CA1109759A - Detergent compositions - Google Patents

Abstract

Abstract of the Disclosure Built laundry detergent compsoitions in solid form containing specific mixtures of selected anionic, nonionic and water-soluble cationic surfactants. The compositions are especially effective in removing greasy soil from fabrics.

Description

9~

Background of the Invention This invention relates to detergent compositions exhibiting improved greasy soil removal capabilities. More specifically, the detergent compositions of this invention pro-vide unexpectedly good detergency performance on greasy and oily soils having a marked particulate soil content.
Cationic surfactants have been frequently incorporated into detergent compositions of various types. However, the inclusion of such cationic surfactants is generally for the pur-pose of providing some adjunct fabric care benefit, and not for the purpo~e of cleaning. For example, certain cationic surfact-ants have been included in detergent compositions for the purpose of yielding a germicidal or sanitization benefit to washed surfaces, as is disclosed in U.S. Patent 2,742,434, Kopp, issued April 17, 1956; U.S. Patent 3,539,520, Cantor et al, issued November 10, 1970; and U.S. Patent 3,965,026, Lancz, issued June 22, 1976. Other cationic surfactants, such as ditallowdimethyl-ammonium chloride, have been included in detergent compositions for the purpose of yielding a fabric-softening benefit, as dis-closed in U.S. Patent 3,607,763, Salmon et al, issued September 21, 1971 and U.S. Patent 3,644,203, Lamberti et al, issued February 22, 1972. Such components are also disclosed as being included in detergent compositions for the purpose of controlling static, as well as softening laundered fabrics, in U.S. Patent 3,951,879, Wixon, issued April 20, 1976; and U.S. Patent 3,959,157 Inamorato, issued May 25, 1976.
Compositions comprising mixtures of anionic, cationic and nonionic surfactants are also known in the art. Thus, compositisons conferring enhanced anti-static character to textiles washed therewith are described in B.P. 873,214 while compositions having enhanced germidical and detergency

-2-7S~

performance are disclosed in B.P. 641,297.
Surprisingly, it has now been found, however, that built detergent compositions comprising water-soluble or dis-persible mixtures of specific anionic, cationic and nonionic surfactants in critical relative amounts provide unexpectedly improved cleaning performance on greasy and oily soils, even where these have a high content of particulate matter. Moreover, this excellent performance is observed at both high and low wash temperatures and over a range of realistic soil types and wash conditions. Furthermore, the enhanced greasy stain removal per-formance is achieved without detriment to detergency performance on conventional soil and stain types and most surprisingly, without detriment to the soil suspending or frabric whitening characteristics of the compositions.
Summar of the Invention y According to the present invention, there is provided a detergent composition in solid form comprising (a) from 2% to 60% of a surfactant system consisting essentially of a water-soluble or water-dispersible combination of anionic, alkoxylated nonionic and water-soluble quaternary ammonium cationic surfactants, wherein the anionic:cationic surfactant weight ratio is in the range from 100:1 to 2:3 and wherein the surfactant system contains anionic and cationic sur-factants in an equivalent ratio of at least 1:1, and (b) from about 10% to about 98% of a detergency builder.
Detergent compositions of the present invention con-tain as an essential ingredient a three-component active system comprising anionic, alkoxylated nonionic and water-soluble cationic surfactants. This active system comprises from about 2% to about 60% by weight of the compositions. In granular ~L~3~7~9 laundry detergent applications, the active system is generally in the range from about 4% to about 30%, more preferably from about 6% to about 15% by weight of the compositions.
The compositions of the present invention are preferably formulated to have a pH of at least about 6 in the laundry solution at conventional usage concentrations (about 1% by weight) in order to optimize cleaning performance. More preferably, they are alkaline in nature when placed in the laundry solution and have a pH greater than about 7, especially greater than about 8.
At the higher pH values, the surface activity of the compositions of the invention is enhanced and, in certain instances, is quite markedly enhanced.
In preferred systems, the anionic and cationic surfact-ants have a combined total of no more than 34 carbon atoms counted in hydrophobic groups having at least 4 consecutive car-bon atoms (eg. alkyl, alkaryl, aryl, alkaryl, aralkyl groups etc.).
In more preferred systems the number of such hydrophobic group carbon atoms totals from about 18 to 33, especially from about 26 to 32, with the anionic surfactant providing at least 12 of the carbon atoms. These hydrophobicity limitations have been found to optimize the interaction of the ternary active system with greasy and oily stains on fabrics and to correspond to compositions of maximum grease detergency effectiveness.
An essential feature of the present compositions is that the surfactant system must be substantially neutral in surfactant anions and cations or else have an ionic excess of surfactant anions over surfactant cations. This is important not only with regard to optimizing grease removal, but also for ensuring good suspension of soil in the detergent wash liquor (ie. for preventing soil redeposition) and also for ensuring that water-insoluble anionic effect agents such as anionic .

7~;9 fluorescers retain their effectiveness in composition. It is, of course, well known, that anionic fluorescers are ~uenched or inhibited in effectiveness in the presence of cationic surfactants.
Surprisingly, the grease and oil detergency benefits of the present invention are secured without suppression of fluorescer activity. It is accordingly highly important that the overall anionic:cationic surfactant equivalent ratio in the present compositions is, within manufacturing error, at least 1:1.
At typical composition levels, the manufacturing error in the anionic and cationic surfactant components is up to about 5% by weight for each component.
Subject to the above conditions the weight ratio of anionic:cationic surfactant can vary in the range from about 5:1 to about 1:3, especailly from about 2:1 to about 1:2, the weight ratio of nonionic:cationic from about 300:1 to about 2:3, especially from about 20:1 to about 1:1, and the weight ratio of anionic:nonionic from about 7:1 to about 1:20, especially from about 2:1 to about 1:10. In terms of surfactant levels, the surfactant system preferably comprises at least about 5% by weight of the water-soluble cationic surfactant and at least about 60% by weight in total of the anionic and nonionic surf-actants. In one preferred embodiment, the surfactant system comprises at least 15% by weight of each of the anionic and cationic surfactants and from 15% to 60% by weight of the non-ionic surfactant. In another preferred embodiment, the sur-factant system comprises at least 5% by weight of each of the anionic and cationic surfactants and at least 60% by weight of the nonionic surfactant.
As mentioned above, the cationic surfactant component of the composition of the invention is characterised as being water-soluble. By water solubility, we refer in this context to the solubility of cationic surfactant in monomeric form, the 97~9 limit of solubility be~ng determined b~ the onset of ~icellisation and measured in terms of critical micelle concentxation ~C.M,C.~.
The cationic surfactant should thus have a C~M C. for the pure material greater than about 200 p.p.m. and preferably greater than about 500 p.p.m., specified at 30C and in distilled water.
Literature values are taken where possible, especially surface tension or conductimetric values - see Critical Micelle Concentra-tions of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS 36, (1971~.
Another important feature is that the ternary active system itself must be water-dispersible or water-soluble in combination with the remainder of the detergent composition.
This implies that, in an equilibrium aqueous mixture of the detergent composition (containing about 1000 p.p.m. of surfactant) the ternary active system exists in one or more liquid (as opposed to solid) surfactant/water phases. Expressed in another way, the surfactant system should have a Krafft point of no higher than about 25C.
A further essential component of the present compositions is at least 10%, preferably from about 20% to about 70~ by weight of a detergency builder, for example, a water-soluble inorganic or organic electrolyte. Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequester-ing agents. Water-insoluble calcium ion exchange materials can also be used with advantage, however. Surprisingly, it is found that the grease removal performance of the present compositions depends sensitively on the ionic strength and the level of free hardness ions in the detergent liquor and these parameters must be closely controlled for optimum performance.
Thus, when the compositions are used in about 1~ solution, the builder: surfactant weight ratio is preferably greater than about 1:3, more preferably greater than about 4:1 and especially greater than about 8:1. me weight ratio of calcium ion sequesting or exchange agent:surfactant, on the other hand, is preferably greater than about 1:1 and especially greater than about 3:1, while the electrolyte:surfactant weight ratio is preferably great~r than about 3:1, especially greater than about 6:1.
Optimum grease and particulate detergency also depends sensitively on the choice of nonionic surfactant and especially desirable from the view-point of grease detergency are biodegradable nonionic surfactants having a lcwer consolute temperature in the range from about 25C to about 65C, more preferably from about 30C to about 50C. Highly suitable nonionic surfactants of this type have the general formula RO(CH2C~20)nH wherein R
is primary or secondary branched or unbranched Cg 15 aIkyl or alkenyl and n (the average degree of ethoxylation) is from 2 to 9, especially from 3 to 8. More hydrophilic nonionic detergents can be employed for providing particulate detergency and anti-xedeposition, however, for instance, nonionic detergents of the general formula given above wherein R is primary or secondary, branched or unbranched C8 24 aIkyl or alkenyl and n is from 10 to 40.
Combinations of the two classes of nonionic surfactants can also be used with advantage of course.
m e individual components of the composition of the invention will now be described in detail.
The Cationic Surfactant The cationic surfactant is a water-soluble quaternary ammonium oompound having a critical micelle conoentration of at least 200 p.p.m.
at 30C. In structural terms, the preferred cationic surfactant ccmprises from 1 to about 4 quaternary ammonium groups of which one and only one has the general formula:-Rl F2 N

w~erein each Rl is a hydrophobic aIkyl or alkenyl group optionally substitutedor interrupted by phenyl, ether, ester or amide groups totalling from 8 to 20 carbon atoms and which may additionally contain up to 20 ethoxy 1~3!97~;~

~roups, m is a number from 1 to 3 and no more than one Rl can hav~ more than 16 carbon atcms when m is 2 and no more than 12 carbon atcms when m is 3, each R2 is an alkyl group containing from one to four carbon atom or a benzyl group w~th no more than one R2 in a moleculé being benzyl, and x is from 0 to 3, provided that (m+x) is not greater than 4.
A hiyhly preferred group of cationic surfactants of this type have the general formula:

Rl R2 N Z
m 4-m wherein Rl is selected from C8-C20 alkyl, alkenyl and alkaryl groups; R2 is selected from Cl 4 alkyl and benzyl groups; Z is an anion in number to give electrical neutrality; and m is 1, 2 or 3; provided that when m is 2, Rl has less than 15 carbon atoms and when m is 3, Rl has less than 9 carbon atoms.
Where m is equal to 1, it is prefèrred that R2 is a methyl group. Preferred compositions of this monolong chain type include those in which Rl is a C10 to C16 alkyl group.
Particularly preferred compositions of this class include C12 alkyl trimethylammonium halide and C14 alkyl trimethylammonium halide.
Where m is equal to 2, the Rl chains should have less than 14 carbon atoms. Thus, ditallowdimethylammonium chloride and distearyldimethylammonium chloride, which are used conventionally as fabric softeners and static control agents in detergent compositions, may not be used as the cationic component in the surfactant mixtures of the present invention. Particularly preferred cationic materials of this class include di-C8 alkyl-dimethylammonium halide and di-Clo alkyldimethylammonium halide materials.
Where m is equal to 3, the Rl chains should be less than 9 carbon atoms in length. An example is trioctylmethyl ammonium 7~9 chloride. The reason for this chain lenyth rest~iction, as is also the case with the di-long chain cationics described above, is the relative insolubility of these tri - and di-long chain materials.
Another group of useful cationic compounds are the poly-ammonium salts of the general formula:

R3 14 ~L(CH2)n R~41-- R4 ~ Z
m wherein R3 is selected from C8 to C20 alkyl, alkenyl and alkaryl groups; each R4 is Cl-C4 alkyl; n is from 1 to 6; and m is from 1 to 3.
A specific example of a material in this group is:

11 w __ ~+ ___- (CH2)3 ---- N (C 3)3 , 3 2 A further preferred type of cationic component, which is described in Canadian Patent Application Serial No. 306,517 of James C. Letton, filed June 29, 1978, has the formula:

R2 _ (zl) _ (R )n ~ Z (CH2)m wherein Rl Cl to C4 alkyl; R2 is C5 to C30 straight or branched chain alkyl or alkenyl, alkyl benzene, or Rl - X Rl - 1 - (CH2)S - ; wherein s is from 0 to 5, .,. Rl g_ 1~ 7~i~

R3 is Cl to C2Q alkyl or alkenyl; a is 0 or 1; n is Q or l;
m is from 1 to 5~ zl and z2 are each selected from the group consisting of:

7 ~
- -O-, -O-C-, -O-, -O- -O-, - -N-, -N- , -O-C-N, -N- -O-, and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the compound water-soluble, preferably selected from the group consisting of halide, methyl sulfate, hydroxide, and nitrate preferably chloride, bromide or iodine.
In addition to the advantages of the other cationic surfactants disclosed herein, this particular cationic component is environmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen-containing segment.
Particularly preferred cationic surfactants of this type are the choline ester derivatives having the following formula:

R2 _ ~ - O - CH2CH2 ~ T+ - CH3 X

as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
Particularly preferred examples of this type of cationic surfactant include caproyl choline ester quaternary ammonium halides (R2 = Cg alkyl~, palmitoyl choline ester quaternary ammonium halides (R = C15 alkyl), myristoyl choline ester quaternary ammonium halides (R2 = C13 alkyl), lauroyl choline ester ammonium halides (R = Cll alkyl), and caproyloyl choline ester quaternary ammonium halides (R2 = C17 alkyl).
Additional preferred cationic components of the choline ~i~

ester variety are given by the structural formulas below, wherein p may be from 0 to 20.

R2 _ o - C - (CH ~ ~ - O CH CH ~ -X~ CH3 - +1_CH2-CH2-0-~- (CN2~ -C-0-CH2-CH2-N -CH3 X

The preferred choline-derivative cationic substances, discussed above, may be prepared by the direct esterification of a fatty acîd of the desired chain length with dimethylamino-ethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction pro-duct is then used to quaternize triethanolamine, forming thedesired cationic component.
Another type of novel particularly preferred cationic material, described in ~.S. Patent No. 4,228,042 of James C.
Letton, granted October 14, 1980, are those having the formula:

R2 IRl R ~O[(~H)n]y~(Zl)a~(R4)t~Z2~(CH2)m~l - Rl X

In the above formula, each Rl is a Cl to C4 alkyl group, prefer-ably a methyl group. Each R2 is either hydrogen or Cl to C3 alkyl, preferably hydrogen. R3 is a C4 to C30 straight or branched chain alkyl, alkenyl, or alkyl benzyl group, pr~ferably a C8 to ~,t`~
:

1~ 5~

to C18 alkyl group, mo$t pxeferably a C12 alkyl group. R4 is a Cl C10 alkylene or alkenylene group. n is f~om 2 to 4, preferably 2; y is from 1 to 20, preferably from about 1 to 10, most pre-ferably about 7; a may be 0 or 1; t may be 0 or 1; and m is from 1 to 5, preferably 2. zl and z2 are each selected from the group consisting of -~-0~ ~, -0-, -0-~-O-, -C-N-, -~-C-, -O-~ C-O-and wherein at least one of said groups is selected from the group consiting of ester, reverse ester, amide and reverse amide. X is an anion which will make the compound water-soluble and is selected from the group consisting of halides, methylsul-fate, hydroxide and nitrate, particularly chloride, bromide and iodide.
These surfactants, when used in the compositions of the present invention, yield excellent particulate soil, body soil, and grease and oil soil removal. In addition, the detergent compositions control static and soften the fabrics laundered therewith, and inhibit the transfer of dyes in the washing solution.
Further, these novel cationic surfactants are environmentally desirable, since both their long chain alkyl segments and their nitrogen segments are biodegradable.
Preferred embodiments of this type of cationic component are the choline esters (Rl is a methyl group and z2 is an ester or reverse ester group), particular formulas of which are given below by which t is 0 or 1 and y is from 1 to 20.

fH3

3 (`CH2cH2O)y (CH2)t-c-o-cH2 CH2-~_CH3 X~

75~

~ fH3 3 2 2 Iy 2 3 ~CH3 ~ fH3 R -o(cHCH2O)y-c-cH2-l CH3 R3-(lHCH2ly~(CH2)t~~~~CH2~CH2~W CH3 X

R3-o(cH2cH2o~y-c-(cH2~t-c-o-cH2cH2-N CH X~

~ f 3 R3-O(cH2cH2cH2cH2o)y C CH2 ~ 3 3 2 2CH2CH2)y (cH2)t-~-o-cH2cH2-N+-cH3 X~

The preferred choline derivatives, described above, may be prepared by the reaction of a long chain alkyl polyalkoxy (preferably polyethoxy) carboxylate, having an alkyl chain of desired length, with oxalyl chloride, to form the corresponding acid chloride. The acid chloride is then reacted with dimethylaminoethanol to form the appropriate amine ester, which is then quaternized with a methyl halide to form the desired choline ester compound. Another way of preparing these compounds is by the direct esterification of the appropriate long chain ethoxylated carboxylic acid together with 2-haloethanol or dimethyl aminoethanol, in the presence of heat and an acid catalyst.

The reaction product formed is then quaternized ~ith methylhalide or used to ~uaternize trimethylamine to form the desired choline ester compound.
The Anionic and Nonionic Surfactant A typical listing of anion~c and nonionic surfactants useful herein appears in U.S. Patent 3,929,678 of Laughlin and Heuring, granted December 30, 1975. The following list of de-tergent compounds which can be used in the instant compositions is representative of such materials.
Water-soluble salts of the higher fatty acids, i.e.
"soaps", are useful as the anionic detergent component of the compositions herein. This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Soaps can be made by direct saponification of fats and soils or by the neutralization of free fatty acids.
Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e. sodium or potassium tallow and coconut soap.
A highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
(Included in the term "alkyl" is the alkyl portion of acyl groups).
Examples of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols C8-C18 carbon atoms) produced by reducing the glycerides of tallow or coconut oil;

and sodium and potassium alkyl benzene sulfonates, in which the ll~g~

alkyl group contains from about 9 to abou-c lS carbon atoms, in straight chain or branched chain configuration, e.g. those of the type descrîbed tn U.S. Patents 2,220,099 and 2,477,383.
Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as Cll 8 LAS.
A preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 mols of ethylene oxide.
Other anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coco-nut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
Other useful anionic detergent compounds herein include the water-soluble salts of esters of a-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group;
water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids contain-ing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 ~Dles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, especially 14 to 18 carbon atoms, and ~-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in 7~

the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Anionic surfactan~ mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures there-of, the cation being an alkali metal preferably sodium; and from about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium. The nonionic detergent materials can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Examples o~ suitable nonionic detergents include:
l. The polyethylene oxide condensates of alkyl phenol, e.g.
the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 1 to 40 moles, preferably from 2 to 9 moles of ethylene oxide per mole of alkyl phenol. The alkyl substitutent in such compounds may be derived, for example, from polymerised propylene, di-isobutylene, octene or nonene. Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol con-densed with 5 moles of ethylene oxide per mole of phenol; nonyl-phenol condensed with 9 moles of ethylene oxide per mole of nGnyl-phenol and di-isc-octylphenol condensed with 5 moles of ethylene oxide.

.

11~9759 2. The condensation product of primary or secondaxy aliphatic alcohols having from 8 to 24 carbon atoms, in either straight chain or branched chain configuration, with from 1 to about 40 moles of alkylene ox;de per mole of alcohol. Preferably, the aliphatic alcohol comprises between g and 15 carbon atoms and is ethoxylated with between 2 and 9 desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. Such nonionic surfactants are preferred from the point of view of providing good to excellent detergency performance on fatty and greasy soils, and in the presence of hardness sensitive anionic surfactants such as alkyl benzene sulphonates. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived) from natural fats prepared by the Ziegler process from ethylene,(e.g.
myristyl, cetyl, stearyl alcohols), or partly branched such as the "Dobanols" and "Neodols" which have about 25% 2-methyl branching ("Dobanol" and "Neodol" being Trade Marks of Shell) or "Synperonics", which are understood to have about 50% 2-methyl branching (~'Synperionic" is a Trade Mark of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Mark "Lial" by Liquichimica.
Specific examples of nonionic surfactants falling within the scope of the invention include "Dobanol 45-4", "Dobanol 45-7", "Dobanol 45-11", "Dobanol 91-3", "Dobanol 91-6", "Dobanol 91-8", "Synperonic 6", "Synperonic 14", the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the coconut alkyl portion having from 10 to 14 carbon atoms, and the con-densation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present compositions, especially tho~e ethoxylates of the ~Tergitol"* series having f~om about 9 to 16 carbon atoms in the alkyl group and up to about 11, especially from about 3 to 9, ethoxy residues per molecule.
3. The compounds formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion generally falls in the range of about 1500 to 1800. Such synthetic nonionic detergents are avail-able on the market under the trade mark of "Pluronic" suppliedby Wyandotte Chemicals Corporation.
A highly preferred mixture of surfactants is a mixture of a C8-C22 alkyl benzene sulfonate and a Cg-Cl5 alkanol ethoxylated with from 3 to 8 moles of ethylene oxide per mole of alkanol. Highly preferred mixtures include C12 alkyl benzene sulfonate and C14-C15 alcohol-(7)-ethoxylate, in ratios of from 2:1 to 1:10, preferably 1:1 to 1:8. In still more preferred compositions, C8-C24 alkanol ethoxy-late with from 10 to 40 moles of ethylene oxide per mole of alkanol is added to the above-described mixture, preferably at a level of from 1% to 5%.
The Builder The Detergent composition of the invention also contains at least about 10% of a detergency builder, especially a water-soluble inorganic or organic electrolyte. Suitable electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents. The builder can also include water-insoluble calcium ion exchange materials, however, non-limiting examples of suitable water-soluble, inorganic detergent *Trademark "Tergitol" is the trademark for a series of highly concentrated n~nionic surfactan~s of the glycol ether type.

~8-5~

builders include: al~ali metal carbonates, borate~ phosphates, polyphosphates, bicarbonates, silicates, sulfates and chlorides.
Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripoly-phosphates, orthophosphates, pyrophosphates, hexametaphosphates and sulfates.
Examples of suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and amino-polyacetates, for example, sodium and potassium glycinates, ethylenediamine tetraacetates, nitrilotriacetates, and N-(2-hydroxyethyl)nitrilo diacetates and diethylenetriamine pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosponates, including sodium, potassium, and lithium salts of ethane-l-hydroxy-l, l-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid;
and the like.

(4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, cyclopentane-cis, cis, cis-tetracarboxylic acid, mellitic acid and pyromellitic acid; (5) water-soluble organic amines and amine salts such as monoethanolamine, diethanolamine and triethanolamine and salts thereof.
Mixtures of organic and/or inorganic builders can be used herein. One such mixture of builders is disclosed in Canadian Patent No. 755.038, e.g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-l-hydroxy-l,l-diphosphonate.
Another type of detergency builder material useful in the present compositions and processes comprises a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product. Such "seeded builder" eompositions are fully diselosed in British Patent Speeification No. 1,424,406.
A further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, partieularly those described in Belgian Patent No. 814,874, issued November 12, 1~74. This patent discloses and elaims deter-gent compositions containing sodium aluminosilicates having the formula Naz(Alo2)z(~io2)yxH2o wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and x is an integer from about 15 to about 264, said aluminosilieates having a calcium ion exchange eapaeity of at least 200 milligrams equivalent/gram and a ealcium ion exchange rate of at least about 2 gxains/gallon/minute/gram.
A preferred material is Nal2 (SiG2 A12~ 1227H2 Additional Ingredients The eompositions of the present invention ean be supple-mented by all manner of detergent eomponents, either by ineluding such eomponents in the aqueous slurry to be dried or by admixing sueh eomponents with the eompositions of the invention following the drying step. Soil suspending agents at about 0.1% to 10% by weight such as water-soluble salts of earboxymethyl-eellulose, carboxyhydroxymethyl cellulose, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the present invention.
Dyes, pitment optical brighteners, and perfumes can be added in varying amounts as desired.
Other materials such as fluorescers, enzymes in minor amounts, anti-caking agents such as sodium sulfo-succinate, and sodium benzoate can also be added. Enzymes suitable for use herein include those discussed in U.S. Patents 3,519,570 and 3,533,139 to McCarty and McCarty et al issued July 7, 1970 and January 5, 1971, respectively~
Anionic fluorescent brightening agents are well-known materials, examples of which are disodium 4,4'-bis-(2-diethanol-amino-4-anilino- s - triazin - 6 - ylamino) stilbene-2:2' disul-phonate, disodium 4,4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylaminostilbene-2:2~-disulphonate, disodium 4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2' -disulphonate disodium 4,4l -bis-(2-anilino-4-(N-methyl N-2-hydroxyethylamino)-s-triazin -6-ylamino)stilbene-2,2' -disulphonate, disodium 4,4' -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2'disulphonate, disodium 4,4'bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2'disulphonate and sodium 2(stilbyl-4'' -(naphtho-1',2':4,5)-1,2,3 - triazole-2" -sulphonate.
An alkali metal, or alkaline earth metal, silicate can also be present. The alkali metal silicate preferably is used in an amount from 0.5% to 10% preferably from 3% to 8%. Suitable silicate solids have a molar ratio of SiO2/alkali metal2O
in the range from about 0.5 to about 4.0, but much more preferably from 1.0 to 1.8, especially about 1.6. The alkali metal silicates suitable herein can be commercial preparations of the combination of silicon dioxide and alkali metal oxide, fused together in varying proportions.
The compositions of this invention can re~uire the presence of a suds regulating or suppressing agent.
Suds regulating components are normally used in an amount from about 0.001% to about 5%, preferably from about 0.05% to about 3% and especially from about 0.10% to about 1%. The suds suppressing (regulat~ng~ agents which are known to be suitable 75~
as suds sUppressing agents in detergent context can be used in the compos;tions herein. These ~nclude the silicone suds suppressing agents, especially the mixtures of silicones and silica described in U~S. Patent No. 3,933,672 of G. Bartolotta et al., granted January 20, 1976. A part~cularly preferred suds suppressor is the material known as "HYFAC",* the sodium salt of a long-chain (C20-C24) fatty acid.
Microcrystalline waxes having a melting point in the range from 35C - 115C and saponification value of less than 100 represent an additional example of a preferred suds regulating component for use in the subject compositions.
The microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
Preferred microcrystalline waxes having a melting point from about 65C to 100C, a molecular weight in the range from 400-lO00; and a penetration value of at least 6, measured at 77C by ASTM-D1321. Suitable examples of the above waxes in-clude microcrystalline and oxidized microcrystalline petrolatum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes;
ozokerite; ceresin; montan wax; beeswax; candelilla; and carnauba wax.
The granular detergent compositions herein can also advantageously contain a peroxy bleaching component in an amount from about 3% to about 40% by weight, preferably from about 8% to about 33% by weight. Examples of suitable peroxy bleach components for use herein include perborates, persulfates, persilicates, perphosphates, percarbonates, and more in general all inorganic and organic peroxy bleaching agents which are known to be adapted for use in the subject compositions. The composition can also advantageously include *Trademark 397~;9 a bleach activator which is normally an organic compound containing an N-acyl, or an O-acyl ~preferably acetyl) group.
Preferred mater;als are N,N',N'-tetraacetyl ethylene diamine and N,N,N',N'-tetraacetylglycouril.
A further preferred ingredient of the instant composi-tions is from about 0.01 to about 4%, especially from about 0.5 to about 2.2% by weight of a polyphosphonic acid or salt thereof which is found to provide bleachable stain detergency benefits.
Especially preferred polyphosphonates have the formula:

N ~ ICH2 ~ CH2 I)n R R
wherein each R is CH2PO3H2 or a water-soluble salt thereof and n is from 0 to 2. Examples of compounds within this class are aminotri-(methylenephosphonic acid), aminotri-(ethylidenephosphonic acid), ethylene diamine tetra (methy-lenephosphonic acid) and diethylene triamine penta (methylene phosphonic acid). Of these, ethylene diamine tetra (methylene phosphonic acid) is particularly preferred.
A furthex optional, though preferred component is from about 0.1% to about 3%, especially from about 0.25%
to about 1.5% of a polymeric material having a molecular weight of rom 2000 to 2,000,000 and which is a copolymer of maleic acid or anhydride and a polymerisable monomer selected from compounds of formula:

(i) IORl HC = CH2 wherein Rl is CH3 or a C2 to C12 alkyl group;

`t?., -:

37~9 (_iil IR2 ::
H2C ~ I

wherein R2 is H or CH3 and R3 is H, or a Cl to C10 alkyl group;
(,iii~ ' HC = CH
10 wherein each of R4 and R5 is H or an alkyl group such that R4 and R5 together have 0 to 10 carbon atoms;
( iv) l\ I
¦ 2 CH2 HC = CH2 (v) ~
HC = CH2 and (vi) mixtures of any two or more thereof, said copolymers being optionally wholly or partly neutralised at the carboxyl groups by sodium or potassium.
Highly preferred examples of such carboxylates are 1:1 styrene/maleic acid copolymer, di-isobutylene/maleic acid copolymers and methyl vinyl ether/maleic acid copolymers.
Other suitable polycarboxylates are poly-~-hydroxy acrylic acids of the general formula ~ [ ~ CRlR2 ~ C(OH) (COOH) ]n wherein Rl and R2 each represent a hydrogen atom or an alkyl .. 24-1~97~9 group containing 1, 2 or 3 carbon atcms and ~herein n represents an integer greater than 3. Such materials may be prepared as described in Belgium Patent 817,678. Also suitable are polylactones prepared frc~ the hydroxy acids as described in British Patent 1,425,307.
In a process aspect of the invention, there is provided a method of making the detergent ccmposition of the invention comprising the steps of spray drying a crutcher mix oontaining the anionic, cationic and builder ccmponents and subsequently absorbing the nonionic surfactant in liquid or molten form into the spray-dried granules. This process is particularly valuable when the builder comprises an aluminosilicate ion-exchange material.
In ancther process aspect of particular applicability to compc, sitions comprising aluminosiliccate builder, the nonionic is included in the crutcher mix for spray drying, but the components of the surfactants are premix0d before addition of the aluminosilicate.
Other processes of nEking the ocmpositions of the invention can be employed, of oourse. ~hus the anionic and nonionic surfactants and the builder and filler components can be spray dried in conventional manner to form a base paW~r ccmposition and the cationic corponent can then be added to the base powder either as an approxlmately 1:1 mixture with part of the builder or filler co~ponents retained for that purpose, or as an inclusion oomplex of, for instance, urea. Alternatively, the cationic surfactant can be sprayed onto the base powder, or added as a dry mixed prill agglcmerated with an inDrganic or organic agglomerating aid, or can be separately spray dried and added to the base powder as a dry nixed granule. Alternatively, the cationic surfactant and base powder compositions can be individll~lly spray dried in separate stages of a mLlti-stage spray drying tower.
Ccmpositions of this invention in the form of detergent laundry bars can be prepared as described in U.S. Patent 3,178,370 issued April 13, 1965 and British Patent 1,064,414 issued April 5, 1967, both to Okenfuss.

~ 97~;9 A preferred process, called "dry neutralization", involved spraying the surfactant in liquid, acid form upon an agitated mixture of alkaline components such as phosphates and carbonates, followed by mechanically working as by milling, extruding as in a plodder, and forming into bars.
The compositions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.1 ~100 parts per million) to 2% (2,000 ppm), preferably from about 0.2 to 1~ of the detergent composition and agitating the soiled fabrics in the solution. The fabrics are then rinsed and dried. When used in this manner, the compositions of the present invention yield exceptionally good grease and oil soil removal performance.
~ he compositions of the invention can also be provided in the form of two or more component products, which are either mixed before use or added separately to a laundry solution to provide a concentration of the ternary surfactant system of from about 100 to about 3000 p.p.m., especially from about 500 to about 1500 p.p.m, Each component product includes one or more of the active ingredients of the ternary surfactant system and a mixture of the products in prescribed amounts should have the requisite granular form. In a preferred embodiment, one product is formulated as a conventional anionic or nonionic detergent composition suitable for use in the main wash cycle of an auto-matic laundry or washing machine, and the other is formulated as a cationic containing additive or ~ooster product for use simultaneously with the conventional detergent during the main wash. In addition to the cationic, the additive product will contain nonionic and~or anionic surfactant such that the total composition formed ~y mixing the component products in specified amounts has the re~uisite ternary active system.

11~P97~9 The compositions of the invention can also be formulated as special prewash compositions desiqned for use before the main wash stage of the conventional laundering cycle. Such pre-wàsh compositions will normally consist of a single product component containing the defined ternary active system.
In the Examples which follow, the abbreviations used have the following designations:
LAS : Linear C12 alkyl benzene sulfonate TAS : Tallow alkyl sulfate TAEn : Tallow alcohol ethoxylated with n moles of ethylene oxide per mole alcohol MTMAC : Myristyl trimethyl ammonium chloride LTMAC : Lauryl trimethyl ammonium chloride "Dobanol 45-E-7"*: A C14-C15 oxo-alcohol with 7 moles of ethylene oxide, marketed by Shell.
"Dobanol 45-E-3"**: A C14-C15 oxo-alcohol with 3 moles of ethylene oxide, marketed by Shell.
Silicate : Sodium silicate having a SiO2:Na20 ratio of 1.6 Wax : Microcrystalline wax - "Witcodur 272"***
M.pt 87C
Silicone ; Comprising 0.14 parts by weight of an 85:15 ~y weight mixture of silanated silica and silicone, granulated with 1.3 parts of sodium tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 25 molar proportions of ethylene oxide.
"Gantrez ANll9" : ~rade Mark for maleic anhydride/vinyl methyl ether copolymer, ~elieved to have an average *Trademark **Trademark ***Trademark . ..

molecular weight of about 240,000, marketed by GAF. This was prehydrolysed with NaOH
before addition.
srightener : Disodium 4,4' - bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) atilbene-2:2': disul-phonate.
TAED : Tetraacetyl ethylene diamine "Dequest 2060" : ~rade Mark for diethylene triamine penta (methylene phosphonic acid,) marketed by Monsanto "Dequest 2040" : Trade Mark for ethylanediamine tetra (methy- -lene phosphonic acid,) marketed by Monsanto.
The level of Zeolite A is given on an anhydrous basis; the material contains 21~ water of crystallisation.
The present invention is illustrated by the following non-limiting examples.

The following compositions were prepared by spray-drying an aqueous slurry of the ingredients except for the "Dobanol" derived nonionic surfactants which were sprayed onto the spray-dried granules, and the sodium perborate and enzyme which were dry mixed into the composition.

7~

EXAMPLES
1 2 3 ~- 5 % 9~ % % %

MTMAC 2.25 5 4 - -LTMAC - - - 2 1.5 "Dobanol 45~E-7" 2.25 4 3 - 2 "Dobanol 45-E-4" - - - - 2 TAEll _ 1 3.5 C22Soap _ 4 2 Pentasodium tripolyphosphate 4 20 0.5 18 Disodium pyrophosphate - - - - 18 Zeolite A (particle size

5 ~) 40 26 45 "Gantrez ANll9" - - - 1.5 "Dequest 2060"
Silicate - 5 - 5 6 Protease enzyme 0.8 O. 5 0.8 Sodium perborate - 32 - 25 20 Silicone - - - 2 2 Wax 2.0 - - 0.3 0.3 Brightener 0.15 0.15 0.15 0.15 0.15 Sodium sulphate, moisture to 100 and miscellaneous These products provide enhanced oil and grease stain removal performance with detriment to particle clay soil detergency, whiteness maintenance and fluorescer brightening characteristics on both natural and man-made fabrics at both high and low wash temperatures.
Products with enhanced performance are also obtained when the sodium alkyl benzene sulphonate is replaced by m~lar equivalents of C10-C22 olefine sulphonates, C10-C20 paraffin sulphonates, and C10-C20 alkyl ether sulphates The lauryl or myristyl trimethyl ammonium chloride in the above examples can be replaced by molar equivalents of lauryl or myristyl-trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, coconut alkyl benzyl dimethyl ammonium chloride, C12 alkylbenzyl dimethyl ethyl ammonium chloride, C12 alkylbenzyl trimethyl ammonium chloride or one of the following compounds C12H25~ -- (CH2) 3 --COOCH2CH2--N (+) --CH3 , Cl ( 14 29 CH2CH2OOOCH2 -- N (+) --CH3, Cl (-) C14 -- OCH2CH2O CO(cH2)3OOOcH2CH2 -- N(~) -- CH3 ,Br( !

., ~ .
. -30 .

The following compositions were prepared similarly to Examples 1-5.

6 7 8 9 10. 11 LAS 1.2 2.2 - 5.0 2.2 2.0 MTMAC 1.0 1.8 2.8 2.0 1.8 1.6 TAS ~ ~ 3-0 "Dobanol 45-E-7" 8.0 6.6 - 1.5 6.6 3.0 11 6.0 - - 1.0 "Dobanol 45-E-4" - - 3.0 2.0 C12 soap - 2.0 C18 soap - - 0.75 Sodium tripoly-phosphate 33.0 2.5 4.0 20.0 4.0 33.0 Zeolite A - - 20.0 Zeolite X - 30.0 - - - -"Gantrez ANll9" - - - - 1.5 0.5 "De~uest 2040" - - - - 1.0 0.5 "Dequest 2060" 2.0 - - 1.0 Protease enzyme 1.2 0.5 1.2 0.5 1.2 0.5 Sodium perborate 12.0 10.0 12.0 5.0 - 10.0 Sodium bicarbonate - - - - 10.0 Polyethylene glycol (Mo. Wt. 6000) - 1.0 1.5 - 1.0 Silicone - - - 2.0 TAED 2.0 - 4.0 - - -Bri~htener 0.15 0.15 0.15 0.15 0.15 0.15 Sodium silicate (SiO2:Na2O=2:1) 5.0 1 2.5 6.0 Wax 0.3 - - 0.3 - 0.3 Sodium sulphate, moisture to 100 miscellaneous llQ9~5~

These products pr~vide enhanced oil and grease stain removal performance without detriment to particulate clay soil detergency, whiteness maintenance and fluorescer brightening cha~acteristics on both natural and man-made fabrics at both high and low wash temperatures.
Products with enhanced performance are also obtained when the "Dobanol 45-E-7" is replaced by a C14 15 alcohol polyethoxylate containing an average of 6 moles of ethylene oxide, a C12 15 alcohol polyethoxylate containing an average of 6.5 moles of ethylene oxide, a Cg 11 alcohol polyethoxylate containing an average of 6 moles of ethylene oxide, a C12 13 alcohol polyethoxylate containing an average of 5 moles of ethylene oxide stripped so as to remove lower ethoxylate and unethoxylated fractions, a secondary ~15 alcohol polyethoxylate containing an average of 9 moles of ethylene oxide, a C12 alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C10 alcohol polyethoxylate containing an average of 5 moles of ethylene oxide, a C14 alcohol polyethoxylate containing an average of 6 moles of ethylene oxide, a C12 alcohol polyethoxylate containing an average of 7 moles of ethylene oxide, and mixtures of those surfactants.
Enhanced performance is also obtained when "Gantrez AN 119" is replaced by, as their sodium salts, a copolymer of methyl methacrylate and maleic acid, the molar ratio of the monomers being about 1:1, of molecular weight about 10,000: an ethylene~maleic acid copolymer of molecular weight about 4,000, a propylene-maleic acid copolymer of molecular weight about 30,000; l-hexene-maleic acid copolymer of molec-ular weight about 30,000; l-hexene-maleic acid copolymer of molecular weight about 25,000; a vinyl pyrrolidone-maleic acid copolymer of molecular weight about 26,000 a styrene-maleic acid copolymer of acrylic acid and itaconic acid; a 1:4 copolymer of 3-butenoic acid and methylenemalonic acid; a 1:1.9 copolymer of methacrylic acid and aconitic acid; and a 1.2:1 copolymer of 4-pentenoic acid and itaconic acid.
Products with enhanced performance are also obtained when the sodium alkyl benzene sulphonate is replaced by molar equivalents of C10-C22 olefine sulphonates, C10-C20 paraffin sulphonates, and C10-C20 alkyl ether sulphates.
The myristyl trimethyl ammonium chloride in the above examples can be replaced by molar equivalents of lauryl or myristyl-trimethyl ammonium bromide, decyl trimethyl ammonium chloride, dioctyl dimethyl ammonium bromide, coconut alkyl ber,zyl dimethyl ammonium chloride, C12 alkylbenzyl dimethyl ethyl ammonium chloride, C12 alkylbenzyl trimethyl ammonium chloride or one of the following compounds C12H25 - O -(CH2)3 ~ COOCH2CH2 - N(-) - CH3 , Cl( ) C~3 fH3 14 29 CH2CH2OOOH2 - N~+) - CH3 , Cl(-~
; CH3 fH3 14 2 2 CO(CH233COOCH2CH2 - N(+) - CH B (~) EXAMPLES 1?- 13 Examples 3 and 10, respectively, are repeated except that instead of spray-drying the ingredients, they are processed into laundry bars according to the dry-neutralization process of Okenfuss hereinbefore described. Enhanced oil and grease stain 30 removal performance is provided as before, without detriment to particulate clay soil detergency, whiteness maintenance and fluor-escer brightening characteristics on either natural or man-made fabrics at either high or low wash temperatures.

Claims (19)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A detergent composition in solid form comprising (a) from 2% to 60% of a surfactant system consisting essentially of a water-soluble or water-dispersible combination of anionic, alkoxylated nonionic and water-soluble quaternary ammonium cationic sur-factants, wherein the anionic:cationic surfactant weight ratio is no more than 5:1 and the nonionic:
cationic surfactant weight ratio is in the range from 100:1 to 2:3, and wherein the surfactant system contains anionic and cationic surfactants in an equivalent ratio of at least 1:1, and (b) from about 10% to about 98% of a detergency builder.

2. The composition according to Claim 1 wherein the cationic surfactant comprises from 1 to 4 quaternary ammonium groups of which one and only one has the general formula R1mR2x?

wherein each R1 is a hydrophobic alkyl or alkenyl group optionally substituted or interrupted by phenyl, ether, ester or amide groups totalling from 8 to 20 carbon atoms and which may additionally contain up to 20 ethoxy groups, m is a number from 1 to 3 and no more than one R1 can have more than 16 carbon atoms when m is 2 and no more than 12 carbon atoms when m is 3, each R2 is an alkyl group containing from one to four carbon atoms or a benzyl group with no more than one R2 in a molecule being benzyl, and x is from 0 to 3, provided that (m+X) is not greater than 4.

3. The composition according to Claim 2 wherein the cationic surfactant has the general formula R1mR24-m? Z

wherein R1 is selected from C8-C20 alkyl, alkenyl and alkaryl groups; R2 is selected from C1-4 alkyl and benzyl groups; Z
is an anion in number to give electrical neutrality; and m is 1, 2 or 3 provided that when m is 2, R1 has less than 15 carbon atoms and when m is 3, R1 has less than 9 carbon atoms.

4. The composition according to Claim 3 wherein the cationic surfactant is a C12-C14 alkyl trimethyl ammonium salt.

5. The composition according to Claim 2 wherein the anionic surfactant is a sulphate or sulphonate having one alkyl group of from 10 to 20 carbon atoms.

6. The composition according to Claim 5 wherein the cationic and anionic surfactant have a combined total of no more than 34 carbon atoms numbered in hydrophobic groups having at least 4 consecutive carbon atoms.

7. The composition according to Claim 6 wherein the total number of carbon atoms is from 26 to 32, at least 12 of the carbon atoms being provided by the anionic surfactant.

8. The composition according to Claim 2 wherein the nonionic surfactant has the general formula RO(CH2CH2O)nH wherein R
is branched or unbranched C8-C24 alkyl or alkenyl and n is from 1 to 40.

9. The composition according to Claim 8 wherein R is C9-C15 alkyl and n is from 3 to 8.

10. The composition according to Claim 8 wherein the nonionic:
cationic surfactant weight ratio is from 20.1 to 1:1.

11. The composition according to Claim 5 wherein the anionic:
cationic surfactant weight ratio is from 5:1 to 1:3.

12. A composition according to Claim 11 wherein the anionic:
cationic surfactant weight ratio is from 2:1 to 1:2.

13. A composition according to Claim 5 wherein the anionic:
nonionic surfactant weight ratio is from 7:1 to 1:20.

14. A composition according to Claim 2 wherein the surfactant system comprises at least 5% by weight of the cationic sur-factant and at least 60% by weight in total of the anionic and nonionic surfactants.

15. A composition according to Claim 14 wherein the surfactant system comprises at least 15% by weight of each of the anionic and cationic surfactants and from 15% to 60% by weight of the nonionic surfactant.

16. A composition according to Claim 14 wherein the sur-factant system comprises at least 5% by weight of each of the anionic and cationic surfactants and at least 60% by weight of the nonionic surfactant.

17. A composition according to Claim 2 wherein the deter-gency builder comprises a water-soluble inorganic or organic electrolyte having an equivalent weight of no more than 210.

18. A composition according to Claim 17 wherein the detergency builder comprises a water-soluble alkaline polyvalent inorganic or organic calcium ion sequestering agent.

19. A composition according to Claim 2 additionally comprising from 0.01 to 2% of an anionic fluorescer.