US3346504A

US3346504A - Detergent compositions

Info

Publication number: US3346504A
Application number: US547117A
Authority: US
Inventors: Kenneth W Herrmann
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1962-08-10
Filing date: 1966-03-25
Publication date: 1967-10-10
Anticipated expiration: 1984-10-10
Also published as: GB1049732A; GB1049734A; GB1049733A; FI41315B; NL6511600A; BE674561A; GB1049735A; GB1049736A; NL6511599A; DE1467652A1; BE674560A

Description

Oct. 10, 1967 K. w. HERRMANN 3,345,504

DETERGENT COMPOSITIONS Filed March 25, 1966 2 Sheets-Sheet. 1

Temperature Melting Tw Point Surfactant in Water Fig. I

Surfactant 2 nd Isotropic Solution Lye Electrolyte Fig. 2

Kenneth W. Herrmann INVENTOiR.

WCwiiu ATTORNEY Oct. 10, 1967 K. w. HERRM ANN 3 DETERGENT COMPOSITIONS Filed March 25, 1966 r 2 Sheets-Sheet 2 Mesomorphic Phase (Middle or Neat) Surfactant Electrolyte Crystals Solubillzing Electrolyte Fig. 3

Kenneth W. Herrmunn INVENTOR.

BYW

ATTORNEY United States Patent 3,346,504 DETERGENT COMPOSITIONS Kenneth W. Herrrnann, Greenhills, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Filed Mar. 25, 1966, Ser. No. 547,117 11 Claims. (Cl. 252137) This application is a continuation-in-part of copending application Ser. No. 421,141, now abandoned, filed Dec. 14, 1964, which is a continuation-in-part of copending applications Ser. No. 291,528, filed June 28, 1963, now abandoned, and Ser. No. 216,119, filed Aug. 10, 1962, now abandoned.

This invention relates to liquid detergent compositions. Specifically this invention relates to liquid detergent compositions containing certain detergent surfactants and certain solubilizing electrolytes.

The formulation of liquid detergent compositions is very complex. Ordinarily, it is desirable to keep inert ingredients at a minimum and yet it often becomes necessary to add some compound to the formula which has no active detergent effect or detergency builder effect merely to make the active ingredients compatible with each other and thereby create a homogeneous composition (i.e., a composition in which there is no bulk separation of a phase). It would therefore be desirable to provide, in liquid detergent compositions, effective, low cost solubilizing agents and solvents.

Accordingly, it is an object of this invention to provide homogeneous liquid detergent compositions.

It is a further and more specific object of this invention to provide such compositions containing solubilizing electrolytes and certain specific detergents.

The aqueous homogeneous liquid detergent compositions of this invention which achieve these objects comprise:

(I) From about 1% to about 40% by weight of the composition of a detergent selected from the group consisting of (A) A detergent having the formula (sultaine detergent) wherein R and R are each selected from the group consisting of hydrogen, methyl, and ethyl groups, R is a straight chain alkylene group containing from two to four carbon atoms, and having from 0 to one hydroxyl group substituted on a secondary carbon, and R is an alkyl chain of from about 10 to about 20 carbon atoms;

(B) A detergent having the formula R R R N O (amine oxide detergent) wherein R is selected from the group consisting of alkyl, alkylmonohydroxy, and alkoxy monohydroxypropyl radicals wherein the alkyl and alkoxy portions of said radicals contain from about to about 20 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;

(C) A detergent having the formula R' R R P O (phosphine oxide detergent) wherein R is selected from the group consisting of alkyl, and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;

(D) Nonionic detergents produced by condensing ethylene oxide on a hydrophobic base, e.g., a detergent havr 3,346,504 Patented Oct. 10, 1967 ing the formula R (C I-I O),,H (nonionic detergent) wherein R represents a hydrophobic base and preferably is selected from the group consisting of (1) alkoxy groups containing from about 8 to about 20 carbon atoms, (2) alkyl phenoxy groups (including dialkyl phenoxy groups) wherein the alkyl group contains from about 6 to about 18 carbon atoms, (3) condensation products of propylene glycol and propylene oxide with a molecular weight of from about 1500 to about 1800, (4) fatty amides containing from about 10 to about 20- carbon atoms, (5) higher alkyl mercaptans containing from about 10 to about 20 carbon atoms, (6) condensation products of propylene oxide and ethylene diamine constituting from about 20% to about 60% by weight of the finished nonionic detergent molecule and (7) condensation products of fatty alcohols containing from about 10 to about 20 carbon atoms and from about three to about 8 propylene oxide units, and wherein x is an integer from about 4 to about 30 for (1), (2), (4) and (5), but not less than about 0.4 of the number of carbon atoms in the hydrophobic base, and sufiiciently large to give the detergent a molecular weight of from about 2,000 to about 10,000 for (3), of from about 5,000 to about 11,000 for (6) and of from about 750 to about 1800 for (7) and wherein y is an integer equal to the number of ethylene oxide chains;

(E) A detergent having the formula (sulfoxide detergent) wherein R is an alkyl radical containing from about 10 to about 20 carbon atoms and contains from 0 to 1 hydroxyl substituents, and from 0 to five ether linkages;

(II) From 0% to about 40% by weight of the composition of a polyvalent electrolyte salt selected from the group consisting of sulfates; carbonates; pyrophosphates; phosphates; hexametaphosphates; ethylenediaminetetraacetates; N-(Z-hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N-(2-hydroxyethyl)-nitrilodiacetates; phytates; ethane-l-hydroxy 1,1 diphosphonates; methylene diphosphonates; ethylidene, isopropylidene, benzylmethylidene and chloromethylidene diphosphonates; salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and ethylene; and mixtures thereof, the cations of the above polyvalent electrolytes being selected from the group consisting of sodium, potassium, ammonium, triethanol ammonium, diethanol ammonium and monoethanol ammonium cations and mixtures thereof;

(III) From about 0.5% to about 20% by weight of the composition and sufficient to keep the composition homogeneous of solubilizing electrolytes having the formula wherein M is a water soluble cation (e.g., sodium, potassium, ammonium, and alkanolammonium cations) and R is selected from the group consisting of unsaturated aliphatic radicals containing from about 2 to about 7 .carbon atoms; aromatic, substituted aromatic, and aroelected from the group consisting of chloro, fluoro, and iitro groups and mixtures thereof; and phenyl alkyl 'adicals wherein the above phenyl radicals are attached alkylene radicals selected from the group consisting )f ethylene, propylene, butylene, pentylene, and hexylene groups; branched chain saturated aliphatic radicals conaining from about three to about six carbon atoms; and :hloro-substituted saturated and unsaturated aliphatic radicals containing from one to about carbon atoms; and

(IV) The balance substantially water, the composition Jeing substantially non-homogeneous when only Components I, II, and IV are present, the amount of Component [1 being no more than can be dissolved in the composition.

The solubilizing electrolyte, Component III, makes homogeneous those aqueous mixtures of Component 1, surfactant, and any polyvalent electrolyte, e.g., builder, present which otherwise would be nonhomogenous due to the presence of a bulk, separated phase, e.g., a crystalline phase, or a second immiscible isotropic liquid phase as hereinafter more fully described.

FIGURE 1 is a representative phase diagram for the sultaine detergents utilized in the compositions of this invention as hereinafter more fully discussed.

FIGURE 2 is a representative phase diagram for a detergent of the compositions of this invention and a typical detergency builder electrolyte at about room temperature (80 F).

FIGURE 3 is a representative phase diagram for a detergent of the compositions of this invention and a solubilizing electrolyte of the compositions of this invention at about room temperature (80 F.).

The first group (A) of the specific detergents, as hereinbefore described, will be referred tohereinafter as sultaines or sultaine detergents. These sultaines are solubilized, according to the instant invention, in an aqueous solution by the solubilizing electrolytes hereinbefore named. Sultaines of particular interest are those in which the long alkyl chain (R) is a mixture of alkyl chains derived from naturally occurring substances, whether hydrogenated or not, and the short alkyl chains are methyl groups. For instance, where R is derived from tallow or coconut oil, R contains three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R and R are methyl groups, the sultaines are of particular interest since they are readily prepared.

Specific examples of the above sultaines include 3-(N, N-dimethyl-N-hexadecyl ammonio)-propane-1-sulfonate, 3-(N-hexadecyiammonio)-propane-1-sulfonate, and 3-(N, N-dimethyl-N-hexadecyl ammonio -2-hydroxypropane-1- sulfonate. Other specific examples include the corresponding decyl, dodecyl, tetradecyl, and octadecyl homologs of the above compounds.

Of special interest as regards the solubilizing electrolytes of this invention are relatively water-insoluble sultaines wherein R is an alkyl chain of (1) from about 12 to about 18 carbon atoms when R and R are hydrogens, (2) from about 16 to about 20 carbon atoms when R R and R contain no substituents, and (3) from about 14 to about 18 carbon atoms when R and R are alkyl chains, and R is a three carbon atom alkylene group with a hydroxyl group substituted on the middle carbon atom. The solubilizing electrolytes of this invention solubilize the crystalline phase of these sultaines as hereinafter described.

All the detergents of this invention normally contain mixtures of long alkyl chains (R, R R R and R These can be derived from naturally occurring substances such as tallow and coconut oil, and can also be derived from petroleum fractions, e.g., by polymerizing propylene or cracking waxes to form the proper chain length, e.g., in the form of an olefin. The method of deriving the alkyl chain is immaterial. The alkyl chains can be unsaturated.

Specific examples of amines oxided detergents include:

dimethyldodecylamine oxide dimethyltetradecylamine oxide ethylmethyltetradecylamine oxide cetyldimethylamine oxide dimethylstearylamine oxide cetylethylpropyla-mine oxide diethyldodecylamine oxide diethyltetradecylamine oxide dipropyldodecylamine oxide bis- 2-hydroxyethyl) dodeeylamine oxide bis-(2-hydroxyethyD-3-dodecoxy-1-hydroxypropylamine oxide (2-hydnoxyprOpyDmethyItetradecyIamine oxide dimethyloleylarnine oxide dimethyl- (Z-hydroxydodecyl) amine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.

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- (Z-hydroxydodecyl) pho sphine oxide and the corresponding decyl, hexadecyl, and octadecyl homologs of the above compounds.

Specific examples of 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 the Well known detergents sold under the tradename Pluronic which are prepared by condensing propylene glycol with propylene oxide to form a hydrophobic base and then condensing said hydrophobic base with ethylene oxide, the hydrophobic base having a molecular weight of from about 1500 to about 1800 and the total molecule having a molecular weight of, e.g., 2000, 3000, and 8000.

Another group of suitable nonionic detergents are sold under the tradename of Tetronic. These are prepared by condensing ethylene diamine with propylene oxide to form a hydrophobic group (molecular weight-from about 2500 to about 3000) and condensing this hydrophobic group with ethylene oxide to give a molecular weight of from about 5000 to 11,000.

Other examples include dodecyl phenol 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- Z-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-iso-octylphenol condensed with 30 moles of ethylene oxide per mole of di-iso-octylphenol.

Specific examples of sulfoxide detergents include:

The liquid detergent compositions of this invention contain from about 1% to about 40% by weight of the composition of the detergents hereinbefore described. The minimum amount is set by practical product considerations of detergency benefits derived per unit volume. The upper limit, on the other hand, is set by several considerations including viscosity, crystalline solubility, and the possibility of forming liquid mesomorphic phases or an insolubilizible, immiscible second isotropic phase.

Although it is not desired to be bound by theory it is believed that certain electrolytes having an anion with relatively low charge density (ratio of number of charges in the anion to volume of the anion) are most effective in preventing separation of a second immiscible isotropic liquid phase. The effective anions are singly charged. Therefore, the anions with large volumes are effective.

R groups which fit the definition hereinbefore given are unsaturated aliphatic radicals containing from about 2 to about 7 carbon atoms and wherein there is unsaturation selected from the group consisting of one three covalent bond linkage and from one to two two covalent bond linkages; phenyl radicals; naphthyl radicals, substituted phenyl radicals containing from one to three substituents selected from the group consisting of methyl, ethyl, propyl, isopropyl, pentyl, isopentyl, butyl, isobutyl, chloro, fluoro and nitro groups and mixtures thereof; naphthyl radicals containing from one to about three substituents selected from the group consisting of chloro, fluoro, and nitro groups and mixtures thereof; phenyl alkyl radicals wherein the above phenyl radicals, including substituted phenyl radicals, are attached to alkylene radicals selected from the group consisting of ethylene, propylene, butylene, pentylene and hexylene groups; branched chain saturated aliphatic radicals containing from about three to about six carbon atoms; saturated aliphatic radicals containing from one to about five carbon atoms and containing from one to about five chlorine atoms; unsaturated aliphatic radicals containing from two to about five carbon atoms wherein there are from zero to one three covalent bond linkages, from zero to two two covalent bond linkages and containing from one to about five chlorine atoms; and mixtures thereof.

Specific R groups fitting the definition hereinbefore given include phenyl, benzyl, naphthyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, isopropylphenyl, butylphenyl, isobutylphenyl, 3-phenylpropyl, 2-phenylethyl, methybenzyl, nitrophenyl, dinitrophenyl, chlorophenyl, methylchlorophenyl, ethylfluorophenyl, chloronaphthyl, dichloronaphthyl, nitronaphthyl, dinitronaphthyl, isopropyl, isobutyl, chloroethyl, chloropropyl, chloroisobutyl, 1,2-dichloro-Z-pentene, 4,4-dichloro-2-butene, 1-chloro-3-pentene, and chloromethylbenzyl.

Examples of electrolytes as generically defined above which are particularly effective in solubilizing the detergent surfactants of this invention include the ammonium, monoethanolammonium, diethanolammonium, triethanolammonium, sodium, and potassium crotonates; sorbates; benzoates; o-nitrobenzoates; p-chlorobenzoates; phenylacetates; cinnamates; naphthoates; isobutyrates; isovalerates; trimethyl acetates; trichlonoacetates; ethylbenzene phosphonates; and furoates. These preferred solubilizing agents are particularly effective in the presence of these polyvalent electrolyte salts which are polyphosphate builder salts such as tetrapotassium pyro-phosphate and polycarboxylate builder salts such as sodium and potassium nitrilotriacetates and ethylenediaminetetraacetates 5 and substituted methylene and ethylene diphosphonate: (e.g., trisodium ethane-l-hydroxy 1,1-diphosphonate).

These electrolytes are the solubilizing agents of this in vention; they perform the solubilizing function wherea other electrolytes having anions with relatively high charg. densities have generally the opposite effect, i.e., promott separation. Examples of electrolytes which tend to caust a separation of a second isotropic liquid phase IHCllldt many of the common ingredients found in detergent com positions such as the polyvalent electrolytes hereinbefori mentioned, e.g., potassium and sodium pyrophosphates sodium and potassium tripolyphosphates, potassium an sodium silicates, potassium and sodium sulfates, potassiurr and sodium ethylenediamine tetraacetates, and sodiurr potassium nitrilo triacetates.

The solubilizing electrolytes of this invention are user in an amount from about 0.5% to about 20% by weigh of the liquid detergent composition and sufficient to pro vide a homogeneous composition. Preferably only suflicient solubilizing electrolyte is used to create ,a single phase in the temperature range desired. It will be understood that all compositions coming within the scope of the ranges 01 components disclosed which are not homogeneous by reason of a second immiscible isotropic liquid phase, are benefited by the presence of a solubilizing electrolyte tc aid in reducing the area of the second isotropic liquid phase on the appropriate phase diagram (e.g., as in FIG. 2) at a given temperature and increasing the area of the first isotropic liquid phase which has the practical efiect of changing more of the second isotropic liquid into the first isotropic liquid phase. (It is believed that this result is effected by a raising of the minimum temperature at which said second isotropic liquid can exist with a concomitant reduction in the area occupied by the second isotropic liquid at a given temperature.) It will be further understood that where the sole separating phase is one which is not affected by the action of the solubilizing electrolyte, e.g., where the sole separating phase is crystalline inorganic builder, there is no benefit from using a solubilizing electrolyte. These solubilizing electrolytes can be used in combination with other solubilizing agents and solvents which solubilize other separating phases as Well as the second liquid phase.

With reference to FIGURES 2 and 3, the effect of the solubilizing electrolytes can be explained readily. The area in each figure defined by the axes and the boundary line is the single (first) isotropic liquid phase region. When a conventional detergent builder or other polyvalent electrolyte is added to aqueous solutions of the detergents utilized in the compositions of this invention (FIGURE 2), the amount of detergent which can be placed in a single homogeneous liquid phase (first isotropic liquid phase) is increased initially because the solubility of the first mesomorphic phase (middle) is initially increased. When the separating mesomorphic phase is neat, an increase in the amount of builder electrolyte decreases the amount of detergent and builder which can be placed in a single homogeneous liquid phase. A second immiscible isotropic liquid (lye) separates as the conventional and highly desirable high electrolyte/ surfactant ratios and it is this phase which normally prevents the formation of a homogeneous liquid composition.

Use of a solubilizing electrolyte in a water-detergent system gives the phase relationship as shown in FIGURE 3. At high ratios of solubilizing electrolyte to detergent the separating phase is electrolyte crystals rather than a second liquid phase and the ,amount of electrolyte that can be present before phase separation occurs is much greater than with polyvalent electrolytes alone. Addition of a solubilizing electrolyte to a composition containing builder electrolyte at a given temperature modifies the builder detergent phase diagram (e.g., FIGURE 2) to look more like FIGURE 3 and more builder can be placed in a homogeneous composition. As hereinbefore discussed, this is believed to occur by raising the minimum temperature at vhic-h the second isotropic liquid can exist and thereby lecreasing the area, on a phase diagram, of the second sotropic liquid for a given temperature.

The presence of a second immiscible isotropic liquid )hase is also a function of temperature. As the temperaure of the composition is raised, a second liquid phase eparates. For some detergents this separation occurs only vhen a polyvalent electrolyte, e.g., builder, is present. The :olubilizing electrolytes raise the temperature at which his separation occurs. The presence of a temperature-de- )endent second liquid phase which exists without a polylalent electrolyte being present is a function of water iolubility and cannot readily be predicted. In general, with respect to the hydrophobic group, the longer chain lengths 1Y6 less soluble and more prone to exhibit this phenome- 1011. With respect to the hydrophilic group, ethylene oxide condensates and phosphine oxide surfacants are more likely to exhibit this phenomenon, whereas amine oxide and sultaine surfactants generally do not. The primary bene- [it from the use of solubilizing electrolytes in a liquid composition of this invention is derived whenever a second liquid phase is the separating phase.

Variation in degree of effectiveness is found in solubilizing the various surfactants with the various solubilizing electrolytes.

When used with the relatively water-insoluble sultaine detergents hereinbefore described, the electrolyte solubilizing agents of this invention are present in the liquid detergent composition in an amount from about 0.5% to about by weight of the liquid detergent composition and sufficient to lower the Krafft temperature of the sultaine detergent in the liquid detergent composition below about 70 F. (room temperature), prefer-ably below 40 F., to prevent the crystalline detergent from separating out of solution during normal use and storage.

These particularly relatively water-insoluble sultaine detergents are unique in that the addition of the electrolytes of this invention to their aqueous solution lowers their Kraift temperature as hereinafter more fully described. This Krafft temperature is really a narrow range of temperature for a given compound within which a small increase in temperature gives a very large increase in solubility of the crystalline surfactant. Lowering of the Krafft temperature for a given sultaine-electrolytewater system has the practical effect of raising the crystalline solubility of the surfactant in water for any temperature which is above the temperature to which the Kralft temperature is lowered and which is below the Krafft temperature of the surfactant in water (without solubilizing electrolyte). Normally, the addition of an electrolyte to an aqueous anionic surfactant solution will raise this Krafft temperature (lowering practical solubility), but the addition of the electrolytes of this invention to the sultaine detergents utilized in the compositions of this invention lowers their Krafft temperature (increases practical solubility).

The effect of this lowering of the Kratft temperature is such that homogeneous liquid detergent formulations can be prepared containing a considerable amount of sultaine detergent by the use of solubilizing electrolytes. To explain, the mechanism by which these particular electrolytes solubilize these sultaine detergents, reference is made to a phase diagram typical of the liquid systems of this invention, FIG. 1, in which the crystalline solubility (to left of point A) of a representative sultaine detergent of this invention in Water is plotted as a function of temperature with a solid line (Tw is the Krafft temperature of the sultaine detergent in water) and the crystalline solubility (to the left of point A of the same representative sultaine detergent in an aqueous solubilizing-electrolyte solution of constant concentration is plotted as a function of temperature with a broken line (T is the Krafft temperature of the sultaine detergent in electrolyte solution). It will be understood that the position of this broken line varies with the concentration 8 of solubilizing-electrolyte in water and that there is a series of these broken line curves for different electrolyte concentrations. Up to a certain limit, the more electrolyte that is present the lower the broken line curve is on the diagram.

The lines on the diagram represent the boundaries for homogeneous solutions. Region B is homogeneous and is commonly referred to as nigre; regions C and C are characterized by the presence of liquid mesomorphic phase; regions D and D are characterized by the presence of another liquid mesomorphic phase; and region E is characterized by the presence of crystals of detergent plus detergent solution.

When the addition of the solubilizing-electrolytes of this invention lowers the Krafft temperature of the sultaine detergent, as hereinbefore described, below the temperature of the liquid detergent composition, the crystalline solubility of the sultaine detergent in water is substantially increased. The practical result is that a greater amount of the sultaine detergent can be used in the detergent composition while maintaining homogeneity. In general, the liquid compositions of this invention containing the relatively water-insoluble sultaines will be to the left of A and A on the accompanying sultainewater phase diagram (FIG. 1). (A and A are the crystalline solubility points hereinbefore described.) The amount of lowering of the Krafft temperature is dependent upon the amount and, particularly, the type of electrolyte present as well as the molecular structure of the sultaine.

In addition to the detergents and solubilizing agents hereinbefore described, the detergent compositions can also contain from 0% to about 40% by weight of the composition of polyvalent electrolytes, but no more than can be dissolved in the compositions. These polyvalent electrolytes can be inert salts, which are associated with the detergent materials, such as sodium sulfate or can be desirable detergent builder electrolytes. Examples of water soluble inorganic alkaline detergency builder salts are alkali metal carbonates, phosphates, polyphosphates, and silicates. Specific examples of such salts are sodium and potassium tripolyphosphates, carbonates, pyrophosphates, phosphates, and hexametaphosphates. Examples of organic alkaline sequestrant builder salts are (1) alkali metal amino polycarboxylatcs [e.g., sodium and potassium ethylenediaminetetraacetates, N-(2-hydroxyethyl)- ethylene diamine triacetates, nitrilo triacetates, and N-(2- hydroxyethyl)-nitrilo diacetates]; (2) alkali metal salts of phytic acid (e.g., sodium and potassium phytates-see U.S. Patent 2,739,942); (3) water soluble ethane-1- hydroxy-1,1-diphosphonates (e.g., the trisodium and tripotassium salts); (4) water soluble salts of methylene diphosphonic acid (e.g., trisodium and tripotassium methylene diphosphonate and the other salts described in the copending application of Francis L. Diehl, Ser. No. 266,025 now Patent No. 3,215,030, filed Mar. 18, 1963); (5) water soluble salts of substituted methylene diphosphonic acids (e.g., trisodium and tripotassium ethylidene, isopropylidene, benzylmethylidene, and halomethylidene diphosphonates and the other substituted methylene diphosphonates disclosed in the copending application of Clarence H. Roy, Ser. No. 266,055, filed Mar. 18, 1963); (6) water soluble salts of polycarboxylic polymers and copolymers as described in the copending application of Francis L. Diehl, Ser. No. 269,359, filed Apr. 1, 1963 now Patent No. 3,308,067, Le, a polyelectrolyte builder material consisting of water-soluble salts of a polymeric aliphatic polycarboxylic acid selected from the group consisting of (a) water soluble salt of a homopolymer of an aliphatic polycarboxylic acid having the following empirical formula:

9 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 carboxyrnethyl, provided that X and Y can be carboxymethyl only when Z is selected from carboxyl and carboxyrnethyl, 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) a water-soluble salt of a copolymer of at least two of the monomeric species having the empirical formula described in (a); and,

(c) a water-soluble salt of a copolymer 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:

H R Y COOH m wherein R is selected from the group consisting ofhydrogen, 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 carboxyrnethyl 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 1 about 80, calculated at 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 other compatible monomers such as ethylene); and (7) mixtures thereof.

Mixtures of any and all of the organic and/or inorganic builders can be used and are generally desirable. Especially preferred are the mixtures of builders disclosed in the copending application of Burton H. Gedge, Ser. No. 398,705, filed Sept. 23, 1964, e.g., ternary mixtures of sodium tripolyphosphate, sodium nitrilotriacetate, and sodium ethane-l-hydroxy-l,l-diphosphonate.

At high ratios of these polyvalent, e.g., builder electrolytes to detergents (as hereinbefore described and as illustrated in FIG. 2) a second liquid tends to separate and it is this second liquid phase which is most readily controlled by the solubilizing electrolytes of this invention as hereinbefore described.

Other ingredients can also be present in the liquid detergent compositions of this invention without detracting from the advantageous properties of the invention.

Anti-redeposition agents such as carboxymethylcel l-ulose and anionic, cationic or nonionic detergents can also be added. Typical minor additives which can be present include suds boosters and suppressants, dyes, opacifiers, perfume, corrosion, inhibitors and anti-microbial agents.

All percentages, ratios and parts herein are by weight unless otherwise specified.

The practice of this invention is demonstrated in the following examples.

' Example I Homogeneous aqueous liquid compositions were preand diiferent solubilizing electrolytes, both with (Composi- Solubilizing Electrolyte Percent Percent Percent Percent Solubilizing Sultaine solubilizing Sultaine K4P O1 Electrolyte Detergent Electrolyte Detergent Sodium crotonate- 7 27 5 30 Sodium acrylate 10 5 10 5 10 Sodium sorbate. 8 30 6 16 32 Sodium benzoate 9 17 5 17 34 Sodium 3,5-dinitrobenzoate 8 24 9 4 8 Potassium o-mtrobenzoate 9 12 6 13 Potassium p-chlorobenzoate 8 16 7 12 23 Sodium phenyl acetate 7 32 6 15 Sodium oinnamatem 8 23 6 13 25 Sodium napthoate. 8 24 8 7 14 Sodium isobutyrate 7 29 7 9 18 Sodium isovalerate 9 10 6 14 28 Sodium trimethylacetate 9 10 6 14 28 Sodium ethylbenzene phosphonate 8 23 6 13 26 Sodium furoate 10 24 10 13 25 None 0 0. 1 0 0. 1

1 Saturated.

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 7,

acid form and an equivalent weight of about 50 to When in the above example, any of the following detergent compounds, or mixtures of the following compounds, are substituted for the specific sultaine detergent, either wholly or in part, substantially equivalent results are obtained in that significantly more of the sultaine detergents and/or builder can be added to form a'homogeneous 1 1 solution than can be added Without the solubilizing electrolytes being present: 3- (N,N-dimethyl-N-hexadecylammonio) -propane-1- sulfonate,

droxymethyl)octadecylamine oxide, bis(3-hydroxypropyl) pentadecylamine oxide, bis(2-hydroxypropyl)heptadecylamine oxide, bis (ethyl)eicosylamine oxide, bis(2,3-dihydroxypropyl)decylamine oxide, bis(propyl)oleylamine 2-(N,N-dihydrogen-N-dodecylammonio)-ethane-1- g g l ff gl z h ri FZ fZIiI Q sulfonate, g c mp un s w erein one o e wos o a y ams 4-(N,N-diethyl-N-tetradecylammonio)-2-hydroxybutaneare f z g d g fi 3 13 3 g methyl, P Lsmionate, p py 1 y e p py Y rp -py. y s 4-(N,N-diethyl-N-eicosylammonio)-butane-1-sulf0nate, methyl, and y r Xypropy1 groups; the corresponding 3-(N-methyl-N-ethyl-N-octadecylammonio)-2-hydroxy- Compounds Wherem Z'hYdTOXY3'decoxypmpyl, Y' propane l sulfonate, droxydodecyl, 2-hydroxy-3-octadecoxypropyl, decyl, tetra- 4-(Nhydrogen-N-rnethyl-N-decylammonio)-3-hydro decyl, Z-decoxypropyl, Z-tetradecoxyethyl, Z-(Z-decoxy- .butane l sulfonate, ethoxy )ethyl, pentadecyl, octadecyl, heptadecyl, eicosyl, 2-(N-hydr0gen-N-ethyl-N-oleylammonio)-ethane-loleyl, llnolcyl, hnolenyl, -P PY yL p py and sulfonate; tetrabutyl groups are substituted for the long chain group. h N h Similarly, when in the above examples any of the folthe g g g i W g? 3 g? group? lowing compounds, or mixtures thereof, are substituted i? i lsmute or i y g for the specifically named detergents, either wholly or in f f 3 sltute or g i E part, substantially equivalent results are obtained in that y groups y rogens are Su sum or more of the detergents and builders are formed into a methgl i F g i g g z i i z homogeneous solution than are formed when the solubi- Poun l erem ecy O ecy Ia eXa ecy octa' lizing electrolytes are not present: octadecyl methyl sulfdecyl, eicosyl, oleyl, linoleyl, linolenyl, 4-pr py oxide, 3-methoxytridecyl methyl sulfoxide, 3-hydroxyg iyi g i fi i g g h i ig g tridecyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl are su S e or e Ong y c ams m e a CV methyl sulfoxide, Z-hydroxypentadecyl methyl sulfoxide; compoun s. E am 1e the corresponding compounds wherein decyl, undecyl, x p dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecy-l, hepta- Homogeneous aqueous liquid compositions were predecyl, octadecyl, eicosyl, tetrapropylene, 2*(2-dodecoxypared containing varying amounts of the sultaine detergent ethoxy) ethyl, 2-methoxypentadecyl, 3-ethoxyundecyl, of Example I in combination with polycarboxylate deterand 3-hydroxy-4-decoxybutyl groups are substituted for gency builders and various electrolyte solubilizing agents. the long chain groups. All percentages are by weight. The figures represent the E I IV maximum amounts of sultaine detergent and builders xamp e which can be solubilized by the respective electrolytes. Homogeneous aqueous liquid compositions were pre- Solubilizing Percent Percent Electrolyte Solubilizing Builder Builder Sultaine Electrolyte Detergent None i. Trisodium nitrilo triacetate Saturatedsoluti0n 1 Sodium isovalerate..- do 13 Sodium cinnamate 6 do 15 10 None Tetrapotassium ethylenediarm'ne- Saturated soluti0n 1 tetraacetate. Sodium crotonate 13 do 32 21 Example 111 Homogeneous aqueous liquid compositions were prepared containing varying amounts of dodecyl dimethyl amine oxide detergent in combination with potassium pyrophosphate builder (13), tetrasodium ethylenediaminetetraacetate builder (4-5) and sodium nitrilo triacetate builder (68); All percentages are by Weight. The figures represent the maximum amounts of amine oxide and builders which can be solubilized by the respective electrolytes.

Percent Percent Percent Solubilizing Electrolyte Solubilizing Amine Builder Electrolyte Oxide (l) None 9 14 (2) c. Potassium sorbate. 9 16 23 (3) Sodium napthoate. 8 14 20 (4), None 12 24 (5) Potassium benzoate 11 18 36 (6)," None 15 30 (7) Sodium phenylacetate. 10 17 34 (8) Sodium trimethyl acetate- 10 17 25 When, in the above examples any of the following compounds, or mixtures thereof, are substituted for the specifically named detergents, substantially equivalent results are achieved in that more of the detergents and builders can be added to form a homogeneous solution than can be added without the solubilizing electrolytes being present: bis(2-hydroxyethyl)tetradecylamine oxide, bis(hypared containing varying amounts of dimethyldodecylphosphine oxide detergent and potassium pyrophosphate builder (1-3), sodium nitrilotriacetate builder (4-5) and potassium ethylenediaminetetraacetic builder (6-10) in ratios of builder to detergent of approximately 2:1. All percentages are by weight and the figures represent the maximum amounts of phosphine oxide and builders which can be solubilized by the respective electrolytes.

When any of the following compounds, or mixtures thereof, are substituted, either wholly or in part for the specifically named detergents in the above examples, substantially equivalent results are obtained in that more de- 13 tergents and builders are solubilized with the solubilizing electrolytes than without:

dimethyltetradecylphosphine oxide; diethyldecylphosphine oxide; bis-(Z-hydroxyethyl)hexadecylphosphine oxide; dihydroxymethylpentadecyl phosphine oxide; dipropylundecylphosphine oxide; bis-(Z-hydroxypropyl)tetrapropylene phosphine oxide; bis-(3-hydroxypropyl)oleylphosphine oxide;

the corresponding compounds in which methyl, ethyl, 2- hydroxyethyl, hydroxy methyl, propyl, 2-hydroxypropyl and 3-hydroxypropy-l groups are substituted for one of the short chain groups in the above compounds; the corresponding compounds in which decyl, undecyl, dodecyl, tetradecyl, pentadecyl, tridecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, tetrapropylene, diheptene, o-leyl, linoleyl, and linolenyl groups are substituted for the long chain group in each of the above compounds.

Example V Homogeneous aqueous liquid compositions were prepared with nonionic detergent (nonylphenol polyethoxy ethanol with an average of about 10 ethoxy groups) and potassium pyrophosphate builder (1-3), sodium nitrilotriacetate builder (45), and potassium ethylene diaminetetraacetate builder (6-8) as builders.

Percent Percent Percent Solubilizing Electrolyte Solubilizing Detergent Builder Electrolyte (1) None 9 (2). Sodium crotonste 5 5 9 (3 Sodium benzoate 8 8 16 5 10 10 20 I 7 14 (7)..- Sotditum trimethylaee- 16 16 32 a e. (8).-- Sodium erotonate 11 11 21 2,6-dimethyldodecanol, 6-hexyldecanol, 8-butylhexadec anol, and Z-butenyl-Z-octanol; (2) tetrapropylenephenol, octylphenol, decylphenol, tridecylphenol, diheptenephenol, octadecylphenol, dioctylphenol, dinonylphenol, 3-hexylheptylphenol, pentadecylphenol, tetradecylphenol, dodecylphenol, and diisoootylphenol; (3) myristamide, stearamide, palrnitamide, oleamide, linoleamide, linolenamide,

and capro-amide; and (4) decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, tetrapropylene mercaptan, oleyl mercaptan, linoleyl mercaptan, linolenyl mercaptan, eicosyl mercaptan, pentadecyl mercaptan, tridecyl mercaptan, heptadecyl mercaptan, and Z-butenyl-Z-octyl mercaptan with ten, fifteen, twenty,-and twenty-five moles respectively of ethylene oxide; nonionic detergents prepared by condensing the aforementioned alcohols wit-h three, I

- amine wit-h twenty, thirty, forty and fifty moles of pro-pylene oxide and thereafter condensing the resulting products with thirty, forty and fifty moles respectively of ethylene oxide; nonionic detergents prepared by condensing propylene glycol with twenty-five, thirty and thirty-five moles 1 respectively of propylene oxide and thereafter condensing the resulting products with twenty, thirty, forty, and

fifty moles respectively of ethylene oxide.

14 Example VI An aqueous homogeneous liquid detergent composition was prepared with the following formula in which all percentages are by weight of the composition.

The composition was adjusted to Na:K ratio of 65:35 by the addition of NaOI-I and KOH and the pH of the composition was 12.5. Without the sodium benzoate the composition was not homogeneous.

Example VII When in the previous examples any of the following solubilizer compounds, or mixtures thereof, are substituted, either wholly or in part, for the specifically named solubilizing electrolytes, substantially equivalent results are obtained in that more of the detergents and builders can be formed into homogeneous solutions with the solubilizing electrolytes than without: crotonates, sorbates, benzoates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, chloronaphthoates, fluoronaphthoates, nitronaphthoates, trichloronaphthoates, chlorodinitronaphthoates, chlorofluoron-aphthoates, isobutyrates, isovalerates, trimethylacetates, ethylbenzene phosphonates, furoates, ,B-chloro propiolates, propiolates, a-chloro acrylates, B-chloro acrylates, acrylates, pentyl benzoates, isopentyl benzoates, butyl benzoates, isobutyl benzoates, propyl benzoates, isopropyl benzoates, ethyl benzoates, methylethyl benzoates, trimethyl benzoates, diisopropyl benzoates, chloromethyl benzoates, methylnitro benzoates, fluoro benzoates, methyl benzoates, 3-phenyl propionates, 2-phenylbutyrates, 4-phenylbutyrates, 5- chloro-l-carboxylate-pentaues, 6-nitrophenyl-l-carboxylate hexanes, mandelates, trichloroacetates, 0c chloro 'butyrates, dimethylbenzoates, and mixtures of any of these Example VIII When in the previous examples any of the following polyvalent electrolytes, or mixtures thereof are substituted, either wholly or in part, for the specifically named polyvalent electrolytes, substantially equivalent results are obtained in that more of the detergents and builders can be formed into homogeneous solutions with the solubilizing electrolytes than without: tripolyphosphates; sulfates; carbonates; pyrophosphates; phosphates; hexamethaphosphates; ethylenediaminetetraacetates; N-(2- hydroxyethyl)-ethylenediaminetriacetates; nitrilotriacetates; N (2 hydroxyethyl) nitrilodiacetates; phytates; ethane-l-hydroxy-l,l-diphosphonates; methylane diphosphonates; and ethylidene, isopropylidene, benzylmethylidene and chloromethylidene diphosphonates; salts of polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with themselves and/or ethylene and/ or acrylic acid in e.g. 1:1 molar ratios and having molecular weights of 75,000; 100,000; and 125,000 (the copolymers with ethylene and/or acrylic acid having equivalent weights, based on the acid form of 65, 70 and 75) in the form of their sodium, potassium, triethanolammonium, diethanolammonium, and monoethanolammonium salts.

What is claimed is:

I claim:

1. An aqueous homogeneous liquid detergent composition consisting essentially of:

(I) from about 1% to about 40% by weight of the 15 composition of a detergent selected from the group consisting of (A) A detergent having the formula R2 wherein R and R are each selected from the group consisting of hydrogen, methyl, and ethyl groups, R is a straight chain alkylene group containing two to four carbon atoms, and having from to one hydroxyl group substituted on a secondary carbon atom, and R is an alkyl chain of from about 10 to about 20 carbon atoms;

(B) A detergent having the formula R R R N O wherein R is selected from the group consisting of alkyl, alkyl monohydroxy, and alkoxy monohydroxypropyl radicals wherein the alkyl and alkoxy portions of said radicals contain from about to about carbon atoms and R and R are each selected from the group consisting of alkyl radicals and allranol radicals containing from one to about three carbon atoms;

(C) A detergent having the formula R' R R P O wherein R is selected from the group consisting of alkyl and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms;

(D) Nonionic detergents having the formula R (C H O) H wherein R represents a hydrophobic base selected from the group consisting of (1) alkoxy groups containing from about 8 to about 20 carbon atoms, (2) alkyl phenoxy groups wherein the alkyl group contains from about 6 to about 18 carbon atoms, (3) condensation products of propylene glycol and propylene oxide with a molecular weight of from about 1500 to about 1800, (4) fatty amides containing from about 10 to about 20 carbon atoms, (5) higher alkyl mercaptans containing from about 10 to about 20 carbon atoms, (6) condensation products of propylene oxide and ethylene diamine constituting from about 20% to about 60% by Weight of the finished nonionic detergent molecule and (7) condensation products of fatty alcohols containing from about 10 to about 20 carbon atoms and from about three to about 8 propylene oxide units and wherein x is an integer from about 4 to about for (1), (2), (4), and (5), but not less than about 0.4 of the number of carbon atoms in the hydrophobic group, and sufiiciently large to give the detergent a molecular Weight of from about 2,000 to about 10,000 for (3); of from about 5,000 to about 11,000 for (6); and of from about 750 to about 1800 for (7), and wherein y is an integer equal to the number of ethylene oxide chains;

(E) A detergent having the formula 0 R iiCH wherein R is an alkyl radical containing from about 10 to about 20 carbon atoms and contains from 0 to 1 hydroxyl snbstituents and from 0 to five ether linkages;

(F) and mixtures thereof;

(11) From 0% to about by weight of the composition of a polyvalent electrolyte salt selected from the group consisting of a polyvalent electrolyte salt selected from the group consisting of (1) sulfates; (2) carbonates; (3) tripolyphosphates; (4) pyrophosphates; (5) orthophosphates; (6) hexametamula:

1 it (JOOH 11 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 charac teristics in an aqueous system; (b) a watersoluble salt of copolymer of at least two of the monomeric species having the emperical, formula described in (a); and (c) a water-soluble salt of a copolymer 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:

i t i H R i-m Y DOOH m n 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 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 acd form; and (19) mixtures thereof, the cations of the above polyvalent electrolytes being selected from the group consisting of sodium, potassium, ammonium; triethanol ammonium, diethanol ammonium and monoethanol ammonium cations and mixtures thereof;

(III) From about 0.5% to about 20% by weight of the composition, and sufficient to keep the composition homogeneous, of solubilizing electrolytes selected from the group consisting of compounds having the formula wherein M is a cation selected from the group consisting of sodium, potassium, triethanolammonium, diethanolammonium, and monoehtanolammonium cations, and mixtures thereof, and R is selected from the group consisting of unsaturated aliphatic radicals containing from 2 to about 7 carbon atoms; aromatic, substituted aromatic, and aromatic alkyl radicals containing from 6 to about 12 carbon atoms selected from the group consisting of phenyl radicals, naphthyl radicals, substituted phenyl radicals containing from one to three substituents selected from the group consisting of methyl, ethyl, propyl, isopropyl, peutyl, isopentyl, butyl, isobutyl, chloro, fluoro, and nitro groups and mixtures thereof, napthyl radicals containing from one to about three substituents selected from the group consisting of chloro, fluoro, and nitro groups and mixtures theerof; and phenyl alkyl radicals wherein the above phenyl radicals are attached to alkylene radicals selected from the group consisting of ethylene, propylene, butylene, pentylene, and hexylene groups; branched chain saturated aliphatic radicals containing from three to about six carbon atoms; chloro-substituted saturated and unsaturated aliphatic radicals containing from one to about carbon atoms; sodium, potassium, triethanolammonium, diethanolammonium, and monoethanolammonium trimethylacetates; sodium, potassium, triethanolammonium, diethanolammonium, and monoethanol ammonium ethyl benzene phosphates; sodium, potassium, triethanolammonium, diethanolammonium and monoethanolammonium furoates; and mixtures thereof; and

(IV) The balance substantially water.

2. The composition of claim 1 wherein the detergent comprises a compound having the formula R R R N O wherein R is selected from the group consisting of alkyl, alkylmonohydroxy, and alkoxy monohydroxypropyl radicals wherein the alkyl and alkoxy contain from about to about 20 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms.

3. The composition of claim 1 wherein the detergent comprises a surface active agent having the formula R' R R P- O wherein R is selected from the group consisting of alkyl and alkyl monohydroxy radicals containing from about 8 to about 16 carbon atoms and R and R are each selected from the group consisting of alkyl radicals and alkanol radicals containing from one to about three carbon atoms.

18 4. The composition of claim 1 wherein the detergent comprises a compound having the formula 0 R -g-om wherein R is an alkyl radical containing from about 10 to about 20 carbon atoms and contains from O to 1 hydroxyl substituents, and from 0 to five ether linkages.

5. The composition of claim 1 wherein the solubilizing electrolyte is selected from the group consisting of crotonates, sorbates, unsubstituted, benzoates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, isobutyrates, isovalerates, trimethyl acetates, trichloro acetates, ethylbenzene phosphonates, furoates and mixtures thereof.

6. The combination of claim 1 wherein the solubilizing electrolyte is a benzoate.

7. The composition of claim 1 wherein the solubilizing electrolyte is a trimethyl acetate.

8. The composition of claim 2 wherein the solubilizing electrolyte is a sorbate and the polyvalent electrolyte is tetrapotassium pyrophosphate.

9. The composition of claim 3 wherein the solubilizing electrolyte is a benzoate.

10. The composition of claim 1 wherein the detergent has the formula 31 RI I R SOa and wherein R and R are each selected from the group consisting of hydrogen, methyl and ethyl groups, R is selected from the group consisting of an alkylene group containing from two to four carbon atoms and an alkylene group of three carbon atoms with a hydroxyl group substituted on the middle carbon atom, and R is an alkyl chain of (A) from about 12 to about 18 carbon atoms when R and R are hydrogens, (B) from about 16 to about 20 carbon atoms when R and R are each selected from the group consisting of methyl and ethyl groups and R is an unsubstituted alkylene group as hereinbefore described, and (C) from about 14 to about 18 carbon atoms when R and R are selected from the group consisting of methyl and ethyl groups and R is a three-carbon atom alkylene group with a hydroxyl group substituted on the middle carbon atom, as hereinbefore described.

11. The composition of claim 1 wherein the solubilizing electrolyte is selected from the group consisting of crotonates, o-nitrobenzoates, p-chlorobenzoates, phenylacetates, cinnamates, naphthoates, isobutyrates, isovalerates, trimethylacetate, trichloroacetates, ethylbenzene phosphonates, furoates and mixtures thereof.

References Cited UNITED STATES PATENTS 2,441,341 5/1948 Vitalis 252363.5 X 2,768,143 10/1956 Henry 252363.5 2,787,595 4/1957 Webb 252138 3,001,945 9/1961 Drew et a1. 252l52 3,086,943 4/1963 Lang et al. 252l52 3,159,581 12/1964 Diehl 252l52 3,213,030 10/1965 Diehl 252l52 FOREIGN PATENTS 1,219,570 5/ 1960 France.

LEON D. ROSDOL, Primary Examiner.

SAMUEL H. BLECH, Examiner.

S. E. DARDEN, Assistant Examiner.

Claims

1. AN AQUEOUS HOMOGENEOUS LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF: (I) FROM ABOUT 1% TO ABOUT 40% BY WEIGHT OF THE COMPOSITION OF A DETERGENT SELECTED FROM THE GROUP CONSISTING OF (A) A DETERGENT HAVING THE FORMULA