergent composition.

22 Additional compgne The detergent compositions or components thereof in accordance with the present 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 or component thereof, and the precise nature of the washing operation for which it is to be used.

The compositions or components thereof, of the invention preferably contain one or more additional detergent components selected from additional surfactants, builders, sequestrants, chlorine-based bleach, bleach catalysts, organic polymeric compounds, additional enzymes, suds suppressors, lime soap dispersants, additional soil suspension and anti-redeposition agents soil releasing agents, perfumes and corrosion inhibitors.

Additional surfactant The compositions or components thereof in accordance with the invention preferably contain an additional surfactant selected from anionic, nonionic, additional cationic. ampholytic, amphoteric and zwritterionic surfactants and mixtures thereof A typical listing of anionic, nonionic. ampholytic, and zwitterionic classes, and species of these surfactants, is given in U.S.P. _3 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 11 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.)1,1981.

The total amount of surfactants is preferably of from 1 % to 95%, preferably 3% to 70%, more preferably 5% to 40%, even more preferably 10% to 30%, most preferably 12% to 25% by weight of the detergent composition.

23 Anionic surfactant The composition or components of the present invention can comprise one or more anionic surfactants. Any anionic surfactant useful for detersive purposes is suitable. Examples 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.

3 5 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 C12-CI8 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C 14 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.

The anionic surfactant is preferably present at a level of 0.5% to 60%, preferably at a level of from 3 % to 50%, more preferably of from 5% to 5%, most preferably from 6% to 20% by weight of the composition.

The ratio of the anionic surfactant to the cationic surfactant is preferably from 25:1 to L3), more preferably from 15:1 to 1: 1. most preferably from 10: 1 to 1: 1.

Anionic sulfate surfactant Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates. fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C 5-C 17 acyl-N-(C I -C4 alkyl) and -N-(C I -C2 hydroxyaBcyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl sulfate surfactants are preferably selected from the linear and branched primary C9-C22 alkyl sulfates, more preferably the C I I -C 15 branched chain alkyl sulfates and the C I 2-C 14 linear chain alkyl sulfates.

24 Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C I O-C 18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C I I -C 18, most preferably C I I -C 15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from I to 5, moles of ethylene oxide per molecule.

A particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate 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, C6C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof Anionic carboxylate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants, and the soaps ('alkyl carboxyis'), especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH20)x CH.)C00-M+ wherein R is a C6 to C 18 alkyl group, x ranges from 0 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 polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR 1 -CHR2-0)x-R3 wherein R is a C-6 to C 18 alkyl group. x is from 1 to 25, RI and R.) are selected from the group consisting of hydrogen. methyl acid radical, succinic acid radical, hydroxysuccinic )o 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 3 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-methyl1 -undecanoic: acid, 2-ethyl- 1 - decanoic, acid, 2-propyl1 -nonanoic acid, 2-butyl- 1 -octanoic acid and 2- pentyl- 1 -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 (R 1) CH2 COOM, wherein R is a C5-C 17 linear or branched alkyl or alkenyl group, R 1 is a Cl -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.

The nonionic surfactant is preferably present at a ratio to the anionic surfactants of the invention of from 10: 1 to 1: 10, more preferably from 5:1 to 1: 10, even more preferably from 1: 1 to 1: 10.

Preferred alkoxylated surfactants can be selected from the classes of the nonionic 210 condensates of alkyl phenols, nonionic ettioxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates With propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxvIated alcohol surfactant The condensation products of aliphatic alcohols with from I 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, more preferably form 9 to 15 carbon atoms, with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic i)olyhydroxv Lan acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR 1 Z wherein: RI is H, C 1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2- 26 hydroxy propyl, ethoxy, propoxy, or a mixture thereof, preferable Cl -C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a C5 C31 hydrocarbyl, preferably straight-chain C5-C I g alkyl or alkenyl, more preferably straight-chain C9-C 17 alkyl or alkenyl, most preferably straight-chain C 11 -C 17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydyl 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: R6CON(R7)2 wherein R6 is an alkyl group containing from 7 to 2 1, preferably from 9 to 17 carbon atoms and each R7 is selected from the group consisting of hydrogen, Cl - C4 alkyl, C 1 -C4 hydroxyalkyl, and -(C2H40)xH, where x is in the range of from 1 to 3.

Noniorue alkylvolysaccharide surfactant Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4,565,647, 0 Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 3 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from 1.3 to 10 saccharide units.

Preferred alkylpolyglycosides have the formula R20(CnH'-?nO)t(glYcOsvl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, 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 denved from glucose.

Amphoteric surfactant Suitable amphoteric surfactants for use herein include the amine oxide surfactants, -35 and the alkyl amphocarboxylic acids.

27 Suitable amine oxides include those compounds having the formula R3(OR4)x NO(R5)2 wherein R3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R4 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 R5 is an alkyl or hydroxyalkyl group containing from I to 3, or a polyethylene oxide group containing from I to 3 ethylene oxide groups. Prefen-ed are C I O-C 18 alkyl dimethylamine oxide, and C 10- 18 acylatnido alkyl dimethylamine oxide.

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

Zwitterionic surfactant Zwitterionic surfactants can also be incorporated into the detergent compositions or components thereof in accord with the invention. 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(WbN+ R2COOwherein R is a C6-CI8 hydrocarbyl group, each RI is typically Cl-C3 alkyl, and R2 is a Cl -C5 hydrocarbyl group. Preferred betaines are C 1218 dimethyl-ammonio hexanoate and the Cl 0- 18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

Additional Cationic surfactants A suitable group of cationic surfactants which can be used m the compositions or components thereof of the invention are cationic ester surfactants.

The cationic ester surfactant is a compound having surfactant properties compnsing at least one ester (i.e. -COO-) linkage and at least one cationically charged group. Preferred cationic ester surfactants are water dispersible.

Suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents Nos. 4228042, 42-39660 and 4260529.

28 1 Other additional cationic surfactants are mono- or bis -alkoxylated amine surfactant. the mono-alkoxylated surfactants are of the general formula:

1 "I' N + I_.', R""' ', R3 ApR 14 X- wherein RI is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, most preferably from about 6 to about 11 carbon atoms; R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms, preferably methyl; R4 is selected from hydrogen 10 (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is selected from C I -C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and p is from 1 to about 30, preferably 1 to about 15, most preferably 1 to about& When used in granular detergent compositions cationic mono-alkoxylated amine surfactants wherein the hydrocarbyl substituent R 1 is C6-C 11, especially Cl 0, are preferred, because they enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.

Cationic bis-alkoxylated amine surfactants which are useful as additional cationic surfactants which have preferably the general formula:

R7 R 1 1 Ap _) N + 11"" '- AqR X wherein R I is an alkyl or alkenyl moiety containing from about 6 to about 18 carbon atoms, preferably 6 to about 16 carbon atoms, more preferably 6 to about 11, most preferably from about 8 to about 10 carbon atoms; R2 is an alkyl group containing from one to three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X- is an 50 anion such as chloride, bromide, methylsulfate. sulfate, or the like, sufficient to 29 provide electrical neutrality. A and A' can vary independently and are each selected from Cl -C4 alkoxy, especially ethoxy, (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof, p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30, preferably 1 to about 4, and most preferably both p and q are 1.

The levels of the cationic mono or bis-alkoxylated amine surfactants used in detergent compositions or components of the invention can range from 0. 1 % to 20%, more preferably from 0.4% to 7%, most preferably from 0.5% to 3.0% by weight of the composition.

Acid Source In particular the solid compositions or components thereof, which can be preferred compositions or components of the invention, preferably comprise an acid source, such that the acid source is capable of reacting with an alkalinity system, in the presence of water to produce a gas.

The acid source is preferably present at a level of from 0. 1 % to 50%, more preferably from 0.5% to 25%, even more preferably from 1% to 12%, even more preferably from 1 % to 7%, most preferably from 2% to 5% by weight of the composition. It can be preferred that the source of acidity is present in the range of about 1 % to about 3 3%, most preferably about 3% by weight of the composition.

The acid source may be any suitable organic, mineral or inorganic acid, or a derivative thereof, or a mixture thereof. The acid source may be a mono-, bi- or triprotonic acid. Preferred derivatives include a salt or ester of the acid. The source of acidity is preferably non-hygroscopic, which can improve storage stability. However. a monohydrate acidic source can be useful herein. Organic acids and their derivatives are preferred. The acid is preferably water-soluble. Suitable acids include citric, )0 glutaric, tartaric acid, succinic or adipic acid, monosodiurn phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred.

Metal containing bleach catalyst The compositions or components thereof, of the invention can contain a metal containing bleach catalyst. Preferably the metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese containing bleach catalyst and most preferably a bi-nuclear complex of manganese or manganese gluconate.

A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron 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, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.

Such catalysts are disclosed in U.S. Pat. 4,430,243.

Preferred 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 MnIV2(u-0)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(PF6)2, Mnll'2(u 0)1(u-OAc)2(1,4,7-trimethyl-1,4,7-triazacyclononane)2-(CI04)2, MnIV4(u 0)6(1,4,7-triazacyclononane)4-(CI04)2, Mnl"MnlV4(u-O) I (u-OAc)2-(1,4,7 trimethyl-1,4,7-triazacyclononane)2-(CI04)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- 1,5,9triazacyclododecane, 2-methyl 1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7- tetramethyl 1,4,7-triazacyclononane, and mixtures thereof.

The bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. 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(1,4,7-trimethyl- 1,47 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.

31 Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, ineso-crythritol, meso-inositol, lactose, and mixtures thereof.

U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition 5 metals, including Mn, Co, Fe, or Cu, with an non-(macro)cyclic ligand. Said ligands are of the formula:

R2 R3 Rl-N=C-B-C=N-R4 wherein R I, R2, R3, and R4 can each be selected from H, substituted alkyl and aryl groups such that each R I -N=C-R2 and R3 -C=N-R4 form a five or six-membered ring. Said ring can further be substituted. B is abridging group selected from 0, S. COO, NR7 and C=O, wherein R5, R6, and R7 can each be H, alkyl, or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, 15 pyndazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings. Optionally, said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro. Particularly preferred is the ligand 2,2'- bispyridylaniine. Preferred bleach catalysts include Co, Cu, Mn, Fe,- bispyridylmethane and -bispyridylamine complexes. Highly preferred catalysts include Co(2,2'-bispyridylamine)CI2, 20 Di(isothiocyanato)bispyridylamine-cobalt (11), trisdipyridylaminecobalt(II) perchlorate, Co(2,2-bispyridylamine)202CIO4, Bis-(2,2'bispyndylaminc) copper(II) perchlorate, tris(di-2-pyridylamine) iron(II) pcrchlorate. and mixtures thereof Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N dentate ligands, including N4Mn111(11-0)2MInIVN4)1and IBIPY2MnIlI(Ii 0)2MnIVbiPY2]-(C104)' 3.

Other bleach catalysts are described, for example, in European patent application, publication no. 408,133 1 (cobalt complex catalysts), European patent applications, 3 )0 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 alurninosilicate catalyst), U.S. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119, 557 (ferric 32 complex catalyst), German Pat. specification 2,054,019 (cobalt chelant catalyst) Canadian 866,191 (transition metal-containing salts) and U.S. 4, 430,243 (chelants with manganese cations and non-catalytic metal cations). Highly preferred catalyst are describedU.S. 4,728,455 (manganese gluconate catalysts).

The bleach catalyst is typically used in a catalytically effective amount in the compositions and processes herein. By "catalytically effective amount" is meant an amount which is sufficient, under whatever comparative test conditions are employed, to enhance bleaching and removal of the stain or stains of interest from the target substrate. The test conditions will vary, depending on the type of washing appliance used and the habits of the user. Some users elect to use very hot water; others use warm or even cold water in laundering operations. Of course, the catalytic performance of the bleach catalyst will be affected by such considerations, and the levels of bleach catalyst used in fully-formulated detergent and bleach compositions can be appropriately adjusted. As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about I ppm to about 200 pprn of the catalyst species in the wash liquor. To illustrate this point further, on the order of _3 micromolar manganese catalyst is effective at 40'C, pH 10 under European conditions using perborate and a peroxyacid bleach precursor. An increase in concentration of 3 3-5 fold may be required under U.S. conditions to achieve the same results.

Alkalinitv In the compositions or components of the present invention preferably an alkalinity system is present to achieve optimal cationic surfactant performance. The alkalinity system comprises components capable of providing alkalinity species in solution.

Examples of alkalinity species include carbonate, bicarbonate, hydroxide. the various silicate anions. percarbonate. perborates, perphosphates, persulfate and persilicate. Such alkalinity species can be formed for example, when alkaline salts selected firom alkali metal or alkaline earth carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, salts and percarbonate, perborates, perphosphates, persulfate and persilicate salts and any mixtures thereof are dissolved in water.

33 Examples of carbonates are the aficaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any mixtures thereof with ultra-fine calcium carbonate such as are disclosedin German Patent Application No. 2,32 1,001 published on November 15, 1973.

Suitable silicates include the water soluble sodium silicates with an Si02:NA20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to 2.0 being preferred, and 2.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO2:Na20 ratio of 2.0 is the most preferred 10 silicate.

Preferred crystalline layered silicates for use herein have the general formula NaMSix02x+Iffi20 wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A 0 164514 and methods for their preparation are disclosed in DE-A-3417649 and DE A-3 3 742043 3. Herein, x in the general formula above preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is 8-Na2Si2O5, available from Hoechst AG as NaSKS-6.

Water-soluble builder com122und The compositions or components in accordance with the present invention preferably contain a water-soluble builder compound, typically present in detergent compositions at a level of from 1 % to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to &M 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.

34 The carboxylate or polycarboxylate builder can be monomeric 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, watersoluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuceinates 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- 1, 1,3 -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 --'0 tetracarboxylates an d 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 monomenc or oligomene 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.

0 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 ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from about 6 to 2 1, and salts of phytic acid.

Partially soluble or insoluble builder coMpQund The compositions or components thereof, of the present invention may contain a partially soluble or insoluble builder compound, typically present in detergent compositions 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 Naz[(A102)z(Si02M. xl-120 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 firom 10 to 264. llie aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water m bound forTn.

The aluminosilicate zeolites can be naturally occurring materials. but are preferably synthetically derived. Synthetic crystalline alurninosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof Zeofite A has the formula Na 12 [(A102) 12 (Si02)121. xH20 wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(A102)86(SiO2)1061. 276 H20.

3 )o Another preferred aluminosilicate zeolite is zeolite builder. The zeolite MAP can be present at a level of from 1% to 80%, more preferably from 15% to 40% by weight of the compositions.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate of the zeolite P type having a silicon to aluminiurn ratio 36 not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite having a silicon to aluminium ratio not greater than 1. 15 and, more particularly, not greater than 1.07.

In a preferred aspect the zeolite detergent builder has a particle size, expressed as a d50 value of from 1.0 to 10.0 micrometres, more preferably from 2.0 to 7.0 micrometres, most preferably from 2.5 to 5.0 micrometres.

The d50 value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may, in particular be determined by conventional analytical techniques such as microscopic determination using a scanning electron microscope or by means of a laser granulometer. Other methods of establishing d50 values are disclosed in EP 384070A.

HeM metal ion sequestrant The compositions or components thereof in accordance with the present 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 I hydroxy disphosphonates and nitrilo trimethylene phosphonates.

Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine 3 tetra (methylene phosphonate) and hydroxy-ethylene 1, 1 diphosphonate.

37 Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetdamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2hydroxypropylenediamine 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 ammonium 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-2hydroxypropyl sulfonic acid and aspartic acid N- carboxymethyl N-2-hydroxypropyl3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The 0-alanine-N,N'-<iiacetic 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 2phosphonobutane- 1,2,4-tricarboxylic acid are also suitable. Glycinamide-N,N'disuccinic acid (GADS), ethylenediamine-N-N'-diglutaric acid (EDDG) and 2hydroxypropylenediamine-N-N'-disuccinic acid (HPDDS) are also suitable.

EMmes The compositions or components thereof of the present Invention may comprise one or more enzymes.

Preferred additional enzymatic materials include the commercially available 3 enzymes. Said enzymes include enzymes selected from lipases, cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, B-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof 38 A preferred combination of additional enzymes in a composition according to the present invention comprises a mixture of conventional applicable enzymes such as lipase, protease, amylase, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes. Suitable enzymes are exemplified in US Patents -33,519,570 and 3,533,139.

Suitable proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASEV by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE9, DURAZYM9 and SAVINASES from Novo and MAXATASES, MAXACALS, PROPERASE(t and MAXAPEM8 (protein engineered Maxacal) from Gist Brocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28. 198-7 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealy- tic enzyme which is called "Protease A" herein. Suitable is what is called herein "Protease C", which is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27. tyrosine replaced valine at position 104, serine replaced asparagine at position 123), and alanine replaced threonine at position 274.

Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16. 1991. Genetically modified variants. particularly of Protease C, are also included herein.

A 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 +99, +101, +103, +104, -107, -,-1233. +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, -206, +210. +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in W095/10591 and 39 in the patent application of C. Ghosh, et al, 'Tleaching Compositions Comprising Protease Enzyines" having US Serial No. 081322,677, filed October 13, 1994.

Also suitable for the present invention are proteases described in patent applications EP 251446 and WO 91/06637, protease BLAPIC described in W091/02792 and their variants described in WO 95/23221.

See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever.

One or a mixture of proteolytic enzymes may be incorporated in the compositions of the present invention, generally at a level of from 0. 0001% to 2%, preferably from 0.00 1 % to 0.2%, more preferably from 0. 005% to 0. 1 % pure enzyme by weight of the composition.

If present in the detergent compositions of the present invention, the lipolytic enzyme component is generally present at levels of from 0. 00005% to 2% of active enzyme by weight of the detergent composition, preferably 0.00 1 % to 1 % by weight, most preferably from 0.0002% to 0.05% by weight active enzyme in the detergent composition.

Suitable lipolytic enzymes for use in the present invention include those produced by micro-organisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipases include those which show a positive immunological cross-section with the antibody of the lipase produced by the microorganism Pseudomonas Hisorescent LkM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Other suitable comm ial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticurn NRRLB 3673, conunercially available from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.

Especially suitable lipases are lipases such as MI LipaseR and Lipom,,xR (Gist Brocades) and LipolaseR and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.

Also suitable are the lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.

-)o 3 Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A- 88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Hurnicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred lipase for use in the present invention.

Another preferred lipase for use in the present invention is D96L lipolytic enzyme variant of the native lipase derived from Humicola lanuginosa- Most preferably the Humicola lanuginosa strain DSM 4106 is used.

By D96L lipolytic enzyme variant is meant the lipase variant as described in patent application WO 92/05249 in which the native lipase ex Humicola lanuginosa has the aspartic acid (D) residue at position 96 changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as: D96L. To determine the activity of the enzyme D96L the standard LU assay may be used (Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A substrate for D96L was prepared by emulsiing glycerine tributyrate (Merck) using gurn-arabic as emulsifier. Lipase activity is assayed at pH 7 using pH stat. method.

0 The detergent compositions of the invention may also contain one or a mixture of more than one amylase enzyme (cc and/or 0). W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also W095/10603, Novo Nordisk A/S, published April 20, 1995. Other arnylases known for use in cleaning compositions include both cc- and Pamylases. cc-Amylases are known in the art and include those disclosed in US Pat. no. 5.003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; 41 11 EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced amyh-ises described in WO94/18314, published August 18, 1994 and W096/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are ainylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).

Examples of commercial a-amylases products are Purafect Ox AmO from Genencor and TermamylO, BanO Fungamyll" and Duramylg, all available from Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases: a-amylases characterised by having a specific activity at least 25% higher than the specific activity of TermamylO 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 PhadebasO cc-amylase activity assay. Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk). Other preferred amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in W095/35382.

The arnylolytic enzymes if present are generally incorporated in the compositions of the present invention a level of from 0.000 1 % to 2%, preferably from 0. 000 18% to 0.06%, more preferably from 0.00024% to 0. 048% pure enzyme by weight of the composition.

The detergent compositions of the invention may additionally incorporate one or more cellulase enzymes. Suitable cellulases include both bacterial or fungal cellulases. Preferably, they will have a pH optimum of between 5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which '30 disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A2.075.028; GB-A-2.095.275; DE-OS-2-247.832 and W095/26398.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.

42 Other suitable ceflulases are cellulases originated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric: point of 5.5 and containing 415 amino acids; and a -43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase activity; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGUI cellulases from Trichoderma longibrachiaturn described in W094/2180 1, Genencor, published September 29, 1994. Especially suitable cellulases are the ceilulases having color care benefits. Examples of such cellulases are cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especially useful. See also W091/17244 and W091/21801. Other suitable cellulases for fabric care and/or cleaning properties are described in W096/34092, W096/17994 and WO95/24471.

Peroxidase enzymes may also be incorporated into the detergent compositions of the invention. Peroxidasis are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo- peroxidase. Peroxidasecontaining detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, W089/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed Februarv -15 20, 1996. Also suitable is the laccase enzyme.

Preferred enhancers are substituted phenthiazine and phenoxasine 10Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC). 1 0-phenoxazinepropionic acid (POP) and 1 0-methylphenoxazine (described in WO 3 30 94/1262 1) and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.

Said cellulases and/or peroxidases, if Present, are normally incorporated in the 3 5 composition at levels from 0.000 1% to 2% of active enzyme by weight of the detergent composition.

43 Said additional enzymes, when present, are normally incorporated in the composition at levels from 0.000 1% to 2% of active enzyme by weight of the detergent composition. The additional enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (e.g. cogranulates).

Organic 12glymen 2c compgund Organic polymeric compounds are preferred additional components of the compositions or components thereof of the present invention, and are preferably present as components of any particulate component of the detergent composition where they may act such as to bind the particulate component together. By organic polymeric compound is meant any polymeric organic compound commonly used as dispersants, anti-redeposition or soil suspension agents in detergent compositions, including any of the high molecular weight organic polymeric compounds described as clay flocculating agents herein.

Such an organic polymeric compound is generally incorporated in the compositions of the invention at a level of from 0. 1 % to 30%, preferably from 0.5% to 15%, most preferably firom 1 % to 10% by weight of the compositions.

"0 3 Examples of organic polymeric compounds include the water soluble organic homoor 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 twocarbonatoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylic acid or polyacrylates of MWt 1000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 2000 to 100,000, especially 40,000 to 80,000. Polymaleates or polyMaleic acid polymers and salts thereof are also suitable examples.

Polyamino compounds useful herein include those derived from aspartic acid including polyaspartic acid and such as those disclosed in EP-A- 305282, EP-A305283 and EP-A-351629.

3 Terpolymers containing monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, particularly those having an average 44 1 molecular weight of from 1,000 to 30,000, preferably 3,000 to 10,000, are also suitable for incorporation into the compositions of the present invention.

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

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

Cationic soil removal/anti-redepQsition compLc)unds The composition or components thereof of the invention may comprise water-soluble cationic etboxylated amine compounds with particulate soil/clay-soil removal and/or anti-redeposition properties. These cationic compounds are described in more detail in EP-B-1 11965, US 4659802 and US 4664848. Particularly preferred of these cationic compounds are ethoxylated cationic monoamines, diamines or triamines. Especially preferred are the ethoxylated cationic monoamines. diarnines and triamines of the formula:

F'! i CH CH 3 X -(- OCH CH ---'N±-CH -(--CH.) N ---CH CH 2 2)n 2 2 a 2 20 --yn- X (CR)CH20 ---n- X (CH2CRyO 4n- X wherein X is a nonionic group selected from the group consisting of H, Cl -C4 alkyl or hydroxyalkyl ester or ether groups, and mixtures thereof. a is from 0 to 20, preferably from 0 to 4 (e.g. ethylene, propylene, hexamethylene) b is 2, 1 or 0; for cationic monoamines (b--0), n is preferably at least 16, with a typical range of from in a -3 20 to 35; for cationic diami es or triarnines, n is preferably at least about 12 with typical range of from about 12 to about 42.

1 These compounds where present in the composition, are generally present in an amount of from 0.01 to 30% by weight, preferably 0.05 to 10% by weight.

Suds sUppressing system The compositions of the invention are preferably substantially free of any suds suppressing agents where high foaming is desired. It can be preferred that the composition require low-sudsing, and that thus incorporation of suds suppressant for foam control are desirable. They are preferably present in amounts no greater than 2.5% and most preferably in amounts no greater than 1.5% or even no greater than 10 0. 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 siloxane units and hydrocarbyl group of various types. Preferred silicone antifoarn 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 alkanolammoniurn salts. 46 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 I 8-C40 ketones (e.g. stearone) Nalkylated 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 an- iine containing I 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) antifoarn compound, preferably silicone antifoarn 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 antifoarn compound; and (ii) silica, at a level of from 1% to 50%. preferably 5% to 25% by weight of the silicone/silica antifoarn compound; wherein said silica/silicone antifoarn 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 polvoxYalkylene 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 30 Coming under the tradename DC0544; an inert carrier fluid compound, most preferably comprising a C 16-C 18 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; 3 5 47 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.

Polyrneric dve transfer inhibitinp- agents The compositions herein may also comprise from 0.0 1 % 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, polyvinylpyrrolidone polymers or combinations thereof. whereby these polymers can be cross-link-ed polymers.

a) Polvamine N-oxide p2Ivmer -)o Polyamine N-oxide polymers suitable for use herein contain units having the following structure formula:

p (1) Ax R -Y - wherein P is a polymensable unit, and 0 R' R10 0 0 R' A Is C N. - N C -. CO. C. - 0 -. - S -. - - N -; x is 0 or 1; R I is H or C 1 -6 linear or branched alkyl; or may form a heterocyclic group with R-, R are aliphatic. ethoxylated aliphatics, aromatic, heterocyclic or alicyclic groups or 0 any combination thereof whereto the nitrogen of the N-0 group can be attached or wherein the nitrogen of the N-0 group is part of these groups.

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

0 A 0 (R,) x -W(R2)y A (R3)z or - W(R1)x wherein RI, 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-0 group can be attached or wherein the nitrogen of the N-0 group forms part of these groups. The N-0 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-0 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 polyarnine N-oxides comprises the aroup of polvarnine N-oxides wherein the nitrogen of the N- 0 group forms part of the R-group- Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine. N-substituted pyrrole, imidazole. N-substituted pyrrolidine, pipendine, quinoline. acridine and derivatives thereof Other suitable polyarnine N-oxides are the polyamine oxides whereto the N- 0 group is attached to the polymensable unit. A preferred class of these polywnine N-oxides comprises the polyamine N-oxides having the general formula (1) wherein R is an aromatic.heterocyclic or alicyclic groups wherein the nitrogen of the N-0 functional group is part of said R group. Examples of these classes are polyarnine oxides wherein R is a heterocyclic compound such as pyridine. N-substituted 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 49 water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copol3gners of N-vinylpyrrolidone and N-vinylimidazole Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone having a preferred average molecular weight range of from 5,000 to 100, 000, or 5,000 to 50,000. The preferred copolymers have a molar ratio of Nvinylimidazole to Nvinylpyrrolidone from 1 to 0.2.

c) PolyyinvIpMolidone The compositions herein may also utilize polyvinylpyrrolidone (WP') 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 K15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are cornmercially available from BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

* )o d) Polyvinyloxazolidone The 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.

c) Polvvinylimidazole The compositions herein may also utilize poly.vinylimidazole as polymeric dye transfer inhibiting agent. Said polyvinylinlidazoles preferably have an average molecular weight of from 2,500 to 400,000.

0mical brightener The 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:

so R, R2 N H H N N O-N C=C -N-ON -Q H 1 1 RN H S03M S03M N- R wherein RI is selected from anilino, N-2-bis-hydroxyethyl and N11-2- hydroxyethyl; R2 is selected firom N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R I 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-bishydroxyethyl)-s-triine-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 Corporation. Tinopal-L N-,PA-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-2methylainino and M is a cation such as sodium, the brightener is 4,4'bis[(4-anilino-6-(N-2h droxyethyl-N-methylamino)-s-triazine-2-yl)amino]2, 2'-stilbenedisulfonic acid y I disodium salt. This particular brightener species is commercially marketed under the 20 tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

-) z, When in the above formula, R1 is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-arulino-6-morphilino- s-triazine-2--,1 [)amino ] 2.21' stilbenedisulfonic acid, sodium salt. This particular brightener species is commercialIv marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

Polymeric Soil Release Agent Known polymeric soil release agents, hereinafter 'SRA". can optionally be employed in the present compositions or components. If utilized, SRA's will generally comprise from 0.0 1 %to 10.0%, ty pically from 0. 1 % to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.

51 Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incorporated into the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric or polymeric ester backbone of terephthaloyl and oxyalkylentoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4, 968,451, November 6, 1990 to JI Scheibel and E.P. Gosselink. Such ester oligomers can be prepared by: (a) ethoxylating allyl alcohol; (b) reacting the product of (a) With dimethyl terephthalate ("DMT') and 1,2-propylene glycol (TW) in a two- stage transesterification/oligomerization procedure; and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1-2propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by transestenfication/oligomenzation of poly(ethyleneglycol) methyl ether. DMT. PG and poly(ethyleneglycol) (TEW). Other examples of SRA's include: the partly- and fully- anionic-end- capped oligomeric esters of U.S. 4.721,580, January 26. 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6dioxa-8hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink. for example produced from DMT, methyl (Me)-capped PEG and EG and/or PG. or a combination of DMT. EG and/or PG, Me-capped PEG and Na-dimethyl-5sulfolsophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4.877.896, October 31, 1989 to Maldonado, Gosselink et al., the latter being typical of SRA's useful in both laundry and fabric conditioning products. an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT, optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene tereplithalate with polyethylene oxide or polypropylene oxide tereplithalate, see U.S. 3,959,230 to Hays, May 25. 1976 and U.S. 3. 893.929 to 52 Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; the CI-C4 alkyl celluloses and C4 hydroxyalkyl celluloses, see U.S. 4,000,093, December 28, 1976 to Nicol, et al.; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose unit from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20C as a 2% aqueous solution. Such materials are available as METOLOSE SMIOO and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

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.

Near neutral wash r)H deterRent formulation While the detergent compositions of the present invention are operative within a wide range of wash pHs (e.g. from about 5 to about 12). they are particularly suitable when formulated to provide a near neutral wash pH, i.e. an initial pH of from about 7.0 to about 10.5 at a concentration of from about 0. 1 to about 2% by weight in water at 20'C. Near neutral wash pH formulations are better for enzyme stability and for preventing stains from setting. In such formulations, the wash pH is preferably from about 7.0 to about 10.5, more preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.

Preferred near neutral wash pH detergent formulations are disclosed to European Patent Application 83.200688.6, filed May 16, 1983. J.H.M. Wertz and P.C.E. Goffinet.

0 Highly preferred compositions of this type also preferably contain from about 2 to about 10% by weight of citric acid and minor amounts (e.g., less than about 20% by weight) of neutralizing agents, buffering agents, phase replants. hydrotropes, enzymes, enzyme stabilizing agents. polyacids, suds regulants, opacifiers, antioxidants. bactericides, dyes. perfumes and bnghteners. such as those described in US 35 Patent 4.285. 841 to Barrat et al., issued August 25, 1981 (herein incorporated by reference).

53 i In a preferred aspect of the invention the cationic surfactant is present in a solid detergent composition in granules which additionally contain an acidic component such as a carboxylic acid, such as citric or tartaric acid. In this way, near neutral to acid conditions may be present in the vicinity of the cationic surfactant for at least part of the delivery and wash process.

Form of the comppsitions The compositions in accordance with the invention can take a variety of physical forms including granular, tablet, flake, pastille and bar and liquid forms. Liquids may be aqueous or non-aqueous and may be in the form of a gel. 71-he compositions may be pre-treatment compositions or may be conventional washing detergents. 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.

Such granular detergent compositions or components thereof M accordance with the present invention can be made via a variety of methods, including spray-drying. drymixing. extrusion, agglomerating and granulation. The cationic quaternised surfactant can be added to the other detergent components by mixing, agglomeration (preferably combined with a carrier material), granulation or as a spray-dried component.

The compositions in accordance with the present invention can also be used in or in combination with bleach additive compositions, for example comprising chlorine bleach.

In one aspect of the invention the mean particle size of the components of _granular compositions in accordance with the invention, should preferably be such that no more than 15% of the particles are greater than 1.8mm in diameter and not more than 15% of the particles are less than 0.25mm in diameter. Preferably the mean particle size is such that from 10% to 50% of the particles has a particle size of from 0.2= to 0.7mrn in diameter.

3 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 sieves, 54 preferably Tyler sieves. The weight fi-actions 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.

In a further aspect of the invention at last 80%, preferably at least 90% by weight of the composition comprises particles of mean particle size at least 0.8 mm, more preferably at least 1.0 mm and most preferably from 1. 0, or 1.5 to 2.5 mm. Most preferably at least 95% of the particles will have such a mean particle size. Such particles are preferably prepared by an extrusion process.

Compacted solids may be manufactured using any suitable compacting process, such as tabletting, briquetting or extrusion, preferably tabletting. Preferably tablets for use in dish washing processes, are manufactured using a standard rotary tabletting press using compression forces of from 5 to 13 KN/cm2, more preferably from 5 to 11 KN/cm2 so that the compacted solid has a minimum hardness of 176N to 2 75N, preferably from 195N to 245N, measured by a Cl 00 hardness test as supplied by I. Holland instruments. This process may be used to prepare homogeneous or layered tablets of any size or shape. Preferably tablets are symmetrical to ensure the uniform dissolution of the tablet in the wash solution.

Laundiy 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 10g 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 con-,.-entional machine laundry, methods. Dosage is dependent upon the particular conditions such as water hardness and degree of soiling of the soiled 30 laundry.

The detergent composition may be dispensed for example, from the drawer dispenser of a washino, machine or may be sprinkled over the soiled laundry placed in the machine.

1:, In one 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.

The dispensing device containing the detergent product is placed inside the drum before the commencement of the wash, before, simultaneously with or after the washing machine has been loaded with laundry. 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-0201 376, EP-A-0288345 and EP-A0288-346. An article by J.131and published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially -,0 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 56 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 arrangement 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. 00 18678. 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.

Machine dishwashing method Any suitable methods for machine dishwashing or cleaning soiled tableware, particularly soiled silverware are envisaged.

A preferred machine dishwashing method comprises treating soiled articles selected from crockery, glassware, hollowware, silverware and cutlery and mixtures thereof. with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective )0 amount of the machine dishwashing composition it is meant from 8g to 60g of I product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.

57 Packgging 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.

58 Abbreviations used in Exarriples In the detergent compositions, the abbreviated component identifications have the following meanings:

)o LAS TAS CxyAS C46SAS 10 CxyEzS CxyEz PAS PAS, QAS QAS 1 APA Soap STS CFAA TFA-A 30 TWA STPP TSPP Zeolite A NaSKS-6 Sodium linear C 11-13 alkyl benzene sulfonate Sodium tallow alkyl sulfate Sodium C I x - C I y alkyl sulfate Sodium C 14 - C 16 secondary (2,3) alkyl sulfate Sodium C I x-C I y alkyl sulfate condensed with z moles of ethylene oxide C I x-C I y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide Salt of R, N- (CH3)2R2, wherein R, is C2_C3 hydroxyalkyl and R, is primary ethylene amine or primary propylene amine Salt of R, N' (CH3)2 R, wherein R, is C,-C, alkyl and R, is primary ethylene amine or primary propylene amine R2N+(CH3)2(C21---140H) with R-? Cl 2 - C 14 R,? N+(CH3)2(C21-140H) with R2 C8 - Cl 1 C8 - Cl 0 amido propyl dimethyl amine Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fattv acids Sodium toluene sulphonate Cl 2-C 14 (coco) alkyl N-methyl glucamide Z-- C 16-C 18 alkyl N-methyl glucamide C 12-C 14 topped whole cut fatty acids Anhydrous sodium tripoly hosphate p Tetrasodium pyrophosphate Hydrated sodium aluminosilicate of formula Nal 2(A1 02Si02)12.17H.)0 having a primary particle size in the range from 0. 1 to 10 micrometers (weight expressed on an anhydrous basis) 12 Crystalline layered silicate of formula 6- Nw)S'205 59 Citric acid Borate Carbonate Bicarbonate Silicate Sulfate Mg sulfate 10 Citrate MA/AA MA/AA (1) AA cmc Cellulose ether Protease Protease 1 Alcalase Cellulase Arnylase Anhydrous citric acid Sodium borate Anydrous sodium carbonate with a particle size between 200pm and 900gm Anhydrous sodium bicarbonate with a particle size distribution between 400gm and 1200prn Amorphous sodium silicate (Si02:Na2O = 2.0: 1) Anhydrous sodium sulfate Anhydrous magnesium sulfate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425gm and 850pm Copolymer of 1:4 maleic/acrylic acid, average molecular weight about 70,000 Copolymer of 4:6 maleic/acrylic acid. average molecular weight about 10, 000 Sodium polyacrylate polymer of average molecular weight 4,500 Sodium carboxymethyl cellulose Methyl cellulose ether with a degree of polymerization of 650 available from Shin Etsu Chemicals Proteolytic enzyme, having 3.33% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Savinase Proteolytic enzyme. having 4% by weight of active enzyme, as described in WO 95/1059 1. sold by Genencor Int. Inc. Proteolytic enzyme. having 5.3% by weight of active enzyme, sold by NOVO Industries A/S Cellulytic enzyme, having 0.23% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Carezyme Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T )5 Lipase Lipase (1) Endolase PB4 PB1 Percarbonate DOBS DDOBS NOBS NAC-OBS TAED DTPA DTPMP EDDS Photoactivated Photoactivated Brightener 1 Brightener 2 HEDP Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Lipolytic enzyme, having 2.0% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Lipolase Ultra Endoglucanase enzyme, having 1.5% by weight of active enzyme, sold by NOVO Industries A/S Sodium perborate ten-ahydrate of nominal formula NaB02.3H20.14202 Anhydrous sodium perborate bleach of nominal formula NaBO1H202 Sodium percarbonate of nominal formula 2Na2C03. 31-12022 Decanoyl oxybenzene sulphonate m the form of the sodium salt Dodecanoyl oxybenzene sulphonate in the form of the sodium salt Nonanovioxybenzene sulfonate in the form of the sodium salt (6nonamidocaproyl) oxybenzene sulfonate Tetraacetylethylenediamine Diethylene triamine pentaacetic acid Diethylene triamine penta (methylene phosphonate). marketed by Monsanto under the Tradename Dequest 2060 Ethyl enediamine-N.N'-disuccinic acid. (S,S) isomer in the form of its sodium salt. Sulfonated zinc phthlocyanine encapsulated in bleach (1) dextrin soluble polymer Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Disodium 4,4'-bis(2-sulphostyryl)biphenyl Disodium 4,4'-bis(4-anilino-6-morpholino- 1.15 triazin-2-y1)amMO) stilbene-2.2'-disulfonate 1. 1 -hydroxyethane diphosphonic acid 61 1 PEGx PEO TEPAE M PVP PVNO PvPV1 QEA SRP 1 SRP 2 PEI Silicone antifoarn Opacifier Wax Polyethylene glycol, with a molecular weight of x (typically 4,000) Polyethylene oxide, with an average molecular weight of 50,000 Tetraethylenepentaamine ethoxylate Polyvinyl imidosole, with an average molecular weight of 20,000 Polyvinylpyrolidone polymer, with an average molecular weight of 60,000 Polyvinylpyridine N-oxide polymer, with an average molecular weight of 50,000 Copolymer of polyvinylpyrolidone and vinylimidazole, with an average molecular weight of 20,000 bis((C2H50)(C2H40)n)(CH3) -N±C6H12-N+(CH3) bis((C2H50)-(C-)H40))n, wherein n = from 20 to 30 Anionically end capped poly esters Diethoxylated poly (1. 2 propylene terephtalate) short block polymer Polyethyleneimine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Polydimethylsiloxane foarncontroller with siloxaneoxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10: 1 to 100: 1 Water based monostyrene latex mixture, sold by BASF Aktiengesellschaft under the tradename Lytron 621 Paraffin wax In the following examples all levels are quoted as % by weight of the composition:

62 Example 1

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

A B C D E F LAS 8.0 8.0 8.0 2.0 6.0 6.0 TAS - 0.5 - 0.5 1.0 0.1 C46(S)AS 2.0 2.5 - - - C25AS - - - 7.0 4.5 5.5 C68AS 2.0 5.0 7.0 - - - C25E5 - 3.4 10.0 4.6 4.6 C25E7 3.4 3). 4 1.0 - - - C25E3)S 2.0 5.0 4.5 QAS 0.8 PASTAS, 2.0 0.8 1.0 4.0 0.5 1.0 QAS (1) 0.5 0.5 Z-1olite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid - - - 2.5 2.5 Carbonate 113.0 113.0 27.0 10.0 10.0 13.0 SKS-6 - - - 10.0 - 10.0 63 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Citrate - 1.0 - 3.0 - - Sulfate 26.1 26.1 26.1 6.0 - Mg sulfate 0.3 - 0.2 - 0.2 N4A/AA 0.3 0.3 0.3 4.0 1.0 1.0 CmC 0.2 0.2 0.2 0.2 0.4 0.4 PB4/PB, 9.0 9.0 5.0 - - - Percarbonate - - - 15.0 18.0 18.0 TAED 1.5 0.4 1.5 - 33.9 4.2 NAC-OBS - 2.0 1.0 - - - NOBS/DDOBS - - - 2.0 - DTPMP 0.25 0.25 0.25 0.25 - - SRP I - - - 0.2 - 0.2 EDDS 0.25 0.4 - 0.5 0.5 CFA-A 1.0 - 2.0 - - HEDP 0.3 0.1 0.1 03 0.4 0.4 QEA - 0.2 - 0.5 64 Protease 1 - 0.26 1.0 Protease 0.26 0.26 - - 1.5 1.0 Cellulase 0.3 - - 0.3 0.3 0.3 Amylase 0.1 0.1 0.1 0.4 0.5 0.5 Lipase (1) 0.3 - - 0.5 0.5 0.5 Photoactivated 15 ppm 15 ppm 15 ppm - 20 ppm 20 ppm bleach (ppm) PYNO/PVM - - - 0.1 - - Briehtener 1 0.09 0.09 0.09 - 0.09 0.09 Perfume 0.3 0.3 0.3) 0.4 0.4 0.4 Silicone antifoam 0.5 0.5 0.5 - 0.3 0.3 Misc/rmnors to 100% Density in g/litre 850 850 850 850 850 850 1 Example 2

The following granular laundry detergent compositions G to L of particular utility under European machine wash conditions were prepared in accord with the invention:

G H I i K L LAS 5.5 7.5 5.0 5.0 6.0 7.0 TAS 1.25 1.86 - 0.8 0.4 0.3 C24AS/C25AS - 2.24 5.0 5.0 5.0 2.2 C25E3S - 0.76 1.0 1.5 3.0 1.0 C45E7 3 3.25 - - - - 3.0 TFAA - - 2.0 C25E5 - 5.5 - QAS 0.8 - QAS 11 - - - 0.5 0.7 PASTAS 0.7 1.2 1.0 4.0 1.0 0.5 STPP 19.7 Zeolite A - 19.5 25.0 19.5 20.0 17.

0 NaSKS-6/cItric 10.6 - 10.6 - - acid (79:21) NaSKS-6 - 9.0 - 10.0 10.

0 66 Carbonate 6.1 21.4 9.0 10.0 10.0 18.

0 Bicarbonate - 2.0 7.0 5.0 - 2.0 Silicate 6.8 - - 0.3 0.5 - Citrate - 4.0 4.0 - - Sulfate 39.8 - - 5.0 - 12.

0 Mg sulfate - - 0.1 0.2 0.2 - MA/AA 0.5 1.6 3.0 4.0 1.0 1.0 CmC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7 - PBI - - 15.0 Percarbonate - 15.0 18.0 15.

0 TAED 0.5 1 4.0 5.0 - i NAC-OBS 1.0 33. 5 - NOBS/DOBS 2.0 -3.0 DTPMP 0.25 0.2 0.3 0.4 - 0.2 HEDP - 0-1) - 0.3 0.3 0.1 QEA - 1.0 1.0 1.0 67 1 1 Protease 1 - - - 0.5 1.2 Protease 0.26 0.85 0.9 1.0 - 0.7 Lipase (1) 0.15 0.15 0.3 0,3 0.3 0.2 Cellulase 0.28 0.28 0.2 0.2 0.3 0.3 Amylase 0.1 0.1 0.4 0.4 0.6 0.2 PVN0/PVM - - 0.2 0.2 - - PVP 0.9 1.3 - - - 0.9 SRP 1 - 0.2 0.2 0.2 - Photoactivated 15 27 - - 20 20 bleach (1) (ppm) ppm ppM ppm pp m Photoactivated 15 - - - - bleach (2) (ppm) ppra Brightener 1 0.08 0.19 - 0.09 0.1 Briahtener 2 - 0.04 - - - Perfume 0.3) 0.4 0. 3 0.4 0.3) Silicone antifoam 0.5 2.4 0. 0.5 0. 3 2.0 Minors/misc to 100% Density in g/litre 1 750 750 750 750 750 7 5 0 68 Example 3

The following detergent formulations of particular utility under European machine wash conditions were prepared in accord with the invention.

M N 0 P Blown powder LAS 6.0 5.0 11.0 6.o TAS 2.0 - - 2.0 PASTAS, - 1.0 Zeolite A 24.0 - - 20.0 STPP - 27.0 24.0 - Sulfate 4.0 6.0 13.0 - MA/AA 1.0 4.0 6.0 2.0 Silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone antifoarn 1.0 1.0 1.0 0.3 DTPMP 0.4 0.4 0.2 0.4 Spray on Brightener 0.0'? - - 0.02 C45E7 - - - 5.0 C45E2 2.5 2.5 2.0 C45E-33 2.6 15 2.0 - Perfume 0.5 0.3) 0.5 0.2 Silicone antifoarn 0-3 0.3 0.3 - Dr- additives QEA - - - 1.0 EDDS 0.13 - - - Sulfate 2.0 3.0 5.0 10.0 Carbonate 6.0 13. 0 15.0 14.0 Citric acid 2.0 QAS 11 0.5 - 0.5 PASTAS, 2.0 1.0 0.7 SKS-6 10.0 - 69 Percarbonate 18.5 PB4 - 18.0 10.0 21.5 TAED 2.0 2.0 - 2.0 DDOBS/NAC-OBS 3.0 2.0 4.0 - Protease 1.0 1.0 1.0 1.0 Lipase 0.4 - 0.2 Lipase (1) 0.4 - 0.4 - Amylase 0.2 0.2 0.2 0.4 Brightener 1 0.05 - - 0.05 Mise/minor to 100% Example 4

The following granular detergent formulations were prepared in accord with the invention.

Q R S T U V Blown powder LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS - - - - 1.0 C45AS 6.0 6.0 5.0 8.0 - C45AES - 1.0 1.0 1.0 - - C45E35 - - - - 2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 NL4,/AA - 0.5 - - - 2.0 NIA/AA (1) 7.0 - - - - - AA - 3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA - 0.9 0.5 - - 0.5 Brightener 2 0.3 0.2 0.3 0.1 03 Spray on C45E7 - 2.0 - 2.0 2.0 C25E9 3-0 - - - - - C23)E9 - 1.5 2.0 - 2.0 Perfume 0.3 03) 0. 2.0 03 0.1 Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 LAS - 2.0 2.0 - - 2.0 Zeolite A - 7.5 7.5 8.0 - 7.5 Carbonate - 4.0 4.0 5.0 - 4.0 PEG 4000 - 0.5 0.5 - - 0.5 Misc (water etc) - 2.0 2.0 2.0 - 2.0 Dry additives 71 QAS (I) - - - 1.0 PAS/PAS, 0.7 1.0 2.0 4.0 1.0 0.8 Citric acid - - - - 2.0 - PB4 - - - 4.0 12.0 PBI 4.0 1.0 3.0 - - - Percarbonate - - - - 2.0 10.0 Carbonate - 5.3 1.8 - 4.0 4.0 TAED 4.0 2.0 - - 5.0 - DDOBSNOBS 4.0 - 3.0 - - 0.6 Methyl cellulose 0.2 SKS-6 8.0 - - STS - - 2.0 1.0 - Cumene sulfonic acid - 1.0 - - 2.0 Lipase 0.2 0.2 - 0.2 0.4 Cellulase 0.2 0.2 0.2 0.1 0.2 0.2 Amylase 0.2 - 0.1 - 0.2 Protease 0.5 0.5 0.5 0. 3) 0.5 0.5 PVPVI - - - - 0.5 0.1 PVP - - - - 0.5 PVNO - - 0.5 0.3 - - QEA - - - - 1.0 - SRPI 0.2 0.5 03 - 0.2 - 3 Silicone antifoarn 0.2 0.4 0.2 0.4 0.1 - Mg sulfate 0.-1 0.2 Misc/minors to 100% 72 Exam]21e 5 The following detergent formulations of particular use in the washing of coloured clothing, according to the present invention were prepared:

W x y Blown Powder Zeolite A 15.0 15.0 Sulfate 0.0 5.0 - PAS/PAS, - 1.0 1.0 LAS 3.0 3.0 - DTPNIP 0.4 0.5 - CMC 0.4 0.4 - MA/AA 4.0 4.0 Agglomerates C45AS - - 11.0 LAS 6.0 5.0 - TAS 3.0 2.0 Silicate 4.0 4.0 PASTAS, - - - Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additi-v,es MA/AA - - 33.0 PASTAS, 1.0 - NaSKS-6 - 12.0 Citrate 10.0 8.0 TAED 4.0 -).o 4.0 Carbonate/Bicarbonate 10.0 10.0 15.0 Percarbonate 18.0 15.0 10.0 PVPVl/PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.

73 Dry additives Sulfate 0.0 9.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density (g/litre) 700 700 700 1 - 74 Example 6

The following granular detergent formulations were prepared in accord with the invention.

z AA BB cc Base granule Zeolite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.0 10.0 7.0 NWAA 3.0 - - - AA - 1.6 2.0 - MA/AA (1) - 12.0 - 6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AES - 1.0 1.0 - Silicate 1.0 0.5 10.0 Soap - 2.0 - - Brightener 1 0.2 0.-) 0.2 0.2 Carbonate 6.0 9.0 10.0 10.0 PEG 4000 - 1.0 1.5 - DTPA 0.4 - - Spray on C25E9 - - 5.0 C45E7 1.0 1.0 - C2-3)E9 - 1.0 2.5 Perfume 0.2 0. 3 0.3 - Drv additives PASTAS, 2.0 1.0 5.0 0.7 Carbonate 5.0 10.0 18.0 8.0 PVPVI/PVNO 0.5 - 0.3 - Protease 1.0 1.0 1.0 0.5 Lipase 0.4 - - 0.4 Amylase 0.1 - - 0.1 Cellulase 0.1 0.2 0.2 0.1 DDOBSNOBS - 4.0 - 4.5 TAED - 1.0 2.0 - PBI 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0 - 5.0 SRPI - 0.4 - - Sud supressor 0.5 0.5 Misc/minor to 100% 1 75 Example 7

The following granular detergent compositions were prepared in accord with the invention.

DD EE FF Blown powder Zeolite A 20.0 - 15.0 STPP - 20.0 - Sulphate - - 5.0 Carbonate 5.0 TAS - - 1.0 LAS 6.0 6.0 6.0 C68AS 2.0 2.0 - Silicate 3.0 8.0 - MA/AA 4.0 2.0 2.0 CW 0.6 0.6 0.2 Brightener 1 0.2 0.2 0.1 DTPMP 0.4 0.4 0.1 STS - - 1.0 Spray on C45E7 5.0 5.0 4.0 Silicone antifoam 0. 3 0.1) 0.1 Perfume 0.2 0.2 Dry additives QEA - - 1.0 Carbonate 14.0 9.0 10.0 PB1 1.5 2.0 - PB4 18.5 110 1-13.0 j TAED 2.0 2.0 2.0 NAC-OBS - - 2.0 DDOBS/NOBS 2.0 - PAS/PAS, 1.0 2.0 1.0 Photoactivated bleach 15 ppm 15 ppin 15ppin SKS-6 33.0 76 Proteasle 1.0 1.0 0.2 Lipase 0.2 0.2 0.2 Amylase 0.4 0.4 0.2 Cellulase 0.1 0.1 0.2 Sulfate 10.0 20.0 5.0 Misc/minors to 100% Density (g/litre) 700 700 700 77 i Example 8

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

GG HH 11 Blown Powder Zeolite A 15.0 15.0 15.0 Sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DT?M[P 0.4 0.2 0.4 EDDS - 0.4 0.2 CMC 0.4 0.4 0.4 MA/AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 -.0 1.0 Silicate 3.0 3.0 4.0 PAS/PTS-1 2.0 - - Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On Perfume 0.3 0.3 03 -1 C45E7 2.0 2.0 2.0 C25E3 2.0 - - Dry additives Citrate 5.0 - 2.0 Bicarbonate 3.0 PAS/PAS, - 1.0 1.0 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 DDOBS/NAC-OBS - 2.0 - PBI 14.0 7.0 10.0 PEO - - 0.2 Bentonite clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 06_ 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoarn 5.0 5.0 5.0 78 Dry additives Sodium sulfate 0.0 3.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density (g/litre) 850 850 850 79 Example 9

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

ii KK LL MM LAS 18.0 14.0 24.0 20.0 QAS 0.7 - - 0.7 PAS/PAS, 2.0 5.0 1.0 0.8 TFAA - 1.0 - - C23E56.5 - 1.0 - C45E7 - 1.0 - - C45E3S 1.0 2.5 1.0 STPP 32.0 18.0 30.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 11.0 7.5 10.0 5.0 Bicarbonate - 7.5 - - PBI 3.0 1.0 PB4 - 1.0 NOBS/DOBS 2.0 1.0 - Percarbonate - - 5.0 10.0 TAED 2.0 2.0 2.0 DTPMP - 1.0 - - DTPA 0.5 - 0.2 0.3 SRP 1 0.3 0.2 - 0.1 MA/AA 1.0 1.5 2.0 0.5 CMC 0.8 0.4 0.4 0.2 PEI - 0.4 - Sodium sulfate 20.0 10.0 20.0 30.0 Mg sulfate 0.2 - 0.4 0.9 Protease 0.8 1.0 0.5 0.5 Amylase 0.5 0.4 - 0.25 Lipase 0.2 - 0.1 - Cellulase 0.15 0.05 Photoactivated 30ppm 20ppm - IOPPM bleach (ppm) Perftime 0.3 0.3 0.1 0.2 Brightener 1/2 0.05 0.2 0.08 0.1 Misc/minors to 100% 1 i i Example 10

The following liquid detergent formulations were prepared in accord with the invention (levels are given in parts per weight):

NN 00 PP QQ RR SS TT UU LAS 10.0 13.0 9.0 - 25.0 - - - C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA - - - 4.5 - 6.0 8.0 8.0 APA - 1.4 - - 3.0 1.0 2.0 TPKFA 2.0 - 13.0 7.0 - 15.0 11.0 11.0 Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1-.0 Dodecenyl/tetradecenyl 12.0 10.0 - - 15.0 - - succinic acid Rape seed fatty acid 4.0 2.0 1.0 - 1.0 - 3.5 - Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0 1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 1-3.0 Monoethanolamine - - - 5.0 - - 9.0 9.0 Triethanolamine - - 8.0 - - - - TEPAE 0.5 - 0.5 0.2 - - 0.4 0.3 DTPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0 Protease 0.5 0.5 0.4 0.25 - 0.5 0.33 0.6 Alcalase - - - - 1.5 - - - Lipase - 0.10 - 0.01 - - 0.15 0.15 Amylase 0.25 0.25 0.6 0.5 0.25 0.9 0.6 0.6 Cellulase 0.05 - 0.15 5 Endolase 0.10 - 0.07 SRP2 M - 035 0.1 - - 0.2 Boric acid 0.1 0.2 1.0 2.0 1.0 1.5 2.5 1 2. 5 Calcium chloride - 0.02 0.01 - - - Bentonite clav - - - - 4.0 4.0 - Brightener I - 0.4 - - 0.1 0.2 0.3 Sud supressor 0.1 0.3 - 0.1 0.4 - - Opacifier 0.5 0.4 - 0.3 0.8 0.7 Water/minors NaOH up to pH 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 PBI 12.0 10.0 5.0 3.0 2.0 4.0 2.0 11.0 TAED 2.0 2.0 2.0 - - 1.0 2.0 5.0 DDOBS/NAC-OBS - - 2.0 2.0 2.0 - - PASIPAS, 1.0 2.0 3.5 0.7 1.5 1.0 5.5 2.0 81 Example 11

The following laundry detergent compositions are in accord with the invention:

W WW xx YY MBAS 16.5,1.8 22 - 5.5 C45 AS 8 10 11 4 C45E I S 4 3 - I LAS 8 14 - 4 PAS/PAS, 1.0 1.5 0.5 3.5 C16 SAS - - 3 - MES - - 12 - C23E6.5 1.5 1.5 1.5 1.5 Zeolite A 17.8 20.8 20.8 27.8 AA 2.3 2.3 2.3 2.3 Carbonate 27.3 27.3 27.3 2 7. 33 Silicate 0.6 0.6 0.6 0.6 Perborate 1.0 1.0 1.0 1.0 Protease 0.3 0.1 0.3) 03 Cellulase 0.3 0.1 03 03 SRPI 0.4 0.4 0.4 0.4 Brightener 0.2 0.2 0.2 0.2 PEG 1.6 1.6 1.6 1.6 PBI 16.0 6.0 - - NOBS/DDOBS 2.4 4.5 0.8 3.5 PC - - 8.0 15.0 Sulfate 5.5 5.5 5.5 Silicone Antifoam 0.42 0.42 0.42 0.42 TAED 0.5 4.5 8.0 2.0 Moisture & Minors --- Balance--Density (g/L) 660 660 660 660 82 Example 12

The following laundry detergent compositions are in accord with the invention:

zz AB AC AD AE NMAS 16.5,1.7 14.8 - - 8.2 - C45 AS 5 7 6 4 12 C45 E3S 2 4 - 5 LAS 14 8 - 18 5 PAS/PAS, 2.0 1.0 3.0 0.5 0.7 C 16 SAS - - I - I MES - 10 - TFAA 1.6 - - - - C24E3 4.9 4.9 4.9 4.9 4.9 Zeolite A 15 15 15 15 15 QAS 1.0 1.5 - - 1.0 NaSKS-6 I I I I I I I I I I Citrate/citric 1.0 2.0 3 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.5 0.5 0.5 v Carbonate -8t.5 8.5 8.5 8.5 8.5 Protease 0.9 0.9 0.9 0.9 0.9 Lipase 0.15 0.15 0.15 0.15 0.15 Cellulase 0.26 0.26 0.26 0.216 0.26 Amylase 0. -3) 6 0.36 0.36 0. -3) 6 0.3 6 NOBS - - 4.0 5.0 NACA-OBS 4.0 2.0 6.0 - - TAED 4.0 - 2.0 1.0 0.5 PBI - - 14.0 8.0 Percarbonate 20.0 14.0 - 22.0 - SRP 1 0.2 0.2 0.2 0.2 0.2 QEAI 1.0 1.5 - - - Brightener 0.2 0.2 0.2 0.2 0.2 Sulfate 2. 3) 2.3 2.3) 2.3 2.3 Silicone Antifoarn 0.4 0.4 0.4 0.4 0.4 83 Moisture & Minors --- BalanceDensity (g/L) 850 850 850 850 1 84 Example 13

The following laundry detergent compositions are prepared in accord with the invention:

AF AG AH Al AJ AK MBAS 16.5,1.7 - 32 - - - 8 C45 AS 5 - 6 12 2 - C45EIS I - - 1 5 2 LAS - 20 8 23 12 16 C16 SAS 1 4 - - - - MES 14 - - - - PASIPAS, 1.0 4.0 0.7 1.0 1.5 1.2 C23E6.5 3.6 3.6 3.6 3.6 3.6 3.6 QAS - 0.5 - - 0.5 - Zeolite A 9.0 9.0 9.0 9.0 9.0 9.0 Polycarboxylate 7.0 TO 7.0 7.0 7.0 7.0 Carbonate 18.4 18.4 18.4 18.4 18.4 18.4 1 Silicate 11.13 11.3 11. -3 1 11.13 11.3 11.-3 PBI - - 3.9 10.0 19 15.0 TAED 2.0 5.0 - - 6.0 2.0 Percarbonate 7.0 7.0 - - - - NOBS/DDOBS 4.1 4.1 4.1 4.1 - 4.1 Protease 0.9 0.9 0.9 0.9 0.9 0.9 SRPI 0.5 0.5 0.5 0.5 0.5 0.5 Brightener 0.3 03 0.3 0.13 0.3 0.1 PEG 0.2 0.2 0.2 0.2 0.2 0.2 Sulfate 5.1 5.1 5.1 5.1 5.1 5.1 Silicone Antifoarn 0.2 0.2 0.2 0.2 0.2 0.2 Moistures & Minors ---Balance-Density (,c,/L) 810 810 810 810 810 810

Claims (1)

1. Claims

   1 A detergent or cleaning composition or component thereof comprising:

   (a) at least 0.0 1 % by weight of the composition or component, one or more cationic surfactants, comprising at least one quaternized ammonium group and at least one primary, secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group.

   (b) at least 0.05% by weight of the composition or component, an oxygen releasing bleach 2. A composition or component according to claim 1 wherein the cationic surfactant is a cationic surfactant of the general formula r_ B-L] C-L; 1 -D (1) A-L-- 1 1 L X - Y j wherein L is a linking unit, and each L is independently selected from the group consisting Of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene. arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly I) hydroxy alkenylene; L can be substituted by one or more A, B, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units Aand D- are each independently selected from R, R4 E) R,?-N- and -N M_ R3 R5 86 1 R,6 ED -B- = N- and i R7 M_ -C- -N R8 wherein RI, R2, R3, R4, R5, R6, R7 and R8 are independently selected from the group consisting Of Cl -C30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group and hydrogen, one of R I, R2, R3, R4, R5, R6, R7 or R8 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or RI and R2, Rjand R2 and R3, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure. or R,- is not present and R I or R2 is double bonded to the nitrogen; or R7 is not present and R,6 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; or, when x and y are 0, R, or R, or R and R, or R5 form together with the - 3 nitrogen atoms of A and D part of a ring structure; M- is one or more countenons, and at least one A or D comprises a quaternized ammonium group in which none of R I, R2 or R. is hydrogen, or at least one B is present in which neither R6 nor R7 is hydrogen, and at least one A or D comprises a primary, secondary or tertiary amine group. or at least one C is present.

   3. A composition or component according to claim 2 wherein the cationic surfactant is a cationic surfactant of the general formula A-LI B-- --D (I) L L - X] wherein L is a linking unit. and each L is independently selected from the group consisting Of C2-C30 linear or branched alkylene, alkenylene, alkarylene, aralkylene. arylene, (poly) hydroxyalkylene, (poly) alkylenoxy, (poly) hydroxy alkenylene; L 87 can be substituted by one or more A, B or D units; x is a num r from 0 to 10; and wherein the unit A is R, E) R2-N-; M_ R., R6 E) -B- -N M_ R7 and -D comprises a primary amine group and wherein RI, R2, R3, R4 or R5 are independently selected from the group consisting Of C I -C3 0 linear or branched alkyl, alkenyl, alkaryl, araLkyl, aryl, (poly) hydroxyalkyl, (poly) hydroxy alkenyl, alkoxy group, one of RI, R2, R3, R4 or R5 can be a linear or branched polyoxyalkylene group with from 2 to 26 oxyalkylene units or R I and R2, R I and R2 and R3, R4 and R5 form together with the nitrogen atom part of a ring structure; or R3 is not present and R I or R2 is double bonded to the nitrogen; or R5 is not present and R4 is double bonded to the nitrogen; M- is one or more counterions.

   3.

   A composition or component according to claim 2 comprising a cationic surfactant wherein x=0.

   A composition or component according to claim 2 or 3) comprising a cationic surfactant wherein R4 and R5 are, independently from each other, C 1 -C6 alkyl or (poly) hydroxyalkyl group or hydrogen atom.

   2 5.

   A composition or component according to any of claims 2 to 4 comprising a cationic surfactant, wherein L is a C2-C4 linear or branched alkyl or hydroxyalkyl group.

   88 6. A composition according to any preceding claim in which the cationic surfactant is present in an amount of from 0.01% to 20% by weight, preferably of from 0.05% to 5% by weight of the composition.

   7.

   A composition or component thereof according to any preceding claim wherein said oxygen-releasing bleach system a hydrogen peroxide source and a peroxyacid precursor.

   8. A composition or component according to claim 7 wherein said precursor is an alkyl fatty peroxyacid precursor, preferably TAED.

   9. A composition or component according to claim 7 wherein said precursor is a hydrophobic organic peroxyacid precursor, preferably an amide substituted alkyl peroxyacid precursor compound selected from the group consisting of R' -C-N-R2-C-L R' -N-C -R2-C-L 0 R5 0 and R5 0 0 wherein L can be essentially any leaving group, R I is an 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 R5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms such that RI and R5 in total not contain more than 18 carbon; or preferably benzenesulfonate derivatives. preferably 3),5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS). sodium nonmoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS).

   10. A composition according to claim 7 in which the is precursor is present in an amount of from 0.5% to 20% by weight. preferably of from 1 % to 15% by weight of the composition.

   A composition or component thereof according to clairn7 wherein the hydrogen peroxide source is a sodium or potassium salt of percarbonate or perborate,