CA1220694A

CA1220694A - Detergent compositions

Info

Publication number: CA1220694A
Application number: CA000441165A
Authority: CA
Inventors: Appaya R. Naik
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1982-11-16
Filing date: 1983-11-15
Publication date: 1987-04-21
Also published as: IN158158B; GR81252B; NO834151L; JPS6050399B2; JPS59126500A; DK523383D0; EP0112045A1; ZA838428B; ATE25101T1; EP0112045B1; GB2130237A; PT77672A; GB8330368D0; DK523383A; GB2130237B; BR8306255A; AU2136383A; AU550658B2; PH18169A; NZ206210A

Abstract

ABSTRACT

A high-foaming liquid detergent composition, suitable inter alia for hand dishwashing, contains from 2 to 60% by weight of an active detergent system including a dialkyl sulphosuccinate (at least 2%), and also contains an added magnesium salt providing from 0.02 to 0.24% by weight of magnesium ions. The last-mentioned ingredient gives improved product stability, as demonstrated by a lower clear point, and increased viscosity at low concentrations, as well as enhanced soft water foaming performance.

Description

- 1 - C.1345 DETERGENT CO~POSITIONS
.

The present invention relates to high-foaming liquid detergent compositions suitable for use in fabric washing, shampoos, and above all, in manual dishwashing operations in both hard and soft water.

The term "dishes" as used herein means any utensils involved in food preparation or consumption which may be required to be washed to free them from foGd particles and other food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues.

GB 1 429 637 (Unilever) discloses hand dishwashing compositions containing as detergent-active material a water-soluble salt of a di(C7-Cg) alkyl ester of sulphosuccinic acid, in combination with an alkyl sulphate or an alkyl ether sulphate.

GB 2 108 520, GB 2 104 913, GB 2 105 325, EP 71413 and EP 71414 Unilever) disclose high-foaming detergent composi~ions based on certain dialkyl sulphosuccinates, particularly those having C6 and C8 chains.

GB 1 164 854 (Shell) discloses the inclusion of 0.5 to 10~ by weight o a water-soluble inorganic magnesium salt in aqueous liyuid detergent compositions based on an 68E23G ~

- 2 - C.1345 alkyl or aryl sulphonate in conjunction with an alkyl ether sulphate or a nonionic detergent.

The present invention is based on the observation that the presence of small quantities of magnesium ions, derived from an added electrolyte, in liquid detergent compositions based on dialkyl sulphosuccinates gives both performance and formulation benefits.

The present invention accordingly provides a foaming liquid detergent composition in the form of a clear, stable aqueous solution containing from 2 to 60~ by weight of active detergent comprising at least 2~ by weight, preferably at least 5~ by weight, based on the whole composition, of a water soluble salt of a dialkyl sulpho-succinic acid, the composition containing at least 0.02%
by weight of magnesium ions derived from an added electrolyte.

According to the invention, magnesium ions arrive in the composition as part of an added water soluble magnesium salt, for example, magnesium sulphate, chloride, or toluene or xylene sulphonate.

The presence of magnesium ions has been found to give improved foaming performance in very soft water. This effect has already been observed with detergent-active materials other than dialkyl sulphosuccinates, for example, alkylbenzene sulphonates, but the additicn of magnesium salts is generally detrimental to low-temperature product stability, causing both cloud and clear points to rise. It should be explained that the cloud point is the temperature at which clarity of the composition is lost as the external temperature is lowered; the clear point is ~he temperature at which a clear solution is regained as the external temperature is raised again~

_ 3 _ C.1345 Surprisingly, it has been found tha~ the addition of low levels of magnesium salts to liquid compositions based on dialkyl sulphosuccinates actually causes a lowering of the clear point, and in relatively :Low-concentration formulations also increases the viscosity.

The amount of added magnesium salt is within the range of from 0.02 to 0~24 % by weight of magnesium ions.
The optimum level of addition within these limits for any particular formulation will depend on the total active detergent concentration, the total level and type of electroly'e present and the hydrotrope level, and can readily be determined experimentally by one skilled in the art.
The magnesium ions are added to the compositions of the invention in the form of water-soluble magnesium salts which are electrolytes. The preferred salts are magnesium sulphate and magnesium chloride. For magnesium chloride hexahydrate, the limits given above correspond to 0.17 to 2.02 % by weight; for magnesium sulphate heptahydrate, the limits given above correspond to 0.21 to 2.46 % by weight.
Accordingly the amount of added magnesium salt present in the compositions of the invention i9 preferably from 0.15 to 2.50~ by weight, and more preferably from 0.50 to 1.50 by weight.

The total active detergent level of the compositions of the invention can range from 2 to 60% by weight, preferably from 5 to 40% by weight. The addition of magnesium salts in accordance with the invention is especially beneficial at to~al active detergent levels of 30~ by weight and below At the low end of the concentration range, 20% and below, the additional beneit of viscosity increase is observed. Thus the present invention alleviates the problem of low viscosities that ~L~2~6~
~ 4 - C.1345 can arise with low-active-detergent dialkyl sulphosuccinate-based compositions.

The dialkyl sulphosuccinate, which is an essential detergent-active material in the composition of the invention, may be either symmetrical (both alkyl groups the same) or unsymmetrical. It may if desired be constituted by a mixture of materials of different chain lengths, of which the individual dialkyl sulphosuccinates themselves may be either symmetrical or unsymmetrical.

The detergent-active dialkyl sulphosuccinates are compounds of the formula I:

~5 CH2 - CH - S03X

COORl COOR2 wherein each of Rl and R29 which may be the same or diEferent~ represents a straight-chain or branched-chain alkyl group having from 3 to 12 carbon atoms, preEerably from 4 to lO carbon atoms~and more preferably from 6 to 8 carbon atoms, and Xl represents a solubilising cation, that is to say, any cation yielding a salt of the formula I
sufficiently soluble to be detergent-active. In the context of the present invention, the solubilising cation Xl will generally be monovalent, for example, alkali metal, especially sodium; ammonium; or substitu~ed ammonium, for example, ethanolamine.
The alkyl groups Rl and R2 in the dialkyl sulphosuccinate are preferably straight-chain or (in mixtures) predominantly straight-chainO

Among dialkyl sulphosuccinates that may advantageously be used in the composition of ~he invention 6!~4 are the C6/C8 unsymmetrical materials described and claimed in CA 407,709 (Unilever); the dioc-tyl sulphosuccinate/dihexyl sulphosuccinate mixtures described and claimed in CA 407,731 (Unilever) and the mixtures of symmetrical and unsymmetrical dialkyl sulphosuccinates described and claimed in CA 407,699 (Unilever).

The composition of the invention may of course with advantage contain other detergent-active agents in addition to the dialkyl sulphosuccinate, provided that the total comp-osition contains at least 2% by weight, preferably a-t least 5~, of dialkyl sulphosuccinate(s). The composition may, for example, include one or more of the sulphonate-type deter-gents conventionally used as the main detergent-active agent in liquid compositions, for example, alkylbenzene sulphonates (especially Cg-Cl5 linear alkylbenzene sulphonates), second-ary alkane sulphonates, alpha-olefin sulphonatqs~ alkyl glyc-eryl ether sulphonates, and fatty acid ester sulphonates. Of course dialkyl sulphosuccinates are themselves sulphonate-type detergents. If such addi-tional sulphonate-type materials are present, the total sulphonate preferably predominates in the active detergent mixture of the composition of the inven-tion. If no such additional sulphonate-type materials are present, the sulphosuccinate alone preferably predominates.

Among the additional sulphonate-type detergents that may be present, alkylbenzene sulphonates and secondary alkane sulphonates are especially preferred. The ratio of di-alkyl sulphosuccinate to alkylbenzene sulphonate or secondary alkane sulphona-te is preferably within the range of from 4:1 to 0.1:1, more preferably from 2.5:1 to 1:1.

Our copending application of even date, Canadian Patent Application No. 441,166, describes and claims liquid detergent 6 - C.13~5 compositions containing dialkyl sulphosuccinate, alkylbenzene sulphonate and/or secondary alkane sulphonate, and alkyl ether sulphate.

If desired there may also be present one or more primary or secondary alkyl sulphates. If present, these together with any sulphonate material as mentioned above, including the dialkyl sulphosuccinate, preferably predominate in the active detergent mixture of the composition of the invention.

The composition of the invention advantageously contains one or more further detergent-active materials in addition to the dialkyl sulphosuccinate and optional additional sulphonate already mentioned. Preferably there are present one or more alkyl ether sulphates and/or one or more ethoxylated nonionic detergents having an alkyl chain length of C8 to C15 and an average degree of ethcxylation of from 5 to 14.

Preferred alkyl ether sulphates are materials of the general formula R - 0 - (CH2CH20)n S03 2

3 is a C10 to C18 alkyl group, X is a solubilising cation~ and n, the average degree of ethoxylation, is from 1 to 12. R3 is preferably a C
to C15 alkyl group and n is preferably rom 1 to 8.
3o In any given alkyl ether sulphate, a range of differently ethoxylated materials, and some unethoxylated material, will be present and the value of n represents an average. The unethoxylated material is, of course, alkyl ~5 sulphate. If desired, additional alkyl sulphate may be admixed with the alkyl ether sulphate, to give a mixture in ,., _ 7 which the ethoxylation distribution is more weighted towards lower values.

It is especially preferred to use alkyl ether sul-phates containing less than 20% by weight of C14 and above material, as described and claimed in our copending applica-tion of even date, Canadian Patent Application No. 441,168.

Examples of preferred ether sulphates for use in the present invention are Dobanol (Trade Mark) 23-3 and Dobanol (Trade Mark) 23-2 ex Shell, both based on C12 to C13 (50% of each) primary alcohol (about 75% straight chain, 25%
2-methyl branched), and having average degrees of ethoxyla--tion n of 3 and 2 respectively.

The ratio of dialklyl sulphosuccinate, plus any other sulphonate-type detergent present plus a~y alkyl sulph-ate present other than that intrinsically presen-t in the eth-er sulphate, to ether sulphate, is preferably within the range of from 5:1 to 0.5 to 1, more preferably from 3:1 to 1 : 1 .

Nonionic detergents that may be used in the compos-ition of the invention include short-chain high-foaming eth-oxylated alcohols of the general formula III:

R4 (CH2C 2 )m (III) wherein R4 is an alkyl group, preferably straight-chain, having from 8 to 12 carbon atoms, and the average degree of ethoxylation m is from 5 to 12.

The weight ratio of alkyl ether sulphate to nonion-ic detergent is preferably at least 1:1 and more preferably -- 8 ~

within the range of from 1.5:1 to 3:1, especially about 2:1.
An especially preferred nonionic detergent is Dobanol (Trade Mark) 91 8 ex Shell, in which R4 is Cg-Cll (predominantly straight-chain) and _ is 8.

Advantageously the compositions of the invention include within their active detergent mixture a C10-C18 car-boxylic acid (C2-C3 alkanol)amide, preferably a diethanol-amide. The inclusion of this material, at a level not ex-ceeding 30% by weight of the active detergent mixture, gives both performance and formulation advantages. Our copending applica-tion of even date, Canadian Patent Application No.
441,167 describes and claims liquid detergent compositions containing a dialkyl sulphosuccinate, an alkyl ether sulphate and/or a nonionic detergent, and a C10-C18 carboxylic acid ~i(C2-C3)alkanolamide, the last-men-tioned component being present in an amount not exceeding 30~ by wei~ht of -the total active detergent present.

As well as active detergent, magnesium ions and water, the composition of the invention will generally need to contain one or more hydrotropes. These are materials pres-ent in a formulation to control solubility, viscosity, clar-ity and stability, but which themselves make no active con-tribution to the performance of the product. Examples of hydrotropes include lower aliphatic alcohols, especially ethanol; urea, lower alkylbenzene sulphonates such as sodium toluene and xylene sulphonates; and combinations of these.
Hydrotropes are expensive and take up room in a formulation without contributing to its performance, and it is therefore desirable to use as small quantities of them as possible.

The compositions of the invention may also contain 3L22~

~ 9 - C.13~5 the usual minor ingredients such as perfume, colour, presarvatives and germicides.

The liquid detergent compositions of the invention, containing 2 to 60% by weight of active detergent in clear, stable aqueous solution, may be used for all normal detergent purposes where foaming is advantageous, for example, fabric washing products, general purpose domestic and industrial cleaning compositions, carpet shampoos, car wash products, personal washing products, shampoos, foam bath products, and, above all, manual dishwashing.

The invention is further illustrated by the following non-limiting Examples.
EXAMPLES 1 & 2 The cloud points, clear points and viscosities of formulations containing dialkyl sulphosuccinate and ether sulphate, at a total active-detergent level of 24~, with 12% urea as hydrotrope, were compared at different levels of magnesium chloride hexahydrate.

The dialkyl sulphosuccinate used was a statis~ical mixture (mole ratio 1:2:1) of di-n-octyl sulphosuccinate, n-hexyl n-octyl sulphosuccinate and di-n-hexyl sulpho-succinate, prepared from a 1:1 mixture of n-hexanol and n-octanol by the method described in Example 1 of GB 2 108 520 tUnilever~. This material contained 2.5% of sodîum sulphate in a 40% solution, so that in the formulations the sodium sulphate level was 1~ by weight.

The ether sulphate used was Dobanol 23-2S ex Shell C12, 50% C13; n = 2; sodium salt).
The magnesium was added in the form of magnesium 6g~
- 10 - C.13~5 chloride hexahydrate.

The results were as follows:

--_____________ ¦ A ¦1 ¦ 2 Sulphosuccinate ¦ 16 ¦16 116 Dobanol 23-2S ¦ 8 ¦8 ¦ 8 Urea ¦ 12 ¦12 ¦12 M9Cl2-6H2 1 _ ¦0.5 ¦l.o '15 1 _ _________ I ._____~.__ I _______ Cloud point (C) ¦ -8 ¦~5 ¦ 3 Clear point (C) ¦ 13. 5 ¦-1 j 7 1 1l Viscosity (cp) I 153 1166 1 162 ________________________________________________________ Although the cloud point rose slightly with increasing magnesium ion level, the clear point was depressed considerably at 0.5% MgCl2.6H2O, (0~06%
Mg2+) giving an a~vantage in terms of product skability;
at 1.0~ MgC12.6H20 (0.12% M92 ) this advantage was smaller, and was offset by the rise in the cloud point.
~0 There was no significant effect on viscosity.

XAMPLES 3 & 4 Examples 1 and 2 were repeated using a dialkyl ~5 sulphosuccin~te sample containing a lower level (1%) of sodium sulphate, so that the overall level of that material .

~ 69~

~ C.1345 in the composition was only 0.4% by weight. At this lower electrolyte level ~he urea content could be reduced to 11%.

The results were as follows:

___~_____~_______________..________________________________ Sulphosuccinate 16 16 16 Dobanol 23-2S 8 8 8 Urea 11 11 11 15 MgCl2.6H20 ~ 0 5 1.0 ______________________________________ _________ __ Cloud point (C) -9 -8 -4 Clear point ~C) lS 14 2 20 ____ __________ It will be seen that at this lower electrolyte level, a higher amount of magnesium chloride hexahydrate was required to effect a significant lowering of the clear point.

EXAMPLES 5 & 6 Examples 3 and 4 were repeated using Dobanol 23-2A
(the corresponding ammonium salt) instead of Dobanol 23-2S~
3Q The results were as follows:

i9~
- 12 - .~ C.1345 _______________________~_____________________________ Sulphosuccinate 16 l6 l6 Dobanol 23-2A 8 8 8 Urea 10 10 10 MgC12.6H20 - 0.5 l.0 _____________________________________________________ Cloud point (C) -8 -4 4 Clear point ~C) 8 0u5 6.5 ___________________~___~______________________________ As can be seen, the use of the ammonium salt of the ether sulphate instead of the sodium salt, at the same total electrolyte level, decreased the level of MgCl2.6H20 required to give a clear point lowering from 1.0 to 0.5~, the level of 1.0% now being higher than optimum.
EXAMPLE 7 & 8 ~xamples 1 and 2 were repeated using a dialkyl sulpho succinate sample free of electrolyte (sodium sulphate). The urea level was 10%.

3o The results were as follows:

~5 ~;22~3~9~
- 13 ~ C.1345 ______ _______________________~________________________ Sulphosuccinate 16 16 16 Dobanol 23-2S 8 8 8 Urea 10 10 10 10 MgC12.6H20 - 0.5 1.0 _____________________________________________________ Cloud point (C) -9 -7 0 Clear point (C) 15 16 2 ---~----------------------___________________________ It can be seen that a magnesium chloride level of 0.5% was insufficient to lower the clear point, but the higher level of 1.0% was effectiveO

This Example demonstrates the improvement in soft-water foaming performance obtained by the addition of magnesium chloride hexahydrate to a dialkyl sulpho-succinate/ether sulphate formulation.

The comparison was carried out by means of a plate-washing test in 1H (French hardness~ water.

In the test, plates soiled with a standard starch/fat/ fatty acid mixture were washed in a standard manner with 5 litres of test solution (total concentration 1 g/litre at 45C) in a bowl, until only a third of the surface of the solution in the bowl was covered with foam.
The number of plates washed before this arbitrary end-point ~2~
- 14 - C.1345 was reached was taken as an indicator of dishwashing and foaming performance.

The dialkyl sulphosuccinate used was the C6/C8 statistical mixture of Example 2, at a concentration of 16%
by weight, and the ether sulphate was Dobanol 23-2S, at a concentration of 8% by weight.

This composition without added magnesium chloride hexahydrate washed 23 plates, and with the addition of 1.0%
by weight of magnesium chloride hexahydrate washed 27 plates.

EXAMPLES 10_- 12 This experiment shows the effect of the addition of a magnesium salt to a relatively low-concentration (16~) formulation containing a fatty acid diethanolamide in addition to a dialkyl sulphosuccinate and an alkyl ether sulphate. The dialkyl sulphosuccinate was the C6/C8 mixture used in Examples 1 and 2, containing 2.5% by weight of electrolyte (sodium sulphate) in a 40% solution. The alkyl ether sulphate was Dobanol 23-3A, and the fatty acid diethanolamide was Empilan (Trade Mark) CDE ex Albright &
Wilson, a coconut diethanolamide.

The results are shown in the following Table~ All three levels of magnesium salt were efEective in lowering the clear and cloud points~ and all three levels raised ~he ~0 viscosity, the level of 1.0% being optimum in this latter respect.

~5 - 15 - C.1345 ______________________ ._______________ ___ ._________ Sulphosuccinate 8 8 8 8 Dobanol 23-3A 4 ~ 4 4 Empilan CDE 4 4 4 4 Urea 8 8 8 8 MgC12.6H2O - 0.5 1.0 1.5 _______________________________________ _____________ Cloud point (C) -7 -8 -8 -8 Clear point (C) 3 Viscosity 50 113 133 104 ___________________ _________________________________ The procedure of Examples 10-12 was repeated using a formulation having the same total active detergent level (16%) but containing a higher proportion (10%) of the dialkyl sulphosuccinate. In this case a magnesium salt level of 0.5~ was found to give optimum benefits.

~0 - 16 ~ C.1345 _______.________________ ______________________________ Sulphosuccinate 10 10 10 Dobanol 23-3A 3 3 3 Empilan CDE 3 3 3 10 Urea 8 8 8 MgC12.6H20 - 0.5 1.0 ______________________________~______________________ Cloud point (C) -5 -8 Clear point (C) 9 - 3 Viscosity tcp)44 90 86 ____________________________________________ _____ EXAMPLES 15 & 16 This experiment illustrates the effect of the addition of a magnesium salt on a relatively low-concentration (18%) formulation containing an alkylbenzene sulphonate (Dob (Trade Mark) 102 ex Shell) in addition to dialkyl sulphosuccinate and alkyl ether sulphate. The dialkyl sulphosuccinate was as used in Examples 10-14.
3o 2~6~
- 17 - C.1345 _______________________________________________________ Sulphosuccinate 10 10 10 Dob 102 4 4 4 Dobanol 23-3A 4 4 4 10 Urea 10 10 10 MgC12,6H20 - 0.5 1.0 ..____________________________ ___________________ ___ Cloud point (C) -7 -7 -2 Clear point (C) 10 10 2.5 Viscosity (cp) 27 60 104 __________________________________________ __________ Both levels of magnesium chloride raised the viscosity, the higher level of 1.0% being more effective.
At 10% the clear point was also lowered, at the cost of a rise in the cloud point.

EXAMPLES 17 & 18 The procedure of Examples 15 and 16 was repeated at a slightly higher total active detergent level (20%)~
3o - 18 - ~ 9~ C.1345 _____________________________________ _________________ Sulphosuccinate 10 10 10 Dob 102 4 4 4 Dobanol 23-3A 6 6 6 Urea 10 10 10 MgC12.6H2O - 0.5 1.0 ____________________________________________________._ Cloud point (C) C-10 <-10 -8 Clear point (C) - - 4.5 ~iscosity (cp) 93 129 1~2 .__________________________________________________~_ Comparative Composition H already had excellent low-temperature stability. The addition of 0.5% magnesium chloride increased the viscosity without detriment to the cloud point. The higher level of magnesium chloride (1.0%) improved the viscosity further to the slight, but insignificant, detriment of the low-temperature stability.

Claims

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

1. A foaming liquid detergent composition in the form of a clear, stable aqueous solution containing from 2 to 60%
by weight of an active detergent mixture comprising at least 2% by weight, based on the total composition, of a water-soluble salt of a dialkyl ester of sulphosuccinic acid, wherein the composition further comprises from 0.02 to 0.24%
by weight of magnesium ions derived from an added electro-lyte.

2. A detergent composition as claimed in claim 1, which comprises from 0.15 to 2.50% of an added inorganic mag-nesium salt selected from magnesium sulphate, magnesium chloride and mixtures thereof.

3. A detergent composition as claimed in claim 2, which comprises from 0.50 to 1.50% by weight of the added magnesium salt.

4. A detergent composition as claimed in claim 1, wherein the total concentration of active detergent is within the range of from 5 to 40% by weight.

5. A detergent composition as claimed in claim 4, wherein the total concentration of active detergent is within the range of from 5 to 30% by weight.

6. A detergent composition as claimed in claim 5, wherein the total concentration of active detergent is within the range of from 5 to 20% by weight.

7. A detergent composition as claimed in claim 1, wherein the dialkyl sulphosuccinate constitutes at least 5%
by weight of the total composition.

8. A detergent composition as claimed in claim 1, wherein the alkyl groups of the dialkyl sulphosuccinate each have from 4 to 10 carbon atoms.

9. A detergent composition as claimed in claim 8, wherein the alkyl groups of the dialkyl sulphosuccinate each have from 6 to 8 carbon atoms.

10. A detergent composition as claimed in claim 1, wherein the active detergent mixture further comprises an alkylbenzene sulphonate and/or a secondary alkane sulphonate.

11. A detergent composition as claimed in claim 10, wherein the weight ratio of dialkyl sulphosuccinate to alkyl-benzene sulphonate and/or secondary alkane sulphonate is within the range o from 2.5:1 to 1:1.

12. A detergent composition as claimed' in claim 1, wherein the active detergent mixture fur-ther comprises a C10 to C18 alkyl polyethoxy sulphate having an average degree of ethoxylation of from 1 to 12.

13. A detergent composition as claimed in claim 12, wherein the alkyl polyethoxy sulphate has an alkyl chain length of Cll to C15.

14. A detergent composition as claimed in claim 12 or claim 13, wherein the alkyl polyethoxy sulphate contains less than 20% by weight of material of chain length of C14 and above.

15. A detergent composition as claimed in claim 12, wherein the weight ratio of dialkyl sulphosuccinate, plus any alkylbenzene sulphonate and/or secondary alkane sulphonate present, to alkyl polyethoxy sulphate is within the range of from 5:1 to 0.5:1.

- 21 - C.1345 GB

16. A detergent composition as claimed in any one of claims 1 to 3, wherein the active detergent mixture further comprises a C10-Cl8 carboxylic acid di(C2-C3 alkanol)amide, in an amount not exceeding 30% by weight of the active detergent mlxture.

17. A detergent composition as claimed in claim 1, wherein the active detergent system consists essentially of:

a) (i) a water-soluble salt of a dialkyl sulphosuccinic acid in which the alkyl groups may be the same or different, and, optionally, (ii) an alkylbenzene sulphonate and/or a secondary alkane sulphonate, and b) (i) a C10-Cl8 alkyl polyethoxy sulphate having an average degree of ethoxylation of from 1 to 12, and, optionally, (i.i)a C8-C15 ethoxylated nonionic surfactant having an average degree of ethoxylation of from 5 to 14, the weight ratio of (b)(i) to (b)(ii) being at least 1:1, the weight ratio of (a) to (b) being within the range of from 5:1 to 0.5:1, and, optionally, c) a C10-Cla carboxylic acid diC2-C3 alkanol) amide, in an amount of from O to 30% by weight of the total active detergent system.