Liquid detergent compositions

Abstract

This invention pertains to homogeneous, preferably clear, liquid detergent compositions which are particularly suitable for the removal of food soils from hard surfaces such as dishes. Said compositions consist essentially of a mixture of organic detergents; organic sequestering builders; polyfunctional anionic surfactants which serve as phase modifiers; and water. The organic sequestering builder is preferably represented by citrates whereas the polyfunctional anionic surfactant can be represented by water-soluble salts of sulfonated higher fatty acids or by water-soluble salts of a component derived from succinic acid. The liquid medium of the instant homogeneous liquid detergent composition is essentially water.

Description

BACKGROUND OF THE INVENTION

Liquid detergent compositions are frequently used for multiple cleaning purposes particularly in households. Said compositions are especially attractive to housewives because of their easy dispensability and, also, because of the apparent preference consumers put, for certain type of cleaning, on homogeneous liquid detergents. However, said liquid detergent compositions are difficult to formulate inasmuch as the attainment of a homogeneous liquid composition limits the quantities of the ingredients needed for performing the cleaning job. This, in turn, results in a lower cleaning activity on a unit weight basis. Said problems are wellknown particularly for compositions containing water-soluble salts of sulfonated C.sub.10 to C.sub.22 fatty acids or surface active ingredients derived from succinic acid. The former are well known in the art and many attempts have been made to incorporate them in liquid detergent compositions, however, without, up to now, leading to commercially acceptable products. Some of the succinic acid derivatives suitable for use are disclosed in, for example. South African patent specification 71/7852, Vincent Lamberti et al., as detergent compositions ingredients for use in solid detergent compositions. Non-solid detergent compositions are also disclosed in some of the examples of said patent application. However, the like compositions suffer the disadvantage of being insufficiently soluble in aqueous medium, and therefore, cannot constitute basis for obtaining homogeneous liquid detergent compositions.

It is well known that, liquid detergent compositions containing either one, or combinations of several except one or more, of the essential ingredients used in the compositions of the instant invention, are not satisfactory for cleaning and particularly dishwashing purposes. The reason for this apparently resides in the narrow spectrum soil removal properties of these prior art liquid detergent compositions.

Another factor for consideration is the limited solubility, with a view to obtain homogeneous liquid detergent compositions, of combinations of several except one or more of the essential ingredients used in the compositions of the instant invention.

It is, therefore, an object of the present invention to provide homogeneous, preferably clear, liquid detergent compositions which are particularly suitable for the removal of food soils.

It is another object of this invention to provide homogeneous liquid detergent compositions which will not separate phases, particularly during prolonged storage.

It is still another object of the instant invention to provide a composition with good cleaning performance without being subject to precipitation or other separation phenomena which, when not taken care of properly, may result in dispensing portions of the products which are not truly representative and, hence, do not provide the cleaning performance the consumer expects.

The above and other advantages are now provided by homogeneous, preferably clear, liquid detergent compositions which consist essentially of organic detergents, organic sequestering builders, polyfunctional anionic surfactants chosen among water-soluble salts of sulfonated higher fatty acids and water-soluble derivatives of succinic acids in combination with water.

SUMMARY OF THE INVENTION

The instant invention provides homogeneous liquid detergent compositions which are particularly efficient for the removal of food soils. Such compositions consist essentially of:

a. from about 3% to about 40% by weight of a water-soluble detergent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactants;

b. from about 2% to about 30% by weight of a water-soluble organic sequestering builder;

c. from about 2% to about 25% by weight of a phase modifier surfactant ingredient selected from the group consisting of water-soluble salts of

i. sulfonated C.sub.8 - C.sub.22 fatty acids;

ii. compounds of the general formula ##EQU1## wherein R.sub.1 represents an alkyl group having from 3 to 20 carbon atoms;

R.sub.2 represents hydrogen or a C.sub.1-4 alkyl group,

R.sub.3 stands for hydrogen, C.sub.1-4 alkyl group or --OH, whereby the total number of carbon atoms of R.sub.2 and R.sub.3 is at most 4;

X represents --O--; --S--; --SO--; --SO.sub.2 --; or --SCH.sub.2 --; M is a water soluble cation; and

iii. mixtures thereof;

whereby the ratio of component (b) to component (c) is from about 6:1 to about 1:6; and the balance to 100% being

d. water.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to homogeneous, preferably clear, liquid detergent compositions which are particularly capable of cleaning hard surfaces soiled with food.

The compositions of this invention contain as essential ingredients (1) an organic detergent; (2) an organic sequestering builder; (3) a particular polyfunctional anionic detergent which serves as a phase modifier in the liquid composition; and (4) water. Each of these components is discussed in detail hereinafter.

Unless indicated to the contrary the "%" indications stand for "percent by weight."

The instant detergent compositions comprise from about 3% to about 40%, preferably from about 5% to about 25%, of an organic detergent selected from the group consisting of anionic, nonionic, zwitterionic and ampholytic surfactants and mixtures thereof. Examples of ingredients suitable for being used as detergent actives in the instant compositions are as follows:

A. Anionic Soap and Non-Soap Synthetic Detergents

This class of detergents includes ordinary alkali metal soaps such as the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms and preferably from about 10 to about 20 carbon atoms. Suitable fatty acids can be obtained from natural sources such as, for instance, from plant or animal esters (e.g., palm oil, coconut oil, babassu oil, soybean oil, castor oil, tallow, whale and fish oils, grease, lard, and mixtures thereof). The fatty acids also can be synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Napthenic acids are also suitable. The particular soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the ammonium and alkylolammonium salts of mixtures of fatty acids derived from coconut oil and tallow, i.e., ammonium or alkylolammonium tallow and coconut soap.

This class of detergents also includes water-soluble salts, particularly the ammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a sulfonic acid or sulfuric acid ester radical. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Examples of this group of synthetic detergents which form a part of the preferred detergent compositions of the present invention are the ammonium alkyl sulfates, especially those obtained by sulfating the higher C.sub.8-18 alcohols produced by reducing the glycerides of tallow or coconut oil; alkali or ammonium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383 (especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl groups is about 13 carbon atoms abbreviated hereinafter as C.sub.13 LAS); sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; alkali or ammonium salts of alkyl phenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 8 to about 12 carbon atoms.

Anionic phosphate surfactants are also useful in the present invention. These are surface active materials having substantial detergent capability in which the anionic solubilizing group connecting hydrophobic moieties in an oxy acid of phosphorus. The more common solubilizing groups, of course, are --SO.sub.4 H, --SO.sub.3 H, and --CO.sub.2 H. Alkyl phosphate esters such as (R-O).sub.2 PO.sub.2 H and ROPO.sub.3 H.sub.2 in which R represents an alkyl chain containing from about 8 to about 20 carbon atoms are useful.

These esters can be modified by including in the molecule from one to about 40 alkylene oxide units, e.g., ethylene oxide units. Formulae for these modified phosphate anionic detergents are ##EQU2## or ##EQU3## in which R represents an alkyl group containing from about 8 to 20 carbon atoms, or an alkylphenyl group in which the alkyl group contains from about 8 to 20 carbon atoms, and M represents a soluble cation such as ammonium or substituted ammonium; and in which n is an integer from 1 to about 40.

Another class of suitable anionic organic detergents particularly useful in this invention includes salts of 2-acyloxy-alkane-1-sulfonic acids. These salts have the formula ##EQU4## where R.sub.1 is R.sub.1 = C.sub.n.sub.-1 --O--C, n being an integer from 9 to 23, or alkyl of about 9 to about 23 carbon atoms (forming with the two carbon atoms an alkane group); R.sub.2 is alkyl of 1 to about 8 carbon atoms; and M is a salt-forming radical.

The salt-forming radical M in the hereinbefore described structural formula is a water-solubilizing cation and can be, for example, an alkali metal cation (e.g. sodium, potassium, lithium), ammonium or substituted-ammonium cation. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethyl- ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.

Specific examples of beta-acyloxy-alkane-1-sulfonates, or alternatively 2-acyloxy-alkane-1-sulfonates, utilizable herein to provide superior cleaning levels under substantially neutral washing conditions include the sodium salt of 2-acetoxy-tridecane-1-sulfonic acid; the potassium salt of 2-propionyloxy-tetradecane-1-sulfonic acid; the lithium salt, of 2-butanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-pentanoyloxy-pentadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-hexadecane-1-sulfonic acid; the potassium salt of 2-octanoyloxy-tetradecane-1-sulfonic acid; the sodium salt of 2-acetoxy-heptadecane-1-sulfonic acid; the lithium salt of 2-acetoxy-octadecane-1-sulfonic acid; the potassium salt of 2-acetoxy-nonadecane-1-sulfonic acid; the sodium salt of 2-acetoxy-uncosane-1-sulfonic acid; the sodium salt of 2-propionyloxy-docosane-1-sulfonic acid; the isomers thereof.

Preferred beta-acyloxy-alkane-1-sulfonate salts therein are the alkali metal salts of beta-acetoxy-alkane-1-sulfonic acids corresponding to the above formula wherein R.sub.1 is an alkyl of about 12 to about 16 carbon atoms, these salts being preferred from the standpoints of their excellent cleaning properties and ready availability.

Typical examples of the above described beta-acetoxy alkanesulfonates are described in the literature: Belgium Pat. No. 650,323 issued July 9, 1963, discloses the preparation of certain 2-acyloxy alkanesulfonic acids. Similarly, U.S. Pat. Nos. 2,094,451 issued Sept. 28, 1937, to Guenther et. al. and 2,086,215 issued July 6, 1937 to DeGroote disclose certain salts of beta-acetoxy alkanesulfonic acids. These references are hereby incorporated by reference.

A preferred class of anionic organic detergents are the beta-alkyloxy alkane sulfonates. These compounds have the following formula: ##EQU5## where R.sub.1 is a straight chain alkyl group having from 6 to 20 carbon atoms, R.sub.2 is a lower alkyl group having from 1 to 3 carbon atoms, and M is a salt-forming radical hereinbefore described.

Specific examples of beta-alkyloxy alkane sulfonates or alternatively 2-alkyloxy-alkane-1-sulfonates, utilizable herein to provide superior cleaning levels under household washing conditions include:

potassium beta-methoxydecanesulfonate,

sodium beta-methoxy-tridecanesulfonate,

potassium beta-ethoxytetradecylsulfonate,

sodium beta-isopropoxyhexadecylsulfonate,

lithium beta-tertbutoxytetradecylsulfonate,

sodium beta-methoxyoctadecylsulfonate, and

ammonium beta-n-propoxydodecylsulfonate.

Other synthetic anionic detergents useful herein are alkyl ether sulfates. These materials have the formula RO(C.sub.2 H.sub.4 O).sub.x SO.sub.3 M wherein R is alkyl or alkenyl of about 10 to about 20 carbon atoms, x is 1 to 30, and M is a salt-forming cation defined hereinbefore.

The alkyl ether sulfates of the present invention are condensation products of ethylene oxide and monohydric alcohols having about 10 to about 20 carbon atoms. Preferably, R has 10 to 14 carbon atoms. The alcohols can be derived from fats, e.g., coconut oil or tallow, or can be synthetic. Lauryl alcohol and straight chain alcohols derived from coconut oil and tallow are preferred herein. Such alcohols are reacted with 1 to 30, and especially 1 to 12 molar proportions of ethylene oxide and the resulting mixture of molecular species, having, for example, an average of 1 or 12 moles of ethylene oxide per mole of alcohol, is sulfated and neutralized.

Specific examples of alkyl ether sulfates of the present invention are ammonium coconut alkyl ethylene glycol ether sulfate; ammonium tallow alkyl triethylene glycol ether sulfate; and sodium tallow alkyl hexaoxyethylene sulfate.

Preferred herein for reasons of excellent cleaning properties and ready availability are the ammonium coconut- and tallow-alkyl oxyethylene ether sulfates having an average of about 1 to about 12 oxyethylene moieties. The alkyl ether sulfates of the present invention are known compounds and are described in U.S. Pat. No. 3,332,876 to Walker (July 25, 1967) incorporated herein by reference.

Additional examples of anionic non-soap synthetic detergents which come within the terms of the present invention are the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; ammonoum or substituted ammonium salts of fatty acid amide of methyl tauride in which the fatty acids, for example, are derived from coconut oil. Other anionic synethetic detergents of this variety are set forth in U.S. Pat. Nos. 2,486,921; 2,486,922; and 2,396,278.

Additional examples of anionic, non-soap, synthetic detergents, which come within the terms of the present invention, are the compounds which contain two anionic functional groups. These are referred to as di-anionic detergents. Suitable di-anionic detergents are the disulfonates, disulfates, or mixtures thereof which may be represented by the following formulae:

R(so.sub.3).sub.2 m.sub.2,

r(so.sub.4).sub.2 m.sub.2,

r(so.sub.3)(so.sub.4)m.sub.2

where R is an acyclic aliphatic hydrocarbyl group having 15 to 20 carbon atoms and M is a water-solubilizing cation, for example, the C.sub.15 to C.sub.20 disodium 1,2-alkyldisulfates, C.sub.15 to C.sub.20 dipotassium-1,2-alkyldisulfonates or disulfates, disodium 1,9-hexadecyl disulfates, C.sub.15 to C.sub.20 disodium-1,2-alkyldisulfonates, disodium 1,9-stearyldisulfates and 6,10-octadecyldisulfates.

The aliphatic portion of the disulfates or disulfonates is generally substantially linear, desirable, among other reasons, because it imparts desirable biodegradable properties to the detergent compound.

The water-solubilizing cations include the customary cations known in the detergent art, i.e., the alkali metals, and the alkaline earth metals, as well as other metals in group IIA, IIB, IIIA, IVA and IVB of the Periodic Table except for Boron. The preferred water-solublizing cations are ammonium or substituted ammonium. These dianionic detergents are more fully described in British Letters Pat. No. 1,151,392 which claims priority on an application made in the U.S. Pat. (No. 564,566) on July 12, 1966.

Other suitable anionic detergents utilizable herein are olefin sulfonates having about 12 to about 24 carbon atoms. The term "olefin sulfonates" is used herein to mean compounds which can be produced by the sulfonation of alpha-olefin by means of sulfur trioxide, followed by neutralization of the acid reaction mixture in conditions such that any sultones which have been formed in the reaction are hydrolyzed to give the corresponding hydroxy-alkanesulfonates. The sulfur trioxide may be liquid or gaseous, and is usually, but not necessarily, diluted by inert diluents, for example, by liquid SO.sub.2, chlorinated hydrocarbon, etc., when used in the liquid form, or by air, nitrogen, gaseous SO.sub.2, etc., when used in the gaseous form.

The alpha-olefins from which the olefin sulfonates are derived are mono-olefins having 12 to 24 carbon atoms, preferably 14 to 16 carbon atoms. Preferably, they are straight chain olefins. Examples of suitable 1-olefins include 1-dodecene; 1-tetradecene; 1-hexadecene; 1-octadecene; 1-eicosene and 1-tetracosene.

In addition to the true alkene sulfonates and a proportion of hydroxy-alkanesulfonates, the olefin sulfonates can contain minor amounts of other materials, such as alkene disulfonates depending upon the reaction conditions, proportions of reactants, the nature of the starting olefins and impurities in the olefin stock and side reactions during the sulfonation process.

A specific anionic detergent which has also been found excellent for use in the present invention is described more fully in the U.S. Pat. No. 3,332,880 of Phillip F. Pflaumer and Adriaan Kessler, issued July 25, 1967, titled Detergent Composition, the disclosure of which is herein incorporated by reference.

Specific preferred anionic surfactants include ammonium linear alkyl benzene sulfonate wherein the alkyl chain averages from about 10 to 18, more preferably about 12, carbon atoms in length; the sodium salt of alkyl glyceryl sulfonate whereby the alkyl groups contains from about 8 to about 20, preferably from about 10 to about 16 carbon atoms in length; ammonium 2-acetoxy-tridecane-1-sulfonic acid; ammonium .beta.-methoxyoctadecylsulfonate; the ammonium salts of the sulfonated condensation product of C.sub.10-20 fatty alcohols with from 1 to 10 moles of ethylene oxide, preferably averaging from 1 to 4 moles of ethylene oxide. Highly preferred are the ammonium salts of sulfonated condensation products of coconut fatty alcohols with 3 moles of ethylene oxide.

B. Nonionic Synthetic Detergents

Nonionic synthetic detergents may be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of "Pluronic." These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility, has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include:

1. The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

2. Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. For example, compounds containing from about 40% to about 80% polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene oxide, said base having a molecular weight of the order of 2,500 and 3,000, are satisfactory.

3. The condensation product of aliphatic alcohols having from 8 to 22 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 1 to 12 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

4. Nonionic detergents include nonyl phenol condensed with either about 10 or about 30 moles of ethylene oxide per mole of phenol and the condensation products of coconut alcohol with an average of either about 5.5 or about 15 moles of ethylene oxide per mole of alcohol and the condensation product of about 15 moles of ethylene oxide with one mole of tridecanol.

Other examples include dodecylphenol condensed with 12 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 15 moles of ethylene oxide per mole of phenol; dodecyl mercaptan condensed with 10 moles of ethylene oxide per mole of mercaptan; bis-(N-2-hydroxyethyl) lauramide; nonyl phenol condensed with 20 moles of ethylene oxide per mole of nonyl phenol; myristyl alcohol condensed with 10 moles of ethylene oxide per mole of myristyl alcohol; lauramide condensed with 15 moles of ethylene oxide per mole of lauramide; and di-isooctylphenol condensed with 15 moles of ethylene oxide.

5. A detergent having the formula

R.sup.1 R.sup.2 R.sup.3 N.fwdarw.O

oxide detergent) wherein R.sup.1 is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R.sup.1 which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each R.sup.2 and R.sup.3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms;

Specific examples of amine oxide detergents includes: dimethyldodecylamine oxide, dimethyltetradecylamine oxide, ethylmethyltetradecylamine oxide, cetyldimethylamine oxide, dimethylstearylamine oxide, cetylethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis-(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyloleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, and the corresponding decyl, hexadecyl and octadecyl homologs of the above compounds.

6. A detergent having the formula R.sup.1 R.sup.2 R.sup.3 P.fwdarw.O

(phosphine oxide detergent) wherein R' is an alkyl group containing from about 10 to about 28 carbon atoms, from 0 to about 2 hydroxy groups and from 0 to about 5 ether linkages, there being at least one moiety of R' which is an alkyl group containing from about 10 to about 18 carbon atoms and 0 ether linkages, and each of R.sup.2 and R.sup.3 are selected from the group consisting of alkyl radicals and hydroxyalkyl radicals containing from 1 to about 3 carbon atoms.

Specific examples of the phosphine oxide detergents include: dimethyldodecylphosphine oxide, dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, cetyldimethylphosphine oxide, dimethylstearylphosphine oxide, cetylethylpropylphosphine oxide, diethyldodecylphosphine oxide, diethyltetradecylphosphine oxide, dipropyldodecylphosphine oxide, bis(hydroxymethyl)dodecylphosphine oxide, bis-(2-hydroxyethyl)-dodecylphosphine oxide, (2-hydroxypropyl)methyltetradecylphosphine oxide, dimethyloleylphosphine oxide, and dimethyl-(2-hydroxydodecyl)phosphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.

7. A detergent having the formula ##EQU6## (sulfoxide detergent) wherein R.sup.1 is an alkyl radical containing from about 10 to about 28 carbon atoms, from 0 to about 5 ether linkages and from 0 to about 2 hydroxyl substituents at least one moiety of R.sup.1 being an alkyl radical containing 0 ether linkages and containing from about 10 to about 18 carbon atoms, and wherein R.sup.2 is an alkyl radical containing from 1 to 3 carbon atoms and from one to two hydroxyl groups; octadecyl methyl sulfoxide, dodecyl methyl sulfoxide, tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 3-methoxytridecyl methyl sulfoxide, e-hydroxy-4-dodecoxybutyl methyl sulfoxide, octadecyl 2-hydroxyethyl sulfoxide, dodecylethyl sulfoxide.

Of all the above-described types of nonionic surfactants, preferred nonionic surfactants include the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide per mole of nonyl phenol, the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide per mole of coconut fatty alcohol, and the condensation product of a secondary fatty alcohol containing about 15 carbon atoms with about 9 moles of ethylene oxide per mole of fatty alcohol. Particularly preferred are amine oxide detergents containing one alkyl group with from about 10 to about 28 carbon atoms and two alkyl or hydroxyalkyl radicals containing from 1 to about 3 carbon atoms. Highly preferred is coconut dimethyl amine oxide.

C. Ampholytic Synthetic Detergents

Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato. Examples of compounds falling within this definition are sodium 3-(dodecylamino)-propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)-propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.

D. Zwitterionic Synthetic Detergents

Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium and phosphonium or tertiary sulfonium compounds, in which the cationic atom may be part of a heterocyclic ring, and in which the aliphatic radical may be straight chain or branched, and wherein one of the aliphatic substituents contains from about 3 to 18 carbon atoms, and at least one aliphatic substituent contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono. Examples of compounds falling within this definition are 3-(N,N-dimethyl-N-hexadecyl-ammonio)-2-hydroxypropane-1-sulfonate, 3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate, 2-(N,N-dimethyl-N-dodecylammonioum)acetate, 3-(N,N-dimethyl N-dodecylammonio)propionate, 2-(N,N-dimethyl-N-octadecylammonio)-ethyl sulfate, 2-(trimethylammonio)ethyl dodecylphosphonate, ethyl 3-(N,N-dimethyl-N-dodecylammonio)propylphosphonate, 3-(P,P-dimethyl-P-dodecylphosphonio)-propane-1-sulfonate, 2-(S-methyl-S-tert.hexadecyl-sulfoniol)ethane-1-sulfonate, 3-(S-methyl-S-dodecylsulfonio)propionate, sodium 2-(N,N-dimethyl-S-dodecylammonio)ethyl phosphonate, 4-(S-methyl-S-tetradecylsulfonio)butyrate, 1-(2-hydroxyethyl)-2-undecylimidazolium-1-acetate, 2-(trimethylammonio)octadecanoate, and 3-(N,N-bis-(2-hydroxyethyl)-N-octodecylammonio)-2-hydroxypropane-1-sulfona te. Some of these detergents are described in the following U.S. Pat. Nos. 2,129,264; 2,178,353; 2,774,786; 2,813,898; and 2,828,332.

Of all the above-described types of zwitterionic surfactants, preferred compounds include 3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; (N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and (N,N-dimethyl-N-hexadecylammonio)acetate.

As an additional essential ingredient, the compositions of the instant invention comprise from about 2% to about 30%, preferably from about 5% to about 20% of an organic sequestering builder. Said organic sequestering builders can be selected from a wide variety of organic sequestering builders which are known to be suitable for use in detergent compositions.

Suitable alkaline organic builder salts include the alkali metal, ammonium and substituted ammonium salts of polyacetates and polycarboxylates.

The polyacetate builder salts suitable for use herein include the sodium, potassium, lithium, ammonium, and subsituted ammonium salts of the following acids: ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylene diaminetriacetic acid, N-(2-hydroxyethyl)-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetraacetic acid and nitrilotriacetic acid. The alkali metal and ammonium salts of the above acids are generally and preferably utilized herein.

The polycarboxylate builder salts suitable for use herein consist of water-soluble salts of polymeric aliphatic polycarboxylic acids selected from the group consisting of

a. Water-soluble salts of homopolymers of aliphatic polycarboxylic acids having the following empirical formula: ##EQU7## wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl, at least one of X, Y, and Z being selected from the group consisting of carboxyl and carboxymethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl, and wherein n is a whole integer having a value within a range, the lower limit of which is three and the upper limit of which is determined by the solubility characteristics in an aqueous system;

b. Water-soluble salts of copolymers of at least two of the monomeric species having the empirical formula described in (a), and

c. Water-soluble salts of copolymers of a member selected from the group of alkylenes and monocarboxylic acids with the aliphatic polycarboxylic compounds described in (a), said copolymers having the general formula: ##EQU8## wherein R is selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl, and carboxyethyl; wherein only one R can be methyl; wherein m is at least 45 mole percent of the copolymer; wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, and carboxymethyl; at least one of X, Y, and Z being selected from the group of carboxyl and carboxymethyl provided that X and Y can be carboxymethyl only when Z is selected from the group of carboxyl and carboxymethyl, wherein only one of X, Y, and Z can be methyl and wherein n is a whole integer within a range, the lower limit of which is three and the upper limit of which is determined primarily by the solubility characteristics in an aqueous system; said polyelectrolyte builder material having a minimum molecular weight of 350 calculated as the acid form and an equivalent weight of about 50 to about 80, calculated as the acid form, (e.g. polymers of itaconic acid; aconitic acid; maleic acid; mesaconic acid; fumaric acid; methylene malonic acid; and citraconic acid and copolymers with themselves and others compatible monomers such as ethylene). These polycarboxylate builder salts are more specifically described in U.S. Pat. No. 3,308,067, issued Mar. 7, 1967 to Francis L. Diehl entitled "Polyelectrolyte Builders and Detergent Compositions."

Additional organic sequestering builder ingredients suitable for being used in the compositions of this invention encompass the water-soluble salts of oxydisuccinic acid; (ethylene dioxide)-diacetic acid; mellitic acid; ether alone or in admixture with nitrilotriacetic acid; benzene carboxylic acids; and particularly pentacarboxylic acid; heterogeneously substituted monoaryl builders such as the water-soluble salts of: polyfunctionally substituted aromatic acid sequestering agents as disclosed in U.S. Pat. Ser. No. 102,159 of Dec. 28, 1970 and now U.S. Pat. No. 3,812,044; homogeneously polyfunctionally substituted aromatic acids as disclosed in U.S. Pat. Ser. No. 102,158 of Dec. 28, 1970 and now U.S. Pat. No. 3,758,420; polyfunctional naphthalene-based sequestrants as disclosed in U.S. Pat. Ser. No. 102,236 of Dec. 28, 1970 and now abandoned; polyfunctional anthracene based sequestrants as disclosed in U.S. Pat. Ser. No. 102,156 of Dec. 28, 1970; polyfunctional phenanthrene-based sequestrants as disclosed in U.S. Pat. Ser. No. 102,169 of Dec. 28, 1970 and now abandoned; polyfunctional bi-aryl sequestrants with separated aromatic nuclei as disclosed in U.S. Pat. Ser. No. 102,048 of Dec. 28, 1970 and now abandoned; polyfunctional tri-aryl sequestrants with separated aromatic nuclei as disclosed in U.S. Pat. Ser. No. 102,051 of Dec. 28, 1970 and now abandoned; and polyfunctional monoaryl sequestrants containing at least two carboxylic groups and one alkyl, halogen or sulfo group as disclosed in U.S. Pat. No. 102,050 of Dec. 28, 1970 and now abandoned.

The preferred organic sequestering builders for use in the compositions of the instant invention include the water-soluble salts of mellitic acid, polyacrylic acid, benzene pentacarboxylic acid, and nitrilotriacetic acid. Particularly preferred are the water-soluble salts of citric acid. For the purpose of this invention, water-soluble salts stands for neutralization product with alkali matter, ammonium and substituted ammonium neutralizing agents. Specific examples of the like neutralizing agents include sodium, potassium, lithium, and ammonium and triethanolamine.

Another essential ingredient for use in the liquid detergent compositions of the present invention is a phase modifier surfactant ingredient selected from the group consisting of water-soluble salts of sulfonated C.sub.8-22 fatty acids; and polyfunctional anionic surface-active agents derived from succinic acid. It can be noted that the phase modifier surfactant ingredients belong to the broad class of anionic surfactants. However, for the purpose of this invention there is a non-equivalency between said phase modifier surfactant ingredients and the anionic portion of said component (a) surfactants. Mixtures of these ingredients can as well be used. This anionic phase modifier surface-active agent is incorporated in an amount of from 2% to about 25%, preferably from about 4% to about 15%.

The higher fatty acids suitable for preparing the sulfonates can be of any origin, i.e. natural or synthetic origin. They can be of branched or straight chain configuration. Especially in the event the sulfonated fatty acids are from natural origin, they constitute a mixture of different chain lengths, although the fatty acid raw material can conceivably be of a substantially uniform chain length. Sulfonated fatty acids are well known in the art of detergent technology and different techniques are available for preparing these surface-active agents. As an example, they can be made by sulfonation of fatty acids with sulfurtrioxide whereby the reaction is carried out in a liquid solvent, for instance, as described in British Patent specification No. 1,214,714. Another well-known procedure resides in the use of gaseous, inert gas diluted, sulfurtrioxide for the purpose of preparing said sulfonated fatty acids. Examples of sulfonated fatty acids compounds suitable for being used in the compositions of this invention include the mono- and di-ammonium salts of the sulfonation products derived from fatty acids including those with 8, 10, 12, 14, 16, 18, 20 and 22 carbon atoms. Synthetic fatty acids having an odd number of carbon atoms in the range of from 8 to 22 can obviously as well be used. Preferred for use in the instant compositions are sulfonated fatty acids derived from natural sources such as hydrogenated "coconut oil." The latter term refers to a mixture of fatty acids having an approximate carbon chain length distribution of 8% C.sub.8 ; 7% C.sub.10 ; 48% C.sub.12 ; 17% C.sub.14 ; 9% C.sub.16 ; and 11% C.sub.18. Fatty acids derived from the other natural sources such as kernel oil, babassu kernel oil and tallow oil constitute additional examples of a preferred starting material for the fatty acids. Highly preferred for use in the compositions of the instant invention are salts of .alpha.-sulfonated fatty acids having from 14 to 18, especially 16 carbon atoms in the fatty acid starting material.

Specific examples suitable for being used include the water-soluble mono- and di-salts of:

.alpha.-sulfo-stearic acid,

.alpha.-sulfo-palmitic acid,

.alpha.-sulfo-myristic acid,

.alpha.-sulfo-lauric acid,

.alpha.-sulfo-decanoic acid,

.alpha.-sulfo-octanoic acid,

sulfo fatty acids derived from hydrogenated coconut fatty acid having the following carbon chain length distribution:

stearic -- 27%

palmitic --9%

myristic --17%

lauric --48 %

decanoic --7%

octanoic --8%

sulfo fatty acids derived from tallow fatty acids.

The water-soluble mono- and di-salts can be represented by alkali ions such as lithium, potassium, sodium, ammonium and substituted ammonium ions. Preferred are the sodium and ammonium salts because of ready availability.

The polyfunctional anionic surface-active agents derived from succinic acid are used in an amount of from about 2 to about 25%, preferably from about 4 to about 15%. They can be described by the general formula ##EQU9## wherein R.sub.1 represents an alkyl group having from 3 to 20 carbon atoms; R.sub.2 represents hydrogen or a C.sub.1-4 alkyl group, R.sub.3 represents hydrogen, C.sub.1-4 alkyl or --OH, whereby the total number of carbon atoms of R.sub.2 and R.sub.3 is at most 4; X represents --O--; --S--; --SO--; --SO.sub.2 --; or --SCH.sub.2 --: and whereby M is a water-soluble cation. Specific examples suitable for being used include the water-soluble mono- or di-salts of

n-tetradecylthio succinic acid;

n-dodecylthiosuccinic acid;

.alpha.-hexadecylthio-.alpha.-methyl-.beta.-ethyl succinic acid;

.alpha.-dodecyloxy-.beta.-hydroxy succinic acid;

.alpha.-dodecylsulfoxy-.beta.-ethyl succinic acid;

n-dodecylsulfonyl succinic acid;

.alpha.-n-hexadecylsulfoxy-.beta.-hydroxy succinic acid;

n-hexadecylthiomethyl succinic acid;

n-octyl thio succinic acid;

n-dodecyl thiomethyl succinic acid;

butyloxy-.alpha.-methyl -.beta.-propyl succinic acid;

octadecylthio-.beta.-hydroxy succinic acid;

The water-soluble mono- and di-salts can be represented by alkali ions such as lithium, potassium, sodium, ammonium and substituted ammonium ions. Preferred are the sodium and ammonium salts because of ready availability.

Preferred for use in the compositions of this invention are the succinic acid derivatives wherein R.sub.1 represents a C.sub.6 -C.sub.18 alkyl group, R.sub.2 is hydrogen, and R.sub.3 is hydrogen or --OH. Especially preferred for use in the instant compositions are the succinic acid derivatives specified in the preceding sentence whereby X stands S.

The homogenous, preferably clear, liquid detergent compositions of this invention can contain, in addition to the essential ingredients, also minor amounts of usual liquid detergent composition additives which may serve different well-known purposes. Examples of the like additives include perfumes, dyes, brightening agents, suds controlling agents such as suds boosters and suds depressors, hydrotropes, enzymes, activators and stabilizing agents for said enzymes, opacifiers, bleaches such as chlorine and oxygen bleaches, and buffers. Particularly well-known among these additives are hydrotropes. They can be used in an amount of up to 15% by weight and can be represented by lower alcohols such as ethanol, propanol and isopropanol, and water-soluble alkaline and ammonium salts of toluene sulfonate, xylene sulfonate, benzene sulfonate and cumene sulfonate. The quantitative and qualitative choice of said hydrotropes for use in the preferred compositions of this invention can easily be determined and depends obviously on the nature of the ingredients selected for use in a particular homogeneous liquid detergent composition as well as their relative amounts.

For obtaining the advantages of the compositions of the instant invention, the weight ratio of the component (b) water-soluble organic sequestering builder to the component (c) polyanionic ingredient shall be from about 6:1 to about 1:6 and preferably from about 3:1 to about 1:3. The detergent compositions of the instant invention having a weight ratio of component (b) to component (c) outside the 6:1 to 1:6 ratio have a tendency toward phase separation particularly during prolonged storage.

The following liquid detergent compositions were prepared by mixing the individual ingredients.

Composition Examples Ingredients A I II ______________________________________ Ammonium salt of sul- fated condensation product of middle- cut coconut alcohol, average chain length C.sub.12, with 3 moles of ethylene oxide 25 25 29 Sodium C.sub.10.sub.-14, alkyl, average chain length C.sub.12, glyceryl ether sulfonate 4 4 -- C.sub.10.sub.-14 alkyl, average chain length C.sub.12, di- methyl amine oxide 5 5 5 Ammonium salt of .alpha.- sulfopalmitic acid -- -- 10 Ammonium citrate 20 10 10 Disodium dodecylthio- succinate -- 10 -- Minor ingredients and moisture balance to 100 ______________________________________

Upon storage, the Composition A composition representing the state of the art was subject to phase separation whereas the compositions of the instant invention -- Examples I and II -- remained unchanged, i.e. homogeneous clear liquid compositions.

A composition of this invention -- Example I -- was used for comparative testing purposes by reference to liquid prior art detergent compositions having the following formulas:

Compositions Ingredient B C ______________________________________ Ammonium salt of sulfated condensation product of middle-cut coconut alcohol, average chain length C.sub.12, with 3 moles of ethoxylene oxide 29 25 Sodium, C.sub.10.sub.-14 alkyl, average chain length C.sub.12, glyceryl ether sulfonate -- 4 Coconut, average C.sub.12, dimethyl amine oxide 5 5 Ammonium salt of .alpha.-sulfopalmitic acid 10 -- Disodium dodecylthio- succinate -- 10 Minor ingredients and moisture balance to 100 ______________________________________

Four aluminum and four stainless steel metal strips were soiled with a mixture of whole milk and commercial gravy and sauce mixtures containing a broad range of soils, appearing in food soils, and allowed to dry. Subsequently said soiled metal strips were treated with an aqueous solution containing the liquid detergent compositions to be tested.

Testing conditions:

Water hardness:7 U.S. grains/U.S. gallon(molar ratio Ca/Mg = 3/1)

Product concentration in dishwashing solution:0.6%

Treatment:The soiled metal strips were placed in the detergent solution at a temperature of 120.degree.F. for 11/2 minutes. At the end of that time, the strips were three times withdrawn and redipped in the soaking solution to eliminate loosened soil. Thereafter the strips were allowed to dry. The soil removal was estimated by comparing the test strips versus standards. The grading was done by an experienced judge who used a scale from 1 to 10 whereby 1 stands for the soil removed obtained from soaking in plain water and 10 represents the perfectly clean strip.

The results were as follows:

Composition Used Soil Removal Grade ______________________________________ B 3.9 C 4.1 Example I 5.9 ______________________________________

The above confirms that the composition of the instant invention, Example I, outperforms prior art Compositions B and C with respect to broad spectrum soil removal. These differences are significant and noticeable to untrained observers.

The compositions of Examples I and II, wherein the .alpha.-sulfopalmitic acid salt and the ammonium citrate (Example IV) and the sodium dodecyl thiosuccinate and the ammonium citrate (Example III) have been reduced from 10% to 5% respectively, have been compared with Composition D, which is identical to Composition A, except that it contains but 10% of ammonium citrate. Egg yolk was applied to twelve aluminum strips for each composition or example which were allowed to dry over night. Two soiled strips were then treated under six different conditions, namely with detergent solutions containing respectively 1% and 2% of the compositions during 1, 2 and 5 minutes.

At the end of the soaking time, the metal strips were three times withdrawn and redipped into the solution in order to insure the loosened soils are eliminated. The soil removal performance was determined by paired comparison (Round Robin design) whereby the more positive score reflects a greater soil removal. The testing results are as follows:

Composition Used Stain Removal ______________________________________ Example III + .68 Example IV - .01 Composition D -1.33 ______________________________________

The above results confirm that the soil removal resulting from the use of prior art Composition D is markedly inferior to what is obtained from the use of the compositions of Examples III and IV as representing the instant invention. These differences are discernible to an inexperienced observer.

A liquid detergent composition representative of the instant invention was used for soil removal test concurrently with a liquid detergent composition belonging to the state of the art. Said compositions had the following formula:

Composition Example Ingredient E V ______________________________________ Ammonium salt of .alpha.-sulfo- palmitic acid 15% 15% Sodium, C.sub.10.sub.-14 alkyl, average chain length C.sub.12, glyceryl ether sulfonate 5% 5% Ammonium salt of the sulfation product of coconut alcohol with 3 moles of ethylene oxide 10% 10% C.sub.10.sub.-14 alkyl, average chain length C.sub.12, di- methyl amine oxide 5% 5% Ammonium citrate -- 10% ______________________________________

Three aluminum strips were dipped into a liquid soil consisting essentially of a slurry of hamburger and water. Said metal strips are then baked at 400.degree.F in order to have the soil adhering more solidly. Aqueous dishwashing solutions containing 1% of the compositions of Composition E and Example V, are used for stain removal. To that effect, the strips are soaked for one hour at 130.degree.F. The water hardness is 7 U.S. grains/U.S. gallon. The metal strips are then removed and rinsed under running water at 120.degree.F. The grading of the soil removed is then done with a 1 - 10 scale as referred to previously. The soil removal results are as follows:

Composition Used Soil Removal ______________________________________ Example V 6.7 Composition E 1.0 ______________________________________

Substantially similar results can be obtained in the event the alkyl glyceryl ether sulfonate and/or the amine oxide of Example V is wholly or partially substituted by an equivalent amount of ammonium linear alkyl benzene sulfonate wherein the chain length averages from about 10 - 18, more preferably about 12 carbon atoms in length; ammonium 2-acetoxy-tridecane-1-sulfonate; ammonium b-methoxyoctadecylsulfonate; and the ammonium salts of the sulfonated condensation products of C.sub.10-20 fatty alcohols with from 1 - 10 moles of ethylene oxide.

Substantially similar results are also obtained in the event the water-soluble organic detergents are replaced with an equivalent quantity of the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide, the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide, and the condensation product of a secondary fatty alcohol containing 15 carbon atoms with about 9 moles of ethylene oxide.

Substantially similar results can be also obtained by replacing, wholly or partially, the water-soluble organic detergents with an equivalent quantity of 3(N,N-dimethyl-N-alkylammonio)-propane-1sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length; 3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; (N-dodecylbenzyl-N,N-dimethylammonio)acetate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate; 6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate; and (N,N-dimethyl-N-hexadecylammonio)acetate.

Substantially similar results are obtained in the event ammonium citrate is replaced with an equivalent amount of ammonium salts of mellitic acid, polyacrylic acid; benzene pentacarboxylic acid; and nitrilotriacetic acid.

Substantially similar results are also obtained in the event the ammonium salts of .alpha.-sulfopalmitic acid is replaced with an equivalent quantity of substituted ammonium salts of sulfonated fatty acids whereby the fatty acids are represented by coconut, kernel, babassu kernel and tallow fatty acids and mixtures thereof.

Substantially similar results are also obtained in the event the ammonium .alpha.-sulfopalmitic acid is replaced by a water-soluble ammonium or substituted ammonium salt of succinic acid derivatives of the general formula of claim 1 wherein R.sub.1 represents an alkyl chain having from 6-18 carbon atoms; R.sub.2 is hydrogen; and R.sub.3 is hydrogen or OH.

Claims

What is claimed is:

1. A homogeneous liquid detergent composition particularly suitable for the removal of food soils consisting essentially of:

a. from about 3% to about 40% by weight of a water-soluble organic detergent selected from the group consisting of sodium C.sub.8-20 alkyl glyceryl sulfonate; ammonium 2-acetoxy-tridecane-1-sulfonate; ammonium .beta.-methoxyoctadecyl-sulfonate; the ammonium salt of sulfated condensation product of C.sub.10-20 fatty alcohol with from 1 to 10 moles of ethylene oxide; the condensation product of nonyl phenol with about 9.5 moles of ethylene oxide; the condensation product of coconut fatty alcohol with about 6 moles of ethylene oxide; the condensation product of a secondary fatty alcohol containing about 15 carbon atoms with about 9 moles of ethylene oxide; 3(N,N-dimethyl-N-alkylammonio)-propane-1-sulfonate and 3(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1-sulfonate wherein in both compounds the alkyl group averages 14.8 carbon atoms in length;

3(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate; 3(N,N-dimethyl-N-hexadecylammonio)-2-hydroxypropane-1-sulfonate; 3-(N-dodecylbenzyl-N,N-dimethylammonio)-propane-1-sulfonate; (N-dodecylbenzyl-N,N-dimethylammonio)-acetate;

3-(N-dodecylbenzyl-N,N-dimethylammonio)propionate;

6-(N-dodecylbenzyl-N,N-dimethylammonio)hexanoate;

(N,N-dimethyl-N-hexadecylammonio)acetate;

and mixtures thereof;

b. from about 2% to about 30% by weight of a water-soluble organic sequestering builder;

c. from about 2% to about 25% by weight of a phase modifier surfactant ingredient selected from the group consisting of water-soluble salts of

i. sulfonated C.sub.8 - C.sub.22 fatty acids;

ii. compounds of the general formula ##EQU10## wherein R.sub.1 represents an alkyl group having from 3 to 20 carbon atoms;

R.sub.2 represents hydrogen or a C.sub.1-4 alkyl group, R.sub.3 stands for hydrogen,

C.sub.1-4 alkyl or -OH, whereby the total number of carbon atoms of R.sub.2 and R.sub.3 is at most 4; X represents --O--; --S--; --SO--; --SO.sub.2 --; or --SCH.sub.2 --; M is a water-soluble cation; and

iii. mixtures thereof;

whereby the ratio of component (b) to component

c. is from about 3:1 to about 1:3;

and

d. the balance to 100% being water.

2. The liquid detergent composition in accordance with claim 1 wherein the component (a) water-soluble organic detergent is present in an amount from about 5% to about 25% by weight.

3. The liquid detergent composition in accordance with claim 2 wherein the Component (b) water-soluble organic sequestering builder is present in an amount from about 5% to about 20% by weight.

4. The liquid detergent composition in accordance with claim 3 wherein the Component (c) ingredient is present in an amount from about 4% to about 15% by weight.

5. The liquid detergent composition in accordance with claim 4 wherein the Component (b) water-soluble organic sequestering builder is selected from the group consisting of the water-soluble salts of mellitic acid; polyacrylic acid; benzene pentacarboxylic acid and nitrilotriacetic acid.

6. The liquid detergent composition in accordance with claim 4 wherein the fatty acids of the Component (c) (i) water-soluble salts of sulfonated fatty acids are selected from the group consisting of coconut, kernel, babassu kernel, and tallow fatty acids and mixtures thereof.

7. The liquid detergent composition in accordance with claim 4 wherein the Component (c) (ii) ingredient is selected from the general formula of claim 1 wherein R.sub.1 represents an alkyl group having from 6 - 18 carbon atoms; R.sub.2 is hydrogen; and R.sub.3 is hydrogen or OH.

8. The liquid detergent composition in accordance with claim 7 wherein the Component (a) water-soluble organic detergent is selected from the group consisting of sodium C.sub.10-16 alkyl glyceryl sulfonate; the ammonium salt of sulfated condensation products of coconut fatty alcohol with 3 moles of ethylene oxide; and dodecyl dimethylamine oxide.

9. The liquid detergent composition in accordance with claim 6 wherein the Component (a) water-soluble organic detergent is selected from the group consisting of sodium C.sub.10-16 alkyl glyceryl sulfonate; the ammonium salt of sulfated condensation products of coconut fatty alcohol with 3 moles of ethylene oxide; and dodecyl dimethylamine oxide.

10. The liquid detergent composition in accordance with claim 9 wherein Component (b) is ammonium citrate.

11. The liquid detergent composition in accordance with claim 6 wherein the Component (c) (i) is a water-soluble salt of C.sub.14-18 .alpha.-sulfonated fatty acids.

12. The liquid detergent composition in accordance with claim 11 wherein Component (b) is ammonium citrate.

13. The liquid detergent composition in accordance with claim 10 whereby in Component (c) (ii) X stands for S.

14. The liquid detergent composition in accordance with claim 4 which also contains up to 15% by weight of a hydrotrope selected from the group consisting of ethanol, n-propanol, isopropanol, water-soluble alkali metal and ammonium salts of toluene sulfonic acid, benzene sulfonic acid, xylene sulfonic acid, cumene sulfonic acid and mixtures thereof.