GB1567421A

GB1567421A - Liquid detergent

Info

Publication number: GB1567421A
Application number: GB35678A
Authority: GB
Original assignee: Colgate Palmolive Co
Current assignee: Colgate Palmolive Co
Priority date: 1977-01-06
Filing date: 1978-01-05
Publication date: 1980-05-14
Also published as: DK5078A; MY8300077A; CH633824A5; DE2800519C2; BE862729A; DE2800519A1; DK153685C; FR2376896A1; DK153685B; FR2376896B1

Abstract

Clear stable, liquid detergent or cleaning agent, which has an improved cleaning efficacy. This detergent or cleaning agent has a decreased content of hydrotropic compounds and contains paraffin-sulphonates, ethoxylated alcohols, alkyl ether sulphates and a system for the regulation of the viscosity and clarity consisting of ethanol and urea, and if desired additionally protein. The protein can be admixed to obtain further advantages. The ethanol content is between 0.15 and 4% by weight of the composition and thus significantly below the amounts of known compositions.

Description

(54) LIQUID DETERGENT (71) We, COLGATE-PALMOLIVE COMPANY, a Corporation organised under the laws of the State of Delaware, United States of America, of 300 Park Avenue, New York, New York 10022, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to liquid detergent compositions.

According to the present invention a liquid detergent composition comprises at least 30 percent by weight of a mixture of (A) a water-soluble salt of a Clo-C20 paraffin sulphonate, (B) a Ce-C12 alcohol or ether alcohol ethoxylated with from 5 to 8 moles of ethylene oxide and (C) a water-soluble alkyl ether sulphate of the formula RO(C2H4O)nSO3X wherein R represents an alkyl group of from 10 to 18 carbon atoms per molecule, n is from 1 to 10 and X is a cation; the weight ratio of (A) to (B) + (C) being in the range from 10:1 to 1:1 and the cation of the sulphonate (A) and the sulphate (C) being selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolammonium; (D) from 1 to 5 percent by weight of urea; (E) from 0.15 to 4 percent by weight of C2-C3 alcohol, the weight ratio of the alcohol (E) to urea (D) being less than 1.3:1; and (F) water.

The compositions may also include a nonionic foam builder (G), a hydrotrope (H), a water-soluble protein (I) for beneficial effects such as hand care, anti-chapping and rinse aid, and other additives.

Liquid detergent compositions are known which comprise an alkyl aryl sulphonate and an alkyl ether sulphate. In order to formulate liquid detergent compositions comprising those two ingredients in sufficient concentration it has been necessary to include in the compositions high proportions of solubilizing agents or hydrotropes such as lower aliphatic alcohols (e.g. ethyl alcohol), urea and low molecular weight alkylbenzene sulphonates (e.g. sodium xylene sulphonate).

Liquid detergent compositions have also been proposed containing paraffin sulphonates and ethoxylated alcohol sulphates. Thus, British patent specification No. 1458798 discloses a liquid detergent composition which contains, as an essential ingredient, from 2% to 12% of a water soluble aliphatic sulphonate which may be a paraffin sulphonate of from 8 to 20 carbon atoms. Another essential ingredient is from 10% to 27% of an ethoxylated alcohol sulphate having from 8 to 22 carbon atoms in the alcohol residue and from 1.5 to 12 ethoxys. The composition may include as an optional ingredient up to 3% by weight of an ethoxylated alcohol having from 8 to 20 carbon atoms in the alcohol residue and from 4 to 15 ethoxys. In Example III the composition contains 2.5% of the paraffin sulphonate, 2% of the ethoxylated alcohol and 12% of the ethoxylated alcohol sulphate.Thus, using the symbols employed above, the ratio A:B + C is about 0.18:1 which is well below the minimum 1:1 ratio required in the present invention. In examples VII and VIII the corresponding ratios are 0.14:1 and 0.24:1, respectively. The compositions may also include, as optional ingredients, alcohols of from 1 to 4 carbon atoms, and urea. The proportions of these and other solubilising ingredients are not specified individually. The totals may range from below 2% to an upper limit of 10%. In the three Examples mentioned above, which include an ethoxylated alcohol, in each case the ethanol content is above the upper limit of 4% of the present invention and none of those Examples includes any urea.

British patent specification No. 1458783 discloses somewhat similar compositions, except that in this case the content of paraffin sulphonate may be higher. Again, an ethoxylated alcohol sulphate is an essential ingredient and optional ingredients include ethoxylated alcohols, and solubilising agents which may be lower alcohols, and urea. Only Examples III and VII contain the three essential detergent ingredients of the present invention, and in neither of those Examples is there any urea, while the content of ethanol is above the upper limit of 4% of the present invention.

In our British patent specification No. 1339069 there is disclosed a composition in which a paraffin sulphonate is one essential detergent ingredient, and an ethoxylated alcohol sulphate is another. An ethoxylated alcohol is an optional ingredient in an amount preferably up to 4%. The composition also includes a viscosity and clarity control system which may be a mixture of urea and alcohol in the range from 0.5 to 5%, preferably 1 to 4%, and from 2 to 10%, preferably 5 to 8%, respectively. It is stated that it is desirable to maintain the weight ratio of urea to alcohol within the range of 1:1.5 to 1:3, equivalent to from 1.5:1 to 3:1 urea to alcohol. In the present invention the ratio of alcohol to urea must be less than 1.3:1. In all the Examples of No 1339069 the amount of alcohol present is above the limit of 4% of the present invention.

In the compositions of the present invention, by appropriately selecting from the wide range of both essential and optional possibilities of the prior art the ingredients which are essential in the present invention, and utilising relative proportions of the selected components only within the specified ranges, unexpected advantages are achieved, for example, the reduction in ethanol content, thereby reducing the cost of the product as well as its flash point.

The liquid detergent compositions of the present invention have significant advantages over the previously known liquid detergent compositions based on alkyl aryl sulphonates and alkyl ether sulphates and are even superior in performance to known compositions containing paraffin sulphonates and ether sulphates, particularly in soft water. This superiority is exhibited in "miniplate" tests of the composition against prior art compositions containing even greater amounts of ether sulphate as well as compositions where there is even present an ethoxylated alcohol. The superiority is believed to be attributable to the particular alkyl chain length and the degree of ethoxylation of the ethoxylated alcohol or ether alcohol (B) in the particular specified blend of ingredients.

The inclusion of the specified ethoxylated alcohol or ether alcohol (B) also enables the amount of ether sulphate (C) to be kept low without loss in detergency.

Further, it has suprisingly been found that a reduced level of ethanol (E) as solubilizer is achieved in direct proportion to the amount of ether sulphate (C) replaced by a corresponding amount of ethoxylated alcohol or ether alcohol (B) at a given level of paraffin sulphonate (A). This provides secondary benefits in that the product has better performance as demonstrated hereinafter, and affords a cost saving in that less ether sulphate and, particularly, less ethanol, are needed, as already indicated. The reduction in ethanol content is achieved without modifying the physical characteristics, e.g. viscosity and cloud points, of the product and without impairing performance, thereby reducing the cost of the product as well as its flash point.Such reduction is believed to be due to the specified correlation of the proportions of ethanol and urea with the selected ethoxylated alcohol.

Among the further advantages of the present invention over previously known liquid detergent compositions are the following: 1. Liquid detergent compositions embodying the invention can be produced having comparable efficacy and properties with lower percentages of active ingredients and comparable clarity with significantly lower percentages of solubilizers than are used in previously known compositions.

2. Compositions embodying the present invention can produce foam as good as or better than that produced by prior art compositions, both in quantity and durability.

3. Compositions embodying the present invention, when diluted to the same concentration for use as the prior art compositions, can give substantially better performance, particularly in dishwashing.

4. Washing solutions made with compositions embodying the present invention have significantly lower surface tension than solutions of the same concentration using prior art compositions.

Additional advantages of the present invention are improved and controlled performance such as foaming and dishwashing ability, viscosity and clarity, which are important features in consumer acceptability.

The paraffin sulphonates (A) used in the compositions of the present invention are usually mixed secondary alkyl sulphonates having from 10 to 20 carbon atoms per molecule; preferably at least 80 percent, usually at least 90 percent, of the alkyl groups will have 13-17 carbon atoms per molecule. Where the major proportion has 14-15 carbon atoms per molecule, optimum foaming performance appears to be obtained at varying concentrations and water hardnesses. These sulphonates are preferably prepared by subjecting a cut of paraffin, corresponding to the chain lengths specified above, to the action of sulphur dioxide and oxygen in accordance with the well known sulphoxidation process. The product of this reaction is a secondary sulphonic acid which is then neutralized with a suitable base to provide the water-soluble secondary alkyl sulphonate suitable for use in the present invention.

Similar useful secondary alkyl sulphonates may be obtained by other methods, e.g. by the sulphochlorination method in which chlorine and sulphur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulphonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulphonates. Such sulphonates are generally present in amounts from 15 percent to 60 percent, preferably 20 percent to 35 percent, by weight of the composition.

The higher alkyl ether sulphates (C) used in the compositions of the present invention are represented by the formula: RO(C2H40)nSO3X in which R represents a primary or secondary alkyl group that may be straight or branched having from 10 to 18 carbon atoms, preferably from 12 to 15, X is a suitable water-soluble cation, as hereinafter defined, and n is from 1 to 10, preferably from 3 to 6. These sulphates are produced by sulphating the corresponding ether alcohol and then neutralizing the resulting sulphuric acid ester.

The cation of the paraffin sulphonate (A) and the alkyl ether sulphate (C) may be an alkali metal (e.g. sodium or potassium), an alkaline earth metal (e.g. magnesium), ammonium or lower amine (including alkylolamines). It is preferred to use the sodium salt of the paraffin sulphuric acid and an ammonium salt of the alkyl ether sulphuric acid ester.

One of the essential active ingredients of the composition is (B) a C8 l2 alcohol, straight or branched chain, ethoxylated with from 5 to 8 moles of ethylene oxide. It has suprisingly been found that the inclusion of this ingredient in substitution in part for the ether sulphate (C) permits a corresponding reduction on a weight basis in the amount of the latter needed, without sacrificing performance. As an added benefit, one may correspondingly reduce the amount of ethanol (E) required in the viscosity and clarity control system (E) + (D).

In certain instances, it is preferred that the liquid detergent composition contain a higher fatty acid alkylolamide (G) in sufficient amount to act as a foam builder. Its presence results in a product which exhibits high foaming power in use, particularly in the stability of the foam generated during dishwashing or laundering operations. It should not be employed in an amount sufficient to impair the desired physical properties. The acyl radical of the alkylolamide is selected from the class of fatty acids having from 8 to 18 carbon atoms and each alkylol group usually has up to 3 carbon atoms. It is preferred to use the monoethanolamides of lauric and myristic acids but diethanolamides and isopropanolamides as well as monoethanolamides of fatty acids having from 10 to 14 carbon atoms in the acyl radical are satisfactory.Examples are capric, lauric and myristic and "heart cut" coconut (C12-C14) monoethanolamides, diethanolamides and isopropanolamides and mixtures thereof. There may be employed also the alkylolamides which are substituted by additional ethenoxy groups; suitable examples may be the above amides condensed with from 1 to 4 moles of ethylene oxide.

While any suitable ratio of paraffin sulphonate (A) to the sum of alkyl ether sulphate (C) and ethoxylated alcohol or ether alcohol (B) may be used in the 10:1 to 1:1 range as described, it has been found that the ratio is preferably in the range from 5:1 to 1.5:1 for an optimum combination of properties, particularly in the presence of amide foam builders.

Suitable ratios are 70:30,75:25 and 80:20 by weight optionally in the presence of from 0.5 to 8 percent alkylolamide, preferably 1 to 6 percent and usually 4 to 6 percent, such as "heart cut" coconut monoethanolamide, diethanolamide or alkanolamide condensed with from 1 to 4 moles of ethylene oxide. The sulphonate (A) and sulphate (C) may be in any suitable water-soluble salt form such as the sodium, potassium, ammonium, and mono-, di- and triethanolamine salts, or mixtures thereof.

The ethoxylated alcohols and ether alcohols (B) used in the compositions of the present invention may be represented by the formula: RO(C2H4O)nH in which R represents an alkyl group that may be straight or branched having from 8 to 12 carbon atoms and n is from 5 to 8. In the case of higher ether alcohols, the preferred chain length for the alkyl group is from Cg-Cll.

The nonionics may be present in the compositions in amounts of from about 2 percent to up to about 10 percent by weight of the composition, preferably at least 4 percent. The weight ratio of these nonionics to the alkyl ether sulphate component (C) is preferably in the range from 3:1 to 1:3 and most preferably is about 1:1.

The viscosity and clarity control system comprises urea (D) and a lower aliphatic alcohol (E), and optionally a water-soluble hydrotrope (H) which is effective in promoting the compatibility of the ingredients in the liquid composition and can be substituted for part of the urea or alcohol. Generally, the viscosity and clarity control system is required in concen trated liquid detergent compositions containing at least 30 percent by weight of active ingredients, namely the sum of paraffin sulphonate (A), alkyl ether sulphate (C), nonionic (Band, optionally, alkylolamide (G).

Suitable hydrotropic substances are the alkali metal organic sulphonated (including sulphated) salts having an alkyl group up to 6 carbon atoms. The preferred sulphonated hydrotropes are alkyl aryl sulphonates having up to 3 carbon atoms in the alkyl group, e.g. the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene (cumene) sulphonates. Sulphonates made from xylene include orthoxylene sulphonate, metaxylene sulphonate, paraxylene sulphonate and ethylbenzene sulphonate. Commercial xylene sulphonates usually contain metaxylene sulphonate as the main ingredient. Analysis of typical commercial xylene sulphonate products shows about 40 to 50 percent metaxylene sulphonate, 10 to 35 percent orthoxylene sulphonate and 15 to 30 percent paraxylene sulphonate with 0 to 20 percent ethylbenzene sulphonate. Any suitable isomeric mixture, however, may be employed.Sodium cumene sulphonate and sodium xylene sulphonate are preferred alkyl aryl sulphonate hydrotropes for use in the compositions of the present invention. It is also permissible to use suitably alkyl sulphate salts having 5 or 6 carbon atoms in the alkyl group such as alkali metal n-amyl and n-hexylsulphates.

The use of the viscosity and clarity control system imparts superior low temperature clarity of the liquid detergent composition and provides control of the viscosity of the product over a wider range for any particular concentration of active ingredients, as will be set forth in greater detail hereinafter.

The alcohols preferably have two or three carbon atoms. Thus, ethyl alcohol, propyl alcohol, isopropyl alcohol or propylene glycol can be used; preferably ethyl alcohol will be used.

The proportions of urea (D), alcohol (E) and hydrotropic substance (H) best suited for any particular composition depend on the active ingredient components and porportions and can be determined by the formulator by conventional tests. The weight content of this viscosity and control system based upon the total composition will vary from 0.5 to 15 percent and preferably is from 3 to 10 percent. Within that range, the urea and the alcohol will vary within the ranges of from 0.5 to 8.0 percent, preferably from 1 to 5 percent, and from 2 to 10 percent, preferably 0.15 to 4 percent, respectively. The ratio of alcohol to urea is maintained below 1.3:1, preferably below 1:1 and most preferably is in the range from 0.37:1 to 0.85:1 when using an active ingredient content above 30 percent by weight, preferably 35 to 45 percent including alkylolamide (G).Varying amounts of hydrotrope (H) such as xylene sulphonate may be added or substituted in part for the alcohol or urea so as to form a ternary system with special properties such as markedly to increase the viscosity. The amount should be selected so as to maintain a satisfactory viscosity and cloud point and maintain other desirable properties. Generally, the hydrotrope may constitute up to 15 percent by weight of the total viscosity and control system.

The protein optionally employed in the compositions of this invention is a water-soluble partially degraded protein and may be a partially enzymatically hydrolyzed protein or a heat derived product of protein. This material may be employed as an agent to overcome the irritant effect upon the skin of the surface active compounds. When the partially degraded protein is applied together with or subsequent to contact with the surface active compounds, the prophylactic effect is found to be present. The partially degraded protein is characterized as having a gel strength of about zero to about two hundred Bloom grams. The partially degraded protein may also provide rinse and drain properties to the composition. Such hydrolysis products include proteoses, peptones and polypeptides, including moieties of a plurality of amino acids.These hydrolysis products may be formed by partial enzymatic hydrolysis, such as by the action of trypsin, erepsin or pancreatic enzymes on protein material. The partially degraded protein may also be a heat-derived decomposition product of protein. Proteins partially degraded by heat and having the required Bloom strength for use in the compositions may be prepared by heating proteinaceous material such as bones, feet or skin of pork or beef which has been reduced to small pieces and immersed in water, by autoclaving. A preferred hydrolyzed protein is a partially enzymatically hydrolyzed protein derived from beef collagen. Typical proteins which may be partially hydrolyzed for use in the compositions include casein, gelatin, collagen, albumin, zein, gliadin, keratin, fibroin, globulin and glutenin. Typical commercial partially enzymatically hydrolyzed proteins include Bacto-Proteose, proteose-peptone, casein-peptone, gelatin-peptone, Bacto-peptone, vegetable peptones, such as soybeans peptone, the solubilized collagen being derived by heating bones, feet or skin of pork or beef. The preferred proteins are solubilized beef collagen and solubilized pork collagen. The partially hydrolyzed protein may have a relatively broad spectrum of molecular weights in the range from about 500 to about 70,000, preferably from about 500 to about 10,000 for hand care effects and from about 25,000 to about 70,000 for good drain properties. The lower molecular weight proteins may contain some completely degraded polypeptides, such as dipeptides and tripeptides and even some amino acids as a result of the degradation process.The protein, where employed, will generally be used in amounts in the range from 0.1 to 2.0 percent by weight, preferably from 0.3 to 0.8 percent by weight.

The liquid detergent compositions of the present invention may also contain any of the additives used in other liquid detergent compositions such as sequestrants, e.g. salts of ethylenediamine tetraacetic acid, such as the sodium and potassium salts, and salts of hydroxy ethyl ethylene diamine triacetate. If it is desirable to tint or colour the liquid detergent composition, any suitable dyes may be used for this purpose. Perfume may also be added to the compositions to give them a pleasant odour.

Water (F) is used as the liquid vehicle for the liquid detergent compositions of the present invention. It may vary in proportion from about 10 to about 90 percent.

In order to illustrate some of the benefits of the present invention, compositions containing 32 percent sodium C13-C17 alkyl sulphonate (SAS), 8 percent ammonium C12-C15 alkyl triethenoxy ether sulphate (ALES), 4.5. percent ethanol, 3 percent urea and the balance water are evaluated against compositions containing 32 percent SAS, 4 percent ALES, 4 percent ethoxylated alcohol (NI), 2.25 percent ethanol, 3 percent urea and the balance water.

Similar compositions having different ethoxylated alcohols therein are also evaluated in order to show the unexpected properties attributed to the composition by employing a select group of ethoxylated alcohols from among those heretofore described in the art to be equivalent. The evaluation results are set forth in Table I.

TABLE I Mini-plate dishwashing test 1.25 g/l Viscosity Number of Dishes cps 25"C Water hardness 50 ppm 300 ppm T 32SAS/8ALES 41 50 91 160 Influence of the degree of ethoxylation 32 SAS/4ALES/4NI C9.11 5 EO 47 49.5 96.5 170 C9,11 6EO 45 53 98 160 C9.11 8 EO 47 52 99 180 C13-C15 5 EO 46 48 94 220 7 EO 44 50 94 210 8 EO 45 49 94 220 Cl0.l2 5 EO 47 50.5 97.5 150 Cm2.14 5 EO 45 47.5 92.5 210 Influence of the alkyl chain C8 5 EO 47 50 97.0 150 C9,11 5 EO 47 49.5 96.5 170 C10-C12 5 EO 47 50.5 97.5 150 C13.C15 5 EO 46 48 94 220 C9-Cll 8 EO 47 52 99 180 C13.15 8 EO 45 49 94 220 Table I compares the results of two different performance tests on washing solutions. One of the performance tests is a dishwashing test which was carried out at two different levels of water hardiness, viz, at 50 and 300 parts per million (PPM) of hardness. The other test is a test of viscosity.

The dishwashing tests carried out are known as a "miniature dishwashing test" as discussed by R. M. Anstett and E. J. Schuck in J.A.O.C.S., Vol. 43, page 576, October, 1966.

The foregoing results indicate that with a C8-12 alkyl chain ethoxylated by at least 5 but not more than 8 moles of ethylene oxide, there is a significant improvement over a composition without the ethoxylated alcohol and a significant improvement over compositions containing the ethoxylated alcohol but with longer carbon chain lengths.

Table II gives the general ranges of the principal ingredients within which the preferred compositions of the invention are formulated.

TABLE II The preferred ranges are as follows: % by weight Paraffin sulphonates 20-35 Alcohol ether sulphates 2-8 C8.12 alcohol 5-8 EO 2-8 Alkylolamide or alkylolamide EtO condensate 0-8 Urea 1-5 Ethanol 0.15-4.0 Water Q.S.

The following Examples illustrate the invention. In the Examples and elsewhere throughout this specification all amounts, ratios and percentages are by weight.

EXAMPLE 1 % by weight Sodium C14C17 paraffin sulphonate (1) 32 Ammonium C12-C15 alkyl triethenoxy ether sulphate (2) 4 C9-Cll alcohol ethoxamer (6EO) 4 Coconut monoethanolamide 2 Urea 3 Ethanol 2.5 Sodium ethylene diamine tetraacetate 0.045 Water (with small amounts of colour, balance preservative and perfume) Total 100 (1) Introduced as an aqueous mixture containing 60 percent by weight of the sulphonate.

(2) Introduced as an aqueous alcoholic solution containing 60 percent by weight of the sulphate and 10 percent by weight of ethanol.

The above product exhibits satisfactory foaming and dishwashing properties combined with preferred physical properties such as a cloud point of about 5"C and a viscosity of about 170 cps at 25"C using a Brookfield Viscosimeter Model LVF Spindle 1 at 30 RPM. The paraffin sulphonate employed has the following approximate composition: 3% C13, 25% C14, 30% C15, 25% C16, 15% C17 and 2% Cl8 with an average molecular weight of about 328. Various impurities may be present in commercial products such as small amounts of free paraffin or disulphonates.

EXAMPLE 2 A liquid detergent composition having similar properties as that of Example 1 is prepared by substituting an equivalent amount of coconut monoethanolamide condensed with about 2 moles of ethylene oxide for the monoethanolamide used in Example 1.

EXAMPLE 3 A satisfactory liquid detergent composition is prepared using the same materials as Example 1 in the following porportions: 22 percent paraffin sulphonate, 6 percent alkyl ether sulphate, 6 percent C9-ll alkanol 8 EO, 5 percent lauric myristic monoethanolamide, 5 percent urea and 3 percent ethanol with the balance being substantially all water.

EXAMPLE 4 A liquid detergent composition having similar properties to that of Example 3 is prepared by increasing the ethoxylated alkanol by 3 percent and decreasing the amount of ether sulphate by 3 percent in that composition.

EXAMPLE 5 A liquid detergent composition having similar properties to that of Example 3 is prepared by decreasing the amount of ethoxylated alkanol therein to 2 percent and by increasing the ethanol therein to 3.3 percent.

EXAMPLE 6 A liquid detergent composition having similar properties to that of Example 1 is prepared having the following consitution: 32 percent sodium C14C17 paraffin sulphonate, 2 percent ammonium Clz-Cl5 alkyl triethenoxy ether sulphate, 6 percent Cg-CI, alkanol ethoxamer (6EO), 1.1 percent ethanol, 3 percent urea and the balance water.

EXAMPLE 7 A satisfactory liquid detergent composition is prepared with the same formulation as Example 1 except that it contains 2.3 percent ethanol, 0.6 percent sodium xylene sulphonate and 1.8 percent urea.

One of the advantages of the urea alcohol control system is that a change in the physical characteristics of the composition is possible by varying the ratio of alcohol to urea using amounts selected from the ranges of 0.15 percent to 4 percent ethanol and 1 percent to 5 percent of urea. In the specific comPositions of Example 1 the ratio of ethanol to urea is 2.55:3 (0.85:1) which resulted in a clear point below 7"C and a viscosity of 170 centipoises.

The ratio of ethanol to urea also is 0.85:1 in Example 2, 0.6:1 in Examples 3-5 and 0.37: 1 in Example 6. By changing the alcohol urea ratio by increasing the alcohol content, it is possible to decrease the viscosity and raise the clear point whereas by decreasing the alcohol content the clear point can be lowered and the viscosity increased. Hydrotropes such as sodium xylene sulphonate tend to have an effect similar to that of the alcohol, i.e. an increase thereof will raise the clear point but lower the viscosity. Example 7 sets forth a composition containing sodium xylene sulphonate, ethanol and urea. As stated above, it is important to balance these constituents of the control system within the cited ranges to obtain the desired results.For optimum balance of clear point and viscosity, the total content of the control system also will vary with the content of the active ingredients (paraffin sulphonate, alcohol ether sulphate and nonionic detergents) in the final composition).

The clear point is also influenced by the amount of esters in the amide and sodium sulphate in the paraffin sulphonate and alkyl ether sulphate used as raw materials in preparing the compositions and, for compositions having a low clear point, raw materials with low content of these impurities should be used. The characteristics given above for the specific composition of Example 1 can best be obtained if the amide does not contain over 2 percent esters and the paraffin sulphonate does not contain over 4 percent sodium sulphate.

EXAMPLE 8 Example 1 is repeated with the inclusion of 0.5 percent of a 55 percent solids solution of protein having a gel strength of 100 Bloom grams.

EXArLE 9 Example 1 is repeated except that the alkanolamide is omitted and the concentration of ethanol is reduced to 2.25 percent, thereby giving an ethanol to urea ratio of 2.25:3 (0.75:1).

WHAT WE CLAIM IS: 1. A liquid detergent composition comprising at least 30 percent by weight of a mixture of (A) a water-soluble salt of a C10-C20 paraffin sulphonate, (B) a C8-C12 alcohol or ether alcohol ethoxylated with from 5 to 8 moles of ethylene oxide and (C) a water-soluble alkyl ether sulphate of the formula RO(C2H4O)nSO3X wherein R represents an alkyl group of from 10 to 18 carbon atoms per molecule, n is from 1 to 10 and Xis a cation; the weight ratio of (A) to (B) + (C) being in the range from 10:1 to 1:1 and the cation of the sulphonate (A) and the sulphate (C) being selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolammonium; (D) from 1 to 5 percent by weight of urea; (E) from 0.15 to 4 percent by weight of C2-C3 alcohol, the weight ratio of the alcohol (E) to urea (D) being less than 1.3:1; and (F) water.

2. A detergent composition as claimed in Claim 1 in which the paraffin sulphonate (A) is a mixture of compounds having 13 to 17 carbon atoms per molecule.

3. A detergent composition as claimed in Claim 1 or Claim 2 in which R is an alkyl group having from 12 to 15 carbon atoms per molecule and n is from 3 to 6.

4. A detergent composition as claimed in any of the preceding claims which also contains a nonionic foam builder (G) selected from mono- and diethanolamides and isopropanolamides of a Cl0-Cl4 fatty acid, in an amount up to 8 percent by weight.

5. A detergent composition as claimed in Claim 4 in which the nonionic foam builder (G) is lauric-myristic monoethanolamide.

6. A detergent composition as claimed in Claim 4 or Claim 5 which contains from 20 to 35 percent by weight of sodium C14-C15 paraffin sulphonate (A); from 2 to 8 percent by weight of C8-C12 alkanol 5-8 EO (B); and from 2 to 8 percent by weight of ammonium C12-C15 alkyl triethenoxy ether sulphate (C); the sum of(A) + (B) + (C) + (G)beingfrom 35 percent to 45 percent by weight of the composition.

7. A detergent composition as claimed in any of the preceding Claims wherein the weight

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **. by decreasing the amount of ethoxylated alkanol therein to 2 percent and by increasing the ethanol therein to 3.3 percent. EXAMPLE 6 A liquid detergent composition having similar properties to that of Example 1 is prepared having the following consitution: 32 percent sodium C14C17 paraffin sulphonate, 2 percent ammonium Clz-Cl5 alkyl triethenoxy ether sulphate, 6 percent Cg-CI, alkanol ethoxamer (6EO), 1.1 percent ethanol, 3 percent urea and the balance water. EXAMPLE 7 A satisfactory liquid detergent composition is prepared with the same formulation as Example 1 except that it contains 2.3 percent ethanol, 0.6 percent sodium xylene sulphonate and 1.8 percent urea. One of the advantages of the urea alcohol control system is that a change in the physical characteristics of the composition is possible by varying the ratio of alcohol to urea using amounts selected from the ranges of 0.15 percent to 4 percent ethanol and 1 percent to 5 percent of urea. In the specific comPositions of Example 1 the ratio of ethanol to urea is 2.55:3 (0.85:1) which resulted in a clear point below 7"C and a viscosity of 170 centipoises. The ratio of ethanol to urea also is 0.85:1 in Example 2, 0.6:1 in Examples 3-5 and 0.37: 1 in Example 6. By changing the alcohol urea ratio by increasing the alcohol content, it is possible to decrease the viscosity and raise the clear point whereas by decreasing the alcohol content the clear point can be lowered and the viscosity increased. Hydrotropes such as sodium xylene sulphonate tend to have an effect similar to that of the alcohol, i.e. an increase thereof will raise the clear point but lower the viscosity. Example 7 sets forth a composition containing sodium xylene sulphonate, ethanol and urea. As stated above, it is important to balance these constituents of the control system within the cited ranges to obtain the desired results.For optimum balance of clear point and viscosity, the total content of the control system also will vary with the content of the active ingredients (paraffin sulphonate, alcohol ether sulphate and nonionic detergents) in the final composition). The clear point is also influenced by the amount of esters in the amide and sodium sulphate in the paraffin sulphonate and alkyl ether sulphate used as raw materials in preparing the compositions and, for compositions having a low clear point, raw materials with low content of these impurities should be used. The characteristics given above for the specific composition of Example 1 can best be obtained if the amide does not contain over 2 percent esters and the paraffin sulphonate does not contain over 4 percent sodium sulphate. EXAMPLE 8 Example 1 is repeated with the inclusion of 0.5 percent of a 55 percent solids solution of protein having a gel strength of 100 Bloom grams. EXArLE 9 Example 1 is repeated except that the alkanolamide is omitted and the concentration of ethanol is reduced to 2.25 percent, thereby giving an ethanol to urea ratio of 2.25:3 (0.75:1). WHAT WE CLAIM IS:

1. A liquid detergent composition comprising at least 30 percent by weight of a mixture of (A) a water-soluble salt of a C10-C20 paraffin sulphonate, (B) a C8-C12 alcohol or ether alcohol ethoxylated with from 5 to 8 moles of ethylene oxide and (C) a water-soluble alkyl ether sulphate of the formula RO(C2H4O)nSO3X wherein R represents an alkyl group of from 10 to 18 carbon atoms per molecule, n is from 1 to 10 and Xis a cation; the weight ratio of (A) to (B) + (C) being in the range from 10:1 to 1:1 and the cation of the sulphonate (A) and the sulphate (C) being selected from sodium, potassium, magnesium, ammonium and mono-, di- and triethanolammonium; (D) from 1 to 5 percent by weight of urea; (E) from 0.15 to 4 percent by weight of C2-C3 alcohol, the weight ratio of the alcohol (E) to urea (D) being less than 1.3:1; and (F) water.

ratio of alcohol (E) to urea (D) is in the range from 0.37:1 to 0.85:1.

8. A detergent composition as claimed in any of the preceding Claims wherein the weight ratio of (B): (C) is about 1:1.

9. A detergent composition as claimed in any of the preceding Claims which further includes an alkyl benzene sulphonate hydrotrope (H).

10. A detergent composition as claimed in any of the preceding Claims which further includes from 0.1 to 2.0 percent by weight of a water-soluble protein (I).

11. A liquid detergent composition substantially as described in any of the Examples.