FI58938B - OLEFINSULFONAT-TVAETTMEDELSKOMPOSITIONER - Google Patents

Abstract

1466155 Detergent compositions containing olefin sulphonates COLGATE-PALMOLIVE CO 8 April 1974 [9 April 1973(3) 11 April 1973] 15407/74 Heading C5D A liquid detergent composition comprises either A (i) water-soluble C 12-18 olefin sulphonate, (ii) water-soluble C 10-18 alkyl ether sulphate containing 1 to 5 ethylene oxide residues per molecule, (iii) water and (iv) an adjuvant selected from (a) 1À5 to 10 weight per cent of amine oxide of formula R 1 R 2 R 3 N#O wherein R 1 is C 10-20 alkyl, alkenyl or monohydroxyalkyl and R 2 and R 3 are methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl or R 2 R 3 N represents a morpholino group, (b) 1-10% of C 8-18 alkanoic acid alkanolamide and (c) 1-8% of water-soluble C 1-4 aliphatic sulphonate, providing that (1) the combined weights of (i) and (ii) constitute 25-35% of the composition, (2) no olefin sulphonate other than (i) is present and (3) the weight ratio (i) : (ii) is in the range 1 : 1 to 3 : 1 or B (i) watersoluble C 12-13 olefin sulphonate, (ii) C 8-18 alkanoic acid diethanolamide and (iii) water, subject to the same provisions as A. In examples the olefin sulphonate is a sodium alpha-olefin sulphonate comprising alkene mono- and disulphonate. Ingredients specified include: alkyl ether sulphates: ammonium alkyl ether sulphate; amine oxides: coconut fatty alkyl bis- (hydroxyethyl)amine oxide, and tallow fatty alkyl bis-(hydroxyethyl)amine oxide; alkanolamides: laurie monoethanol-amide, laurie diethanolamide, myristic monoethanolamide, myristic diethanolamide; aliphatic sulphonates: sodium isethionate, trisodium sulphosuccinate, sodium allyl sulphonate; other ingredients: ethanol, propanol, sodium xylene sulphonate, ammonium cumene sulphonate and C 5-6 alkylsulphonates as hydrotropes, collagen hydrolysate, hydroxyethyl ethylene diamine triacetic acid tri-sodium salt, magnesium sulphate heptahydrate, coconut monoethanolamideethylene oxide adduct, laurie monoethanolamide-ethylene oxide adduct, sodium gluconate and sodium citrate.

Description

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Patent and registration authorities AnattkM utlafd och uti. * Krift * n public · rad 30 * 01.81 (32) (33) (31) • euelkeM — B «| lrrf prloritet 09 * 04.73 09.0ll.73, 09.0U.73, ll .0U.73 USA (US) 3U8873, 3U9035, 3U9IH, 350268 (71) Colgate-Palmolive Company, 300, Park Avenue, New York, NY 10022, USA (72) Stephen, Cajetan Klisch, Somerset, Nev Jersey, Charles Andrew Martin,

Morris Plains, New Jersey, USA (7U) Berggren Oy Ab (5U) Olefin Sulfonate Detergent Mixtures - Olefin Sulfonate Surface Compound Composer

The present invention relates to improved liquid detergent compositions. According to the invention, the detergent composition comprises 25 to 35% by weight of a mixture of (i) at least one water-soluble salt of a sulfonated C 2 -C 2 -gefin as the sole olefin sulfonate component present, containing up to 20% by weight of vinylidene olefin sulfonate, and (ii) ) either a water-soluble salt of ethoxylated C 1 -C 4 alkyl sulfate having 1 to 5 ethyleneoxy groups in the molecule, or a C 12 -C 4 alkanoic acid diethanolamide or a mixture of diethanolamides having up to 25% by weight of a C 1 -C 4 alkanoic acid monoethanolamide, provided that when (ii) is diethanolamide, the weight ratio of (i) :( ii) is 3: 1 to 1: 1; and (iii) a curative additive comprising either (a) 1.5 to 10 weight percent of a foaming agent. an amine oxide of the formula R 1 -RRN-►O, wherein R 1 is C 1 -C 1 alkyl, alkenyl or monohydroxyalkyl, R 2 and R 2 are each methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl or together form an oxygen with a bonded nitrogen atom to a moriolino group, (b) 1-10 wt. # C., QC g-alkanoic acid diethanolamide or ethoxylated C8-C18-fatty acid pornethanolamide and their mixture with each other and / or C1-C4-C4-fatty acid monoethanolamide, (c) 1-8% by weight of anti-gelling agents, which are water-soluble salts of organic aliphatic C 1 -C 4 sulfonic acids and a mixture of two or more compounds of groups (a), (b) and (c), further provided that when (ii) is alkyl sulfate and (iii) ) amine oxide, is the weight ratio of (i) :( ii) 1.4: 1 to 0.9: 1 when (ii) is alkyl sulfate and (iii) is alkanolamide, is the weight ratio of (i): (ii) 1.4: 1 - 0.9: 1 and a weight ratio of (i) + (ii): alkanolamide 40: 1 to 4: 1 and when (ii) is diethanolamide, there is no healing additive (iii) at all or it is (c) j and (iv) ) aqueous medium. These compositions are generally classified as household detergents and are very suitable as dishwashing detergents and for delicately washing fabrics.

According to one embodiment of the present invention, there is provided a liquid detergent composition comprising a mixture of three surfactants in an aqueous medium comprising substantially a mixture of (a) 3,58938 sodium alpha-olefin sulfonates having an average of about 1 to 4 carbon atoms; (b) an ammonium salt of an alkyl ethoxamer sulfate which is a monosulfate of an alkanol ethoxylation product having an average of about 12 to 15 carbon atoms, and said ethoxylated product has about 3 ethyleneoxy groups per alkanol group, and (o) a tertiary amine oxide having the formula N - * 0 y R3 in which the formula has a higher alkyl group having 10 to 20 carbon atoms, preferably 12 to 18 carbon atoms, and and R1 are each a radical selected from the group consisting of alkyl and hydroxyalkyl groups in which is 1 to 4 carbon atoms, or R 2 and R 2 together form an oxygen-bound nitrogen with a pi atom a heterocyclic morpholino group

R 1 -CH 2 -CH 2 I 0 0 N - * 0 ^ ch 2 -ch 2 ^ wherein e.g. the weight ratio (a) :( b) is about 1.4: 1 to 0.9: 1 »preferably 1.3-'1 -1.1: 1, the weight ratio of (a) and (b) to (c) is about 20: 1-3: 1, preferably about 15: 1-3.5: 1 · These mixtures have very good efficiency as shown, for example, by the foaming ability, the properties of the foam, the washing power, the degradation by organisms, the storage capacity, the low toxicity, the favorable viscosity, the resistance to gel formation and the easy redissolution of the gel formed.

Another embodiment of the invention relates to a liquid detergent composition comprising a mixture of three surfactants dispersed in an aqueous medium consisting essentially of a mixture of (a) sodium alpha-olefin sulfonate having an average of about 14 to 16 carbon atoms, (b) alkyl ethoxy an ammonium salt of sulfate, which is a monosulfate of an ethoxylated product of an alkanol, wherein the alkanol has an average of about 12-15 carbon atoms and the ethoxylation product has about 3 ethyleneoxy groups per alkanol group, and (c) an alkanolamide having about 12-14 carbon atoms or a mixture of diethanolamide and monoethanolamide, wherein the weight ratio of (a) to (b) is about 1.4: 1 to 0.9: 1 and 21,58938 is preferably 1.3: 1 to 1.1: 1, weight ratio between (a) and (c) is about 30: 1-2: 1, preferably about 10: 1-3: 1, and the weight ratio of (a) and (b) to (c) is about 40: 1 to 4: 1, preferably about 30 : 1 to 5: 1. These detergent compositions also have very good efficacy, as evidenced, for example, by their foaming ability, foam properties, detergency, degradability, action of organisms, storage capacity, low toxicity, low viscosity and particularly good resistance to gel formation, and possibly gel formation.

Another embodiment of the invention relates to an aqueous liquid detergent composition comprising a sodium alpha-olefin sulfonate having an average of about 14 to 16 carbon atoms, which is preferably the ammonium salt of an ethoxylated alkyl sulfate diethanolamide monooliamide ethanolamide monide amide, which may be or a mixture thereof, and a water-soluble salt of an aliphatic monosulfonic acid having less than 5 carbon atoms dispersed in an aqueous medium, wherein the weight ratio of olefin sulfonate to monosulfonate is about 16: 1-2: 1, preferably about 7: 1-3: 1, e.g. about 4 : 1. Such mixtures exhibit reduced gel formation and easy redissolution of the gel that may have formed, and in addition have good foaming, washing, disintegration and viscosity properties.

One highly suitable olefin sulfonate for use in these mixtures is the sulfonation product of an olefin mixture containing about 75-85% of a straight chain alpha olefin (e.g., an olefin of the formula R-CH = CH 2 where R is an aliphatic hydrocarbon), about 8 or 10-20 % olefin in which the unsaturation occurs in the vinylidene group (e.g. an olefin of formula R-C R 'il ch2 in which R and R' are aliphatic hydrocarbon groups each preferably having 4 carbon atoms), and about 5-12% of an internal olefin (e.g. an olefin of the formula R-CH = CH-R ', wherein R and R' are an aliphatic hydrocarbon). A preferred method of preparing such an olefin mixture comprises polymerizing ethylene with a Ziegler-type catalyst to form a mixture of alpha-olefins of different chain lengths, separating a fraction containing mainly C 1-6 and C 1-8 alpha-olefins, and separating such a fraction, contains alpha-olefins having a lower molecular weight of 58938 (e.g., those having 6 and 8 carbon atoms), and dimerizing the latter fraction and combining the former fraction with said dimerized fraction.

A very suitable olefin mixture has an average of about 14-15 (e.g. 14.2-14.7) carbon atoms. The most preferred form of the olefin mixture contains less than 10% (e.g. less than 5% »such as 2 5) olefins having more than 16 carbon atoms.

Sulfonation of olefins can be accomplished using sulfur trioxide at its low partial pressure (e.g., less than about 100 mm Hg, preferably less than about 25 mm Hg). SO 2 may be in gaseous form diluted with an inert diluent (e.g. air) or undiluted (vacuum). It may also be in liquid form (e.g. as a solution in SO 2 at a low temperature such as 0 ° C). The molar ratio of SO 2 to olefin is usually about 1: 1 to 1.2: 1, preferably less than about 1.12: 1, such as about 1.05 to 1.1: 1. The reaction product from sulfonation can then be stirred With a 10-15 molar excess of aqueous alkali to effect neutralization of sulfonic acids and heat to effect hydrolysis, thereby opening the ring of the sultons that make up the majority of the reaction product. The product obtained usually contains, by weight, an amount of alkenyl sulfonate in the range of about 40-80% (preferably about 50-70%)> an amount of hydroxyalkane sulfonate in the range of about 15-70% (preferably 20-40%), about 5-12% by weight of hydroxyalkane sulfonate and alkene di sulfonate, and always about 7.15% of impurities such as sodium sulfate, free oil and sodium chloride. Sulfonation methods are described, for example, in various patents published between 1969 and 1971.

The invention also broadly encompasses the use of olefins as a feedstock, e.g., olefins prepared by cracking petroleum wax, relatively pure α-olefins prepared by polymerizing ethylene, and olefins prepared by dehydration of higher alcohols having the average chain length and molecular weight distribution. The average carbon content may also be, although less preferred, outside the range of about 14-16, with the number of carbon atoms being e.g. 12, 15, 17 or 18. The olefin sulphonate may also be in whole or in part in the form of a water-soluble salt other than the sodium salt. , such as in the form of a potassium, ammonium, mono-, di- or triethanolammonium salt or mixtures thereof.

The most preferred ethoxylated alkyl sulfate contained in such a liquid mixture can be prepared by ethoxylating with ethylene oxide a natural or synthetic alcohol, the latter prepared by the Ziegler or oxo method having about 12 to 15 carbon atoms, which is preferably a primary alcohol, and sulfating. then this reaction product to form a monosulfuric acid and then neutralizing to form an ammonium monosulfate salt. The invention also broadly encompasses the use of other salts, e.g., sodium or triethanolammonium salts, and ethoxylated products having a different degree of ethoxylation (such as about 1-5 moles of ethylene oxide per mole of alkanol).

Typical suitable alkanols have the following carbon chain distribution: 0.5% C10, 33.6% C12, 0.6% C16, 6.1% C2, 0.1% 3.6% and 0.4% above 39, 9% ^> 5% C18, 51.9% 1.4% C15, 3.4% Cl6, and 0.1% over Clg; 31.2% C ± 2> 1.8% o, 61.2% cl4, 1.6% C15 and 3.6% Cl6; 0.8% Cl 2, 18.7% Cl 2, 24.2% Cl 2, 2.3% Cl 2, 20.0% and 0.3% Cl 2. Such alcohol sulfates have an average of about 10-18 carbon atoms.

A third essential ingredient in such liquid detergent compositions is a healing additive selected from the group consisting of higher alkyl, tertiary amine oxide compounds that promote foam formation, and foam forming agents that are alkanoic acid / alkanolic acid amide or amide. water - soluble organic monosulphonates with less than 5 carbon atoms. Amine oxides and alkylolamides generally improve the foaming properties by increasing the volume of the foam and / or its stability in the presence of greasy dirt while reducing the tendency to gel. On the other side of the lower aliphatic organic monosulfonate reduce the overall liquid mixtures of aqueous liintymistaipumusta a gel containing olefin sulfonate and / or alkanolamide or an amine oxide foaming enhancing 7 58 938 and possibly also ethoxylated alkyl sulfate detergent.

Preferred tertiary amine oxides which promote foam formation have the general formula R 1, R 1, R 2, N, N, N, N, N, R, N, R, N, R, N, R, N, R, N, R, N, R, N, R, N, R, N, R, N, R, are each selected from the group consisting of methyl, ethyl, propyl, ethanol and propanol, or R 2 and R 2 together with the oxygen-bonded nitrogen form a heterocyclic morpholino group. Typical higher alkyl groups that may be present include e.g. desyl, lauryl, myristyl, cetyl and stearyl, as well as mixed alkyl groups derived from coconut oil or tallow. Tertiary amine oxides can be prepared by reacting a tertiary amine or polyethoxylated amine with an aqueous solution of hydrogen peroxide in approximately equal molar amounts in a reactor that provides temperature stability. The most preferred commercially available tertiary amine oxides are e.g. bis (2-hydroxyethyl) coconut amine oxide, bis (2-hydroxyethyl) thallium oxide and N-coconut morpholine oxide.

Suitable foam-forming alkanoic acid alkanolamides include e.g. diethanolamide, ethoxylated monoethanolamide and a mixture of mono- and diethanolamides of alkanoic acids having 8 to 18, preferably 12 to 14 carbon atoms. The most preferred alkanoic acids have the following carbon chain distribution: up to 1%

Cg_10.0, 71.2-2% C12, 27.8-2% and up to 1% Cl2. The ethoxylated methanol amide can be prepared by reacting 1 mole of the corresponding alkanoic acid monoethanolamide with about 1-4, preferably 1, mole of ethylene oxide in the presence of a basic catalyst such as sodium hydroxide, and the most preferred alkanoic acid diethanolamide can be prepared by reacting 1 mole of With an excess of 5-10%) diethanolamine at elevated temperature and using a basic catalyst such as sodium methylate.

Although the foam-promoting alkanolamide is commonly used in combination with a mixture of olefin sulfonate and ethoxylated alkyl sulfate active ingredients, the ethoxylated alkyl sulfate detergent may be omitted from liquid mixtures containing C that the weight ratio of olefin sulfonate to alkanolamide is about 3: 1 to 1: 1 and preferably about 3: 1 to 1.5: 1. Such mixtures of the olefin sulfonate salt generally comprise from about 5 to about 40% by weight of the liquid detergent mixture, and preferably from about 10 to about 35% by weight, and the amount of C 8 -C 10 alkanoic acid diethanolamide is generally selected from about 3 to 15%, preferably from about 7.5 to 10%. weight, which is sufficient to provide improved foam stability or increased foam volume.

Suitable anti-gelling agents that can be used in these liquid mixtures include water-soluble salts of an organic sulfonic acid, preferably a monosulfonic acid having less than 5 carbon atoms. Preferred anti-gelling agents are sodium ethethionate, trisodium sulfosuccinate and sodium allyl sulfonate. In addition, sodium salts as well as water-soluble potassium, ammonium and mono-, di- and triethanolammonium salts can be used.

Gelling inhibitors can be advantageously included in liquid mixtures containing olefin sulfonate and alkanoic acid or a foam-promoting amine oxide in the presence or absence of ethoxylated alkyl sulfate. However, the best results are obtained when ethoxylated alkyl sulfate is present in the most preferred amounts.

The amount of the mixture of water-soluble olefin sulfonate and water-soluble alkyl ethoxamer sulfate salts is generally about 10-40% by weight of the liquid detergent mixture and is preferably about 25-35% by weight, although at least about 18% by weight of the mixture is usually used when the foam-promoting trialkylamine present.

In such most preferred liquid mixtures containing a foaming agent, the weight ratio of olefin sulfonate to ethoxamer alkyl sulfate is further maintained in the range of 1.4: 9.9: 1, preferably 1.3: 1-1.1: 1.

The amount of tertiary amine oxide in a liquid detergent composition containing the mixture of active ingredients is in the range of about 1.5 to 10, preferably 2 to 8% by weight, sufficient to provide improved stability or an increased amount of foam. In addition, the weight ratio of the sum of olefin sulfonate and ethoxamer alkyl sulfate to amine oxide is adjusted to a range of 22: 1 to 3: 1, preferably 15: 1 to 3.5: 1.

Likewise, the amount of alkanoic acid alkanolamide mixtures in the detergent mixture containing the mixture of active ingredients is generally in the range of 1.0 to 10, preferably 2 to 6% by weight, which is sufficient to provide improved foam stability or a higher amount of foam. In addition, the weight ratio of the sum of olefin sulfonate and ethoxamer sulfate detergents to alkanoic acid alkanolamide should be maintained in the range of 40: 1-4: 1, preferably 30: 1-5: 1.

The amount of anti-gelling salts in liquid detergent compositions comprising either an olefin sulfonate or a mixture of olefin sulfonate and ethoxylated alkyl sulfate is generally in the range of about 1-8, preferably about 2-6%, e.g. about 4% by weight, which is sufficient to reduce the tendency of the detergent mixture to form a gel-like film and this also improves the ability of the mixture to rapidly dissolve any gel that may have formed. This provides a significant advantage over previously known compositions because gel formation causes clogging of nozzles and cams in containers used to dispense such liquid detergent compositions. In liquids that do not contain ethoxylated alkyl sulfate, gelling inhibition properties are provided when the weight ratio of olefin sulfonate to gelling salt is about 16: 1-2: 1, preferably 7: 1-3: 1, and most preferably 4: 1.

The detergent or detergent mixture and the performance enhancing additive, e.g., a foaming agent and / or anti-gelling agents, are generally dissolved in an aqueous medium to provide a homogeneous liquid product. This aqueous medium may be water only, in which the ingredients are sufficiently soluble or dispersible, or it may consist of a mixture of water and a co-solvent selected from the group consisting of C2-C1 monohydric alcohols, water-soluble salts of organic sulphonated or sulphated hydrotropes and mixtures of these. Suitable alcohols include ethanol, propanol and isopropanol, with ethanol being most preferred. Suitable organic sulfonate hydropropes include alkylarylsulfonates having up to 3 carbon atoms in the alkyl group, such as sodium, potassium and ammonium toluene, xylene and cumene sulfonates. Suitable organic sulphate hydrotropes include the sodium, potassium, ammonium or mono-, di- and triethanolammonium salts of C 1 -C 6 alkyl sulphate.

The amount of aqueous medium is generally about 30-95%, preferably about 40-85% by weight, of the liquid detergent. If an alcoholic solvent is used, its concentration is about 1 to 10, preferably 3 to 7% by weight, and the concentration of the hydrotropic agent is about 0.5 to 10, preferably 1 to 8% by weight, based on the weight of the liquid detergent.

The pH of the liquid light wash mixture is adjusted to 6-8 by the addition of a suitable acid or alkali.

According to a preferred embodiment, these liquid detergent compositions contain 0.25-3%, preferably 1-2% by weight, of a water-soluble, substantive protein to reduce skin irritation in the hands of the detergent. Chemically, such a protein component is a low molecular weight polypeptide obtained by hydrolyzing proteinaceous materials such as human and animal hair, horns, hides, hooves, gelatin, collagen, etc. During hydrolysis, these proteins gradually degrade to their polypeptide and amino acid components over time. e.g. with sulfuric acid, or with alkalis, e.g. sodium hydroxide, or when treated with an enzyme, e.g. peptidase. Hydrolysis first results in the formation of high molecular weight polypeptides, and as the hydrolysis progresses, these gradually become increasingly simple polypeptides, tripeptides, dipeptides, and finally amino acids. It is apparent that the polypeptides derived from the proteins are complex mixtures, and in practice the average molecular weight of the hydrolysis product varies between 120 (amino acids) and about 20,000. All satisfactorily hydrolyzed polypeptides are characterized by their water solubility. In mixtures containing soluble protein, it is preferred to use hydrolyzed collagen that is so low in molecular weight that it is completely soluble in water, does not gel, and does not denature under the most preferred average molecular weight of less than 15,000, most preferably in the range of about 500-10,000, and optimal results are obtained. with a molecular weight of about 1000.

U 58938

In addition, the detergent compositions of the invention may also contain other conventional ingredients commonly used in such compositions which are substantially free of their builder salts. For example, water hardening salts such as magnesium sulfate and calcium chloride can be used at concentrations of 0.5 to 4% by weight to improve foaming in soft water. Sequestrating agents such as alkali metal citrates, gluconates and aminopolycarboxylates may be present in amounts of 0.1-1% by weight to sequester metal ions such as iron in wash water. Other additives such as bleaches, dyes, plasticizers, perfumes, bactericides, etc. can be added to detergent compositions in concentrations ranging from about 2% by weight to improve its various properties.

In addition to the above ingredients, the liquid detergent composition may, although less preferred, also contain minor amounts of other surfactants that do not adversely affect the excellent properties of the composition. The amount of such detergents is generally well below about 10%, preferably less than about 5%, of the total detergent content of the mixture. As such a detergent, any suitable anionic, nonionic, amphoteric and polar nonionic detergent can be used which provides good detergent, wetting or foaming properties or some other advantageous detergent properties.

Suitable anionic detergents include e.g. higher monocyclic alkyl aromatic sulfates, such as higher alkylbenzene sulfonates having from 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, e.g., higher alkyl benzene sulfonates Paraffin sulfonates containing about 10 to 20 carbon atoms, e.g., primary paraffin sulfonates, are prepared by reacting long chain alpha-olefins and bisulfites and paraffin sulfonates having a sulfonated group distributed along the paraffin chain as described in the prior art. by reacting sodium and potassium sulfates of higher alcohols containing from 8 to 18 carbon atoms, such as sodium lauryl sulfate and sodium tallow alcohol sulfate, or by using sodium and potassium salts of α-sulfonic fatty acid esters containing about 10 to 20 carbon atoms in the acyl group methyl α-sulfomyristate and methyl α-sulfothallovate, ammonium sulphates of higher mono- or di-glycerides of cio-Cl8 fatty acids, e.g. stearic monoglyceride monosulphate, higher sodium alkyl (C10-C18 glyceryl ethers) t and potassium alkylphenol polyethyleneoxy ether sulfates having about 1 to 6 oxyethylene groups per molecule and wherein the alkyl radicals contain about 8 to 12 carbon atoms.

Other suitable anionic surfactants include C8-C18 acyl sarcosinates (e.g. sodium lauroyl sarcosinate), sodium and potassium salts of the reaction product of higher fatty acids having 8 to 18 carbon atoms per molecule esterified with isethionic acid, and Sodium and potassium salts of N-methyltaurides, e.g. sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.

Other types of surfactants useful in the practice of the present invention include nonionic synthetic organic detergents, which are generally the condensation product of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic ethylene oxide groups. Virtually any hydrophobic compound having a carboxy, hydroxy, amido or amino group, and free hydrogen attached to nitrogen, can be condensed with ethylene oxide or its polyhydration product, polyethylene glycol, to form a nonionic detergent. Furthermore, the length of the polyethyleneoxy chain can be adjusted to achieve the desired balance between hydrophobic and hydrophilic elements.

Nonionic detergents also include polyethylene oxides derived from 1 mole of alkylphenol containing about 6 to 12 carbon atoms in a straight or branched chain condensed with about 5 to 30 moles of ethylene oxide, e.g., lauryl myristyl alcohol condensed with about 16 moles of ethylene oxide.

One group of non-ionic detergents is on the market under the trademark "Pluronic". These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol. The hydrophobic portion of the molecule has a molecular weight in the range of 950-4000 and preferably 1200-2500. The addition of polyoxyethylene radicals to the hydrophobic moiety tends to increase the solubility of the entire molecule. Such block polymers have a molecular weight in the range of 1000-15,000 and may have a polyethylene oxide content of 20-80% by weight.

Amphoteric detergents of the following formula, such as betaines and sulfobetaines, are also useful: R2 R — N- Rn- X == 0 r / | wherein R 3 is 0-0 wherein R is an alkyl group having about 8 to 18 carbon atoms, R 2 and R 2 are each an alkylene or hydroxyalkylene group having about 1 to 4 carbon atoms, R 1 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms. 4 carbon atoms, and X is C or S = 0. The alkyl group may contain one or more intermediate bonds, such as amido, ether or polyether bonds, or non-functional substituents, such as hydroxyl or halogen, which do not substantially affect the hydrophobic properties of the group. When X is C, the detergent is called betaine. When X is S = 0, the detergent is called sulfobetaine or sultaine. The most preferred betaine and sulfobetaine detergents are 1- (lauryldimethylammonium) acetate, 1- (myristyldimethylammonium) propane-3-sulfonate and 1- (myristyldimethylammonium) -2-hydroxypropane-3-sulfonate.

Relational nonionic detergents are those in which the hydrophilic group contains a semipolar bond directly between two atoms, e.g. As-K) and S- * 0. There is a difference in charge between two directly bonded atoms, but there is no net charge in the detergent molecule and it does not dissociate into ions.

Useful polar nonionic detergents include open-chain aliphatic phosphine oxides of the general formula riR2R3R- * O, wherein R1 is an alkyl, alkenyl or monohydroxyalkyl radical having a chain length of 10 to 18 carbon atoms, and R2 and Rj are each alkyl and monohydroxyalkyl radicals having 1 to 3 carbon atoms.

! ”5 89 38

Examples of suitable ampholytic detergents are alkyl beta-aminopropionates, RN (H) C 2 H 2 COOM; alkyl beta-iminodipropionates, ΚΝ (02Η4002Μ) 2 and long-chain imidazole derivatives of the following formulas

CH

^ CH "

Il I (I)

R - C - N -W

“(II) N NCH.

Il R - C - ^

^ R2 - COOM Y

wherein R is an acyclic group having about 7 to 17 carbon atoms, W is selected from the group consisting of R 2 OH, R 2 COOM and R 2 OR 2 COOM, Y is selected from the group consisting of OH 'and R 1 OSO 4, R 2 is an alkylene or hydroxyalkylene group having 1 to 4 carbon atoms, R 1 is selected from the group consisting of alkyl, alkylaryl and fatty acyl glyceride groups having 6 to 18 carbon atoms in the alkyl or acyl group, and M is a water-soluble cation, e.g. sodium, potassium, ammonium or alkyloliammonium.

Detergents of formula I are described in Part II of the book "Surface Active Agents and Detergents", and detergents of formula II are described in the patent literature. The acyl groups may be derived from coconut oil fatty acids (a mixture of fatty acids having 8 to 18 carbon atoms), lauric fatty acid, oleic fatty acid, and the most preferred groups are Cy-C 1-6 alkyl groups. The most preferred detergents are sodium N-lauryl beta-aminopropionate, disodium N-lauryl iminodipropionate and 2-laurylcycloimidium-1-hydroxyl, 1-ethoxyacetic acid, disodium salt of 1-acetic acid.

The following examples illustrate the detergent compositions of the invention. All concentrations in these examples are by weight unless otherwise indicated.

58938 15

Example 1

The following liquid detergent mixture was prepared.

Ingredient%

Sodium alpha-olefin sulfonate * 16.1

Stoxylated (^ 2-15) alcohol ammonium sulphate ** 13.8

Bis-2-hydroxyethylcocosamine oxide 4.0

Sodium cetionate 5.0

Hydroxyethylethylenediaminetetraacetic acid trisodium salt ("hydroxy EDTA") 0.08

Water soluble protein 1.0

Ethanol 6.0

Water Remaining 100.0 * A mixture of 50-70% alkenyl sulfonate, 20-40% hydroxyalkane sulfonate and 5-12% hydroxyalkane disulfonate and alkene di sulfonate prepared by sulfonating an olefin mixture having a carbon distribution of 2.0% or less C12, 66.2 - 2.0%

Cl45 ^ 3.4 * 2.0 ^ Cl6J average carbon chain length 14.6, average molecular weight 205, alpha-olefin to vinylidene-olefin ratio 6.4: 1 and alpha-olefin to internal olefins ratio 9.6: 1.

Ethoxylated? 12-15 alcohol triethoxamer ammonium sulfate with a carbon chain distribution of 0.8% C11, 18.7% c12> 24.2% ^ 13 * 32.3% C · ^, 20.0% and 0, 3% Cl 2 and average molecular weight 436.

XXX

Partially hydrolysed collagen protein with an average molecular weight of 1000.

The olefin sulfonate, water and alcohol are combined and mixed using stirring at low speed at room temperature. To this mixture are added appropriate amounts of bis-2-hydroxyethylcocosamine oxide, sodium ethethionate, magnesium sulfate, hydroxy-EDTA and ethoxylated alcohol (C12-c4) -immonium sulfate. The ingredients are mixed together for about 5 minutes, i.e. until the mixture is homogeneous. The pH of the mixture is adjusted to 7> 3 to 0.3 by adding an acid or a base if necessary and then the required amount of skin protection agent is added. A dye or perfume can then be added if desired. If necessary, the mixture can then be filtered to obtain a clear product which can be stored for future use.

Example 2

The following liquid detergent mixture was prepared as described in Example 1.

Ingredient%

Sodium alpha-olefin sulfonate * 16.1

Ethoxylated (^ 2-15) alcohol ammonium sulphate ** 13.8 Bis-2-hydroxyethyl thallamine oxide 4.0

Sodium cetionate 5.0 "Hydroxy EDTA" 0.08

Magnesium sulphate t iheptahydrate i 1, o

Water soluble protein 1.0

Ethanol 6.0

Water remaining 100.0

X XX. XXX

, and are the same as in Example 1.

Examples 3-7

Other satisfactory liquid detergent compositions containing a tertiary amine oxide as a foaming agent include:

Ingredient% 3 4 5 6 7

Sodium alpha-olefin (0Ίί, sulphonatex1 iD 16.1 16.1 16.1 16.1 16.1

Ethoxylated (C, 2_ic;) alcohol ammonium sulfate ** 13.8 13.8 13.8 13.8 13.8

Bis-2-hydroxyethylthallamine oxide - - 6.0 8.0

Bis-2-hydroxyethylcocosamine oxide 2.0 6.0 8.0

Laurin-myristic monethanolamide **** 2.0 -

Sodium xylene sulfonate 1.6 -

Sodium ethethionate 5.0 5.0 5.0 5.0 5.0 "Hydroxy EDTA" 0.08 0.08 0.08 0.08 0.08

Magnesium sulphate heptahydrate

• XXX

Water soluble protein

Ethanol 6.0 6.0 6.0 6.0 6.0

Water rest rest rest rest rest 100.0 100.0 100.0 100.0 100.0 17 5 8938

Xf UU flux, and are the same as in Example 1 **** Prepared by reacting 1 mole of laurine-myristic fatty acid with 1 mole of monoethanolamine at elevated temperature. The carbon chain distribution of the acyl radical is as follows: Maximum 1% Cg-C10, 71.2 - 2.0% Cl2, 27.8 - 2.0% 0χ1 | and not more than 1 * C16 ‘

It has been found that the compositions of Examples 1-7 provide detergent compositions having good foaming ability, foam properties, washing performance, biodegradability, anti-theft function, low toxicity, good viscosity, good resistance to gel formation and good re-dissolution of the formed gel.

Highly suitable compositions having the above-mentioned excellent detergent properties include those containing amine oxides and foam-promoting amides, such as C 5). These amides can replace part of the amine oxide, i. 20, 40 or 60% of the amine oxide may be replaced by an equivalent weight of one of the above-mentioned foam-promoting amides. Example 3 above illustrates such mixtures.

Examples 8-10

Ingredient% 8 9 10

Sodium alpha-olefin sulfonate * 19.0 16.0 13.0

Ethoxylated (c,?, Σ) alcohol-ammonium sulphate1'5 12.0 15.0 18.0 uuvu

Laurun-myristin-diethanolamide 5.0 5.0 5.0

Ethanol 8.0 8.0 8.0

Water rest rest rest 100.0 100.0 100.0

X XX

and have the same meaning as in Example 1 xxxx ·

Prepared by reacting 1 mole of laurine-myristic methyl ester with 1.2 moles of diethanolamine in the presence of sodium methylate. The acyl radical has the following carbon distribution: up to 1% Cg10, 71.2 to 2.0% C12, 27.8 to 2.0% and up to 1% C18.

58938 18

The olefin sulfonate, water and alcohol are combined and mixed on a low speed rotary mixer at room temperature. To this mixture are added the indicated amounts of laurine-myristine-diethanolamide and ethoxylated C} 2-15 alcohol ammonium sulfate. The ingredients are mixed together for about 5 minutes, i.e. until the mixture is homogeneous. The pH of the mixture is adjusted to 7.3 to 0.3 by adding either base or acid as needed. If necessary, the mixture can then be filtered to obtain a clear product that can be stored for future use.

The mixtures of Examples 8-10 are tested for the amount of gel formation and their ability to redissolve the formed gel as follows.

Approximately 100 ml of each liquid detergent (Examples 8-10) is poured into a flask, which is then sealed and placed in a -4 ° C bath. After three days, the flasks are removed and the amount of gel formed is determined by visual inspection. The flasks are then allowed to stand at room temperature and the time required for the gel to redissolve is recorded.

The presence of gel formation causes clogging of certain dispensers, nozzles or cams in which the liquid detergent is packaged.

The number of plates washed with these detergent mixtures is also tested using the test method "The Miniature Dishwashing Evaluation Method" (Journal of the American Oil Chemists Society,

Vol. 43, No. 10, pp. 576-580). In this method, two glasses of different sizes are soiled with a weighed amount of greasy dirt (mini-plates) and washed with a solution of the detergent to be tested, and the foamability of the solution is measured by the number of mini-plates that can be washed before foaming ceases.

The results obtained from Examples 8-10 are shown in Table A.

19 5 8938

Table A

Olefin Sulfo- Gel Formation- Gel Re- Plate-Nate Ratio

Example 8 1.6: 1 6.0 l8h 36

Example 9 1.1: 1 0.5 l8h 36

Example 10 0.7 = 19 »5 6 days 37

It can be seen that the compositions according to the invention tend to form a harmful gel layer very little and the number of washed plates is higher.

The following examples illustrate compositions that take advantage of the invention in preparing excellent detergent compositions.

Example 11

A liquid detergent was prepared with the following composition.

Ingredient%

Sodium alpha-olefin C (14-16) sulfonate * 16.1

Ethoxylated (C.p.J alcohol ammonium sulphate ** 13.8

Laurimι-myristin-diethanolamide 3.0

Laurin-myristin-monoethanolamide 1.5

Sodium xylene sulfonate 1,2

Sodium isethionate 4.0

Hydroxyethylethylenediaminetetraacetic acid trisodium salt ("Hydroxy EDTA") 0.08

Magnesium sulphate heptahydrate 1.0

Water soluble protein 1.0

Ethanol 6.0

Water remaining 100.0 and *** as in Example 1 **** as in Examples 3-7 as in Examples 8-10

Example 12 '

A liquid detergent having the following composition was prepared using the methods of Examples 8-10.

20 5 8 9 3 8

Ingredient%

Sodium alpha-olefin (¢ -.4.15) sulfonate 16.1

Ethoxylated (C, 2_ic) alcohol ammonium sulfate ** 13.8

Laurin-myristic-diethanolamide 3.0

Laurin-myristin-monoethanolamide 2.0

Sodium xylene sulfonate 1.6

Sodium isethionate 4.0 "Hydroxy EDTA" 0.08

Magnesium sulphate heptahydrate 1.0

Water soluble protein 1.0

Ethanol 6.0

Water remaining 100.0 χ, χχ, χχκ as in Example 1 **** as in Examples 3-7 xxxxx as in Examples 8-10

As shown in Examples 11 and 12, certain amounts of monoethanolamide may be added to the detergent composition instead of diethanolamide, provided that the amount of monoethanolamide does not exceed about 55%, more preferably about 50% by weight, of the total amount of foam-promoting alkanolamide.

Examples 13-16

Ingredient% 13 14 15 16

Sodium alpha-olefin (C 1-4) sulfonate * 16.1 16.1 16.1 16.1

Ethoxylated (C, 2 alcohol ammonium sulfate ** 1 D 13.8 13.8 13.8 13.8

Laurin-myristic diethanolamide ***** 1.0 3.0 4.0 6.0 "Hydroxy EDTA" 0.2 0.2 0.2 0.2

Magnesium sulphate heptahydrate

Sodium isethionate

Water soluble protein

Ethanol 3.0 3.0 3.0 3.0

Water rest rest rest rest 100.0 100.0 100.0 100.0 *, ** and *** as in Example 1 y yy yy as in Examples 8-10 21 5 89 38

Examples 17-24

The following liquid detergent compositions were prepared in the same manner as in Examples 11 and 12.

17 18 19201122232 ^

Sodium alpha-olefin (C, h, sulphonate * 10 16.1 16.1 16.1 16.1 16.1 16.1 16.1 16.1

Ethoxylated (C 1-4 alcohol ammonium sulfate D 13.8 13.8 13.8 13.8 13.8 13.8 13.8 13.8

Ethoxylated coconut monoethanolamide (EtO) 1.0 2.0 3.0 4.0

Ethoxylated laurine monoethanolamide (EtO) 1.0 2.0 3.0 4.0 “Hydroxy EDTA” 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

Magnesium sulphate iheptahydrate 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0 1,0

Sodium isethionate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 • yy

Water soluble protein

Ethanol 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0

Water rest rest rest rest rest rest rest rest 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 ** and m as in Example 1

Examples 25-26 show the importance of adjusting the ratios of plephin sulfonate to alkanoic acid-ethanolamide to a range of 3: 1 to 1: 1 in mixtures containing diethanolamide and olefin sulfonate detergent as the preferred foaming agent.

Examples 25-26% Ή

Ingredient 25 - 26

Sodium alpha-olefin sulfonate * 22 ~ 748 22748

Laurin-ristrine-monoethanolamide **** 2 »25

Laurin-myristic-diethanolamide 5.25 7.50

Magnesium sulphate heptahydrate

Hydroxyethylethylenediaminetetraacetic acid

Sodium xylene sulfonate 1.8

Sodium isethionate

Ammonium cumene sulfonate 6,667 6,667

Ethanol - 3.0

Water rest remaining 100.0 100.0 58938 22 χ as in Example 1 vyvv as in Examples 3-7 xxx ** ^ α1-θη in Examples 8-10

The olefin sulfonate, water and any ethanol used are combined and mixed with a low speed stirrer at room temperature. To this mixture are added the amounts of laurine-myristic mono- and / or diethanolamide shown in the composition. The ingredients are mixed for about 5 minutes, that is, until the mixture is homogeneous. The pH of the mixture is adjusted to 7.3 to 0.3 by adding, if necessary, alkali or acid. If necessary, the mixture can then be filtered to obtain a clear product which can be stored for future use.

The number of plates washed with these mixtures has been tested using "The Miniature Dishwashing Evaluation Method" to give the following results.

Table B

Washed plates 25 26 0 mo 32 29 50 mo 34 38 150 no 33 37 This comparison of the dishwashing capacity of the above mixtures clearly shows that a mixture using a large amount of lauric myristic-diethanolamide has superior dishwashing properties to a mixture with a lower amount. laurine-myristic-diethanolamide with the exception of the use of very soft water.

Examples 27-28

Liquid detergents having the following composition were prepared in the same manner as in Examples 25 and 26.

Ingredient%

Sodium alpha-olefin sulfonate * 22.5 17.9

Laurin-myristin-monoethanolamide xxxx 2.25 1.8

Laurin-myristic-diethanolamide ***** 6.25 10.0

Sodium xylene sulfonate

Ammonium cumene sulfonate 6,667 6,667 "Hydroxy EDTA" 0.2 0.2 9 ”58938

Sodium isethionate

Magnesium sulphate heptahydrate

Water remaining remaining 100.0 100.0 * as in Example 1

Ease

as in Examples 3-7 as in Examples 8-10

The mixtures of Examples 27 and 28 were tested and compared again using the "Miniature Dishwashing Evaluation Method" with the following results.

Table C

Washed Plates 27 28 0 mo 32 36 50 mo 35 40 150 mo 34 38 Again, it is apparent that a mixture using a large amount of laurine-myristine-diethanolamide surprisingly provided an unexpected improvement in washing performance contrary to what has previously been assumed, as e.g. U.S. Patent No. 3,332,878, which discloses that diethanolamides give poor results. It may also be noted that small amounts of methanolamide may be added to the detergent composition provided that the amount of monoethanolamide does not exceed about 25% by weight of the total amount of foam-promoting alkanolamide and preferably not more than about 20% (e.g. about 15%).

The advantages of using a gelling agent in an olefin sulfonate-containing liquid detergent composition are set forth in Examples 29 and 30.

Examples 29-30

Ingredient%

Sodium alpha-olefin sulfonate * 22.0 22.0

Ethoxylated ^ 12-15 ^ alcohol ammonium sulfate ** 12.0 12.0

Laurin-myristime-diethanolamide 5.0 5.0

Trisodium sulfosuccinate - 3.2

Magnesium sulfate iheptahydrate 2.0 2.0 58938 2h

Sodium gluconate

Sodium citrate

Ethanol 6.0 6.0

It would take the remaining 100.0 to 100.0 K and ** as in Example 1 ***** as in Examples 8-10

The olefin sulfonate, water and alcohol are combined with each other and mixed together in a low speed mixer at room temperature. To this are added, respectively, the amounts of laurine-myristic diethanolamide, trisodium sulfosuccinate, magnesium sulfate, sodium gluconate, sodium citrate and ethoxylated alcohol (^ 2-15) ammonium sulfate shown in the recipe. The ingredients are mixed together for 5 minutes, i.e. until the mixture is homogeneous. The pH of the mixture is adjusted to 7.3 to 0.3 by adding, if necessary, an acid or a base, and then the amount of protein hydrolyzate shown in the recipe is added as a skin care agent. After this, colorants and perfumes can also be added if desired. If desired, this mixture can then be filtered to obtain a clear product that can be stored for future use.

The mixtures of Examples 29 and 30 were tested to determine the effect of the addition of a gelling inhibitor and a gelling inhibitor as follows: 1 ml of the liquid mixture is allowed to flow freely downwards on a glass plate kept in normal outdoor air and at an angle of 30 ° to the horizontal. Measure the distance that the fluid flows and determine the nature of the track (straight or winding).

A curved line indicates that gel formation has occurred, while a straight line indicates that little or no gel formation has occurred. The flow distance indicates resistance to gel formation. The results show the relative gelling tendencies of the liquids shown in Table D.

58938 25

Table D

Flow distance Track characteristics

Example 29 29 cm At least 18.8 cm from the bend

Example 30 57.8 cm Straight

The table above shows that the addition of trisodium sulfosuccinate increases the resistance to gel formation.

Examples 31-35

The following liquid detergent compositions were prepared and tested as described in Examples 29 and 30.

Ingredient% 11 32 33 34 35

Sodium alpha-olefin (0Ίί1, sulphonate * 14-10 19.6 19.6 19.6 19.6 19.6

Ethoxylated (C,?, Σ) alcohol ammonium sulfate 5 11.0 11.0 11.0 11.0 11.0

Laurin-myristin-diethanolamide ***** 5.0 5.0 5.0 5.0 5.0

Trisodium sulfosuccinate - 1.6 3.2 4.8 4.8

Ethanol 8.0 7.0 7.0 7.0 5.0

Water rest rest rest rest rest 100.0 100.0 100.0 100.0 100.0 and as in Example 1 ***** in Examples 8-10

Table E

Flow distance Flow path characteristics

Example 31 37 cm At least 22.8 cm from the bend

Example 32 42 cm At least 22.8 cm from the bend

Example 33 50 cm At least 22.8 cm from the bend

Example 34 72 cm Straight

Example 35 58.5 cm Straight

The table above shows that the addition of various amounts of trisodium sulfosuccinate increases the resistance to gel formation.

Other compositions containing an anti-gelling additive are shown in Examples 1-7 and 11-28.

Claims (9)

58938 26 Although the present invention has been described with reference to certain embodiments and examples, it is to be understood that the invention is not limited to the details shown, but may be modified without departing from the scope of the invention. A light detergent liquid detergent composition, characterized in that it contains 25 to 35% by weight of a mixture of (i) at least one sulfonated water-soluble salt as the sole olefin sulfonate component present, containing up to 20% by weight of vinylidene olefin sulfonate, and (ii) either A water-soluble salt of a C 1 -C 4 alkyl sulfate having 1 to 5 ethyleneoxy groups in the molecule, or a C 1 -C 4 alkanoic acid diethanolamide or a mixture of diethanolamides having up to 25% by weight of a C 1 -C 4 alkanoic acid monoethanolamide, provided that when (ii) is diethanolamide, the weight ratio of (i) :( ii) is 3: 1 to 1: 1; and (iii) a healing additive consisting of either (a) 1.5 to 10% by weight of a foam-promoting amine oxide of the formula R 1 -R 2 -N-O 0 -O 0 O-C 1-6 alkyl-alkenyl, or -monohydroxyalkyl, R 2 and R 2 are each methyl, ethyl, propyl, hydroxyethyl or hydroxypropyl or together with the oxygen-bonded nitrogen atom form a morpholino group, (b) 1-10% by weight of a C 10 -C 18 alkanoic acid diethanolamide or ethoxylated C 8 -C 18 -fatty acid monoethanolamide and their mixture with each other and / or C 1-4 C 1-4 fatty acid monoethanolamide, (c) 1-8 weight-inhibitors which are water-soluble salts of organic aliphatic C 1-4 sulfonic acids and a mixture of two or more compounds of groups (a), (b) and (c), further provided that when (ii) is alkyl sulfate and (iii) amine oxide, the weight ratio of (i) :( ii) 1.4 : 1 to 0.9: 1> when (ii) is an alkyl sulfate and (iii) is an alkanolamide, the weight ratio of (i) :( ii) is 1.4: 1 to 0.9: 1 and the weight the ratio of (i) + (ii): alkanolamide 40: 1 to 4: 1 and when (ii) is diethanolamide, there is no or no curing additive (iii); and (iv) an aqueous medium. A liquid detergent composition according to claim 1, characterized in that (ii) is an ethoxylated C 1 -C 4 alkyl sulfate, said additive is a tertiary amine oxide which promotes foaming, and the aqueous medium is water or a mixture of water soluble. with a substance consisting of 1 to 10% by weight of T-α'-chloro, 0.5 to 6% by weight of water-soluble lower alkyl benzene sulfonate having 1 to 3 carbon atoms in the lower alkyl group, and 0.5-6% by weight of C 1 -C 6 alkyl sulfate. Liquid detergent composition according to Claim 2, characterized in that up to 60% by weight of the foam-promoting amine oxide is replaced by a foam-promoting alkanoic acid amide consisting of C 1-4 C 1-4 alkanoic acid monoethanolamide, C 1-4 alkanoic acid alkanoic acid alkane or ethoxylated C, qC, p-alkanoic acid monoethanolamide. A liquid detergent composition according to claim 1, characterized in that (ii) is ethoxylated C 1 -C 4 alkyl sulfate, said additive is an alkanoic acid alkanolamide and the aqueous medium is water or a mixture of water with a solubility enhancer consisting of 1-10 a C2-C2 alcohol and 0.5 to 6% by weight of a water-soluble lower alkyl benzene sulfonate having 1 to 3 carbon atoms in the lower alkyl group, and a 0.5 to 6 weight C1-C8 alkyl sulfate. Liquid detergent composition according to Claim 4, characterized in that the alkanoic acid group of the alkanoic acid alkanolamide has 12 to 14 carbon atoms. Liquid detergent composition according to claim 4, characterized in that it also contains about 0.25 to 3% by weight of a water-soluble protein hydrolyzate having a molecular weight of about 120 to 20,000 and intended to reduce skin irritation. Liquid detergent composition according to claim 1, characterized in that (ii) is a C 1 -C 4 alkanoic acid diethanolamide, the aqueous medium is water or a mixture of water with a solubilizer comprising 1 to 10% by weight of N-alcohol and 0.5 to 6% by weight of water-soluble lower alkylbenzene sulfonate having 1 to 3 carbon atoms in the lower alkyl group, and 0.5 to 6% by weight of C 1 -C 6 alkyl sulfate. Liquid detergent composition according to one of Claims 2 to 7, characterized in that it also contains 1 to 8 weight-inhibitors. 28 5 8 9 3 8 Liquid detergent composition according to Claims 7 to 8, characterized in that the gelling agent is sodium ethethionate, trisodium sulphosuccinate or sodium allyl sulphonate, the weight ratio of sulphonated olefin to gelling agent being 16: 1 to 2: 1.