WO2001019507A1 - Ternary surfactant blends comprising cationic, anionic, and bridging surfactants and methods of preparing same - Google Patents

Abstract

The present invention relates to ternary surfactant blends comprising a mixture of at least one cationic surfactant, at least one anionic surfactant and at least one 'bridging surfactant' selected from semi-polar nonionic, ethoxylated alkanolamide, and amphoteric/zwitterionic surfactants, and mixtures thereof. More specifically, the invention relates to stable, synergistic mixtures of cationic, anionic, and bridging surfactants that are useful as bulk surfactant blends. Surfactant blends of the present invention are useful for preparing a variety of finished consumer cleaning products, including for example, liquid dish detergents, laundry detergents, automatic dishwasher detergents, hand soaps, laundry bars, personal cleansing bars, multi-purpose cleaners, multi-functional shampoos, body washes, and textile treatment compositions. Surfactant blends of the present invention also may be employed as surfactants in agricultural and pesticide applications. Additionally, the surfactant blends may be utilized in antimicrobial detergent formulations (e.g., antimicrobial hard surface cleaners, hand soaps, shampoos, and dish detergents), soft-terg delivery systems and pre-spotter compositions.

Description

Title: Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging Surfactants and Methods of Preparing Same

Specification

This application claims benefit of U.S. Provisional Application No. 60/154,750, filed September 17, 1999.

(Case No. T00,015-C)

TO ALL WHOM IT MAY CONCERN:

Be it know that we, Daniela T. Bratescu, a citizen of Romania and a resident of 1927 West Central Road, Town of Glenview, County of Cook, State of Illinois, 60025; and Randal J. Bernhard, a citizen of the United States and a resident of 39771 North Wittenburg Drive, Town of Lindenhurst, County of Lake, State of Illinois, 60002, have invented certain new and useful improvements in

Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging Surfactants and Methods of Preparing Same

of which the following is a specification.

Ternary Surfactant Blends Comprising Cationic, Anionic, and Bridging Surfactants and Methods of Preparing Same

This application claims benefit of U S Provisional Application No 60/154,750, filed September 17, 1999

Field of the Invention

The present invention relates to surfactant blends comprising a mixture of at least one cationic surfactant, at least one anionic surfactant and optionally at least one "bridging surfactant" selected from semi-polar nonionic, ethoxylated alkanolamide, and amphoteπc/zwitteπonic surfactants, and mixtures thereof More specifically, the invention relates to stable, synergistic mixtures of cationic, anionic, and bridging surfactants that are useful as bulk surfactant blends

Background of the Invention Anionic-cationic surfactant mixtures are well known to the art See generally, U S Pat Nos

5,441 ,541 , 5,472,455, 5,204,010, 4,790,856, 4,298,480, 3,730,912 (all to The Colgate-Palmolive Company), 5,622,925, 5,607,980, 5,565,145, 4,913,828, 4,659,802, 4,436,653, 4,338,204, 4,333,862, 4,132,680 (all to The Procter & Gamble Co ), also see WO 97/03164, WO 97/12022 and WO 96/37591 (all to The Procter & Gamble Co ), and WO 97/28238 and WO 97/15647 (both to Reckit & Colman, Inc ) See also, U S Pat Nos 5,610,187 and 4,247,538 (both to Witco Corp ), 5,344,949 (to Th Goldschmidt AG), 5,332,854 and 5,324,862 (both to Dai-lchi Kogoyo Seiyaku Co , Ltd ), 4,273,760 (to National Starch and Chemical), and 4,264,457 (to DeSoto, Inc ) Mixed surfactant systems have also been disclosed in "Mixed Surfactant Systems", ACS Symposium Series 501 , P M Holland and D N Rubingh (June 17-19, 1991 ) Additionally, there have been many studies and symposia on mixed surfactant systems See, for example, Scamehorn, J F , ed , "Phenomena in Mixed Surfactant Systems", ACS Symposium Series 311 , Washington, D C (1986) The effects of alkyl groups and oxyethylene groups in nonionic surfactants on the surface tension of anionic-nonionic systems have been described See Abe et al , J Colloid Interface Sci , 107, p 503 (1985), Ogino et al , J Colloid Interface Sci , 107, p 509 (1985), and Rosen et al , J Colloid Interface Sci , 95, 443 (1983) Interaction between betaines and cationic surfactants has also been studied See Zhu et al , J Colloid Interface Sci , 108, 423 (1985)

Mixed surfactant systems have shown synergistic improvements in surfactant properties compared to the properties of their individual surfactant components Synergism increases with the degree of charge difference Thus, the greatest synergistic surfactant property improvements are realized when mixing anionic and cationic surfactants See Rosen et al in "Phenomena in Mixed Surfactant Systems" (Scamehorn, J F , ed ), ACS Symposium Series 311 , Washington, D C (1986), pp 144-162, Zhao et al in "Phenomena in Mixed Surfactant Systems" (Scamehorn, J F , ed ) ACS Symposium Series 311 , Washington, D C (1986) pp 184-198 In detergent applications, although in principle any surfactant is suitable, in practice only anionic and nonionic surfactants typically are used Cationic surfactants, especially quaternary ammonium salts, can decrease detergency and enhance soil redeposition when used in heavy-duty liquid detergents Consequently, there is a general notion that anionic and cationic surfactants cannot be used in the same formula without loss of efficacy Similar worries regarding potential loss of efficacy exist when contemplating use of cationic surfactants in hair and skin conditioning applications Thus, anionic-cationic surfactant mixtures have been used only sparingly in the production of consumer cleaning products and personal care products

Studies on anionic-cationic systems are recent and few compared to studies on other mixed surfactant systems However, strong synergism has been exhibited by these systems Surface activity properties, particularly the critical micelle concentration (cmc), surface tension, and microemulsion behavior (Bourrel et al , Tenside Detergents, 21 , 311 (1984)), were the most studied properties For example, the surface activities of mixed aqueous solutions of sodium dihexylsulfosuccinate with dιoctyl(hydroxyethyl)methylammonιum chloride and sodium dihexylsulfosuccinate with octyl(hydroxyethyl)dιmethylammonιum chloride were much higher than those of the single surfactants See Zao, G , Huoxue Xuebo, 43, 705 (1985) (Ch Chem Abstracts 103 184033n) The strong synergistic effect on surface pressure for mixed solutions of cationic and anionic surfactants has been studied quantitatively When dilute solutions of sodium dodecylsulfate and dodecyltrimethylammonium bromide were mixed, tile surface pressure increased by more than 40 mN/rπ Also, the cmc and the minimum surface tension were lower for the mixture than for either the anionic or cationic surfactants alone (Lucassen-Reynders et al , J Colloid Interface Sci , 81 , p 150 (1981 ))

However, mixed anionic-cationic mixtures also have shown antagonistic effects relative to the properties of the individual surfactant components See Chobanu et al , Izv Akad Nauk Mold SSR, Ser Biol Khim Nauk , 5, p 66 (1982) Unlike other mixed surfactant systems, most anionic-cationic surfactant mixtures studied are insoluble or only slightly soluble in water Hence, practical use of anionic- cationic surfactant mixtures has been very limited in areas where a relatively high concentration of surfactants is needed (see U S Pat No 5,472,455, to Mehreteab, issued Dec 5, 1995) Thus, there is a need for soluble anionic-cationic surfactant mixtures At present, very few anionic-cationic surfactant mixtures have been found which produce clear solution phases over a wide concentration range at equimolar composition See generally, Khan, A , Marques, E , Spec Surfactants 1997, 37-80, edited by Robb, I D Blackie Typically, anionic-cationic surfactant mixtures are present as microemulsions, rather than as clear, homogeneous solutions Usually, the anionic and/or cationic surfactant must be alkoxylated to even maintain such a microemulsion

Because the probability of synergism between surfactants increases with the strength of interaction, the greatest probability of synergism with anionic surfactants exists in anionic-cationic or anionic-zwiteπonic mixtures See generally, Surfactant and Interfacial Phenomena, Rosen, M , John Wiley & Sons, Inc 1989 p 402 Surfactant performance is gauged by the so-called β value, which is a negative number indicating how much less a system's actual surface tension is compared to its calculated surface tension Surfactant mixtures exhibiting larger deviations between calculated and actual surface tension perform better, thus, surfactant performance increases with progressively more negative β values However, with respect to anionic-cationic mixtures, the variations in surfactant type and size that produce progressively more negative β values unfortunately are accompanied by decreasing solubility Hence anionic-cationic synergism is limited by the formation of an insoluble salt, which typically occurs when the combined number of carbon atoms in the chains of both surfactants totals more than about twenty See generally, Lomax, E, Specialty Chemicals 1993, v 13 n 4 p 223-227) A method for enhancing the solubility of anionic-cationic surfactant mixtures is therefore needed to allow achieving maximum negative β values

Without being bound by any particular theory, the benefits associated with solubihzed anionic/cationic systems are best explained by the theory that surfactant molecules of opposite charge pack more closely to each other in micelles due to the absence of any electrostatic repulsion This close packing in turn leads to more efficient soil removal See generally, Lomax, E , supra Prior art attempts to solubihze anionic-cationic surfactant systems include the use of organic solvents, such as butanol or ethanol Also, reported is the use of nonionic surfactants as solubilizing agents or incorporation of alkoxy groups into the anionic and/or cationic surfactants Unfortunately, addition of organic solvents presents a fire hazard Additionally, addition of nonionic components tends to keep the anionic and cationic surfactant molecules further apart, decreasing the overall efficacy of the system Once again without being bound by any particular theory, the oppositely charged surfactant molecules are kept further apart due to stearic hindrance and because of the osmotic effects which force water molecules between the two surfactant molecules, diminishing the beneficial effect of closer packing Thus, there is a need for anionic-cationic surfactant blends that are efficacious, readily soluble in water at a variety of concentrations, easy to handle, and safe to handle Accordingly, it has been surprisingly discovered that soluble and substantially soluble mixtures of anionic and cationic surfactants can be prepared without the use of flammable organic solvents The anionic-cationic blends of the present invention generally form clear solutions at a variety of concentrations in water

Summary of the Invention

Surfactant blends of the present invention are useful for preparing a variety of finished consumer cleaning products, including for example, liquid dish detergents, laundry detergents, automatic dishwasher detergents, hand soaps, laundry bars, personal cleansing bars, multi-purpose cleaners, multi-functional shampoos, body washes, and textile treatment compositions Surfactant blends of the present invention also may be employed as surfactants in agricultural and pesticide applications Additionally, the surfactant blends may be utilized in antimicrobial detergent formulations (e g , antimicrobial hard surface cleaners, hand soaps, shampoos, and dish detergents), soft-terg delivery systems and pre-spotter compositions Surfactant blends of the present invention may be prepared in various concentrations and exhibit a wide range of rheological behavior The surfactant blends display excellent detergent and conditioning properties

One aspect of the present invention relates to surfactant complexes comprising at least one cationic surfactant, at least one anionic surfactant, and at least one "bridging surfactant" selected from nonionic, semi-polar nonionic, and amphoteπc/zwitterionic surfactants, and mixtures thereof These complexes are useful as rheology modifiers in a wide variety of surfactant compositions

The present invention furnishes substantially water-soluble ternary surfactant blends which provide improved performance, such as for example, increased surface tension reduction, improved wetting times, and increased foam volume and stability, to detergent and personal care surfactant formulations Additionally, ternary blends of the present invention provide for improved greasy, oily soil removal from surfaces and textiles The blends are also capable of providing conditioning properties to skin, hair and textiles

Surprisingly, it has been discovered that complexes of anionic and cationic surfactants can be utilized in combination with a bridging surfactant to produce ternary surfactant blends which allow the anionic-cationic complex to remain relatively soluble in aqueous solutions, and at a variety of concentrations, without the use of solubilizing organic solvents or insertion of alkoxy chains into the anionic or cationic surfactants Surprisingly, blends of the present invention generally are flowable at concentrations as high as about 80 percent by weight Additionally, the surfactant blends when diluted to a concentration of about 0 1 percent by weight in water generally form a clear aqueous solution substantially free of precipitates As used herein, the term "flowable" means fluid under gravity at ambient conditions (about 1 atmosphere of pressure at about 25°C) without application of mechanical energy As used herein, the term "clear" means allowing at least 50% transmittance measured spectrophotometπcally at 700 nanometers using water as the standard for 100% transmittance Typically, the ternary surfactant blend comprises (a) at least one cationic surfactant, (b) at least one anionic surfactant, and (c) at least one bridging surfactant, wherein the molar ratio of (a) (b) (c) is generally about 1 1 1 However, to optimize performance, the molar ratio of the components can vary as conditions may dictate In one aspect, the invention provides a surfactant blend comprising (a) a cationic surfactant which is a quaternary ammonium compound of the formula

+

R₂-N-R₃ X

where

R-i, R₂, and R₃ are independently ethyl or methyl, R₄ is an alkyl group having an average of from about 8 to about 16 carbon atoms, and

X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate,

(b) an anionic surfactant which is (1) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms,

(n) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms,

(in) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide,

(iv) an -olefin sulfonate having an average of from about 12 to about 18 carbon atoms,

(v) an α-sulfonated C C₆ alkyl ester of a fatty acid having an average of from about 11 to about 16 carbon atoms,

(vi) a sulfosuccinate having an average of from about 10 to about 16 carbon atoms,

(vn) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or (vni) a sulfoacetate having an average of from about 12 to about 20 carbon atoms, or mixtures thereof, and

(c) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines, wherein the total concentration of combined cationic, anionic, and bridging surfactants is from about 30 to about 80 percent by weight, and wherein the surfactant blend is flowable In another aspect, the invention provides a method of preparing a ternary surfactant composition comprising combining (a) a cationic surfactant which is a quaternary ammonium compound of the formula

R₂-N-R₃ R₄

where

R R₂, and R₃ are independently ethyl or methyl,

R₄ is an alkyl group having an average of from about 8 to about 16 carbon atoms, and

X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate, and

(b) an anionic surfactant which is

(i) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms,

(II) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms,

(in) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide,

(iv) an α-olefin sulfonate having an average of from about 12 to about 18 carbon atoms,

(v) an α-sulfonated Ci-Ce alkyl ester of a fatty acid having an average of from about 11 to about 16 carbon atoms, (vi) a sulfosuccmate having an average of from about 10 to about 16 carbon atoms,

(vn) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or

(VIII) a sulfoacetate having an average of from about 12 to about 20 carbon atoms, or mixtures thereof, and

(c) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines, wherein the bridging surfactant is added first or second, and wherein the total concentration of combined cationic, anionic, and bridging surfactants is from about 30 to about 80 percent by weight, and wherein the surfactant blend is flowable

In still another aspect, the invention provides a method for enhancing the solubility of an anionic- cationic surfactant complex comprising combining (a) an anionic-cationic complex formed by combining in any order

(i) a cationic surfactant which is a quaternary ammonium compound of the formula

+

Ri

R₂-N i--R₃ X

R₄

where

R-), R₂, and R₃ are independently ethyl or methyl, R₄ is an alkyl group having an average of from about 8 to about 16 carbon atoms, and

X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate, and (II) an anionic surfactant which is

(1 ) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms, (2) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms,

(3) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide,

(4) an α-olefin sulfonate having an average of from about 12 to about 18 carbon atoms, (5) an α-sulfonated C^Ce alkyl ester of a fatty acid having an average of from about

11 to about 16 carbon atoms,

(6) a sulfosuccinate having an average of from about 10 to about 16 carbon atoms,

(7) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or

(8) a sulfoacetate having an average of from about 12 to about 20 carbon atoms, or mixtures thereof, and

(b) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines

Thus, the invention provides surfactant blends comprising a synergistic mixture of anionic and cationic surfactants that are generally water soluble without the use of organic solvents or insertion of alkoxy chains into either the anionic or cationic surfactant The invention further provides surfactant blends exhibiting excellent detergent properties comprising a synergistic mixture of anionic and cationic surfactants that are generally flowable at concentrations as high as about 80 percent by weight, and, when diluted to a concentration of about 0 1 percent by weight in water, generally form clear aqueous solutions substantially free of precipitates

These and other aspects and advantages, as well as the scope, nature, and utilization of the claimed invention will become apparent to those skilled in the art from the following detailed description and claims

Detailed Description of a Preferred Embodiment

Cationic and anionic surfactants form complexes that are generally insoluble because the charged heads (anionic or cationic) responsible for water solubility are neutralized during complexation Surprisingly, it has been found that if the cationic surfactant and anionic surfactant are combined with a bridging surfactant to form a ternary blend, a substantially water-soluble system is produced In ternary surfactant blends of the invention, the use of additional hydrophihc groups (such as ethylene oxide groups or additional charge that remains un-neutra zed during complexation) on the anionic or cationic surfactant is not necessary to produce a water-soluble complex Water solubility is assured if an appropriate bridging surfactant is utilized in combination with the anionic and cationic surfactant

The present invention provides ternary blends of cationic, anionic and bridging surfactants wherein anionic/cationic complexes are formed While not intending to be limited by a particular theory, it is believed that the quaternary ammonium agent (a cationic surfactant) and anionic surfactants typically form ion pair complexes in aqueous solutions The ion pairs formed between tn-short chain, mono-long chain quaternary ammonium halides and many anionic surfactants have low solubility and precipitate as a solid salt at typical use concentrations This not only has a negative effect on cleaning performance, but also prevents use of such anionic-cationic ion pair complexes in isotropic liquid detergents On the other hand, ion pairs formed by such cationic surfactants and many anionic surfactants in the presence of a bridging surfactant are much more soluble in bulk surfactant compositions, as detailed herein This increased solubility allows for greater flexibility in formulating with the bulk surfactant compositions (i e the surfactant blends), such as for example, the formulation of isotropic liquid detergents Ternary surfactant blends of the invention are generally flowable at concentrations as high as about 80 percent by weight Additionally, the surfactant blends when diluted to a concentration of about 0 1 percent by weight in water generally form a clear aqueous solution substantially free of precipitates

One indication that an anionic-cationic complex is solubilized within the ternary surfactant blends of the invention is the unique surface tension properties exhibited by the ternary surfactant blends The interfacial surface tension and detergency behavior of an anionic-cationic complex is very different compared to either of the individual anionic and cationic surfactant components In particular, an anionic- cationic complex exhibits significantly lower interfacial surface tension and significantly higher foaming than either an anionic or cationic surfactant alone In similar fashion, the interfacial tension between certain oils and an aqueous solution of a ternary surfactant blend of the invention was found to be lower than the interfacial tension between the same oils and an aqueous solution of the individual anionic, cationic, or bridging surfactants, or combinations of two of these surfactants This indicates that an anionic-cationic complex, once formed, remains solubilized in aqueous solutions of ternary surfactant blends of the invention Surprisingly, anionic-cationic complexes remain solubilized within aqueous solutions of ternary surfactant blends even when one or both of the cationic and anionic surfactants contain substantially no alkylene oxide groups or additional charges that remain unneutralized during complexation

Long-term storage stability is often lacking in mixtures employing anionic-cationic complex mixtures due to the tendency of anionic and cationic surfactants in combination to produce precipitates in water Typically, such compositions are not stable and separate into two phases on storage, rendering them aesthetically and functionally unacceptable Surprisingly, ternary surfactant blends of this invention are generally provided in the form of a flowable composition that can be expected to be stored for long periods of time prior to sale or use The formation of an anionic-cationic precipitate is avoided herein, and a lack of such a precipitate in the compositions of this invention is one of this invention's advantages In another embodiment, the invention provides methods for preparing ternary surfactant blends The ternary blends of the invention are readily obtained by merely pre-mixing either the anionic or the cationic surfactant with the bridging surfactant, followed by mixing with the surfactant not pre-mixed

In other embodiments, the present invention provides complexes useful as rheology modifiers The present invention further encompasses consumer detergent, laundry and personal care products prepared using the surfactant blends and/or complexes detailed herein The essential, as well as the optional, components of the present invention are described below Cationic Surfactants

Generally, the cationic surfactant is a surfactant selected from the group comprising fatty amine salts, fatty diamine salts, polyamine salts, quaternary ammonium salts, polyoxyethyleneated fatty amine salts, quaternized polyoxyethyleneated fatty amines, and mixtures thereof A variety of cationic surfactants useful in the present invention are well known in the art Cationic surfactants useful herein include those disclosed in the following documents, all of which are incorporated by reference herein M C Publishing Co , McCutcheon's Detergents & Emulsifiers, (North American Ed , 1993), Schwartz et al , Surface Active Agents, Their Chemistry and Technology, New York, Interscience Publisher, 1949, U S Pat No 3,155,591 , Hilfer, issued Nov 3, 1964, U S Pat No 3,929,678, Laugh n et al , issued Dec 30, 1975, U S Pat No 3,959,461 , Bailey et al , issued May 25, 1976, and U S Pat No 4,387,090, Bo ch, Jr , issued June 7, 1983 Suitable anions include but are not limited to halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, and carboxylate Cationic surfactants in the form of quaternary ammonium salts include mono-long chain alkyl-tn- short chain alkyl ammonium halides, wherein the long chain alkyl group has from about 8 to about 22 carbon atoms and is derived from long-chain fatty acids, and wherein the short chain alkyl groups can be the same or different but preferably are independently methyl or ethyl Examples of quaternary ammonium salts useful herein include but are not limited to cetyl tnmethyl ammonium chloride and lauryl tnmethyl ammonium chloride A particularly preferred quaternary ammonium salt is cetyl tnmethyl ammonium chloride

Salts of primary, secondary and tertiary fatty amines are also suitable cationic surfactant materials The alkyl groups of such amine salts preferably have from about 12 to about 22 carbon atoms, and may be substituted or unsubstituted Secondary and tertiary amine salts are preferred, tertiary amine salts are particularly preferred Suitable amine salts include the halogen (i e fluoride, chloride, bromide), acetate, phosphate, nitrate, citrate, lactate and alkyl sulfate salts Amine salts derived from amine, such as for example, stearamido propyl dimethyl amine, diethyl ammo ethyl stearamide, dimethyl stearamine, dimethyl soyamine, soyamine, myπstyl amine, tndecyl amine, ethyl stearylamine, N-tallowpropane diamine, ethoxylated (5 moles E O ) stearylamine, dihydroxy ethyl stearylamine, and arachidylbehenylamine, are useful herein Such salts also include stearylamine hydrogen chloride, soyamine chloride, stearylamine formate, N-tallowpropane diamine dichloπde and stearamidopropyl dimethylamine citrate Additionally cationic surfactants included among those useful in the present invention are disclosed in U S Pat No 4,275,055, Nachtigal, et al , issued June 23, 1981 , incorporated herein by reference

In addition to the above, cationic surfactants particularly useful herein are those of the general formula

R

R₂-N-R₃ X R_

where R^ R₂, and R₃ are independently ethyl or methyl, R₄ is an alkyl group having an average of from about 8 to about 16 carbon atoms, and X is an a suitable ion including but not limited to halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate

Other quaternary ammonium compounds and amine salt compounds include those of the above general formula in the form of ring structures formed by covalently linking two of the radicals Examples include imidazolines, imidazoliniums, and pyπdiniums, etc , wherein said compound has at least one nonionic hydrophile-containing radical as set forth above Specific examples include 2-heptadecyl-4,5- dιhydro-1 H-ιmιdazol-1-ethanol, 4,5-dιhydro-1-(2-hydroxyethyl)-2-ιsoheptadecyl-1-phenylmethylιmιdazolιum chloride, and 1-[2-oxo-2-[[2-[(1-oxoctadecyl)oxy]ethyl]amιno]ethyl] pyπdiniurπ chloride Additionally, useful polymenzable surface active agents include those of the above general formula in the form of ring structures formed by covalently linking two of the Ri-R₄ groups The quaternary ammonium salts of the present invention may be prepared by a variety of methods known to the art, including for example, hahde exchange, wherein a halide based quaternary ammonium compound is ion exchanged with X, where X is defined above

The most preferred cationic surfactants for use in the present invention include octyltπmethyl ammonium chloride, decyltnmethyl ammonium chloride, dodecyltnmethyl ammonium bromide, dodecyltn methyl ammonium chloride, Cetac^®-30, BTC^®-65NF, BTC^®-835 and BTC^®-885, all commercially available from Stepan Company Anionic Surfactants

The anionic surfactants that may be utilized according to the present invention are well known to the art and are described below in a representative manner Generally speaking, a variety of anionic surfactants useful in the present invention are well known in the art Anionic surfactants useful herein include those disclosed in the following documents, all of which are incorporated by reference herein M C Publishing Co , McCutcheon's Detergents & Emulsifiers, (North American Ed , 1993), Schwartz et al , Surface Active Agents, Their Chemistry and Technology, New York, Interscience Publisher, 1949, U S Pat No 4,285,841 , Barrat et al, issued Aug 25, 1981 , and U S Pat No 3,919,678, Laughlin et al, issued Dec 30, 1975

The anionic surfactants of the present invention generally include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, dι-, and tπethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosmate surfactants Other suitable anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauπde, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated Cι₂-C₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C₆-C-i₄ diesters), and N-acyl sarcosinates Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use in the compositions of the invention include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleyl glycerol sulfates, alkyl phenol ethoxylate sulfates, alkyl phenol ethylene oxide ether sulfates, the C₅-C₁₇ acyl-N-(CrC₄ alkyl) and -

N-(C_!-C₂ hydroxyalkyl) glucamine sulfates, and sulfates of alkylpolysacchandes such as the sulfates of alkylpolyglucoside

Alkyl sulfate surfactants are preferably selected from the group consisting of the C₈-C₂₂ alkyl sulfates Most preferably, the alkyl sulfate surfactant is a C₈-C₁₆ alkyl sulfate Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C₈-C₂₂ alkyl sulfates that have been ethoxylated with from about 0 5 to about 30 moles of ethylene oxide per molecule Most preferably, the alkyl ethoxysulfate surfactant is a C₈-C₁₆ alkyl sulfate which has been ethoxylated with from about 1 to about 30 moles of ethylene oxide A particularly preferred aspect of the invention employs mixtures of C₈ alkyl sulfate (Polystep^® B-

29, commercially available from Stepan Company, Northfield, Illinois) and alkyl ethoxysulfate surfactants

Such mixtures have been disclosed in WO 93/18124, incorporated by reference herein

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C₅-C₂₀ linear alkylbenzene sulfonates, alkyl ester sulfonates, C₆-C₂₂ primary or secondary alkane sulfonates, C₆-C₂₄ olefin sulfonates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof

Anionic sulfonate surfactants are preferably selected from the group consisting of the C₈-

C₂₂ alkyl sulfonates and C₈-C₂₂ α-olefin sulfonates Most preferably, the anionic sulfonate surfactant is an C₈-C₁₈ alkyl sulfonate, such as Bioterge^® PAS-8S (commercially available from Stepan Company,

Northfield, Illinois), or a C₁₂-C₁₈ α-olefin sulfonate, such as Bioterge^® AS-40 (commercially available from

Stepan Company, Northfield, Illinois)

Anionic carboxylate surfactant

Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ("alkyl carboxyls"), especially certain secondary soaps as described herein

Suitable alkyl ethoxy carboxylates include those with the formula RO(CH₂CH₂0)_xCH₂COO M⁺ wherein R is a C₆ to C₁₈ alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than about 20 percent and M is a cation Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO(CHR₁CHR₂0)R₃ wherein R is a C₆ to C_1β alkyl group, x ranges from 1 to 25, Ri and R₂ are selected from the group consisting of hydrogen, methyl acid radical, succmic acid radical, hydroxysuccinic acid radical, and mixtures thereof, and R₃ is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof

Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoιc acid, 2- ethyl-1 -decanoic acid, 2-propyl-1 -nonanoic acid, 2-butyl-1 -octanoic acid and 2-pentyl-1 -heptanoic acid Anionic sulfosuccinate surfactant

Suitable anionic sulfosuccinates include those having the formula o o Q o

XO CCH₂CHC O M⁺ or XO CCH₂CHC OY

SO₃ ^" M⁺ SO₃ ^' M⁺ where X and Y are the same or different and are selected from the group consisting of

R and R(CH₂CH₂0)_x, where x has an average value from about 1 to about 30, R is C₈-C₂₂ alkyl, and M is an alkali metal countenon Anionic sulfosuccinate surfactants are preferably selected from the group consisting of the C₈-C₂₂ sulfosuccinates Most preferably, the anionic sulfosuccinate surfactants is a rπono-

C₁₀-Ci₆ alkyl sulfosuccinate such as disodium laureth sulfosuccinate (Stepan-Mild^® SL3, commercially available from Stepan Company, Northfield, Illinois) Anionic α-sulfonated methyl ester surfactant

Suitable α-sulfonated methyl esters include those having the formula O O

XO— CHC II O^"M _t or XO— CHC II OY

SO₃ ^" M⁺ SO₃ ^" M⁺ where

X and Y are the same or different and are selected from the group consisting of C₈-C₂₂ alkyl, and M is an alkali metal counteπon

Anionic α-sulfonated methyl ester surfactants are preferably selected from the group consisting of the α-sulfonated C Cβ alkyl esters of fatty acids having an average of from about 8 to about 22 carbon atoms Most preferably, the anionic α-sulfonated methyl ester surfactants is selected from the group consisting of the α-sulfonated d-C₆ alkyl esters of fatty acids having an average of from about 11 to about 16 carbon atoms Most preferably, the anionic α-sulfonated methyl ester surfactants is Alpha Step^® MC-48 or Alpha Step^® ML-40 (both commercially available from Stepan Company, Northfield, Illinois) Alkali metal sarcosinate surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula RCON(R₁)CH₂COOM, wherein R is a C₅-C₂₂ linear or branched alkyl or alkenyl group, R, is a C₁-C₄ alkyl group and M is an alkali metal ion Preferred alkali metal sarcosinate surfactants include but are not limited to the myπstyl and oleoyl methyl sarcosinates in the form of their sodium salts Most preferably, the alkali metal sarcosinate surfactant is a C₁₀-C₁₆ sarcosinate such as Maprosyl^® 30 (commercially available from Stepan Company, Northfield, Illinois) Alkyl sulfoacetates

Other suitable anionic surfactants are the alkyl sulfoacetates of the formula RO(CO)CH₂S0₃M, wherein R is a C₁₂-C₂₀ alkyl group and M is an alkali metal ion Preferred alkyl sulfoacetates include but are not limited to the lauryl and myπstyl sulfoacetates in the form of their sodium salts Most preferably, the alkyl sulfoacetate is Lathanol^® LAL (commercially available from Stepan Company, Northfield, Illinois) Bridging Surfactants

The bridging surfactants of the present invention are selected from the group consisting of semi- polar nonionic, ethoxamide, and amphotenc surfactants and mixtures thereof Especially preferred bridging surfactants include amine oxides, ethoxylated alkanolamides, and betaines Semi-Polar Nonionic Surfactants

Semi-polar nonionic surfactants include water-soluble amine oxides having an alkyl moiety containing from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms Semi-polar nonionic surfactants also include water-soluble sulfoxides having alkyl moieties containing from about 10 to about 18 carbon atoms and a moiety selected from the group comprising alkyl groups and hydroxyalkyl groups of from about 1 to about 3 carbon atoms

The present invention encompasses semi-polar nonionic surfactants that are amine oxides formed as shown in Scheme I. wherein R^ R₂, R₃ independently are substituted or unsubstituted hydrocarbyl groups of from about 1 to about 30 carbon atoms, or hydrocarbyl groups having from about 1 to about 30 carbon atoms and containing one or more aromatic, ether, ester, amido, or ammo moieties present as substituents or as linkages in the radical chain, and wherein X is an anion group selected from the group consisting of halogen, sulfonate, sulfate, sulfinate, sulfenate, phosphate, carboxylate, nitrate, and acetate Additionally, useful semi-polar nonionic surfactants include those of the below general formula in the form of ring structures formed by covalently linking two of the R₁-R₄ groups Examples include unsaturated imidazolines, imidazoliniums, and pyndiniums, and the like Particularly preferred semi-polar nonionic surfactants include alkylamine and amidoamine oxides

Scheme I Amine Oxide-Derived Surface Active Agents

Particularly preferred amine oxides include but are not limited to Ammonyx^® C8 (octylamine oxide), Ammonyx^® C10 (decylamine oxide), Ammonyx^® LO (laurylamine oxide), Ammonyx^® MO (myπstylamine oxide), Ammonyx^® MCO (myπstyl/cetylamine oxide), and Ammonyx^® CDO (cocamidoproylamine oxide), all commercially available from Stepan Company, Northfield, Illinois Ethoxamides

Ethoxamides (also termed ethoxylated alkanolamides or polyethylene glycol amides) suitable for use in the present invention include those having the formula

Q O

CH₃(CH₂)_mC-N(CH₂CH₂O)_nH or RC-N(CH₂CH₂O)_nH

Y Y where

RCO- represents the fatty acids derived from coconut oil, m is an integer from about 8 to about 16, n has an average value of about 3,

Y is hydrogen or (CH₂CH₂0)_pH; and p is 0, 1 or more Preferred ethoxamides include but are not limited to Amidox^® C-2 (PEG-3 cocamide), Amidox^® C-5 (PEG- 6 cocamide), and Amidox^® L-5 (PEG-6 lauramide), all commercially available from Stepan Company, Northfield, Illinois

Amphoteπc Surfactants

Suitable amphoteπc surfactants are selected from the group consisting of alkyl glycmates, propionates, imidazolines, amphoalkylsulfonates (sold under the tradename Miranol® by Rhone Poulenc),

N-alkylaminopropionic acids, N-alkyliminodipropiomc acids, imidazolme carboxy-lates, N-alkylbetaines, amido propyl betaines, sarcosinates, cocoamphocarboxyglycmates, amine oxides, sulfobetames, sultaines and mixtures thereof Additional suitable amphotenc surfactants include cocoamphoglycinate, cocoamphocarboxyglycinate, lauramphocarboxyglycinate, coco-amphopropionate, lauramphopropionate, stearamphoglycinate, cocoamphocarboxypropionate, tallowamphopropionate, tallowamphoglycinate, oleoamphoglycinate, caproamphoglycmate, caprylamphopropionate, caprylamphocarboxyglycinate, cocoyl imidazolme, lauryl imidazolme, stearyl imidazolme, behenyl imidazolme, behenylhydroxyethyl imidazoline, capryl-amphopropylsulfonate, cocamphopropylsulfonate, stearamphopropylsolfonate, oleoampho- propylsulfonate and the like

Examples of betaines and sultaines which are suitable for use as bridging surfactants are alkyl betaines and sultaines sold under the tradename Miratame^® by Rhone Poulenc, and Lonzaine^® by Lonza, Inc , Fairlawn, N J Additional examples of betaines and sultaines include cocobetaine, cocoamidoethyl betaine, cocoamidopropyl betame, lauryl betame, lauramidopropyl betame, palmamidopropyl betame, stearamidopropyl betaine, stearyl betaine, cocosultame, lauryl sultame, tallowamidopropyl hydroxysultame and the like Particularly preferred amphotenc surfactants include Amphosol^® CA (cocamidopropyl betaine) and Amphosol^® DM (lauryl betaine), both commercially available from Stepan Company, Northfield, Illinois Optional Ingredients

The following optional ingredients can be present in various quantities The ternary surfactant blends may be formulated with optional components, such as fragrances, emollient, solvents, humectants, optical bnghtners, thickeners, powders, viscosity modifiers, hydrotropes, preservatives, bluing agents, and dyes, to produce a wide variety of end use products

Although the use of such optional components is not essential to the present invention, and may in fact be somewhat less preferred depending on the desired final formulation and end use application, suitable optional emollients useful in formulating with blends of the present invention include, for example, stearyl alcohol, glyceryl ncinoleate, glyceryl stearate, propane-1 ,2-dιol, butane-1 ,3-dιol, mink oil, cetyl alcohol, stearamidopropyl dimethylamme, isopropyl isostearate, steanc acid, isobutyl palmitate, isocetyl stearate, oleyl alcohol, isopropyl laurate, hexyl laurate, decyl oleate, octadecan-2-ol, isocetyl alcohol, eicosanyl alcohol, behenyl alcohol, cetyl palmitate, silicone oils such as dimethylpolysiloxane, dimethicone copolyols, di-n-butyl sebacate, isopropyl mynstate, isopropyl palmitate, isopropyl stearate, butyl stearate, polyethylene glycol, tπethylene glycol, lanolin, cocoa butter, corn oil, cotton seed oil, tallow, lard, olive oil, palm kernel oil, rapeseed oil, safflower seed oil, soybean oil, sunflower seed oil, olive oil, sesame seed oil, coconut oil, arachis oil, castor oil, acetylated lanolin alcohols, petrolatum, mineral oil, butyl mynstate, isosteaπc acid, palmitic acid, isopropyl linoleate, lauryl lactate, mynstyl lactate, decyl oleate, and mynstyl mynstate, and mixtures thereof Optional solvents useful in formulating with blends of the present invention include, for example, ethyl alcohol, propylene glycol, water, isopropanol, castor oil, ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, dimethyl sulphoxide, dimethyl formamide, and tetrahydrofuran, and mixtures thereof Optional humectants useful in formulating with blends of the present invention include, for example, glycerin, sorbitol, sodium 2-pyrrolιdone-5-carboxylate, soluble collagen, dibutyl phthalate, propylene glycol, and gelatin, and mixtures thereof

Optional powders useful in formulating with blends of the present invention include, for example, chalk, talc, fullers earth, kaolin, starch, gums, colloidal silicon dioxide, sodium polyacrylate, tetra alkyl and/or tnalkyl aryl ammonium smectites, chemically modified magnesium aluminum silicate, organically modified montmorillonite clay, hydrated aluminum silicate, fumed silica, carboxyvinyl polymer, cellulosics such as hydroxyethyl cellulose and sodium carboxymethyl cellulose, ethylene glycol monostearate, zinc or magnesium stearate, zinc oxide and magnesium oxide, and mixtures thereof These components may also be used as thickeners in fluid or semi-fluid compositions Examples of other optional ingredients useful in formulating with blends of the present invention include, for example, volatile and non-volatile si cones, silicone polymers, preservatives, such as para- hydroxy benzoate esters, humectants, such as butane-1 ,3-dιol, glycerol, sorbitol, polyethylene glycol, stabilizers, such as sodium chloride or ammonium chloride, buffer systems, such as lactic acid together with a base such as sodium hydroxide, oils and waxes, such as avocado oil, Evening Primrose oil, mineral oil, petrolatum, sunflower oil, beeswax, ozokerite wax, paraffin wax, lanolin, lanolin alcohol, emollients, thickeners, activity enhancers, colorants, whiteners, fragrances, and bacteπcides, and mixtures thereof

The blends of the present invention may also be formulated with optional detergent builder materials Nearly any detergent builders known in the art can be formulated with the present blends Examples of useful detergent builders are described in U S Pat Nos 4,321 ,165, (to Smith et al, issued Mar 23, 1982) and 5,565,145 (to Watson et al , issued Oct 15, 1996), both incorporated herein by reference Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness Inorganic as well as organic builders can be used Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils The level of builder can vary widely depending upon the end use of the composition and its desired physical form When present in a final formulation, the compositions will typically comprise at least about 1% builder Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder Granular finished formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder Lower or higher levels of builder, however, also can be acceptable

Enzymes and enzyme stabilizers can be formulated with blends of the instant invention for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglycende-based stains, for example, and for fabric restoration Examples of useful enzymes and enzyme stabilizers are described in U S Pat No 5,565,145 (to Watson et al , issued Oct 15, 1996), incorporated herein by reference Useful enzymes include, for example, proteases, amylases, lipases, and cellulases, as well as mixtures thereof Other types of enzymes may also be included They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin However, a particular enzyme choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases

Suitable examples of proteases are the subtilisms which are obtained from particular strains of B subti s and B licheniforms Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE The preparation of this enzyme and analogous enzymes is described in British Pat Specification No 1 ,243,784 of Novo Proteolytic enzymes suitable for removing protein- based stains that are commercially available include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc (The Netherlands) Other proteases include Protease A (see European Patent Application 130,756, published Jan 9, 1985) and Protease B (see European Patent Application Ser No 87303761 8, filed Apr 28, 1987, and European Patent Application 130,756, Bott et al, published Jan 9, 1985)

Amylases include, for example, -amylases described in British Patent Specification No 1 ,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc and TERMAMYL, Novo Industries Cellulases suitable for use with ternary surfactant blends of the present invention include both bacteπal or fungal cellulase Preferably, they will have a pH optimum of between 5 and 9 5 Suitable cellulases are disclosed in U S Pat 4,435,307, Barbesgoard et al, issued Mar 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212- producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander) Suitable cellulases are also disclosed in GB-A-2 075 028, GB-A-2 095275 and DE-OS 247 832CAREZYME (Novo) is especially useful

Suitable lipase enzymes include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeπ ATCC 19.154, as disclosed in British Patent 1 ,372,034 See also lipases in Japanese Patent Application 53,20487, laid open to public inspection on Feb 24, 1978 This lipase is available from Amano Pharmaceutical Co Ltd , Nagoya, Japan, under the trade name Lipase P Amano, hereinafter referred to as Amano-P Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e g Chromobacter viscosum var lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co , Tagata, Japan, and further Chromobacter viscosum lipases from U S Biochemical Corp , U S A and Diosynth Co , The Netherlands, and lipases ex Pseudomonas gladioli The LIPOLASE enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EPO 341 ,947) is a preferred lipase for use herein

A wide range of enzyme materials and means for their incorporation into synthetic detergent compositions are also disclosed in U S Pat No 3,553,139, issued Jan 5, 1971 to McCarty et al Enzymes are further disclosed in U S Pat No 4,101 ,457, Place et al, issued Jul 18, 1978, and in U S Pat No 4,507,219, Hughes, issued Mar 26, 1985, both Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U S Pat No 4,261 ,868, Hora et al, issued Apr 14, 1981 Enzymes for use in detergents can be stabilized by various techniques Enzyme stabilization techniques are disclosed and exemplified in U S Pat No 3,600,319, issued Aug 17, 1971 to Gedge, et al, and European Patent Application Publication No 0 199 405, Application No 86200586 5, published Oct 29, 1986, Venegas Enzyme stabilization systems are also described, for example, in U S Pat No 3,519,570 The optional enzymes useful herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used Additional stability can be provided by the presence of various other disclosed stabilizers, especially borate species See Severson, U S Pat No 4,537,706 Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition This concentration can vary somewhat, depending on the amount of enzyme present and its response to the calcium or magnesium ions The level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc , in the final composition Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts A small amount of calcium ion, generally from about 0 05 to about 04 millimoles per liter, is often also present in the final composition due to calcium in the enzyme slurry and formula water In solid detergent compositions the final formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor In the alternative, natural water hardness may suffice

Generally, the aforementioned levels of calcium and/or magnesium ions are sufficient to provide enzyme stability to a finished formulation More calcium and/or magnesium ions can be added to the compositions to provide an additional measure of grease removal performance Accordingly, final formulations prepared from the blends disclosed herein typically will comprise from about 0 05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both The amount of water- soluble ion can vary with the amount and type of enzyme employed in the final composition Final compositions based on the blends detailed herein may also optionally contain various additional stabilizers, especially borate-type stabilizers Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e g , sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable Substituted boric acids (e g , phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid) can also be used in place of boric acid

Bleaching agents, bleach activators, chelatmg agents, anti-redeposition agents, polymeric dispersing agents, optical bπghteners, suds suppressors, dye transfer inhibition agents, optical bπghteners, and soil release agents can be formulated with blends of the instant invention Examples of such materials are generally described in U S Pat No 5,565,145 (to Watson et al , issued Oct 15, 1996), incorporated herein by reference

Various other detergent additives or adjuvants may be present in the detergent product to give it additional desired properties, either of functional or aesthetic nature Thus, there may be included in the formulation minor amounts of soil suspending or anti-redeposition agents, e g polyvmyl alcohol, fatty amides, sodium carboxymethyl cellulose, hydroxy-propyl methyl cellulose, optical bnghteners, e g cotton, amine and polyester bnghteners, for example, stilbene, tnazole and benzid e sulfone compositions, especially, sulfonated substituted tnazinyl stilbene, sulfonated naphthotπazole stilbene, benzidme sulfone, etc , most preferred are stilbene and tnazole combinations Bluing agents such as ultramarine blue, enzymes, preferably proteolytic enzymes, such as subtilism, bromelm, papam, trypsm and pepsin, as well as amylase type enzymes, bacteπcides, e g tetrachlorosalicylani de, hexachlorophene, fungicides, dyes, pigments (water dispersible), preservatives, ultraviolet absorbers, anti-yellowmg agents, such as sodium carboxymethyl cellulose, complex of C-_|2 ^to

C22 alkyl alcohol with C12 to C-13 alkylsulfate, pH modifiers and pH buffers, color safe bleaches, perfume and anti-foam agents or suds suppressors, e g silicon compounds, can also be used

In the case of final formulations, other optional ingredients include neutralizing agents, buffering agents, phase regulants, hydrotropes, polyacids, suds regulants, opacifiers, antioxidants, preservatives, bacteπcides, dyes, perfumes, and bnghteners described in the U S Pat No 4,285,841 , Barrat et al, issued Aug 25, 1981 , incorporated herein by reference Other ingredients useful in final detergent compositions can be formulated with blends of the instant invention, including carders, processing aids, pigments, solvents for liquid formulations, solid fillers for bar compositions, sodium sulfate, sodium chloride, protein hydrolysates, cholesterol derivatives, UV absorbers, chelatmg agents, etc If high sudsing is desired, suds boosters such as the C-_|r_j-C-|6 alkanolamides can be incorporated into the final compositions, typically at 1%-10% levels The C1_Q-C-14 monoethanol and diethanol amides illustrate a typical class of such suds boosters If desired, soluble magnesium salts such as MgCl2, MgSO and the like, can be added at levels of, typically, 0 1%-2%, to provide additional suds and to enhance grease removal performance to a final formulation Additionally, the blends may contain non-conventional surfactants, such as fluorosurfactants, gemini surfactants and polymeric cationic and anionic surfactants Blends of the present invention are prepared from readily available, economical raw materials, and generally their preparation does not require any special handling or equipment The blends may be prepared in a batch mode or a continuous mode The ternary surfactant blends of the present invention typically contain water as the so'vent, however, other solvents may optionally be employed, either alone or in combination with water Low molecular weight primary or secondary alcohols, exemplified by methanol, ethanol, propanol, and isopropanol, are suitable optional solvents Monohydnc alcohols are preferred optional solvents, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e g , 1 ,3-propanedιol, ethylene glycol, glycerine, and 1 ,2-propanedιol) can also be used The compositions may contain from about 5 to about 90 percent, typically from about 10 to about 50 percent by weight of water and/or optional solvent

While pH is of secondary significance herein, the ternary surfactant blends of the present invention typically are prepared having a pH of between about 2 and about 10, preferably between about 5 and about 8 Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc , and are well known to those skilled in the art Suitable materials for adjusting the pH of these compositions include triethanolamme, diethanolamine, sodium carbonate, sodium bicarbonate, and the

Ternary surfactant blends of this invention may be formulated into commercially useful products having an active level of cationic, anionic and bridging surfactants combined of from about 0 1 to about 98 percent by weight solids More typically, ternary surfactant blends of the present invention are flowable and have a total surfactant concentration of from about 5 to about 80 percent by weight of the composition Ternary surfactant blends of the invention are preferably clear and exhibit no precipitate formation upon aging Additionally, the ternary surfactant blends may be processed into a variety of forms such as, for example, liquids, solutions, solids, powders, flakes, semi-solids, gels, "ringing" gels, G- phase liquids/pastes, hexagonal liquid crystal phases, or thick non-flowable pastes The ternary surfactant blends may be spray dried, flaked, or extruded Although not critical to the present invention, the blends may be prepared "neat" or in a conventional solvent such as water, low molecular weight alcohol or hydrocarbon, or a mixture thereof, to produce a solution of the ternary surfactant blend The present invention encompasses ternary surfactant systems in dry form and as aqueous solutions Ternary surfactant blends in concentrations up to 100 percent by weight may be isolated by drying a solution of the blend Conversely, ternary surfactant blend solutions may be prepared by dissolving a solid form of the blend in water, low molecular weight alcohol, low molecular weight glycol, or mixtures thereof

One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention The invention is illustrated further by the following examples, which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein All documents, e g , patents and journal articles, cited above or below are hereby incorporated by reference in their entirety

As used in the Examples appearing below, the following designations, symbols, terms and abbreviations have the indicated meanings

Material Definition Alpha Step^®MC-48 Sodium alphasulfo methyl C₁₂-₁₈ ester (and) disodium alphasulfo C_{12 18} fatty acid salt (commercially available from Stepan Company, Northfield Illinois)

Alpha Step^®ML-40 Sodium alphasulfo methyl ester (and) disodium alphasulfo lauπc acid salt (commercially available from Stepan Company, Northfield Illinois)

Polystep^® B-29 Sodium octyl sulfate (commercially available from Stepan Company,

Northfield Illinois) Polystep^® B-25 Sodium decyl sulfate (commercially available from Stepan Company,

Northfield Illinois)

Polystep^® B-22 Ammonium lauryl ether sulfate (3EO) (commercially available from

Stepan Company, Northfield Illinois)

Polystep^® B-20 Ammonium lauryl ether sulfate (12EO) (commercially available from

Stepan Company, Northfield Illinois) Bioterge^® PAS-8S Sodium octyl sulfonate (commercially available from Stepan Company, Northfield Illinois)

Maprosyl^®30 Sodium lauroyl sarcosinate (commercially available from Stepan Company, Northfield Illinois)

Stepan-Mild^® SL3 Disodium laureth sulfosuccinate (commercially available from Stepan Company, Northfield Illinois)

Steol^® CS-370 Sodium laureth sulfate (3EO) (commercially available from Stepan Company, Northfield Illinois)

Stool" CS-460 Ammonium laureth sulfate (3EO) (commercially available from Stepan Company, Northfield Illinois)

Stepanol^® WA-Extra Sodium lauryl sulfate (commercially available from Stepan Company, Northfield Illinois) Bioterge^® AS-40 Sodium C14-16 olefin sulfonate (commercially available from Stepan Company, Northfield Illinois)

QC8 Octyltrimethylammonium chlonde

QC10 Decyltπmethylammonium chloride

QC12 or DTMAB Dodecyltπmethyiammonium bromide

Cetac^® 30 Cetyltπmethylammonium chloride (commercially available from Stepan Company, Northfield Illinois)

BTC^® 65NF Dimethylbenzylammonium chloride (commercially available from Stepan Company, Northfield Illinois)

BTC^® 885 Quaternium 24 (and) dimethylbenzylammonium chloride (commercially available from Stepan Company, Northfield Illinois)

Ammonyx^® LO Lauramme oxide (commercially available from Stepan Company, Northfield Illinois)

Ammonyx^® MCO Myπstyl/cetyl amine oxide (commercially available from Stepan Company, Northfield Illinois) Ammonyx^® C8 Octylamine oxide (commercially available from Stepan Company, Northfield Illinois)

Ammonyx^® C10 Decylamine oxide (commercially available from Stepan Company, Northfield Illinois)

Amphosol^® CA Cocamidopropyl betaine (commercially available from Stepan Company, Northfield Illinois)

Amphosol^® DM Lauryl betaine (commercially available from Stepan Company, Northfield Illinois) Amidox^® C-2 PEG-3 Cocamide (commercially available from Stepan Company, Northfield Illinois)

Amidox^® C-5 PEG-6 Cocamide (commercially available from Stepan Company, Northfield Illinois)

Amidox^® L-5 PEG-6 Lauramide (commercially available from Stepan Company, Northfield Illinois)

One skilled in the art will recognize that modifications may be made in the present invention without deviating from the spirit or scope of the invention. The invention is illustrated further by the following examples, which are not to be construed as limiting the invention or scope of the specific procedures or compositions described herein.

In the following examples, all amounts are stated in percent by weight of active material unless indicated otherwise Surface tension measurements, Draves wetting measurements, and Ross Miles foaming initial and final measurements all were taken at 0 1 % concentration of the surfactant blend in water

Example 1

Various surfactant blends were prepared as shown in Table I The appearance of each blend as a concentrated (30-40%) and dilute (0 1-1 0%) composition was noted

None of the prepared blends comprising only anionic and cationic surfactants were single-phase at both concentrations This observation confirms the limited solubility nature of anionic-cationic complexes

Surprisingly, however, the addition of an amine oxide, ethoxamide, and/or betaine bridging surfactant to the anionic-cationic blends eliminated precipitation and produced clarity improvements in all cases, in most cases producing solutions that were clear at both concentrations This observation demonstrates that the bridging surfactant promotes solubility of the anionic-cationic complex

Table I

Example 2

A ternary surfactant blend of an anionic surfactant, a cationic surfactant, and a bridging surfactant was prepared by mixing at room temperature equal moles of Alpha Step^® ML-40, QC10, and Amphosol^® CA. A 33.03% clear liquid phase free of precipitate was obtained. This surfactant blend displayed remarkable synergism, as shown in Table II, which shows that the ternary surfactant blend possesses surface tension, wetting, and foaming properties all dramatically better than the properties of any single surfactant or combination of two surfactants.

Table II

Example 3

Several ternary surfactant blends as shown in Table III were prepared by mixing at room temperature equal moles of an anionic surfactant, a cationic surfactant, and a bridging surfactant. Appearance, surface tension, wetting, and foaming properties were evaluated for each blend over a range of pH. For the systems tested, when a betaine is used as the bridging surfactant, clarity can be maintained over a wide pH range. When an amine oxide is used as the bridging surfactant, clarity can be maintained when pH is above about 7.

Table III

Example 4

Several ternary surfactant blends as shown in Table IV were prepared by mixing at room temperature equal moles of an anionic surfactant, a cationic surfactant, and a bridging surfactant. Appearance, surface tension, wetting, and foaming properties were evaluated for each blend. The results indicate that when magnesium ions are added to the ternary surfactant blends, the clarity and surfactant properties of the mixture are maintained.

Table IV

Example 5

Several ternary surfactant blends as shown in Table V were prepared by mixing at room temperature equal moles of an anionic surfactant, a cationic surfactant, and a bridging surfactant. Surface tension, wetting, and foaming properties were evaluated for each blend. The results indicate that surfactant properties of the ternary blends can be tailored by altering the identity of the bridging surfactant, or the chain length of the anionic and/or cationic surfactant. For example, increasing the chain length of the cationic surfactant decreases wetting time (12 seconds, compared to 5 seconds). Furthermore, increasing the chain length of the anionic surfactant also decreases wetting time (7 seconds, as compared to 3 seconds). Finally, changing the bridging surfactant from an amine oxide to a betaine increases foaming (14.7 cm., compared to 17.3 cm.).

Table V

Example 6

Several ternary surfactant blends as shown in Table VI were prepared by mixing at room temperature equal moles of an anionic surfactant, a cationic surfactant, and a bridging surfactant. Appearance, surface tension, wetting, and foaming properties were evaluated for each blend. The results indicate that clarity and surfactant properties of the ternary blends of the invention can be maintained for a range of anionic, cationic, and bridging surfactants.

Table VI

Table VI (cont'd)

Example 7

Various surfactant blends were prepared as shown in Table VII. The appearance of each blend as a concentrated (33-38%) and dilute (0.1-1.0%) composition was noted. These blends comprised multiple anionic surfactants and were clear upon the addition of an amine oxide, demonstrating that the bridging surfactant promotes solubility of anionic-cationic complexes even in mixed anionic systems.

Table VII

Example 8

Various concentrated (30-40%) surfactant blends were prepared as shown in Table VIII The appearance of each blend was noted. None of the concentrated blends in Table VIII that comprised only anionic and cationic surfactants were flowable Surprisingly, however, the addition of an amine oxide, ethoxamide, and/or betaine bridging surfactant to the anionic-cationic blends rendered a final composition that was flowable This observation demonstrates that the present invention allows for production of flowable concentrated surfactant blends comprising anionic, cationic, and bridging surfactants

Table VIII

Example 9

Various concentrated (30-40%) surfactant blends were prepared as shown in Table IX and Table X. The appearance of each blend was noted. The concentrated blends in Table IX, which comprised anionic, cationic, and bridging surfactants, were flowable. The concentrated blends in Table X, presented for comparison purposes, were not flowable even though these blends comprised anionic, cationic, and bridging surfactants and were prepared according to the same procedure used in preparing the blends in Table IX. This observation demonstrates that not every combination of anionic, cationic, and bridging surfactant is flowable. However, routine screening of combinations of anionic, cationic, and bridging surfactants allows determining which ternary surfactant blends are flowable.

Table IX

Table X

The invention and the manner and process of making and using it, are now described in such full, clear, concise and exact terms as to enable any person skilled in the art to which it pertains, to make and use the same Although the foregoing describes preferred embodiments of the present invention, modifications may be made therein without departing from the spirit or scope of the present invention as set forth in the claims To particularly point out and distinctly claim the subject matter regarded as invention, the following claims conclude this specification

Claims

What we claim is 1 A surfactant blend comprising (a) a cationic surfactant which is a quaternary ammonium compound of the formula + R2-N-R3 X R4 where RL R2, and R3 are independently ethyl or methyl, R4 is an alkyl group having an average of from about 8 to about 16 carbon atoms, and X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate, and (b) an anionic surfactant which is (i) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms, (n) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms, (in) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide, (iv) an α-olefin sulfonate having an average of from about 12 to about 18 carbon atoms, (v) an α-sulfonated d-C6 alkyl ester of a fatty acid having an average of from about 11 to about 16 carbon atoms, (vi) a sulfosuccinate having an average of from about 10 to about 16 carbon atoms, (VII) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or (VIII) a sulfoacetate having an average of from about 12 to about 20 carbon atoms, or mixtures thereof, and (c) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines, wherein the total concentration of combined cationic, anionic, and bridging surfactants is from about 30 to about 80 percent by weight, and wherein the surfactant blend is flowable 2 A blend according to claim 1 , wherein the molar ratio of cationic surfactant to anionic surfactant to bridging surfactant is about 1 1 1 3 A blend according to claim 1 , wherein the surfactant blend when diluted to a concentration of about 0 1 percent by weight in water forms a clear aqueous solution substantially free of precipitates 4 An aqueous liquid phase comprising the blend of claim 1 , wherein the cationic surfactant, anionic surfactant, and bridging surfactant are each present in an amount of from about 5 to about 35 percent by weight 5 A blend according to claim 1 , wherein the anionic surfactant is an alkyl sulfate having an average of from about 10 to about 12 carbon atoms 6 A blend according to claim 1 , wherein the anionic surfactant is an α-sulfonated C^Ce alkyl ester of a fatty acid having an average of from about 11 to about 16 carbon atoms 7 A blend according to claim 1 , wherein the anionic surfactant is an alkyl sulfonate having an average of about 8 carbon atoms 8 A blend according to claim 1 , wherein the anionic surfactant is an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide 9 A method for preparing a ternary surfactant blend comprising combining (a) a cationic surfactant which is a quaternary ammonium compound of the formula R1 R2-N-R3 X R4 where R R2, and R3 are independently ethyl or methyl, R4 is an alkyl group having an average of from about 8 to about 16 carbon atoms, and X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate, and (b) an anionic surfactant which is (1) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms, (11) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms, (in) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide, (iv) an α-olefm sulfonate having an average of from about 12 to about 18 carbon atoms, (v) an α-sulfonated d-Ce alkyl ester of a fatty acid having an average of from about 1 1 to about 16 carbon atoms, (vi) a sulfosuccinate having an average of from about 10 to about 16 carbon atoms, (vn) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or (VIII) a sulfoacetate having an average of from about 12 to 20 carbon atoms, or mixtures thereof, and (c) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines, wherein the total concentration of combined cationic, anionic, and bridging surfactants is from about 30 to about 80 percent by weight, and wherein the surfactant blend is flowable 10 A method according to claim 9, wherein the molar ratio of cationic surfactant to anionic surfactant to bridging surfactant is about 1 1 1 11 A method according to claim 9, wherein the surfactant blend when diluted to a concentration of about 0 1 percent by weight in water forms a clear aqueous solution substantially free of precipitates 12 A method for enhancing the solubility of an anionic-cationic surfactant complex comprising combining (a) an anionic-cationic complex formed by combining in any order (i) a cationic surfactant which is a quaternary ammonium compound of the formula where Rι, R2, and R3 are independently ethyl or methyl, R4 is an alkyl group having an average of from about 8 to about 16 carbon atoms, and X is halogen, sulfate, methosulfate, ethosulfate, tosylate, acetate, phosphate, nitrate, sulfonate, or carboxylate, and (11) an anionic surfactant which is

(1 ) an alkyl sulfate having an average of from about 8 to about 16 carbon atoms,

(2) an alkyl sulfonate having an average of from about 8 to about 18 carbon atoms,

(3) an alkyl ether sulfate having an average of from about 8 to about 16 carbon atoms in the alkyl portion and from about 1 to about 30 moles of ethylene oxide,

(4) an α-olefin sulfonate having an average of from about 12 to about 18 carbon atoms,

(5) an α-sulfonated

alkyl ester of a fatty acid having an average of from about 11 to about 16 carbon atoms,

(6) a sulfosuccinate having an average of from about 10 to about 16 carbon atoms,

(7) a sarcosinate having an average of from about 10 to about 16 carbon atoms, or

(8) a sulfoacetate having an average of from about 12 to about 20 carbon atoms, or mixtures thereof, and

(b) a bridging surfactant selected from the group consisting of amine oxides, ethoxamides, and betaines

13 The composition of claim 7 further comprising from about 1 to about 20 percent by weight of a detergent builder material

14 The composition of claim 13 wherein the detergent builder material is citric acid present at from about 1 to about 10 percent by weight

15 The composition of claim 1 further comprising an enzyme selected from the group consisting of proteases, amylases, lipases, cellulases and mixtures thereof at a level sufficient to provide from about 0 01 mg to about 3 mg of active enzyme per gram of the composition