GB2332445A

GB2332445A - Solid detergent compositions

Info

Publication number: GB2332445A
Application number: GB9726896A
Authority: GB
Inventors: Barry Thomas Ingram; Stephen Wayne Heinzman
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1997-12-20
Filing date: 1997-12-20
Publication date: 1999-06-23
Also published as: GB9726896D0

Abstract

Solid detergent compositions or components thereof containing a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group, and additional ingredients, are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and good dispensing and/ or dissolution.

Description

1 2332445 Solid Detergent Compositions

Technical Field

The present invention relates to solid detergent compositions or components thereof containing a cationic surfactant, which contains at least one cationically charged quaternary amine group and at least one primary, secondary or tertiary amine group. and additional ingredients. The compositions or components of the invention are particularly useful in laundry and dish washing processes to provide enhanced greasy stain removal and good dispensing and/ or dissolution.

Backffound to the Invention It is kno,,,-n to use cationic surfactants in detergent compositions. For example, GB 2040990A describes granular detergent compositions comprising cationic surfactants. Cationic surfactants are also described in combination with anionic surfactants, for example in EP-A-0 121949.

The Applicants have found that certain cationic surfactants, or polyamine 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.

suitable for use in cleaning or detergent compositions. These compounds are found to be very surface active under alkaline 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 quaternarv amine compounds.

2 It has been found that the stability of the polyamine cationic surfactants is not affected by changes of the pH. Furthermore, it has been found that, depending on their structure, most of the polyamine cationic compounds of the present invention and detergent compositions containing these polyamine cationic surfactants, are stable under standard storage and washing conditions.

is The Applicant has furthermore found that the use of these polyamine cationic surfactants. in solid detergents provides improved dispensing (via the drawer of washing machine or via a dosing device inside the washing machine), dispersion through the wash and even dissolution in the wash water. Gelling problems which occur using conventional detergent compositions in particular those which contain the cationic surfactants, are reduced for both high and low density detergent compositions. Without wishing to be bound by theory, the Applicant believes that this is because the particular cationic surfactants used in the detergent compositions of the present invention have surprisingly good solubility and form an association in the presence of anionic components to produce surprisingly soluble anionic/cationic complexes, which leads to good dispensing and dispersion of the solid compositions or components thereof Furthermore, the Applicants have found that the incorporation of these cationic surfactants in solid detergent compositions or components thereof. also improves the easy of formulation of these compositions or components. It has been found that when the process for making the compositions or components involves the step of formation of a slurry, the viscosity of the slurry can be reduced by incorporation of these cationic surfactants. Thus, the flowability of the composition or component or the slurry can be improved.

All documents cited in the present description are incorporated herein by reference.

Summarv of the invention The present invention provides a solid detergent composition or component comprising:

(a) at least 0.01% by weight of the composition or the component thereof. one or more cationic surfactants, comprising at least one quaternized ammonium 3 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) from 0. 1 % to 99.99% by weight of the composition or the component thereof, additional detergent ingredients.

It can be preferred that the solid composition or component thereof, is a compact or concentrated composition or component thereof, having a bulk density of 570gr/1 or more.

The invention also relates to the use of a at least 0.0 1 %, preferably at least 0.05%, more preferably at least 0.3% by weight of one or more cationic surfactants, comprising at least one quaternized ammonium group and at least one primary, is secondary or tertiary amine group, whereby not more than one linear or branched polyoxyalkylene group is present as substituent group. in a solid detergent composition for improving the dispensmig and/ or dispersion or the dissolution of the composition into the wash water.

Detailed description of the invention

Cationic surfactant The compositions or components of the invention comprise at least 0.0 1 % by "-elo:ht of the composition or the component thereof, a cationic surfactant. which contains at least one quaternized ammonium group and at least one primary. secondary or tertiary ainine group. whereby not more than one linear or branched polyoxyalkylene,group is present as substituent group.

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

4 F A---L--- [B -L 1 1 C-L 1 Y 1 1 ---D(1) X wherein L is a linking unit, and each L is independently selected from the group consisting Of C2-C-')O 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, C or D units; x is a number from 0 to 10, y is a number from 0 to 10; and wherein the units A- and D- are each independently selected from R, R4 9) R.-) -- N and -N R5 M_ R, 3 l 0 R6 e -B - = ----N : and M_ R7 C - = ---N R8 wherein RI. R,?, R3. R4 R5 R,6 R7 and R8 are independently selected from the group consisting Of C 1 -C 30 linear or branched alkyl, alkenyl, alkaryl, aralkyl, aryl, 2 C (poly) hydroxyalkyl. poly) hydroxy alkenyl, alkoxy group and hydrogen, one of RI, R2. R... R45 R;. R6. R7 or R8 can be a linear or branched polyoxyalkylene group 11 - A th from) to 2 6 oxyalkylene units or R 1 and R-). R 1 and R,? and R3, R4 and R5 or 1 - R6 and R7 form togetherwrith the nitrogen atom part of a ring structure; or R-, is not 1 present and R I 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 R, or R3 and R4 or R5 form together with the nitrogen atoms of A and D part of a ring structure; Mis one or more counterions, and at least one A or D comprises a quaternized ammonium group in which none of R I. R,) or R3 is hydrogen, or at least one B is present in which neither R,6 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.

The units B-L 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 groups A, B, C or D is a secondary or primary ammoruum group.

More preferably. x=0 and y is a number from 1 to 4. Even more preferably, both x and Y are 0.

If x-, y does not equal 0. It is preferred that the surfactant comprises only one quaternary group A or D.

Preferably R,6, R7 and/or R8 are each independently selected from a C I C6, more preferably C I -C 3 alkyl., alkoxyalkyl or (poly) hydroxyalkyl group or, most preferably hydrogen.

Preferably., R I is a C6-C 14 alkyl, (poly) hydroxyalkyl or alkoxy group or an aralkyl group. Most preferably a 2-ethylhexvl group, R-) and R- are each independently C I - C6- more preferably C I -C3 alkyl or hydroxyalkyl groups and preferably R4 and R5 (and R6. R7 and R8 when present) are each independently C I -C6, more preferably C I -C 3 alkyl. alkoxyalkyl or (poly) hydroxyalkyl groups or. most preferably, h-,-drofzen atoms.

In a further preferred alternative, R4 is preferably a C6-C14 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 -C 3 alkyl, (poly ) hydroxyalkyl 6 group or hydrogen and Rl, R2 and R3 (and R6, R7 and R8 when present) are each independently preferably C I -C6, more preferably C I -C3 alkyl, alkoxyalkyl or (poly) hydroxyalkyl groups or aralkyl groups.

When R 1 and R,?, R 1 and R2 and R3, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure, the ring structure is preferably a benzene ring structure, morpholino nng structure or a piperazino ring structure, or a subtituted benzene or substituted morpholino or substituted piperazino ring structure.

When x+y is 0 and R, or R, or R, and R4 or R, form together with the nitrogen atoms of group A and D part of a nng structure, the ring structure is preferably a benzene ring structure, morpholino ring structure or a piperazino ring structure, or a substituted benzene or substituted morpholino or substituted piperazino ring structure.

is L groups are independently preferably a C22-C8. more preferably a C2-C4 linear or branched alkyl, hydroxy alkyl, alkoxy or hydroxy alkoxy group. If x+y Is 0, the 1 group is preferably a C, alkyl group. If group L comprises more than 2 carbon atoms. the surfactant preferably comprises at least one pnmary or secondary A. B, C or D group.

Examples of preferred polyamine cationic surfactants of the present invention are:

R,) R N ---L -- NH M_ R3 R,y R N -- L ---- N -- CH3 ED M_ R3 R4 7 R2 CH3 R,-N-L-N-L-NH,) (IV) E) ED R3 M_ R6 M_ R2 RIO-N-L-NH,? (v) E) M_ R3 R2 R4 RIO -N--L---N (VI) E)M- R3 R5 R,? R4 RIO ---N---L (D M_ -N---L----N R3 R8 R5 is wherein R 1, R4, R,6 and R8 are as described above; R.) R3 and R5 are independently selected from the group consisting of methyl, ethvi, hydroxvethv.l, hydroxypropyl polyhydroxy 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 and/or R4 are most preferably a 2ethylhexyl group.

c 8 1 1 1 A highly preferred cationic polyamine surfactant is of formula VI, as defiried above, wherein R2 is a hydroxypropyl or hydroxyethyl group, R3 and RIO are methyl groups, L is C22-C3 alkyl group.

Highly preferred polyarnine cationic surfactant are those of the formulas:

N1f CH3 Nf CH3 NE,) R, -N (D CH2 - CH2 - NH2 or CH3 - N - CH2 -- CH2 - CH CH3 CH3 R, 1 or M_ CH3 --- N CR.) ---- CH.) CHy --- N1H, 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 3 5 RI groups are hydroxyalkyl groups, where the alkyl groups have 2 to 5 carbon atoms, especially hydroxyethyl and hydroxypropyl are preferred; particularly preferred alkyl RI groups have up to 9 carbon atoms. most preferably R I is a ethythexvl group- and RI I is a C-2-C 14 alkyl, (poly) hydroxv alkyl. alkoxy or aralkyl group or a A or D unit as described above.

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

The cationIc polyamine 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 C 9 even 3% by weight. The benefits of the invention are found even with very small amounts of the cationic polyamine surfactant of the invention. Generally there will be at least 0.0 1 % by weight, preferably at least 0. 05% or at least 0. 1 % by weight of the cationic surfactant in the detergent compositions of the invention.

is Additional ingredients The solid compositions or components thereof, comprise at least 0. 1 % by weight of additional ingredients. These ingredients can be selected from essentially all detergent ingredients known in the art and commonly used for solid laundry or dish washing detergents. The precise nature of these additional components, and levels of incorporation thereof will depend on the physical forin of the composition or component thereof, the specific performance and/ or benefits needed form the composition, and the precise nature of the washing operation for which it is to be used.

The cationic surfactant is in particularly useful in solid detergent compositions or components, which comprise additional ingredients which can cause dispensing, dispersion or dissolution problems and which thus may require a dispensing.

dispersion or dissolution aid. Therefore, the cationic surfactant is particularly incorporated in in particularly solid compositions or components thereof, which comprise as additional ingredients anionically charged components such as anionic surfactants, such a sulfate and sulfonate surfactants, certain polymeric components.

but also silicate builder materials and nonionic surfactants.

However, to further improve the dispensing andi or dispersion and/ or dissolution of the solid compositions or components thereof, additional dispensing. dispersion,' dissolution aids can be present, for example hydrotropes or effervescence systems, based on an aciditv source and an alkalinity source capable of forming carbondioxide.

The compositions or components thereof, of the invention preferably contain one or more additional detergent components selected from additional surfactants, builders. sequestrants, bleach, bleach precursors, 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 zwitterionic surfactants and mixtures thereof.

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

is 2 0 Anionic surfactant The detergent compositions or components of the preferably comprise an anionic surfactant. Any anionic surfactant useful for detersive purposes is suitable. These can include salts (including, for example, sodium. potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate. carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.

Particularly preferred compositions of the invention comprise both an alkyl sulfate surfactant and an sulfonate surfactant (preferably a linear alkylbenzene sulfonate). preferably in ratios of from 15:1 to 1:2. most preferably from 12:1 to 2: 1.

Amounts of the one or mixtures of more than one anionic surfactant in the preferred composition may be from 1% to 50%, however, preferably anionic surfactant is present in amounts of from 5% to 40%, or even more preferred from 7% to 25% by weight of the composition. Preferred amounts of the alkyl sulfate surfactant are from 3 )% to 40%, or more preferably 6% to 30% by weight of the detergent composition.

Preferred amounts of the sulfonate surfactant, preferably the alkyl benzene sulfonate surfactant in the detergent composition are from at least 1%. preferably at least 2%, or even at least 4% by weight. Preferred amounts of the alkyl benzene sulfonate surfactant are up to 23%, more preferably no greater than 20%, most preferably up to 15% or even 10%.

Other suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C 12-C 18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C 6-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 performance benefits which result when an anionic surfactant is also used in the compositions of the invention are particularly useful for longer carbon chain length anionic surfactants such as those having a carbon chain length Of C 12 or greater, particularly Of C 14/15 or even up to Cl 6-18 carbon chain lengths.

In preferred embodiments of the compositions of the invention there will be a significant excess of anionic surfactants, preferably a weight ratio of anionic to cationic surfactant of from 50:1 to 2: 1. most preferably 3 0:1 to 8: 1. or from 20:1 to 5: 1. However. the benefits of the invention are also achieved where the ratio of cationic surfactant to anionic surfactant is subsmntially. stoichiometric, for example from 3:2 to 4:33 In a preferred embodiment of the invention the essential cationic is intimately mixed with one or more anionic surfactants prior to addition of the other detergent composition components to provide a readily soluble anionic/cationic complex. It may be useful to intimately mix substantially stoichiometric amounts of anionic and cationic surfactant prior to addition to any other detergent components, including any additional anionic surfactant.

Anionic sulfate surfactant Anionic sulfate surfactants suitable for use in the compositions or components of the invention include the primary and secondary alkyl sulfates, having a linear or branched alkyl or alkenyl moiety having from 9 to 22 carbon atoms or more preferably C 12 to C 18 alkyl; alkyl ethoxysulfates; fatty oleoyl glycerol sulfates; alkyl phenol ethylene oxide ether sulfates; the C5-C 17 acyl-N-(C I -C4 alkyl) and -N-(C I - 12 2 IC 3 0 C2 hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C9-C22 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.

is Anionic sulfonate surfactant Anionic sulfonate surfactants suitable for use herein include the salts of a C5-C'?O. more preferably a C 1 O-C 16, more preferably a C 11 -C 13 (linear) alkylbenzene sulfonates. alkyl ester sulfonates. C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates. sulfonated polycarboxylic acids, alkyl glycerol sulfonates. fatry acyl glycerol sulfonates. fatty oleyl glycerol sulfonates, and any mixtures thereof The alkyl ester sulfonated surfactant are preferably of the formula RI - CH(S03M) - (A), - C(O) - OR2 wherein RI is a C6-C-?i hydrocarbvl. R2 is a Cl -C6 alkvl. A is a C6-C-- alkylene. alkenylene. x is 0 or 1. and M is a cation. The counterion M is preferably sodium, potassium or ammonium.

The alkyl ester sulfonated surfactant is preferably a ct-sulpho alkyl ester of the formula above, whereby thus x is 0. Preferably, R' is an alkyl or alkenyl group of from 10 to 22, preferably 16 C atoms and x is preferably 0. R 2 is preferably ethyl or more preferably methyl.

13 It can be preferred that the RI of the ester is derived from unsaturated fatty acids, with preferably 1, 2 or -33 double bonds. It can also be preferred that R' of the ester is derived from a natural occurring fatty acid, preferably palmic acid or stearic acid or mixtures thereof.

Dianionic Surfactants Dianionic surfactants are also suitable anionic surfactants for use In the compositions or components of the present invention. Preferred are the dianionic surfactants of the formula:

R A - X- - M + (B)Z - Y- - M+ v.-here R is an, optionally substituted, alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C I to C28, preferably C3 to C24, most preferably C8 to C?O. or hydrogen; A nad B are independently selected from alkylene, alkenylene.

(poly) alkoxylene, hydroxyalkylene, arylalkylene or anudo alkylene groups of chain length C I to C-28 preferably C I to C5. most preferably C I or C-), or a covalent bond.

2 G and preferably A and B in total contain at least 2 atoms, A, B, and R in total contain from 4 to about -3 3 1 carbon atoms; X and Y are anionic groups selected from the group comprising carboxylate, and preferably sulfate and sulforiate, z is 0 or preferably 1; and M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion. or an alkali or alkaline earth metal ion.

The most preferred dianionic surfactant has the formula as above where R is an alkyl group of chain length from C 10 to C 18, A and B are independently C I or C2, both X and Y are sulfate groups, and M is a potassium, ammonium, or a sodium ion.

14 Preferred dianionic surfactants herein include:

(a) 3 disulphate compounds, preferably 1,133 C7-C23 3 (i.e., the total number of carbons in the molecule) straight or branched chain alkyl or alkenyl disulphates.

more preferably having the formula:

R __COSO 3- m + OS03-M + wherein R is a straight or branched chain alkyl or alkenyl group of chain length from -,o about C4 to about C 20; (b) 1.4 disulphate compounds, preferably 1.4 C8-C22 straight or branched chain alkyl or alkenyl disulphates. more preferably having the formula:

R-,--OSO, - M - OS01-m- wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Cl 8; preferred R are selected from octanyl, nonanyl, decyl, dodecyl., tetradecyl, hexadecyl. octadecyl, and mixtures thereof. and 23 (c) 1.5 disulphate compounds, preferably 1.5 C9-C233 straight or branched chain alkyl or alkenyl disulphates, more preferably having the formula:

OSO 3 M 0SO, m Y wherein R is a straight or branched chain alkyl or alkenyl group of chain length from about C4 to about Cl 8.

It can be preferred that the dianionic surfactants are alkoxylated dianionic surfactants.

is The dianionic surfactant is typically present at levels of incorporation of from about 0. 1 % to about 20%, preferably from about 0.3% to about 15%, most preferably from about 0. 5 % to about 10% by weight of the detergent composition.

Mid-chain branched alkyl sulfates or suIRhonates Mid-chain branched alkyl sulfates or sulphonates are also suitable anionic surfactants for use in the compositions or components of the inevntion. Preferred are the midchain branched alkyl sulfates.

Preferred mid-chain branched primary alkyl_sulfate surfactants are of the formula R RI R2 1 1 1 CH3CH2(LH2)W(-H(CH2)X4-;ki(l;k12)yk,H(CH-))ZOS03v1 These surfactants have a linear primary alkyl sulfate chain backbone (i.e. , the longest linear carbon chain which includes the sulfated carbon atom) which preferably comprises from 12 to 19 carbon atoms and their branched Primary alkyl moieties comprise preferably a total of at least 14 and preferably no more than 20, carbon atoms. In compositions or components thereof of the invention comprising more than one of these sulfate surfactants, the average total number of carbon atoms for the branched primary alkyl moieties is preferably within the range of from greater than 14.5 to about 17.5. Thus, the surfactant system preferably comprises at least one branched primary alkyl sulfate surfactant compound having a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of carbon atoms including branching must be at least 14, and further the average total number of carbon atoms for the branched primary alkyl moiety is within the range of greater than 14.5 to about 17.5.

Preferred mono-methyl branched primary alkyl sulfates are selected from the P oup r consisting of 33-methyl pentadecanol sulfate, 4-methvl pentadecanol sulfate, 5- 16 methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, I I-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 35-methyl hexadecanol sulfate, 4-methyl hexadecanol sulfate, 5-methyl hexadecanol sulfate, 6-methyl hexadecanol sulfate, 7methyl hexadecanol sulfate, 8-methyl hexadecanol sulfate, 9-methyl hexadecanol sulfate, I 0-methyl hexadecanol sulfate, I I -methyl hexadecanol sulfate, 12-methyl hexadecanol sulfate, 13-methyl hexadecanol sulfate, 14-methyl hexadecanol sulfate, and mixtures thereof Preferred di-methyl branched primary alkyl sulfates are selected from the group consisting of 2,3-methyl tetradecanol sulfate. 2.4-methyl tetradecanol sulfate. 2,5methyl tetradecanol sulfate, 2,6-methyl tetradecanol sulfate. 2,7-methyl tetradecanol sulfate, 2,8-methyl tetradecanol sulfate, 2,9-methyl tetradecanol sulfate, 2, 1 0-methyl tetradecanol sulfate, 2,11 -methyl tetradecanol sulfate, 2,12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate. 2.4-methyl pentadecanol sulfate. 2.5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, -2.7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2.9-methyl pentadecanol sulfate, 2. 10methyl pentadecanol sulfate, 2.11 -methyl pentadecanol sulfate. 22A 2-methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate. and mixtures thereof Anionic carboxvIate surfactant Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates. the alkyl polvethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyis').

especially certain secondary soaps as described herein.

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH. )CH.)0)x CH.)C00-M' wherein R is a C6 to Cl 8 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 -CHR-y-0)-R3 wherein R is a C6 to Cl 8 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 acid radical, and mixtures thereof, and R_, is selected from the group consisting of 17 hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon. Preferred secondary soap surfactants for use herein are water-soluble members selected from the aroup consisting of the t:l water-soluble salts of 2-methyl- 1 -undecanoic acid, 2-ethvl- 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.

i c Alkali metal sarcosinate surfactant Other suitable anionic surfactants are the alkali metal sarcosmates of formula R-CON (R1) CH2 COOM, wherein Ris a C5-Cl 7 linear or branched alkyl or alkenyl group, R I is a C I - 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.

AlkoxvIated 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. if present. 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 condensates of alkyl phenols. nonionic ethoxylated alcohols. nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and tile nonionic ethoxylate condensation 1 products with propylene oxide/ethylene diamine adducts.

Nonionic alkoxvlated alcohol surfactant The condensation products of aliphatic alcohols With from 1 to 25 moles of alkviene 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 croup containing from 8 to 18 1 carbon atoms, more preferably form 9 to 15 carbon atoms, with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic polvhvdroxv fatty acid amide surfactant Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R2CONR 1 Z wherein: R 1 is H. C 1 -C4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, ethoxy, propoxy, or a mixture thereof. preferable C 1 -C4 alkyl, more preferably Cl or C2 alkyl, most preferably Cl alkyl (i.e., methyl); and R2 is a C5 C 31 hydrocarbyl, preferably straight-chain C 5 -C 19 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 polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl.

Nonionic fatty acid amide surfactant Suitable fatty acid amide surfactants include those having the formula: R6CON(R7 t wherein R6 is an alkyl group containing from 7 to 21. preferably from 9 to 17 carbon 2 G atoms and each R7 is selected from the group consisting of hydrogen, C 1 -C4 alkyl.

Cl -C4 hydroxvalkyl, and -(C.Y1140)xH. where x is in the range of from 1 to 3.

Nonionic alkylpolysacchande surfactant n 5 1 Suitable alkylpolysaccharides for use herein are disclosed in U.S. Patent 4.565,647. Llenado. issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms and a polysacchande. e.g.. a polyglycoside, hydrophilic group containing from 1.3) to 10 saccharide units.

Preferred alkylpolyglycosides have the formula R2 O(CnH'-nO)t(glYcOS'Y'I)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 19 to 18 carbon atoms; n is 2 or 3; t is from 0 to 10, and x is from 1.3 to 8. The glycosyl is preferably derived from glucose.

Arniffioteric surfactant Suitable amphoteric surfactants for use herein include the arnine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include those compounds having the formula 3 R')(OR4)xNO(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. Preferred are C I O-C 18 alky I dimethy lamine oxide, and C 10- 18 acylamido alkyl dimethylamine oxide.

is 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 zA-itterionic surfactants for use herein.

Suitable betaines are those compounds having the formula R(k)2N+R2C00 C wherein R is a C6-C 18 hydrocarbyl group, each R1 is ty 2 pically Cl -C3 alkyl, and R is a Cl -C 5 hydrocarbyl group. Preferred betaines are C 12-18 dimethyl- ammonio hexanoate and the C 10- 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 in the 1 1 compositions or components thereof of the invention are cationic ester surfactants. The cationic ester surfactant is a compound having surfactant properties comprising 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, 4239660 and 4260529.

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

R 1 N -,,- R " "- R3 ApR 4 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 ftom 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 (preferred), methyl and ethyl, X- is an anion such as chloride, bromide, methvlsulfate, sulfate. or the like. to provide electrical neutrality, A is selected from C 1 -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 8.

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 3.3 surfactants which have preferably the general formula:

21 1 R 1 3 1 N + X R7 AqR 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 anion such as chloride, bromide, methyisulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C 1 -C4 alkoxy, especially ethoxy, (i.e., -CH2C1420-), 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 ranae from 0. 1 % to '10%, t-- more preferably from 0.4% to 7%. most preferably from 0.5% to 3.0% by, weight of the composition.

Acid Source In the solid compositions or components thereof, can 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 5 0%, 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%, 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.

22 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, glutaric, tartaric acid, succinic or adipic acid, monosodium phosphate, sodium hydrogen sulfate, boric acid, or a salt or an ester thereof. Citric acid is especially preferred.

is Alkalini!y In the compositions or components of the present invention preferably an alkalinity system is present to achieve optimal cationic surfactant perforTnance. 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 from 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.

Examples of carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and any. mixtures thereof with ultra-fine 2,3 calcium carbonate such as are disclosed in German Patent Application No. 2.3 2 1.001 published on November 15, 1973.

Suitable silicates include the water soluble sodium silicates with an SiO. ):NA20 ratio of from 1.0 to 2.8, with ratios of from 1.6 to '22.0 being preferred, and 22.0 ratio being most preferred. The silicates may be in the form of either the anhydrous salt or a hydrated salt. Sodium silicate with an SiO.):Na.?O ratio of 2.0 is the most preferred silicate.

Preferred crystalline layered silicates for use herein have the general formula NaMSix02x+1.yH.)O 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-A0 164514 and methods for their preparation are disclosed in DE-A-3417649 and DEA-3 742043. Herein, x in the general formula above preferably has a value of 2, 3 3 or 23 1 4 and is preferably 2. The most preferred material is 8-Na2Si2O5, available from Hoechst AG as NaSKS-6.

Water-soluble builder compound 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 60% by weight of the composition.

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

is The carboxylate or polycarboxylate builder can be monomenc or oligomeric in type although monomenc 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 furnaric 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 carboxymethyloxysuccinates described in British Patent No. 13 79.241. lactoxysuccinates described in British Patent No. 1, 389.732, and aminosuccinates described in Netherlands Application 72058713. and the oxypolycarboxylate materials 30 such as 2-oxa- 1, 1,3propane 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. 13. 3 3-propane tetracarboxylates and 1, 1,2,3-propane tetracarboxylates. Polycarboxylates containing suifo substituents include the sulfosuccinate derivatives disclosed in British Patent 24 Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,93)6,448, and the sulfonated pyrolysed citrates described in British Patent No. 1.439.000. Preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.

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

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

Suitable examples of water-soluble phosphate builders are the alkali metal tripoly phosphates, sodium, potassium and ammonium pyTophosphate, 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 conivound The compositions or components thereof, of the present invention may contain a present in detergent partially soluble or insoluble builder compound, ty icall, pi compositions at a level of from 1 % to 80% by weight, preferably ftom 10% to 70% by weight, most preferably ftom 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[(A10--))Z(S1O.))y].

xH.)0 wherein z and y are at least 6; the molar ratio of z to y is from 1. 0 to 0.5 and x is at least 5. preferably from 7.5 to 276, more preferably from 10 to 264. The alurninosilicate materials are in hydrated form and are preferably crystalline.

containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. Zeolite A has the formula Na 12 [(A102) 12 (Si02)121. xH.)O wherein x is from 20 to -330, especially 27. Zeolite X has the formula Na86 [(A102)86(SiO-'2)1061.276 H20.

Another preferred aluminosilicate zeolite is zeolite MAP 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.

Zeofite MAP is described in EP -384070A (Unilever). It is defiried as an alicali metal alumino-silicate of the zeolite P type having a silicon to aluminium ratio not greater than L')3, 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 MAP 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 nucrometres.

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 aranulometer. Other methods of establishing d50 values are disclosed in EP 384070A.

Hvdrotrope Hydrotropes can be used in the solid detergent compositions or components thereof By the term hydrotrope when used herein is meant any of the hydrotropes known in the art, capable of reducing the viscosity of a mixture., comprising water and a surfactant component, in particular comprising a an anionic sulphonate surfactant. Among such hydrotropes there can be mentioned the short-chain (C 1 -C4) alk-ary 1 26 sulfonates. The water-soluble salts usefW in the present invention include the alkali metal, alkaline earth metal, alkyl amine and ammonium salts of the sulfonic acid. Preferred salts are sodium, potassium, and monoethanolamine sulfonate, and mixtures thereof.

In particular, the toluene sulfonates, the cumene sulfonates, the xylene sulfonates may be used in this invention. Most preferred is a sodium toluene sulfonate, being preferably a sodium toluene mono sulfonate.

The level of the hydrotrope is preferably from 0.0 1 % to 25%, preferably from 0. 1 % to 15%, more preferably from 0.2% to 5%, even more preferably from 0.5% to 2%, most preferably from 0.8% to 1.8% by weight of the composition.

Heavy metal ion sequest:rarit is 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 tetra (methylene phosphonate) and hydroxy-ethylene 1, 1 diphosphonate.

Other suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriarnine pentacetic acid. ethylenediamine disuccinic acid, ethylenedianune 27 diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof Especially preferred is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.

D 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-23517,542 and EP-A-399, 133. The iminodiacetic acid-N-2hydroxypropyl sulfonic acid and aspartic acid N-carboxyinethyl N-2-hydroxypropyl- -33-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The P-alanine-N,N'-diacetic acid, aspartic acid-N,N'-diacetic acid, aspartic acid-Nmonoacetic 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. Diplcolinic 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'-disuceinic acid (HPDDS) are also suitable.

Organic peroxvacid bleaching Ustern A preferred feature of compositions or component thereof in accordance with the invention is an organic peroxyacid bleaching system. In one preferred execution the bleaching system contains a hydrogen peroxide source and an organic peroxyacid .1, bleach precursor compound. The production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative preferred execution a preformed organic peroxyacid is incorporated directly into the composition. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.

Inorganic perhydrate bleaches Inorganic perhydrate salts are a preferred source of hydrogen peroxide. These salts are normally incorporated in the form of the alkali metal, preferably sodium salt at a 28 level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.

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

Sodium perborate is a preferred perhydrate salt and can be in the form of the monohydrate of nominal formula NaB02H.)0-) or the tetrahydrate Nal3O. )H202.3H20- Alkali metal percarbonates. particularly sodium percarbonate are preferred perhydrates herein. Sodium percarbonate is an addition compound having a formula corresponding to 2Na.)C0-.3H.)O.), and is available commercially as a crystalline solid.

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

Peroxyacid bleach precursor Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid. Generally peroxyacid bleach precursors may be represented as 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 29 0 X-C-OOH Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1% to 15% by weight, most preferably ftorn 1.5% to 10% by weight of the compositions.

Suitable peroxyacid bleach precursor compounds typically contain one or more N- or 0-acyl groups, which precursors can be selected from a wide range of classes.

Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials Within these classes are disclosed in GB-A- 1586789. Suitable esters are disclosed in GB-A-836988, 8647M 1147871, 2143231 and EP-A-0170386.

Leaving-2 TOURS The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time ftarne (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.

2 5 Preferred L groups are selected from the group consisting of- Y R3 R5Y 1 --y and - ---- 0 - 0 ---N----C-Rl, -N N, N-C-CH-R4 R5 R3 Y Y R3 1 -(.)-(;ti=(;-CH=CH2 1 0 0 11 4 11 U 1 R3 1 -0-C=CHR4, and Y i 1 0 Y 11 1 A -N-S-CH-R' 1 11 R3 0 1 0 Y -N NR4 U and mixtures thereof wherein R 1 is an alkyl, aryl. or alkaryl group containing from 1 1 4to 14 carbon atoms, W' is an alkyl chain containing from 1 to 8 carbon atoms, R is 1 H or R-, R5 is an alkenyl chain containing from 1 to 8 carbon atoms and Y is H or a 1 4 solubilizing group. Any of R. R and R may be substituted by essentially any, -,0 functional group including, for example alkyl. hydroxy, alkoxy. halogen. amine.

nitrosyl. armde and ammonium or alk.,yl ammonium groups.

+ 1 The preferred solubilizing groups are -SO, -M 1 ' -CO - M ', -SO -M-T" -N- (R-' - 1 3 + 2 _+_ 4 ')4X and O<-N(W')3 and most preferably -SO, -M and -CO 2_ M wherein W' is an alkyl is chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide. hydroxide, methylsulfate or acetate anion.

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

Preferred alkyl percarboxylic precursor compounds of the imide type include the N,N,N IN 1 tetra acetylated alkvIene diamines wherein the alkylene group contains 31 r_ from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.

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

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

R' -- C - N - R2 - C - L R' --- N -- C --- R2 ---- C -- L 0 R5 0 or R5 0 0 is wherein RI is an alkyl group with from 1 to 14 carbon atoms. R2 is an alk- Aene group containing from 1 to 14 carbon atoms, and R5 is H or an alkyl group L- containing 1 to 10 carbon atoms and L can be essentially any leaving group. Amide substituted bleach activator compounds of this type are described in EP-A-0 1703) 86.

Perbenzoic acid precursor Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis. Suitable 0-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, and the benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents. and those of the imide type including N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas. Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole. Otheruseful N-acyl group-containing perbenzoic acid precursors include Nbenzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.

Cationic p2rOxvacid precursors Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.

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

The peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore. Alternatively. the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4, 751,015; 4,988,451; 4,397,757; 5.269,962. 5127,852.. 5,093,022; 5,106,528. U.K. 1,382,594; EP 475.512, 458.396 and 284.292. and in JP 87-33 18.3332 Examples of preferred cationic peroxyacid precursors are described in UK Patent Application No. 9407944.9 and US Patent Application Nos. 08/298903, 08/298650, " 0 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. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams and the trialkyl ammonium methylene alkyl caprolactams.

3 c Benzoxazin organic peroxyacid precursors Also suitable are precursor compounds of the benzoxazin-type, as disclosed for example in EP-A-3)') 2, 294 and EP-A-482.807, particularly those having the formula:

33 0 11 U, 0 1 a U-K1 wherein R is H, alkyl, alkaryl, aryl, or arylalkyl.

1 1 Preformed organic 12groxyacid The organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid, typically at a level of from 1 % to 15% by weight, more preferably from 1 % to 10% by weight of the composition.

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

R' ---C --- N - -R2-C -OOH 0 R5 0 or R' ---N--C--R2-,-C-OOH 1-5 R5 0 0 wherein R 1 is an alky]. aryl or alkaryl group with from 1 to 14 carbon atoms, R2 is an alkylene. arylene, and alkarylene group containing from 1 to 14 carbon atoms, and R-' is H or an alkyl, aryl. or alkaryl group containing 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A0170386.

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

34 EggMes The compositions or components thereof of the present invention may compnse one or more enzymes.

Preferred additional enzymatic materials include the commercially available 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, 8-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof 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 3.519.570 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 ESPERASE9 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 ALCALASE(K. DURAZYMC and SAVINASEV- from Novo and MAXATASE(K, MAXACALO. 5 PROPERASEI) and MAXAPEM@ (protein engineered Maxacal) from GistBrocades. Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 30-3761.8. filed April 28, 1987 (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 protealytic 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 12-35, and alanine replaced threonine at position 274. Protease C is deschbed in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 199 1. 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, + 123, +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 in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, filed October 13, 1994.

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

See also a high pH protease from Bacillus sp. NCIMB 403.3) 8 described in WO 9-3/18140Ato 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 94/2558-3) 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 0.000 1 % to 2%, preferably from 0.001% 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 0.001% to 1% by weight, most 36 1 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 IAM 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 commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticurn NRRLB 3673, commercially 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 LipomaxR (GistBrocades) and LipolaseR and Lipolase UltraR(N ovo) 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.

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 94/149633 and WO 94/14964 (Unilever). The LIPOLASE enzyme derived from Humicola lanugi _-inosa and commercially available from Novo (see also EPO 3 341.947) 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 92105249 in which the native lipase ex Hurnicola lanuginosa has the aspartic acid (D) residue at position 96 changed to Leucine (L). According to this 37 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 emulsifying glycerine tributyrate (Merck) using gum-arabic as emulsifier. Lipase activity is assayed at pH 7 using pH stat. method.

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 amylases known for use in cleaning compositions include both a- and 0 amylases. a-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; EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable amylases are stability-enhanced arnylases described in W094/183 3 14, 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 amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).

Examples of commercial (x-amylases products are Purafect Ox.AMO from Genencor and Termamyis, BanO Fungamy10 and Duramy1110, all available from Novo Nordisk A/S Denmark. W095/26-397 describes other suitable arnylases: cc-arnylases characterised by having a specific activity at least 25% higher than the specific activity of Termarnyls at a temperature range of 25C to 55'C and at a pH value in the range of 8 to 10, measured by the Phadebass ct-amy.lase 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 W095135382.

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.

38 r 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 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. Other suitable cellulases are cellulases originated from Humicola insolens. having a molecular weight of about 50KI)a 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 EGIII cellulases from Trichoderma loneibrachiatum described in W094/21801, Genencor, published September 29. 1994. Especially suitable cellulases are the cellulases 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 2 18 0 1. Other suitable cellulases especially useful. See also W091/17244 and W091/_ for fabric care and/or cleaning properties are described in W096/3)4092, W096/17994 and W095/24471.

Peroxidase enzymes may also be incorporated into the detergent compositions of the invention. Peroxidasis are used in combiriationwith oxygen sources, e.g.

percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for 11 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. Peroxidase containing detergent compositions are disclosed, for example, in PCT International Application WO 89/0998 1 3), W089/098 13 and in European Patent application EP 39 No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.

_) r Preferred enhancers are substituted phenthiazine and phenoxasine 10Phenothiazinepropionicacid (PPT), 1 0-ethylphenothiazine-4-carboxylic acid (EPC), 1 0-phenoxazinepropionic acid (POP) and 1 0-methylphenoxazine (described in WO 94/12621) 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 composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.

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 pLDlvmeric compound 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 polymefic compound is meant any polvmenc 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 C - 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 from 1 % to 10% by weight of the compositions.

Examples of organic polymeric compounds include the water soluble organic homoor co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid 1 1 comprises at least two carboxyl radicals separated ftom each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are 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.

Terpolymers containing monomer units selected from maleic acid, acrylic acid, aspartic acid and vinyl alcohol or acetate, particularly those having an average 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. carboxyinethylcellulose, hydroxvpropylmethylcellulose, ethy-thydroxyethylcellulose 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 removallanti-redeposition compounds The composition or components thereof of the invention may comprise water-soluble cationic ethoxylated arnine 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 monoarnines, diamines or triamines. Especially preferred are the ethoxylated cationic monoarnines, diamines and triamines of the formula:

41 CH3 X --(- OCH2CH2)n CH3.N + - CH2 CH2 -t- CH2)a - - N+ - CH2CH20 -n- X (CH2CH20 X -D (CH2CH20 -In- 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 to 35; for cationic diamines or triamines, n is preferably at least about 12 with a typical range of firom about 12 to about 42.

These compounds where present in the composition, are generally present in an amount of from 0.0 1 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 m amounts no greater than 2.5% and most preferably in amounts no greater than 1.5% or even no greater than 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 antifoarn 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 antifoarn compounds also ty pically contain a silica 42 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 alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (e.g. fatty acid tfiglycerides), 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 cvanuric chloride with two or three moles of a primary or secondary amine 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 2 5 (a) antifoam compound, preferably silicone antifoam compound. most preferably a silicone antifoarn compound comprising in combination polydimethyl siloxane, at a level of from 50% to 99%, preferably 75% to 95% by weight of the silicone antifoam compound; and (ii) silica, at a level of from 1% to 50%, preferably 5% to 25% by weight of the silicone/silica antifoam compound.

43 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 polyoxYalkylene content of 72-78% and an ethylene oxide to propylene oxide ratio of from 1:0.9 to 1: 1. 1, at a level of from 0. 5% to 10%, preferably 1 % to 10% by weight; a particularly preferred silicone glycol rake copolymer of this type is DC0544, commercially available from DOW Corning under the tradename DC0544; (c) an inert carrier fluid compound, most preferably comprising a 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; A highly preferred particulate suds suppressing system is described in EP- A-021073) I 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.

Polvmeric dve transfer inhibiting @gents 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 Nvinylimidazole, polyvinylpyrrolidone polymers or combinations thereof, whereby these polymers can be cross-linked polymers.

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

44 p (1) Ax R wherein P is a polymerisable unit, and 0 RI R10 0 0 R' A is - C - N -, -N-C-, CO, C, --0--. -S-, -N-;xisOorl; 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 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.

The N-O group can be represented by the following general structures 0 A 0 A (R,) x -W(R2)y (R3)z or W(R1)x -. 5 wherein RI. R2, and R-33 are aliphatic groups, aromatic. heterocyclic or alicyclic groups or combinations thereof. x or/and v or/and z is 0 or I and wherein the nitro(:Yen of the N-0 group can be attached or wherein the nitrog en 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 polyaniine N-oxides wherein the N-0 group forms part of the polymensable unit comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the N-0 group forms pan of the R-group. Preferred polyamine Noxides are those wherein R is a heterocyclic 1 group such as pyridine, N-substituted pyrrole, imidazole, N-substituted pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Other suitable polyamine N-oxides are the polyamine oxides whereto the N0 group is attached to the polymensable unit. A preferred class of these polyamine 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 polyamine 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 water-solubility and dye-suspending power. Typically, the average molecular weight is within the range of 500 to 1000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinvIlmidazole 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) Polyvinvlpvnolidone The compositions herein may also utilize polyvinylpyrrolidone ("PVP") having an average molecular weight of from 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York. NY and Montreal.

Canada under the product names PVP K- 15 (viscosity molecular weight of 1 0,000) 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 of360,000). PVP K 15 is also available from ISP Corporation. Other suitable polyvinylpyrrolidones which are commercially available ftom BASF Corporation include Sokalan HP 165 and Sokalan HP 12.

i 46 d) Polyyinyloxazolidone 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.

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

Ovtical 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:

Ri R, N R.7 H H N 1 1 N N -C=C-- N-ON -Q H o-1 1 S03M S03M R, wherein RI is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl; R,) is selected from N-2-bis-hvdroxveth-.,.1. N-)hvdroxvethyl-N-metliylainino, morphilino, chloro and amino, and M is a salt-forming cation such as sodium or potassium.

When in the above formula- RI is anilino. R-) is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N2-bishydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodiurn salt. This particular brightener species is commercially marketed under the tradename Tinopal-LTNPA-GX by Ciba-Geigy Corporation. Tinopal-LTNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

47 1 When in the above formula, R I is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'bis[(4-aniIino-6-(N-2hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino] 2, 2'-stilbenedisulfonic acid disodium salt. This particular brightener species is cornmercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, RI is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilMO-s-triazine-2- yl)amino]2,2'stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy 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%, typically from 0. 1 % to 5%, preferably from 0.2% to 3.0% by weight, of the compositions.

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.

2 5 Suitable SRA's include a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric or polymeric ester backbone of terephthaloYl and oxyalkyleneoxy repeat units and allyl-derived sulfonated ternlinal moieties covalently attached to the backbone, for example as described in U.S. 4, 968,451, November 6. 1990 to JJ. 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 ("DM7) 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 1,2 propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al., for example those produced by 48 1 transesterification/oligomerization 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 (TW), PG, DMT and Na-3,6dioxa-8-hydroxyoctanesulfonate; 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-5-sulfoisophthalate; 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 ni-sulfobenzoic acid monosodium salt, PG and DMT. optionally but preferably further comprising added PEG, e.g., PEG 3400.

* SRA's also include: simple copolymenc blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 33,959,230 to Hays, May 25, 1976 and U.S. 3,893, 929 to 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 20'C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names of methyl cellulose ethers manufactured by Shin-etsu Kagaku Kogyo KK.

Other ovtional ineredients 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.

i)H of eterizent 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 49 7.0 to about 10.5 at a concentration of from about 0. 1 to about 2% by weight in water at 2CC, whereby it can be beneficial for an optimum performance of the cationic surfactants present in the compositions of the invention that the pH is adjusted to be above 7.0, i.e. more alkaline. In such formulations. the wash pH is preferably from about 8.0 to about 10.5, most preferably from 8.0 to 9.0.

Form of the comp2sitions The solid compositions in accordance with the invention can take a variety of physical forms including granular, tablet, flake or pastille forms. The compositions may be pre-treatment compositions or may be conventional washing detergents. The compositions are preferably compacted, particularly the so-called concentrated granular detergent compositions.

The beneifts of the inevntion are in particularly found for granular compositions which have a bulk density of at least 570g/1, or even at least 680g/L The granular detergent compositions or components thereof in accordance with the present invention can be made via a variety of methods. including spray- drying, dry mixing. extrusion. agglomerating and granulation. The cationic surfactant can be rn C 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 chlorme 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 or components are greater than I.Smm 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 0.2nun to 0.7trim in diameter.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of sieves, preferably Tyler sieves. The weight fractions thereby obtained are plotted against the -'s 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 min 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, which are not in a granular form, 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 275N, preferably from 195N to 245N, measured by a Cl 00 hardness test as supplied by 1. 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.

Laundn. 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 3002 of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres. as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods. Dosage is dependent upon the particular conditions such as water hardness and degree of soiling of the soiled laundrv.

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

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 51 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.

7,- 2 S Especially preferred dispensing devices for use with the composition of the invention have been described in the following patents; GB-B-2, 157. 717, GB-B-2, 157, 718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J.131and published in Manufacturing Chemist, November 1989, pages 41-46 also describes especially preferred dispensing devices for use with granular laundry products which are of a type commonly know as the "granulette". Another preferred dispensing device for use with the compositions of this invention is disclosed in PCT Patent Application No. W094/11562.

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 amount of the machine dishwashing composition it is meant from 8g to 60g of 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.

Packaging for the coniDositions 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.

52 Abbreviations used in Examples In the detergent compositions, the abbreviated component identifications have the following meanings:

LAS TAS CxyAS C46SAS CxyEzS CxyEz PAS PAS, PAS, PAS3 QAS QAS 1 Soap STS CFAA TFAA TPKFA STPP TSPP Zeolite A Sodium linear C I 1- 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)2R.,, wherein R, is G-C, 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 Pnmary propylene arnine Salt of 2-ethylhexyl, methyl, hydroxethy 1 -ammonium di(C,-C4 alkyl) ethylene amine Salt of 2- ethylhexyl, methyl. hydroxethyl-ammonium di (C,-C, alkyl) propylene amine R.)N+(CH3)2W2H4011) With R. C 12 - C 14 R2N(CH3bW,)H4OH) With R,) = C8 - Cl 1 Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut fatty acids Sodium toluene sulphonate C 1 2-C 14 (coco) alkyl N-methyl glucamide C 16-C 18 alkyl N-methyl glucamide C 12-C 14 topped whole cut fatty acids Anhydrous sodium tripolyPhosphate Tetrasodium pyrophosphate Hydrated sodium aluminosilicate of formula Na 1 2(A 1 02SiO2)12.27H.) 0 having a primary partic le 53 NaSKS-6 Citric acid Citric acid 1 Borate Carbonate Bicarbonate Silicate Sulfate Mg sulfate Citrate MA/AA MA/AA (1) AA CW Cellulose ether Protease Protease 1 Alcalase Cellulase size in the range from 0. 1 to 10 micrometers (weight expressed on an anhydrous basis) Crystalline layered silicate of formula 6- Na-)Si205 Anhydrous citric acid Crystaline citric acid Sodium borate Anydrous sodium carbonate with a particle size between 200pm and 900pm Anhydrous sodium bicarbonate with a particle size distribution between 400Lrn and 1200pm Amorphous sodium silicate (Si02:Na,?O = 2.0: 1) Anhydrous sodium sulfate Anhydrous magnesium sulfate Tri-sodium citrate dihydrate of activity 86.4% with a particle size distribution between 425pm and 850Lxn Copolymer of 1:4 maleic/acrylic acid. average molecular weight about 70. 000 Copolymer of 4:6 maleic/acr-,-Iic acid. average molecular weiQht about 10.000 Sodium polyacrylate polymer of average molecular weight 4, 500 Sodium carboxymethyl cellulose Methyl cellulose etherwith a degree of polymerization of 650 available from Shin Etsu Chemicals Proteolytic enzyme, having 3.3% 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 M by weig t of active - _-h 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 54 Arnylase Lipase is Lipase (1) Endolase PB4 PB1 Percarbonate NOBS NAC-OBS TAED DTPA DTPMP EDDS Photoactivated Photoactivated Brightener 1 Brightener 2 HEDP Amylolytic enzyme, having 1.6% by weight of active enzyme, sold by NOVO Industries A/S under the tradename Termamyl 120T 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 tetrahydrate of nom-inal formula Na1302.3H20.1---1202 Anhydrous sodium perborate bleach of nominal formula NaB02.H-)0- Sodium percarbonate of nominal formula 2Na2CO-3.3H.)O.) Nonanoyloxybenzene sulfonate in the form of the sodium salt (6nonamidocaprovi) oxybenzene sulfonate Tetraacetylethylenedianline Diethylene triamine pentaacetic acid Diethylene triamine penta (methylene phosphonate). marketed by Monsanto under the Tradename Dequest 2060 Ethylenediamine-N.N'-disuccinic acid, (S.S) isomer in the form of its sodium salt. Sulforiated zinc phthlocy-anine encapsulated in bleach (1) dextrin soluble polymer Sulfonated alumino phthlocyanine encapsulated in bleach (2) dextrin soluble polymer Disodium 4,4'-bis(2sulphostyryl)biphenyl Disodium. 4,4'-bis(4-anilino-6-morpholino-1.-").tnazin-2-yl)amino) stilbene-2:2'-disuifonate 1, 1 -hydroxyethane diphosphonic acid PEGx PEO TEPAE PV1 PVP PVNO PvM :L 5 2 0 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 poiyvinylpyrolidone and vinylimidazole, %kith an average molecular weight of 20,000 bis((C2H50)(C, )H40)n)(CH3) -N±C6H]2-N+(CH3) bis((C-)H50)-(Cffl40))m wherein n = from 20 to 30 Anionically end capped poly esters Diethoxylated poly (L 2 propylene terephtalate) short block polymer Polyethyleneirnine with an average molecular weight of 1800 and an average ethoxylation degree of 7 ethyleneoxy residues per nitrogen Polydimethylsiloxane foam controller with siloxaneoxyalkylene copolymer as dispersing agent with a t- ratio of said foam controller to said dispersinia acTent of 10:1 to 100:1 Paraffin wax QEA SRP 1 S R P 2 PEI Silicone antifoam Wax In the following examples all levels are quoted as % by weight of the composition:

56 Example 1

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 14 3.4 1.0 - - - C 2 5 E 33 S 2.0 5.0 4.5 STS 0.5 0.5 1.0 PAS 3.0 1.0 0.5 1.4 1 1; -).o 7.0 0.1 PAS, QAS 0.8 - - QAS (1) - - 0.5 1.0 Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid - - - 2.5 2. 5 57 Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 SKS-6 - - - 10.0 - 10.0 Silicate 1.4 1.4 3.0 03 0.5 M Citrate - 1.0 - 33.0 - - Citric acid 1.0 2.0 - - 1.0 Sulfate 26.1 26.1 26.1 6.0 - - Mg sulfate 0.3 - - 0.2 - 0.2 MA/AA 0.3 M 03 4.0 1.0 1.0 CmC 0.2 0.2 0.2 0.2 0.4 0.4 PB4 9.0 9.0 5.0 Percarbonate - - - 18.0 18.0 TAED 1.5 0.4 1.5 -3.9 4.2 NAC-OBS 2.0 1.0 DTPMP 0.25 0.25 0.25 0.25 SRP I - - - 0.2 - 0.2 EDDS 0.25 0.4 - 0.5 0.5 CFAA 1.0 - - - 58 - 1 HEDP 0.3 0.3 0.3 0.3 0.4 0.4 QEA - - - 0.2 - 0.5 Protease I - - 0.26 1.0 - - Protease 0.26 0.26 - - 1.5 1.0 Cellulase 0.3 - M 0.1 0.3) j Arnylase 0.1 0.1 0.1 0.4 0.5 0.5 Lipase (1) M - - 0.5 0.5 0.5 Photoactivated 15 ppm 15 ppm 15 ppm - 20 ppm 20 ppm bleach (ppm) PVN0/PWV1 - - - 0.1 - - Brightener 1 0.09 0.09 0.09 1 - 0.09 0.09 Perfume 0.1 0.31 0.3 0.4 0.4 0.4 Silicone antifoam 0.5 0.5 0.5 - 0.3) 0.3 Misc/minors to 1 i 100% Density in g/litre 850 850 850 850 850 850 1 59 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 0.31 C24AS/C25AS - 2.24 5.0 5.0 5.0 2.2 C 2 5 E 3 S 0.76 1.0 1.5 3.0 1.0 C45E7 3.25 - ').0 TFAA - 2.0 C25E5 - 5.5 - STS 1.0 - 1.0 QAS 0.8 - - QAS 11 - 0.7 PAS 1.0 1.5 0.7 0.3) - - PAS, - 0.3 1.0.5.8 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- - 9.0 - 10.0 10.0 6/silicate 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 - - 0.33 0.5 Citrate - - 4.0 4.0 - - Citric acid 3.0 1.0 - 0.5 1.0 - Sulfate -39.8 - 5.0 12.0 Mg sulfate - - 0.1 0.2 0.2 t -MA/AA 0.5 1.6 3.0 4.0 1.0 1 1.0 CmC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 1-2. 7 - - - Percarbonate 18.0 15.0 TAED 0.5.3. 1 - 5.0 i - NAC-OBS 1.0 3.5 - - 2.5 DTPMP 0.25 0.2 0.3) 0.4 -TO T2 HEDP 0.3 0.3 0.3 0.33 61 QEA 1.0 1.0 1.0 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 M 0.3 j Arnylase 0.1 0.1 0.4 0.4 0.6 0.2 PVN0/PWV1 - 0.2 0.2 - - PVP 0.9 1. 0.9 SRP 1 - - 0.2 0.2 0.2 - Photoactivated 15 2-1 7 20 20 bleach (1) ppm ppm ppm PPM (Ppm) Photoactivated 15 bleach (2) P1)m (Ppm) Brightener 1 0.08 0.19 - 0.09 0.15 Brightener 2 - 0.04 - - - Perfume M 0.1) 0.4 0.33 0.4 0.3 Silicone 0.5 2.4 0.3) 0.5 0.35 2.0 antifoam Minors/misc to 1 1 100% 62 Densityin 750 750 750 750 750 750 g/litre 63 Example 3

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

M N 0 p Blown powder LAS 6.0 5.0 11.0 6.0 TAS 2.0 - - 2.0 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 33.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.-' 0.2 0 - Silicone antifoarn 1.0 1.0 1.0 M DTPMP 0.4 0.4 0.2 0.4 Spray on Brightener 0.02 0.02 C45E7 - 5.0 C45E2 2.5 2.5 2.0 - C45E3) 2.6 2.5 2.0 Perfume 0.5 0-3 0.5 0.2 Silicone antifoarn 0.13 0.3 0-17 - Dry additives QEA - - - 1.0 EDDS 03 - - - -1 Sulfate 2.0 -3.0 5.0 10.0 Carbonate 6.0 113.0 15.0 14.0 Citric acid 2.5 - - 2.0 PAS 0.5 - - 1.5 PAS, - 1.0 4.0 SKS-6 10.0 - - Percarbonate 18.5 64 PB4 - 18.0 10.0 21.5 TAED 2.0 2.0 2.0 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 Misc/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 MA/AA - 0.5 - - - 2.0 MA/AA (1) 7.0 - - - AA - 10.5.0 1.0 1 3.0 Sulfate 5.0 6.3 14. 3 11.0 15.0 19.13 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 0. 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 03 0.2 0.3 0.1 0.3 Spray on C45E7 - 2.0 - 2.0 2.0 C25E9 3.0 - - - - - C23E9 1.5 2.0 2.0 Perfiu-ne 0.3 0.13 03 2.0 U 0.3 3 Agglomerates C45AS - 5.0 5.0 2.0 - 5.0 PAS 10 0.6 - - 0.4 - PAS, - - 2.0 1.0 0.4 0.3 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 66 Misc (water etc) - 2.0 2.0 2.0 2.0 Dry additives QAS (1) - - - - 1.0 - Citric acid - 2.0 - PB4 - - - - 12.0 1.0 PBI 4.0 1.0 3.0 2.0 - - Percarbonate - - - - 2.0 10.0 Carbonate - 5.3 1.8 4.0 4.0 NOBS 4.0 6.0 0.6 Methyl cellulose 0.2 - - SKS-6 8.0 - - STS - - 2.0 1.0 - Cumene sulfonic - 1.0 - - 2.0 acid Lipase 0.2 - 0.2 0.2 0.4 Cellulase 0.2 0.2 0.2 0.3 0."

0.-) Amylase 0.2 - 0.1 - 0.2 Protease 0.5 0.5 0.5 0.13) 0. 0.5 PVPVI - - 0.5 0.1 PVP - - - 0.5 - PVNO - - 0.5 0.3 - - QEA - - - - 1.0 - SRPI 0.2 0.5 0.1 - 0.2 - -1 Silicone antifoam 0.2 0.4 0.2 0.4 0.1 Mg sulfate - 0.2 - 0.-) ScImi nors to I Oio011 -6 67 Example 5

The following nil bleach-containing 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 - LAS 33.0.3.0 DTPMP 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 PAS, 0.4 0.9 PAS3 - - Silicate 4.0 4.0 Zeolite A 10.0 15.0 i 1-13.0 CMC 0.5 MA/AA 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0.3 0.1 0.5 C45E7 4.0 To 4.0 ___C25E3) 2.0 -)0 2.0 Drv additives MA/AA - 1.0 PAS, 2.0 - NaSKS-6 - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 1:

Carbonate 8.0 5.0 7.0 1 PVPVl/PVNO 0.5 0.5 0.5 Alcalase 0.5 03 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 1 Cellulase 0.6 U-.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives 68 Sulfate 0.0 9.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density (g/litre) 700 700 700 69 Example 6

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 MA/AA 3.0 - - - AA - 1.6 2.0 - N4A/AA (1) - 12.0 - 6.0 LAS 14.0 10.0 9.0 20.0 PAS 2.0 7.0 - - 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 0.2 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 - C23E9 - 1.0 2.5 Perfume 0.2 0.3 03 Dry additives Carbonate 5.0 10.0 18.0 8.0 PVPVI/PVNO 0.55 - 03 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 NOBS - 4.0 - 4.5 PAS, - - 0.9 1.5 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 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 STP,p - 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 - NIA/AA 4.0 2.0 10 - 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 1 Spray on C45E7 5.0 5.0 4.0 Silicone antifoam 0.3 M 0.1 J Perfume 0.2 0.2 0.3 Dry additives QEA - - 1.0 Carbonate 14.0 9.0 10.0 PB1 1.5 2.0 - PB4 18.5 13.0 13.0 TAED 2.0 2.0 2.0 QAS (1) - - 1.0 PAS 1.0 1.5 1.0 PAS, 0.5 - - Photoactivated bleach 15 ppm 15 ppm 15ppm SKS-6 3.0 71 Protease 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 72 1 Example 8

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

GG RH 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 DTPMP 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 1.0 Silicate -3.0 -3.0 4.0 Zeolite A 8.0 8.0 8.0 PAS, - 0.7 0.5 Carbonate 8.0 8.0 4.0 Spray On Perfurne 0.3 0.13 0.3 C45E7 2.0 2.0 2.0 C25E') 2.0 - - Drv additives Citrate 5.0 - 2.0 Bicarbonate - 3 - 3.0 Carbonate 8.0 15.0 10.0 PAS 1.8 1.0 TAED 6.0 -).o 5.0 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 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoarn 5.0 5.0 5.0 Dry additives 1 %,; 73 Sodium sulfate 0.0 3.0 0.0 Misc/minors to 100% 100.0 100.0 100.0 Density (g/litre) 850 850 850 74 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 1.0 - - TFAA - 1.0 - PAS 1.0 2.0 - PAS, - 1.0 - 0.5 C23E56.5 - 1.0 - C45E7 - 1.0 - C45E3S 1.0 2.5 1.0 STPP 32.0 18.0 130.0 22.0 Silicate 9.0 5.0 9.0 8.0 Carbonate 11.0 7.5 10.0 Bicarbonate - 7.5 - PBl 3.0 1.0 PB4 - 1.0 NOBS 2.0 1.0 - - DTPMP - 1.0 DTPA 0.5 - 0.2 0.3 SRP 1 03 0.2 - 0.1 3 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 i 0.5 Amylase 0.5 0.4 0.25 Lipase 0.2 - 0.1 Cellulase 0.15 - 0.05 Photoactivated 30ppm 20ppm I Oppm bleach (ppm) Perfume 0.1 0.3 0.1 0.2 Brightener 1 /2 0.05 0.2 0.08 0.1 Misc/minors to 1 1 100% Example 10 r; The following laundry bar detergent compositions were prepared in accord with the invention (levels are given in parts per weight).

AD A-E AF AG AH Al AJ AK LAS - - 19.0 15.0 21.0 6.75 8.8 - C28AS 30.0 13.5 - - - 15.75 11.2 22.5 Sodium laurate 2.5 9.0 - - - - Zeolite A 2.0 1.25 - - 1.25 1.25 1.25 Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 Calcium27.5 39.0 35.0 - - 40.0 - 40.0 carbonate Sulfate 5.0 5.0 3.0 5.0 3.0 - TSPP 5.0 - - - - 5.0 2.5 1 - STPP 5.0 15.0 10.0 - - 7.0 80 10.0 Bentonite clay - 10.0 - - 5.0 - DTPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7 CMC - 1.0 1.0 1.0 1.0 1.0 Talc - - 10.0 15.0 10.0 Silicate - - 4.0 5.0 3.0 PVNO 0.02 0.03) 0.01 - 0.02 - MA/AA 0.4 1.0 - - 0.2 0.4 0. 5 0.4 SRP 1 0.3 03 03 03 03 0., 0.3 0.-, Protease 0.12 0.08 0.08 0.1 Lipase - 0.1 - 0.1 Amylase - - 0.8 0.1 Cellulase - 0.15 - - 0.15 0.1 PEO - 0.-) - 0.2 0.3) - 0.3 Perftime 1.0 0.5 0. 0.2 0.4 0.4 Mg sulfate - - ".0 -3.0 3.0 - Brightener 0.15 0.10 0.1 - - 0.1 Photoactivated - 15.0 15.0 15.0 15.0 15.0 bleach (ppm) PAS, i 0.7 1.0 1.0 1.5 0.5 76 j PAS 1- 1 - j - 1 - 1 - 1 0.5 1 _ 2.8 1 _1.0] 77 Example 11

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

AL AM AN AO C45 AS 8 10 11 4 C45EIS 4 - I LAS 8 14 - 4 C16 SAS - - 3 - PAS 5.0 0.5 0.7 1.0 MES - - 12 - PAS/PAS, 1.0 3.0 1.0 1.0 C23E6.5 1.5 1.5 1.5 1.5 Zeolite A 17.8 20.8 20.8 27.8 AA 2.33 2. 3) 2.33 2. 33 Carbonate 27.33 27.33 2 7.33 27.3 Silicate 0.6 0.6 0.6 0.6 Perborate 1.0 1.0 1.0 1.0 Protease 0.3 0.3 1 0 3 0.3 Cellulase 03 03 0.3 0.3 SRP 1 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 1 2.4 4.5 0.8 3. 5 PC - - 8.0 15.0 Sulfate 5.5 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 78 Example 12

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

AP AQ AR AS AT C45 AS 5 7 6 4 1-) C45 E3)S 4 - 5 LAS 14 8 - 18 2 PAS/PAS, 0.5 1.5 1.0 4.0 0.8 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 - - - 1.0 NaSKS-6 I I I I I I I I I I Citrate/citric 1.0 2.0 MA/AA 4.8 4.8 4.8 4.8 4.8 HEDP 0.5 0.5 0.; 0.5 0.5 Carbonate 8.5 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 0.26 0.26 Amvlase 0. 33 6 0.36 0.336 0.36 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 - SRPI 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. 33 2.3 2. 33 2. 33 Silicone Antifoam 0.4 0.4 0.4 0.4 0.4 Moisture & Minors --- Balance--- 79 1 1 - -- 1 1 1 Density (g/L) 850 1 850 1 850 1 850 1 850 1 Example 13

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

AU AV AW AX AY AZ C45 AS 5 6 12 C45EIS I - 1 5 MBAS 16.5,1.7 32 - - 16 - 8 LAS - 20 8 23 12 16 C16 SAS 1 4 - - - - MES 14 - - - - - PASTAS, 1.0 4.0 0.7 1.0 1.5 1.2 C23E6.5 3.6 3.6 3.6 3. 6 -37.6 _33.6 PASTAS, 2.0 1.0 0.5 5.5 0.8 1.0 j QAS - 0.5 - - 0.5 - Zeolite A 9.0 9.0 9. 9.0 9.0 9.0 0 Polycarboxylate 7.0 7.0 7.0 7.0 7.0 7.0 Carbonate 18.4 18.4 18.4 18.4 18.4 18.4 Silicate 11. 3) 11.-3 11. 3) 11.3 11.-3 11.3 PBI - - 3.9 10.0 1.9 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 SRP 1 0.5 0.5 0.5 0.5 0.5 0.

Brightener 0.3 03 0.3 0 3 1 0.3) 03 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 Antifoam 0.2 0.2 0.2 0.2 0.2 0.2 Moistures & Minors --- Balance- I Density (g/L) 810 810 810 810 1 810 810 81

Claims

Claims

1. A solid detergent composition or component comprising:

(a) at least 0.01% by weight of the composition or the component thereof. 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.

is b) from 0. 1 % to 99.99% by weight of the composition or the component thereof, additional detergent ingredients.

2 A composition or component according to claim 1,k.herein the cationic surfactant is a polyamme cationic surfactant of the general formula:

1 F -1.

1 --L 11 [C-L] ------- D (I) J 1 A ----L --- j B L v j wherein L is a linking unit, and each L is independently selected from the group C consisting Of C2-C30 linear or branched alkylene. alkenylene. alkar".1ene, aralkylene.

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 10. y is a number from 0 to 10; and wherein the units A- and D- are each independentl-, selected from R, R4 ED R,) -- N - and N M_ R3 R5 82 1 i R6 - B- = ---N--. and M_ R7 E) -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 RI. R-). R-. R4, R5. K6, R7 or R8 can be a linear or branched polvoxyalkylene group with from 2 to 26 oxyalkylene units or R I and R.Y, R I and R-) and R-, R4 and R5 or R6 and R7 form together with the nitrogen atom part of a ring structure: or R3 is not present and R I or R-? is double bonded to the nitrogen: or R-7 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 R, or R, and R, 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 quatemized ammonium group in which none of RI. Ri or R- is hydrogen, or at least one B is present in which neither R,6 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.

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

4. A composition or component according to claim 2 or 3 comprising a polyarnine catioruc surfactant wherein K4 and R5 are. independently from each other, Cl -C6 alkyl or (poly) hydroxyalkyl group or hydrogen atom.

83 5.

A composition or component according to any of claims 2 to 4 comprising a polyarnine cationic surfactant. wherein L is a C27-C4 linear or branched alkyl or hydroxyalkyl group.

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 in which the anionic surfactant is selected from linear or branched C9-C22, preferably C 16-18, alkyl sulfate surfactants; or alkoxylated alkyl sulfates and C 10-20, preferably C I 1- 13 alkyl benzene sulfonate surfactants.

8. A composition or component thereof according to any preceding claim, having a bulk density of at least 570 g/1, preferably at least 680 g/1.

9. A composition or component thereof according to any preceding claim.

comprising an effervescence system comprising an acidity source and an t alkalinity source, capable of forming carbon dioxide upon contact With water.

10. A composition or component thereof according to any preceding claim., comprising a nonionic surfactant, preferably selected from group consisting of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, norlionic ethoxylate/propoxylate condensates with propylene glycol, and the norllonic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.

A composition according to any preceding claim. comprising an agglomerated component which comprises the cationic surfactant.

12. A composition according to any of claims 1 to 10, comprising an spraydried component which comprises the cationic surfactant.

13. The use of at least 0.0 1 %, preferably at least 0.05% by weight of one or more cationic surfactants, comprising at least one quaternized ammonium group 84 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. in a solid detergent composition for improving the dispensing and,' or dispersion of the composition into the wash water.