Detergent compositions

Abstract: A liquid detergent composition suitable especially for dishwashing by hand contains four components: (a) any anionic detergent except alkyl ether sulphate (b) alkyl ether sulphate (any alkyl sulphate therein contribut­ ing to component (a) above) (c) a lather booster which is an alkanolamide, dialkanolamide, betaine or amine oxide (d) a non-ionic detergent, preferably an ethoxylated non-ionic of HLB value 12.0 to 16.0. The amount of (a) is limited to an amount depending on its qualitative nature, and the ratio of (a) to (b) is 2:1 to 1:10. Compositions of the invention can provide a combina­ tion of satisfactory performance, particularly good mildness and cost effectiveness.

Description: The present invention relates to liquid detergent compositions suitable for use especially, but not exclusively, 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 food particles and other food residues, greases, proteins, starches, gums, dyes, oils and burnt organic residues. Light-duty liquid detergent compositions such as are suitable for use in washing dishes are well-known. Many of the formulations in commercial use at the present time are based on a sulphonate-type anionic detergent, especially on alkyl benzene sulphonate, in conjunction with an alkyl polyethoxy sulphate (alkyl ether sulphate). The sulphonate-type detergent generally predominates. The use of conventional dishwashing liquids based on alkyl benzene sulphonate/alkyl ether sulphate or on alkyl sulphate/alkyl ether sulphate is seen to have deleterious influence on hand conditions of users. Hence mildness in washing-up liquid is considered a desirable quality, and many specially formulated products on the market make claims for it. Protein denaturation by surfactants is considered to be one of the major causes of skin irritation and skin roughness induced by surfactants (G. Imokawa et al JAOCS 52 484-489 Dec. 1975). The degree of surfactant denaturation of protein depends on the type of surfactants and their concentration. At present the dishwashing formulations that are on the market which are less interactive with protein and hence considered to be milder are those based on a combination of ether sulphates and amine oxides. See for example US-A-3 928 249 (Procter and Gamble). In place of amine oxides, betaines can also be used. See for example US-A-4 554 098. However, such formulations - particularly with amine oxides - are expensive not only because the active ingredients are expensive but also because they require a large amount of expensive hydrotropes such as xylenesulphonate and/or ethanol to produce liquids which are stable and of accepted viscosity. Therefore there is a need for the development of more cost-effective mild dishwashing formulations, which are based on relatively less expensive detergent raw materials and which also require lesser amounts of expensive hydrotropes. EP-A-36625 discloses compositions intended to give mildness and performance. One Example contains alkyl sulphate, alkyl ether sulphate, betaine and an ethoxylated alkyl phenol, together with isopropanol in aqueous solution. The present invention is based on the realisation that cost-effective mild liquid dishwashing formulations with adequate performance can be obtained by careful choice of the active ingredients and their preparations in particular by restricting the main anionic detergent active present and including also selected amounts of alkyl ether sulphate, lather boosters and non-ionic detergent active material. According to the present invention there is provided a stable detergent composition in liquid or gel form containing from 10 to 80% by weight of active detergent mixture and water, the active detergent mixture comprising four components as follows: (a) anionic detergent active other than alkyl ether sulphate and which is present in an amount in the range 10 to 60% by weight of the active detergent mixture; (b) alkyl ether sulphate containing one or more ethylene oxide residues per molecule, the weight ratio of components (a) and (b) being in the range 2:1 to 1:10, the proportion of component (b) with a single ethylene oxide residue per molecule being not substantially greater than the proportion with the most frequently occurring higher number of ethylene oxide residues per molecule; (c) lather booster selected from the group consisting of monoalkanolamides, dialkanolamides, betaines, amine oxides and mixtures thereof in a total amount in the range 5 to 30% by weight of the active detergent mixture, the amount of monoalkanolamide not exceeding 20% by weight, the amount of amine oxide not exceeding 10% by weight, and the total amount of monoalkanolamide, dialkanolamide and betaine plus 1½ times the amount of amine oxide being at least 7.5% by weight of the active detergent mixture; (d) nonionic detergent active material in an amount in the range 5 to 35% by weight of the active detergent mixture, which nonionic detergent active is selected from the group consisting of polyethoxylated aliphatic alcohols of the general formula: R - (OCH₂CH₂)m - OH wherein R is straight or branched alkyl having from 8 to 16 carbon atoms, and the average degree of ethoxylation m is from 5 to 14, and polyethoxylated alkanolamides of the general formula wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R₈ is an ethyleneoxy or propyleneoxy group Y is hydrogen or -R₈(CH₂CH₂O) q H p is 1 or more and q is 0, 1 or more; with a further limitation on the amount of anionic detergent active (a) which is explained below and the proviso that primary alkane sulphonate is absent and the weight of any hydrotrope in the composition is not more than 12% calculated on the weight of the active detergent mixture. For reasons of cost effectiveness, and availability of materials, at least a major proportion of the component (a) is preferably selected from secondary alkane sulphonate, alkylbenzene sulphonate, primary alkyl sulphate, fatty acyl ester sulphonate, dialkylsulphosuccinate and alpha-olefin sulphonate. The anionic detergent active (a) must not exceed a maximum amount which is dependent on the nature of this active. For instance if secondary alkane sulphonate is substantially the only active (a) then the amount of it should not substantially exceed 50% by weight of the weight of the active detergent mixture. Maxima for other detergent actives, when substantially alone, are: alkyl aryl sulphonate 30% alkyl sulphate 40% fatty acyl ester sulphonate 50% dialkylsulphosuccinate 60% alpha olefin sulphonate 60% If anionic detergent active (a) is a mixture, then the maximum for the mixture is calculated as the total of the above maxima scaled in proportion to the amount of each active in the mixture. The maximum amount of anionic detergent active (a) is expressed by specifying that the active detergent mixture has maximum contents: u of alkyl aryl sulphonate w of alkyl sulphate x in total of secondary alkane sulphonate and fatty acyl ester sulphonate y in total of dialkylsulphosuccinate amd alpha-olefin sulphonate, and z in total of any other anionic active present - except of course for the alkyl ether sulphate which is component (b)-where u, w, x, y and z are all percentages by weight of the detergent active mixture and are given by the relationship: u 30 + w 40 + x 50 + y 60 + z 60 ≦ 1 As already stated, the anionic detergent active (a) is at least 10% by weight of the active detergent mixture. Preferably it is at least 15% or 20%. It does not provide more than 60% of the active detergent mixture. Preferred maxima for anionic detergent actives are lower: alkyl aryl sulphonate 22.5% alkyl sulphate 30% secondary alkane sulphonate 37.5% fatty acyl ester sulphonate 37.5% dialkylsulphosuccinate 50% alpha-olefin sulphonate 50% any other anionic detergent active 50% or 40% Compositions of the invention can give performances in detergency tests as good as those of conventional compositions containing alkyl benzene sulphonate, but are considerably milder. A significant form of this invention employs secondary alkane sulphonate as anionic detergent active (a) and monoethanolamide or diethanolamide as the lather booster (c), the active detergent mixture having in addition to the secondary alkane sulphonate and alkyl sulphate introduced with the alkyl ether sulphate a maximum content of 5% in total of alkyl sulphate and alkylaryl sulphonate material and preferably being substantially free of such additional sulphate and sulphonate material. It is particularly surprising that the harsh actives alkylarylsulphonate and primary alkyl sulphate can be tolerated at levels as high as 30 and 40% by weight of the detergent active mixture. A significant aspect of this invention therefore resides in a four component composition as specified above in which primary alkyl sulphate, alkylbenzene sulphonate or a mixture of the two constitutes at least 10% of the active detergent mixture and at least a majority of the component (a). In this invention it may be preferred that the total amount of alkyl benzene sulphonate and primary alkyl sulphate is no greater than the total of components (c) and (d). The total of these anionic detergents plus any secondary alkane sulphonate and fatty acyl ester sulphonate may be no greater than the total of (c) and (d). The total amount of component (a) is preferably no greater than 1¼ times the total of (c) and (d). In some forms of the invention the total amount of (a) is no greater than the total of (c) and (d). Although in principle the concentration of the active detergent mixture may be as high as desired in the range 10 to 80%, provided that a stable liquid or gel product can be obtained, the range of 10 to 60% by weight is preferred, and aqueous liquid compositions with an active detergent mixture in the range of 10 to 40% by weight are of especial interest. Six detergent actives have been mentioned above as possibilities for component (a). Of these, secondary alkane sulphonate may be preferred. It is generally produced by a free radical reaction, either a sulphochlorination reaction (Reed reaction) of a paraffin RH + SO₂ + Cl₂ → RSO₂Cl + HCl followed by hydrolysis and neutralisation, or by a sulphoxidation reaction RH + SO₂ + ½O₂ → RSO₃H followed by neutralisation. The secondary alkane sulphonate component (a) will normally be a mixture of materials of different alkyl chain lengths, of the formula: R₁R₂CHSO₃X where R₁ and R₂ which may be the same or different are each a straight or branched chain alkyl group having at least one carbon atom, the alkyl chain length (i.e. total number of carbon atoms of R₁ and R₂ plus 1) preferably being in the range 13 to 18, and X is a solubilising cation. An example of such material is SAS 60 of Hoechst (SAS is a Registered Trade Mark) which is produced by a sulphoxidation process. A suitable secondary alkane sulphonate produced by a sulphochlorination process is Mersolat (trade mark) of Bayer. Alkylbenzene sulphonate for use in component (a) is preferably derived from an alkylbenzene with a C₈ to C₁₆ primary or secondary alkyl group. This may in particular be C₈ to C₁₃ alkyl. Suitable alkylbenzene sulphonates are Dobs 102 of Shell and Marlon A of Hüls. (Dobs and Marlon are Registered Trade Marks) Primary alkyl sulphate (primary alcohol sulphate) for use in component (a) is preferably of the formula R-OSO₃X where R is a C₈ to C₁₆ primary alkyl group and X is a solubilising cation. Suitable is Dobanol 23A of Shell in which R is predominantly C₁₂ and C₁₃. As will be explained in more detail below alkyl sulphate is a constituent of alkyl ether sulphates which provide component (b). Dobanol is a Registered Trade Mark. Suitable detergent-active dialkyl sulphosuccinates are compounds of the formula wherein each of R₁ and R₂, which may be the same or different, represents a straight-chain or branched-chain alkyl group having 3 to 12 carbon atoms, preferably from 4 to 10 carbon atoms and more preferably from 6 to 8 carbon atoms, and X represents a solubilising cation. The alkyl groups R₁ and R₂ are preferably straight-chain or (in mixtures) predominantly straight-chain. Among dialkyl sulphosuccinates that may advantageously be used in the composition of the invention are the C₆/C₈ unsymmetrical materials described and claimed in GB-A-2 105 325 (Unilever); the dioctyl sulphosuccinate/dihexyl sulphosuccinate mixtures described and claimed in GB-A-2 104 913 (Unilever); and the mixtures of symmetrical and unsymmetrical dialkyl sulphosuccinates described and claimed in GB-A-2 108 520 (Unilever). Appropriate alpha-olefin sulphonates will generally be in the range having from twelve to sixteen carbon atoms. An example of such a material is Liporan 440, a C₁₄ alpha-olefin sulphonate from Lion Corporation, Japan. Liporan is a Registered Trade Mark. Appropriate fatty acid ester sulphonates are of formula where R₁ is straight or branched C₈ to C₁₆ alkyl R₂ is straight or branched C₁ to C₄ alkyl and X is a solubilising cation. R₁ is preferably C₁₀ to C₁₂ and R₂ is preferably butyl. Component (a) of the active detergent mixture may also include one or more other detergent actives used in liquid compositions, for example alkyl glyceryl ether sulphonates, or alkyl sarcosinates. The amount is preferably less than half of component (a), more preferably not more than a quarter of it. The second essential component (b) of the active detergent mixture is alkyl ether sulphate (sometimes called alcohol ether sulphate or alkyl polyethoxy sulphate) having at least one ethylene oxide residue per molecule. This will normally be provided by incorporating into the composition an alkyl ether sulphate which is a mixture of materials of the general formula: R - (OCH₂CH₂) n - OSO₃X wherein R is a C₁₀ to C₁₈ primary or secondary alkyl group, X is a solubilising cation, and n , the average degree of ethoxylation, is at least 1.5, preferably from 2 to 12, more preferably 3 to 8. Particularly preferred values of n are 3, 4 and 5. R₃ is preferably a C₁₀ to C₁₆ alkyl group. 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 sulphate and this contributes to component (a). The amount of alkyl sulphate in any alkyl ether sulphate will depend on the average degree of ethoxylation n . When n is 3, alkyl sulphate typically constitutes 15 to 20% of the mixture, and less than this when n is 4 or more. When the proportion of alkyl sulphate is low, it may prove convenient to ignore it. Nevertheless it contributes to component (a). When the average degree of ethoxylation is 2, alkyl sulphate typically constitutes 30% of the mixture provided as "alkyl ether sulphate". Such a mixture can provide both component (b) and component (a), with the latter then consisting entirely of alkyl sulphate. We have found that it is not feasible to use only an alkyl ether sulphate with an average degree of ethoxylation below 1.5. Unless the alkyl sulphate content of the ether sulphate is providing much or the whole of component (a), it is preferred that the alkyl ether sulphate is provided by material with an average of at least 2 or 2.5 ethylene oxide residues per molecule. An alkyl ether sulphate usually contains molecules with differing numbers of ethylene oxide residues in a statistical distribution. In such an alkyl ether sulphate, provided the average degree of ethoxylation is sufficiently great, the proportion of molecules with a single ethylene oxide residue will be not substantially greater than, or less than, the proportion with two ethylene oxide residues and the proportion with the most frequently encountered number of ethylene oxide residues (if this is more than two) as this invention requires. Preferred alkyl ether sulphates of the component (b), excluding alkyl sulphate, are mixtures of compounds of the above formula R-(OCH₂CH₂) n -OSO₃X in which n is any positive integer. It is preferred, for this invention, to use primary alkyl ether sulphates containing less than 20% by weight of material with alkyl groups of C₁₄ and above material, more preferably substantially C₁₂ and C₁₃ material only. Such material preferably has an average degree of ethoxylation of 2 to 6, more preferably 3 to 5. Examples of preferred alkyl ether sulphates for use in the present invention are Dobanol (Registered Trade Mark) 23-3 from Shell in which the degree of ethoxylation (n) is 3 and the equivalent material in which the degree of ethoxylation is 4. These materials are based on C₁₂-C₁₃ (50% of each) primary alcohol (about 75% straight chain, 25% 2-methyl branched). Another preferred material is an alkyl ether sulphate based on Lial (Registered Trade Mark) 123 from Chimica Augusta, which is a branched chain primary alcohol with a degree of ethoxylation of 3 to 4. A suitable example of a secondary alcohol ether sulphate is a material derived from an alcohol such as Tergitol 15/S/3 (Registered Trade Mark) of Union Carbide (this material itself is not at present available). The conventional process of manufacture of secondary alkyl ether sulphates is such that there is only a very small quantity of alkyl sulphate in the product. Component (b) provides at least 12% of the active detergent mixture, preferably it provides at least 15 or 20%. It preferably provides not more than 60 or 65% of the active detergent mixture. The solubilising cations of the anionic detergent actives of components (a) and (b), denoted as X in formulae above, may be any which provide the desired solubility of the anionic material. Monovalent cations such as alkali metal ions, ammonium and substituted ammonium are typical. Divalent ions giving adequate solubility may be used, and especially magnesium ions may be present to improve soft water performance and can be incorporated as magnesium salt of the anionic actives or as inorganic magnesium salts, or in the hydrotrope system. Component (c) of the active detergent mixture of the composition of the invention is preferably one or more mono- or dialkanolamides, preferably C₈ to C₁₈, more preferably C₁₀-C₁₈ carboxylic acid mono- or di(C₂-C₃) alkanolamides. These have the general formulae R₄- CO - NHR₅ and R₄ - CO - N(R₅)₂ respectively wherein R₄ is a C₇-C₁₇ aliphatic group, preferably straight-chain and preferably saturated, and R₅ is a hydroxyethyl or hydroxypropyl group. R₅ is preferably a 2-hydroxyethyl group. Materials of this type are generally made from fatty acids of natural origin and contain a range of molecules having R₄ groups of different chain lengths; for example, coconut ethanolamides consist predominantly of C₁₂ and C₁₄ material, with varying amounts of C₈, C₁₀ and C₁₆ material. Preferred are ethanolamides derived from so-called middle cut coconut fatty acid, most preferably from lauric acid. Monoalkanolamide may be used alone (in an amount in the range 7.5 to 20% of the active detergent mixture) or dialkanolamide may be used alone (in an amount in the range 7.5 to 30% of the active detergent mixture). It is preferred to use a mixture of mono- and dialkanolamide, most preferably in a weight ratio of 2:1 to 1:2. The other possibilities for component (c) are betaines and amine oxides. It is preferred to avoid using substantial amounts of these, especially amine oxides, for the sake of economy and consequent cost effectiveness. Preferably then the amount of amine oxide is not more than 10% by weight of the active detergent mixture. Preferably the amount of betaine is not more than 20% by weight of this mixture. The total amount of amine oxide and betaine is preferably not more than 20% and more preferably not more than 15% or 10% by weight of the active detergent mixture. It may be convenient to use amine oxide and/or betaine at such low levels, as part or even all of component (c). In important forms of the invention, however, amine oxide is excluded. Suitable betaines include simple betaines of formula and amido betaines of formula: In both formulae R is a C₇ to C₁₆ straight or branched alkyl group. It may be a lauryl group or a middle cut coconut alkyl group. R₆ and R₇ are each C₁ to C₃ alkyl or C₁ to C₃ hydroxyalkyl. Examples of sulphobetaines have the above formulae with -CH₂CO - / 2 replaced by -(CH₂)₃SO - / 3 or A suitable simple betaine is Empigen BB from Albright and Wilson (Empigen is a Registered Trade Mark). It has the formula quoted above in which R is C₁₂ to C₁₄ alkyl, derived from coconut, and R₆ and R₇ are both methyl. Suitable amine oxides have the formula R R₆ R₇ N → O wherein R is a straight or branched chain C₈ to C₁₈ alkyl group and R₆ and R₇ are each C₁ to C₃ alkyl, or C₁ to C₃ hydroxyalkyl. A suitable amine oxide is Empigen OB from Albright and Wilson. In it R is C₁₂ to C₁₄ alkyl, derived from coconut and R₆ and R₇ are both methyl. Component (c) preferably constitutes at least 10% e.g. 12% to 25%, by weight of the active detergent mixture. Component (d) is one or more non-ionic detergent active materials. The alkanolamides, betaines and amine oxides of component (c) do not form part of component (d). It is desirable that component (d) should have an HLB value in the range from 12.0 to 16.0. Component (d) is preferably a polyethoxylated aliphatic alcohol having an alkyl chain length of from C₈ to C₁₆, and an average degree of ethoxylation of from 4 to 14. Suitable nonionic detergents include short-chain high-foaming ethoxylated alcohols of the general formula R - (OCH₂CH₂) m - OH wherein R is an alkyl group, preferably straight-chain, having from 8 to 16 and yet more preferably 9 to 11, carbon atoms, and the average degree of ethoxylation m is from 5 to 14, more preferably 6 to 12. An especially preferred nonionic detergent is Dobanol 91-8 from Shell, in which R is C₉-C₁₁ (predominantly straight-chain) and m is 8. Alternative suitable materials are those in which R is a secondary alkyl having from 8 to 16, preferably 11-15, carbon atoms and m is from 5 to 14 preferably 6-12. An example is Tergitol 15/S/12 of Union Carbide (not available at present) or the material of the Softanol A series (from Japan Catalytic). Tergitol and Softanol are Registered Trade Marks. Preferably the polyethoxylated alcohol mixture is stripped, to reduce odour imparted to the composition. As stated earlier, an alternative possibility for the component (d) is an ethoxylated alkanolamide of the general formula wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R₈ is an ethyleneoxy or propyleneoxy group Y is hydrogen or -R₈(CH₂CH₂O) q H p is 1 or more and q is 0, 1 or more. R may be lauryl or coconut alkyl. Examples of ethoxylated alkanolamide are Amidox L5 and Amidox C5 from Stepan Chemical Company. Amidox is a Registered Trade Mark. Component (d) preferably constitutes at least 10% by weight of the active detergent mixture e.g. 12 to 25%. The total of components (c) and (d) together may constitute at least 25% by weight of the active detergent mixture. As well as the active detergent mixture and water, the liquid detergent compositions of the invention will generally need to contain one or more hydrotropes. Hydrotropes are materials present in a formulation to control solubility, viscosity, clarity and stability but which themselves make no active contribution 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. Preferred are alcohol, urea, and xylene sulphonate. 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. For example, the use of amine oxides as mentioned above requires a large amount of alcohol as hydrotrope. For this reason and because of expense, it is preferred to avoid the use of a substantial amount of any tertiary amine oxide in the present invention. In this invention the weight of hydrotrope in the composition is not more than 12% of the weight of the active detergent mixture. The compositions of the invention may also contain the usual minor ingredients such as perfume, colour, preservatives and germicides. The stable liquid detergent compositions of the invention may be used for all normal detergent purposes especially 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. EXAMPLE 1 The foaming performances of various aqueous formulations were compared using a plate washing test. 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 of the product 1 g/litre in 24 o H (French hardness) water at 45 o C in a bowl, until 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 was reached was taken as an indicator of dishwashing and foaming performance. In Table 1 below, the content of each component is given as percentage by weight of the whole composition. For each composition the total active detergent concentration (including the ethanolamide materials) was kept constant at 40%. In Table 2 below the content of the same compositions is expressed as percentages by weight of the detergent active mixture, with the primary alkyl sulphate (from the alkyl ether sulphate) shown separately. The foaming performance, cloud point and viscosity of various compositions of the invention (I-VI), a comparable composition containing alkyl benzene sulphonate (A), a comparable composition containing only secondary alkane sulphonate and alkyl ether sulphate (B), and a comparable composition containing no sulphonate (C) were obtained. The lauric diethanolamide used was a commercial narrow-cut coconut diethanolamide, referred to as LDEA, and the cocomonoethanolamide was Empilan CME of Albright & Wilson. The formulations and results are set out in Table 1 below and repeated in Table 2 expressed as percentages by weight of the active detergent mixtures. The compositions (I-VI) of the invention had acceptable hydrotrope levels and viscosities and foaming performances only slightly inferior to composition A, as good as that of composition B and much better than that of composition C. Mildness of some of the above formulations was estimated using a test of protein denaturation potency. Several in vitro and in vivo methods for evaluating protein denaturation potency of surfactants and their mixtures have been reported (see K. Miyazawa et al Int J Cos Sci 6 33-46 1984 and the references cited therein). One such method is the study of interaction of skin acid phosphatase enzyme with detergents under realistic conditions reported by Prottey et al (Int J Cos Sci 6 263-273 1984). Formulations II, IV, A, B, and C above were tested by Prottey's method using dilute solutions at active concentrations giving equal plates test performance. The results expressed qualitatively as a rank order of predicted mildness are as follows: C > IV ≈ II > A ≈ B C was significantly better than IV and II, which were close together. A and B gave results similar to each other and very much worse than IV and II. EXAMPLE 2 Human volunteers were employed to compare the active detergent mixtures of compositions II, IV and V and a commercial product identified as relatively mild. The detergent active in this product was a 4:1 mixture of secondary alkane sulphonate and alkyl ether sulphate (average 3 ethylene oxide residues per molecule). Thus it was closely similar to composition B. The compositions were prepared at an active detergent concentration of 25% by weight without hydrotropes. Each trial involved panellists washing each volar forearm with a different one of the above products 4 times daily for 4 days and 3 times on day 5. For each wash 0.5 g of product was dosed onto the wetted volar forearm and it was washed with a gloved hand for 60 seconds. The forearm was rinsed after each wash. The products were randomly allocated to the panellists. Each volar forearm was graded for erythema dryness before each wash and 2 hours after the final wash. Any site reaching an erythema score denoting moderate erythema or a dryness score denoting moderate to severe dryness was discontinued. The results showed that for potential to induce irritation V was significantly better than II and IV which were significantly better than the commercial product (composition B). For potential to induce skin dryness V was better than II or IV which were significantly better than composition B These results are consistent with Example 1. EXAMPLE 3 A number of formulations were tested for interaction with skin acid phosphatase, by Prottey's method, using solutions of equal dilution. The compositions and the percentage inhibition (i.e. 100% minus percentage activity remaining) are set out in Table 3 below, where the compositions are expressed as percentages by weight of the formulation and then repeated in terms of percentages by weight of active detergent mixtures. Water gave no inhibition at all, i.e. 100% of activity remained. EXAMPLE 4 In this and subsequent examples mildness is assessed by measuring the inhibition of wheatgerm acid phosphatase (WGAP). This has been found to correlate well with the results obtained with human volunteers: for instance the inhibition of WGAP by compositions B, IV and V in a series of comparative experiments was 100%, 75% and 69% respectively. It is notable that the commercial product (composition B) gave total inhibition of this enzyme. Even a 3:7 mixture of SAS 60: Dobanol 23-3A gave 91% inhibition. A series of compositions was assessed in which the nature of component (a) was varied, and the proportions of components (a) and (b) were also varied. These compositions were also assessed for foaming performance by means of a modified Schlachter-Dierkes test based on the principle described in Fette und Seifen 1951, 53 , 207. A 100ml aqueous solution of each material tested, having a concentration of 0.04% active detergent in 24 o H water (French hardness) at 45 o C was rapidly oscillated using a vertically oscillating perforated disc within a graduated cylinder. After the initial generation of foam, increments (0.2g) of soil (9.5 parts commercial cooking fat, 0.25 parts oleic acid, 0.25 parts stearic acid and 10 parts wheat starch in 120 parts water) were added at 15-second intervals (10 seconds' mild agitation and 5 seconds' rest) until the foam collapsed. The result was recorded as the number of soil increments (NSI score): a score difference of 6 or less is generally regarded as insignificant. Each result was typically the average of 3 or 4 runs. The compositions and the results obtained are set out in Table 4 below. In this table the compositions are quoted, and then calculated figures are given for the amounts of alkyl sulphate and alkyl ether sulphate excluding alkyl sulphate. As can be seen from Table 4, the compositions' foaming performance was satisfactory in that it was never worse than the control composition, effectively composition V, shown in the final column of Table 4. Inhibition was never the total inhibition encountered with composition B (i.e. the commercial product). It can be seen that levels of 25% alkyl benzene sulphonate with 3.5% alkyl sulphate, and a level of 37.5% alkyl sulphate give about 85% inhibition, which is intermediate between the commercial product (composition B) and composition V. EXAMPLE 5 A number of compositions were assessed for WGAP inhibition. These included a series which were each the same as composition V, except that the secondary alkane sulphonate was replaced with an equal weight of another anionic detergent active. Some were also assessed for foaming performance by means of the modified Schlacter-Dierkes test referred to above. The compositions and the results obtained are set out in Table 5 below. "Sulphosuccinate" denotes a statistical mixture (mole ratio 1:2:1) of di-n-octyl sulphosuccinate, n-hexyl n-octyl sulphosuccinate and di-n-hexyl sulphosuccinate (sodium salts), prepared from a 1:1 mixture of n-hexanol and n-octanol by the method described in Example 1 of GB 2 108 520 (Unilever). "Butyl FAES" denotes the sulphonate of n-butyl laurate. The mildness arising with the different actives is apparent. It can also be seen that the composition of this invention, with sulphosuccinate as component (a) was superior in mildness to the sulphosuccinate compositions which were 4:2:1 sulphosuccinate: alkyl ether sulphate: diethanolamide, yet was fairly close in foaming performance, and better than the composition with secondary alkane sulphonate (composition V of Example 1). EXAMPLE 6 The foaming performance of some further compositions was assessed by means of the modified Schlacter-Dierkes test. The compositions and the results obtained are set out in Table 6 below. Component Percentages by weight of active detergent mixture SAS 60 32.5 32.5 32.5 Dobanol 23-A 21 21 32.5 Dobanol 23-4A 32.5 32.5 42 42 Lauryl mono<-> ethanolamide 10 10 10.5 10.5 10 LDEA 10 10 10 Empigen OB 10.5 Empigen BB 10.5 Dobanol 91-8EO 16 16 15 Amidox L5 15 Amidox C5 15 Performance 41 37 45 50 36 Amidox L5 is lauric monoethanolamide 5EO (ethylene oxide) Amidox C5 is coconut monoethanolamide 5EO Both are supplied by Stepan Chemical Company. Empigen OB is C₁₂ to C₁₄ alkyl dimethyl amine oxide. Empigen BB is C₁₂ to C₁₄ alkyl dimethyl betaine.

Claims: A stable detergent composition in liquid or gel form containing from 10 to 80% by weight of active detergent mixture and water, the active detergent mixture comprising four components as follows: (a) anionic detergent active other than alkyl ether sulphate and which is present in an amount in the range 10 to 60% by weight of the active detergent mixture; (b) alkyl ether sulphate containing one or more ethylene oxide residues per molecule, the weight ratio of components (a) and (b) being in the range 2:1 to 1:10, the proportion of component (b) with a single ethylene oxide residue per molecule being not substantially greater than the proportion with the most frequently occurring higher number of ethylene oxide residues per molecule; (c) lather booster selected from the group consisting of monoalkanolamides, dialkanolamides, betaines, amine oxides and mixtures thereof in a total amount in the range 5 to 30% by weight of the active detergent mixture, the amount of monoalkanolamide not exceeding 20% by weight, the amount of amine oxide not exceeding 10% by weight, and the total amount of monoalkanolamide, dialkanolamide and betaine plus 1½ times the amount of amine oxide being at least 7.5% by weight of the active detergent mixture; (d) nonionic detergent active material in an amount in the range 5 to 35% by weight of the active detergent mixture, which nonionic detergent active is selected from the group consisting of polyethoxylated aliphatic alcohols of the general formula: R - (OCH₂CH₂) m - OH wherein R is straight or branched alkyl having from 8 to 16 carbon atoms, and the average degree of ethoxylation m is from 5 to 14, and polyethoxylated alkanolamides of the general formula wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R₈ is an ethyleneoxy or propyleneoxy group Y is hydrogen or -R₈(CH₂CH₂O) q H p is 1 or more and a is 0, 1 or more; the active detergent mixture having maximum contents u of alkylaryl sulphonate, w of alkyl sulphate, a maximum total content x of secondary alkane sulphonate and fatty acyl ester sulphonate, a maximum total content y of dialkylsulphosuccinate and alpha-olefin sulphonate and a maximum total content z of any other anionic detergent active except said alkyl ether sulphate, where u, w, x, y and z are all percentages by weight of the detergent active mixture and are given by u 30 + w 40 + x 50 + y 60 + z 60 ≦ 1 with the proviso that primary alkane sulphonate is absent and the further proviso that the weight of any hydrotrope in the composition is not more than 12% calculated on the weight of the active detergent mixture. A composition according to claim 1 wherein at least a major proportion of said component (a) is selected from the group consisting of secondary alkane sulphonate, fatty acyl ester sulphonate, dialkylsulphosuccinate, alpha-olefin sulphonate, primary alkyl sulphate, and mixtures thereof. A composition according to claim 1 wherein u, w, x, y and z are given by A composition according to claim 1 wherein component (a) comprises secondary alkane sulphonate, and component (c) is selected from the group consisting of monoalkanolamides and dialkanolamides, the active detergent mixture having, in addition to the secondary alkane sulphonate (a) and alkyl sulphate from the alkyl ether sulphate which provides component (b), a maximum content of 5% by weight in total of alkyl sulphate, alkane sulphonate and alkylaryl sulphonate material. A composition according to claim 4 wherein the secondary alkane sulphonate is a mixture of materials of different alkyl chain lengths, of the formula R₁R₂CHSO₃X where R₁ and R₂ are each a straight or branched chain alkyl group having at least one carbon atom, the alkyl chain length (i.e. total number of carbon atoms of R₁ and R₂ plus 1) being in the range 13 to 18, and X is a solubilising cation. A composition according to claim 1 or claim 3 wherein a major fraction of component (a) is primary alkyl sulphate in an amount which is at least 10% of the active detergent mixture. A composition according to any one of the preceding claims wherein the weight ratio of the components (a) and (b) is in the range 1.5:1 to 1:3. A composition according to any one of the preceding claims wherein the total amount of alkyl aryl sulphonate, primary alkane sulphonate and alkyl sulphate is not substantially greater than the total amount of components (c) and (d). A composition according to any one of the preceding claims wherein the amount of component (a) is not greater than 1¼ times the total amount of components (c) and (d). A composition according to any one of the preceding claims wherein the total amount of amine oxide and betaine is not more than 20% by weight of the active detergent mixture. A composition according to any one of the preceding claims wherein component (c) contains substantially no amine oxide. A composition according to any one of the preceding claims wherein component (d) constitutes at least 10% by weight of the active detergent mixture. A composition according to any one of the preceding claims wherein each of components (c) and (d) constitutes at least 10% by weight of the active detergent mixture, and the total of components (c) and (d) constitutes at least 25% by weight of the active detergent mixture. A composition according to any one of the preceding claims wherein the active detergent mixture has a maximum content of 5% in total of primary alkane sulphonate and alkyl aryl sulphonate. A composition according to any one of the preceding claims which is an aqueous liquid composition containing 10 to 40% by weight of the active detergent mixture. A detergent composition according to any one of the preceding claims wherein the alkyl ether sulphate (b) is provided by a mixture of materials of the general formula: R - (OCH₂CH₂) n - OSO₃X wherein R is a C₁₀ to C₁₈ alkyl group, X is a solubilising cation, and n , the average degree of ethoxylation, is from 2 to 12. A detergent composition according to claim 16 wherein the alkyl ether sulphate (b) is provided by a primary alkyl ether sulphate in which the alkyl groups R are such that less than 20% of material of alkyl chain lengths C₁₄ and above is present, and the average degree of ethoxylation n is from 3 to 8. A detergent composition according to any one of the preceding claims wherein both monoalkanolamide and dialkanolamide are present, in a weight ratio of monoalkanolamide to dialkanolamide in the range 2:1 to 1:2. A detergent composition according to any one of the preceding claims wherein component (d) is selected from the group consisting of polyethoxylated aliphatic alcohols of the general formula: R - (OCH₂CH₂) m - OH wherein R is straight or branched alkyl having from 9 to 16 carbon atoms, and the average degree of ethoxylation m is from 5 to 14, and the said polyethoxylated alkanolamides of the general formula wherein R is a straight or branched alkyl having from 7 to 18 carbon atoms, R₈ is an ethyleneoxy or propyleneoxy group Y is hydrogen or -R₈(CH₂CH₂O) q H p is 1 or more and q is 0, 1 or more. A detergent composition according to any one of claims 1 to 18 wherein the nonionic component (d) consists essentially only of said polyethoxylated aliphatic alcohol. A detergent composition according to claim 20 wherein R in the general formula: R - (OCH₂CH₂) m - OH is straight or branched alkyl having from 9 to 11 carbon atoms. A detergent composition according to claim 18 or claim 21 wherein m is from 6 to 12. A method of preparing a liquid detergent composition which comprises mixing together materials as set forth in any one of the preceding claims and water, so as to form a composition as set forth in any one of the preceding claims. A method of washing articles which comprises diluting a composition according to any one of claims 1 to 22 with water, and washing articles by hand in the resulting solution.

Inventors: COXON ANDREW CHARLES, NAIK APPAYA RAGHUNATH, COXON, ANDREW CHARLES, NAIK, APPAYA RAGHUNATH
Applicants: UNILEVER NV, UNILEVER PLC, UNILEVER N.V.
Application year: 1987
Main classification: C11D1
IPC codes: C11D1, A61K8, A61Q19, A61Q5