BUILT LIQUID DETERGENTS WITH BORIC-POLYOL COMPLEX TO INHIBIT PROTEOLYTIC ENZYME

Abstract: Included are liquid detergent compositions containing alphahydroxyacid builder, anionic and/or nonionic surfactant, proteolytic enzyme, second enzyme, and a mixture of certain vicinal polyols and boric acid or its derivative. The equilibrium constants for the boric/polyol reaction are K1 between about 0.1 and 400 l/mole and K2 between 0 and about 1000 l<2>/mole<2>.

Description: BUILT LIQUID DETERGENTS WITH BORIC-POLYOL COMPLEX TO INHIBIT PROTEOLYTIC ENZYME FIELD OF THE INVENTION This invention relates to liquid detergent compositio containing alphahydroxyacid builder, anionic or nonioni surfactant, proteolytic enzyme, second enzyme, and a mixture o certain vicinal polyols and boric acid or its derivative. Mor specifically, the equilibrium constants for the boric/polyo reaction are: Ki between about 0.1 and 400 liter/mole and K between 0 and about 1000 1 iters 2 /mole2. BACKGROUND OF THE INVENTION A commonly encountered problem with protease-containin liquid detergents is the degradation of second enzymes in th composition by the proteolytic enzyme. The stability of th second enzyme upon storage in product and its effect on cleanin are impaired by the proteolytic enzyme. Boric acid and boronic acids are known to reversibly inhibi proteolytic enzymes. A discussion of the inhibition of one serin protease, subtilisin, by boronic acid is provided in Philipp, M. and Bender, M.L.. "Kinetics of Subtilisin and Thiolsubtil isin". Molecular i Cellular Biochemistry, vol. 51, pp. 5-32 (1983). One class of boronic acid, peptide boronic acid, is discussed as an inhibitor of trypsin-like serine proteases, especially in pharmaceuticals, in European Patent Application 0 293 881, Kettner et al . , published Decemoer 7, 1988. However, in liquid detergents built with alphahydroxyacid. boric acid and its derivatives appear to complex with the builder and are adversely affected as proteolytic enzyme inhibitors. The proteolytic enzyme then is free to degrade second enzymes in these built liquid detergent compositions. The extent to wnich the builder complexes with boric acid is believed to be a function of the type of alphahydroxyacid builder, and the type of boric acid derivative which is employed in the composition. For example, the effect is αramatic for boric acid in a protease-containing iiαuiα detergent composition built with citric acid. A second enzym such as lipase in such a system is degraded by the proteolyti enzyme, rendering the lipase ineffective. The effectiveness of these boric acid/derivatives can b increased by the addition of a vicinal polyol of the genera structure: R5 where Ri is selected from the group consisting of Cι_c6 alkyl. aryl , substituted Cχ-C6 alkyl, substituted aryl , nitro, an halogen; R2, R3 and R4 are independently selected from the grou consisting of hydrogen, Cχ-C6 alkyl, aryl, substituted Cχ-C6 alkyl, substituted aryl, halogen, nitro, ester, amine, amine derivative, substituted amine, hydroxyl , and hydroxyl derivative; Rl and R3 may be linked via a non-aromatic ring; R5, Re, R7, and 20 R8 are independently selected from the group consisting of hydrogen, Cj-Cβ alkyl, aryl, substituted C1-C5 alkyl, substituted aryl, halogen, nitro, ester, amine, amine derivative, substituted amine, hyαroxyl , substituted hydroxyl, aldehyde, acid, sulfonate and phospnonate and at least one R5-R8 is R\ . Catechol . 1.2 • > tχ propane diol and glycerine are preferably not included. The equilibrium constants for the reaction of the two ingreαients are: Ki between about 0.1 and 400 1/mole and K2 between 0 and about 1000 l2/mole2. Without meaning to be bound by theory, it is believeα that a 0 predominantly 1:1 boric/polyol complex is formed which is capable of binding with the active site (serine) on the oroteolytic enzyme. This is believed to be better than, for examoie. a 1:2 boric/polyol complex. The boric/polyol mixture is believed not to be compromised by the alphahydroxyacid builder like boric acid and 5 its derivatives alone are. The second enzyme is not degraded by the proteolytic enzyme, which has been reversibly inhibited by t boric/polyol mixture. Upon dilution, such as under typical wa conditions, the proteolytic enzyme is no longer inhibited and c function (e.g. to remove protease-sensitive stains from fabrics i the wash) . The importance for protease inhibition of the low K2 val (below about 1000 l2/mole2) and the importance of 1:1 complexi of the boric:polyol mixture in liquid detergent compositio comprising alphahydroxyacid builder, anionic and/or nonioni surfactant, proteolytic enzyme, and a second enzyme, are no disclosed or taught by the art. European Patent Application 0 381 262. Aronson et al published August 8, 1990, mixtures of proteolytic and lipolyti enzymes in a liquid medium are disclosed. The stability o lipolytic enzyme is said to be improved by the addition of stabilizer system comprising boron compound and a polyol which ar capable of reacting with one another, whereby the polyol has first binding constant of at least 500 1/mole and a second bindin constant with the boron compound of at least 1000 l2/mole2. German Patent 3 918761, Weiss et a , published June 28, 199 discloses liquid enzyme concentrate which is said to be usable a a raw material solution for making liquid detergents and the like The concentrate contains hydrolase, propylene glycol and bori acid or its soluble salt. U.S. Patent 4.900.475, Ramachandran et al , issued Februar 13, 1990, discloses a stabilized enzyme-containing detergen containing surface active detergent material, builder salt and a effective amount of enzyme or enzyme mixture selected from th group containing protease and alpha-a ylase enzymes. Th composition also contains a stabilization system comprised o glycerine, a boron compound and a carboxylic compound with 2- carbon compounds. U.S. Patent 4.537.707, Severson, Jr., issued August 27. 198 describes heavy duty liquid detergents containing anioni surfactant, fatty acid, builder, proteolytic enzyme, boric aci calcium ions and sodium formate. The combination of boric aci and formate provides improved proteolytic enzyme stability in th compositions. European Patent Application 0 080 223, Boskamp et al published June 1, 1983 describes aqueous enzymatic detergen compositions containing boric acid or an alkali metal borate wit a polyfunctional a ino compound or a polyol, together with reducing alkali metal salt. Similarly in GB 2 . 079 305, Boskamp, published January 20 1982, it is disclosed that enhanced enzyme stability can b obtained in a built liquid detergent composition by inclusion of mixture boric acid and polyol in a weight ratio of more than 1:1, and a cross linked neutralized polyacrylate polymer. The procedure used to determine thermodynamic constants fo boric/polyol complexes is based on Hβoron NMR as described b Dawber et al in the Journal of Chemical Society, Volume 1, pages 41-56 (1988). Thermodynamic constants for some of the compounds of interest are listed in the above article. SUMMARY OF THE INVENTION The present invention relates to a liquid detergent composition containing: a. a mixture of (1) from about 0.1 to 30 weight % of the composition of vicinal polyol of the structure R 5 where Ri is selected from the group consisting of C1-C5 alkyl, aryl, substituted C1-C5 alkyl, substituted aryl, nitro, and halogen; R2, R3 and R4 are independently selected from the group consisting of hydrogen. C1-C5 alkyl, aryl, substituted ■ Ci-Cβ alkyl, substituted aryl halogen, nitro, ester, amine, amine derivativ substituted amine, hydroxyl and hydroxyl derivativ R5, R5, R7, and Rs are independently selected from t group consisting of hydrogen, C1-C6 alkyl, aryl substituted Ci-Ce alkyl, substituted aryl, haloge nitro, ester, amine, amine derivative, substitut amine, aldehyde, acid, sulfonate and phosphonate; and least one R5-8 is R]; and (2) from about 0.05 to 20 weight % of the composition boric acid or its derivative; wherein the equilibrium constants for the reacti between (1) and (2) are: Ki between about 0.1 and 40 1/mole and 2 between 0 and about 1000 l 2 /mole 2 ; b. from about 0.0001 to 1.0 weight % of active proteolyti enzyme; c. a performance-enhancing amount of a detergent-compatibl second enzyme; d. from about 1 to 80 weight % of anionic or nonioni surfactant; and e. from about 0.1 to 30 weight % of alphahydroxyaci builder. DESCRIPTION OF THE INVENTION The present liquid detergent compositions contain certai essential ingredients: (a) mixture of vicinal polyol and bori acid or its derivative; (b) proteolytic enzyme; (c) detergent compatible second enzyme; (d) anionic and/or nonionic detersiv surfactant; and (e) alphahydroxyacid builder. These composition will most commonly be used for cleaning of laundry, fabrics textiles, fibers, and hard surfaces. Heavy duty liquid laundr detergents are the preferred liquid detergent compostions herein. A. Polvol/Boric Mixture The present liquid detergent compositions contain a mixtur of vicinal polyol of the general structure; R5 where Ri is selected from the group consisting of Ci-Cβ alkyl, aryl, substituted C1-C6 alkyl, substituted aryl, nitro, an halogen; R2, R3 and R4 are independently selected from the grou consisting of hydrogen, Ci-Ce alkyl, aryl, substituted Ci-C alkyl, substituted aryl", halogen, nitro, ester, amine, amin derivative, substituted amine, hydroxyl and hydroxyl derivative: where R5, Re, R7, and Rg are independently selected from the group consisting of hydrogen, Cχ-C6 alkyl, aryl, substituted alkyl, substituted aryl, halogen, nitro, ester, amine, amine derivative, substituted amine, hydroxyl, aldehyde, acid, sulfonate or phosphonate; and boric acid or its derivative (called herein "polyol/boric" or "boric/polyol"). The equilibrium constants for the polyol/boric reaction are i between about 0.1 and 400 1/mole and K2 between 0 and about 1000 l 2 /mole2. The preferred ratio of 2/ 1 is ≤ 20, preferably between about 1 and 5. The equilibrium reaction is as follows: KT B÷ P ~ ^ ~ BP KI = ^P] [B] [P] K2 B + 2P c " BP2 K2 = βp 2] [B] [P]2 where "B" is boric acid or its derivative and "P" is vicinal polyol. Kj is the first equilibrium constant and indicates the formation of 1:1 boric:polyol complexes. K is the second equilibrium constant. It indicates the formation of 1: boric:polyol complexes. It is believed that a significantly larg K2 and a small K ] results in the formation of a predominantly 1: boric/polyol complex. Conversely, a large K and a relatively small generally K2 results in 1:1 boric/polyol complex formation, which is preferred herein. For example, it ha been shown by Pizer & Babcock in "Mechanism of Complexation o Boron Acids with Catechol and Substituted Catechols" that mannitol (K] = 237 K2 = 7424) forms a 2:1 complex with boric acid, wherea catechol (Ki ■ 129 K2 = 2.4) forms a 1:1 complex. It is preferred that the vicinal polyol and bori acid/derivative be mixed together within a few days prior to th addition to the liquid detergent. This is done by neutralizin boric acid with an inorganic/organic alkali not capable o complexing with boric acid/derivative. These include sodiu hydroxide and potassium hydroxide. This is followed by addition of the vicinal polyol at room temperature. The complex may also be formed in-situ in a liquid laundry detergent composition by addition of boric acid or its salt and the polyol directly to the composition. Boric-polyol premix can be added to the detergent composition. The final concentration of boric acid in the detergent composition is between about 0.05 and 20% by weight and the final concentration of vicinal polyol is between about 0.1 and 30% by weight. Preferably, the concentration of boric acid or its derivative in the composition is between about 0.1 and 10 weight % and most preferably between about 0.5 and 5 weight %. The concentration of vicinal polyol in the composition is preferably between about 0.2 and 20, most preferably between about 1 and 20. weight %. Ki is between about 0.1 and 400 1/mole, preferably between about 0.2 and 200 1/mole; and K2 is between about 0 and 1000 l2/mole2, preferably between about 0.1 and 200 l2/mole 2 , more preferably between about 0.2 and 100 l2/mole2. The boric/polyol molar ratio is preferably between about 20: and 1:20, more preferably between about 6:1 and 1:15, mos preferably between 3:1 and 1:10. The ratio of this mixture of boric acid derivative an vicinal polyol to alphahydroxyacid builder is preferably betwee about 10:1 and 1:30, most preferably between about 5:1 and 1:10. The boric acid or its derivative used in the mixture include boric acid, borax, boric oxide, polyborates, orthoborates pyroborates, metaborates, or mixtures thereof. Salts of thes compounds are included.. Preferred compounds are the alkali salt of boric acid, such as sodium borate. These salts can be forme in the formulation by in-situ neutralization of boric acid with a appropr ate alkali. The vicinal polyol herein is a compound with two or mor hydroxyl groups, at least two of which are on adjacent carbo atoms. It has the general structure described above. As define here, Ri and R3 may be linked by a non-aromatic ring (cyclopenty or cyclohexyl). Catechol, 1,2 propanediol and glycerine ar preferably not included herein. Preferably, Ri on the vicinal polyol is C1-C5 alkyl, substit Ci-Ce alkyl, phenyl or substituted phenyl and R2, R3, and R4 ar hydrogen. More preferred vicinal polyols are 1,2 butanediol, 1. hexanediol, 3 chloro 1.2 propane diol. propylgallate, gallic acid, 1 phenyl, 1,2 ethanediol, and 1 ethoxy 2,3 propanediol. Most preferred are 1,2 butanediol, 1.2 hexanediol, 3 chloro 1,2 proσane diol, 1 phenyl 1,2 ethanediol, and propylgallate. B. Proteolytic Enzyme A second essential ingredient in the present liquid detergent compositions is from about 0.0001 to 1.0, preferably about 0.0005 to 0.3. most preferably about 0.002 to 0.1, weight % of active proteolytic enzyme. Mixtures of proteolytic enzyme are also included. The proteolytic enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurifieo forms of this enzyme may be used. Proteolytic enzymes produced b chemically or genetically modified mutants are included Particularly preferred is bacterial serine proteolytic enzym obtained from Bacillus subtilis and/or Bacillus 1 icheniformis. Suitable proteolytic enzymes include Alcalase ® , Esperase ® Savinase® (preferred); Maxatase ® , Maxacal ® (preferred), an Maxapem 15® (protein engineered Maxacal ® ); and subtilisin BPN an BPN' (preferred); which are commercially available. Preferre proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and i European Patent Application 199,404, Venegas, published Octobe 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Preferred proteolytic enzymes, then, are selected from the group consisting o Savinase ® , Maxacal®, BPN', Protease A and Protease B, and mixtures thereof. Protease B is most preferred. C. Second Enzyme The third essential ingredient in the present liquid compositions is a performance-enhancing amount of a detergent- compatible second enzyme. By "detergent-compatible" is meant compatibility with the other ingredients of a liquid detergent composition, such as detersive surfactant and detergency builder. These second enzymes are preferably selected from the group consisting of lipase, amylase, cellulase, and mixtures thereof. The term "second enzyme" excludes the proteolytic enzymes discussed above, so each composition herein contains at least two kinds of enzyme, including at least one proteolytic enzyme. The amount of second enzyme used in the composition varies according to the type of enzyme and the use intended. In general, from about 0.0001 to 1.0, more preferably 0.001 to 0.5, weight % on an active basis of these second enzymes are preferably used. Mixtures of enzymes from the same class (e.g. lipase) or t or more classes (e.g. cellulase and lipase) may be used. Purifie or non-purified forms of the enzyme may be used. Any lipase suitable for use in a liquid detergent compositio can be used herein. Suitable upases for use herein include thos of bacterial and fungal origin. Second enzymes from chemically o genetically modified mutants are included. Suitable bacterial upases include those produced b Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154, a disclosed in British Patent 1,372,034, incorporated herein b reference. Suitable upases include those which show a positiv immunological cross-reaction with the antibody of the lipas produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been describe in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference. This lipase is available under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Such lipases should show a positive immunological cross reaction with the Amano-P antibody, using the standard and well-known immunod ffusion procedure according to Ouchterlony (Acta. Med. Scan., 133, pages 76-79 (1950)). These lipases, and a method for their immunological cross-reaction with Amano-P, are also described in U.S. Patent 4,707,291, Thorn et al .. issued November 17, 1987, incorporated herein by reference. Typical examples thereof are the Amano-P lipase, the lipase ex Pseudomonas fraqi FERM P 1339 (available under the trade name Amano-B), lipase ex Psuedomonas nitroreducens var. lipo yticum FERM P 1338 (available under the trade name A ano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. polyticum NRRLB 3673, and further Chromobacter viscosum lipases, and lipases ex Pseudomonas gladioli . Other lipases of interest are Amano AKG and Bacilli ' s Sp lipase. Suitable fungal lipases include those producible by Humicola lanuqinosa and Thermomyces lanuqinosus. Most preferred is lipase obtained by cloning the gene from Humicola lanuqinosa a expressing the gene in Asoergillus orvzae as described in Europe Patent Application 0 258 068, incorporated herein by referenc commercially available under the trade name Lipolase ® . From about 2 to 20,000, preferably about 10 to 6,000, lipa units of lipase per gram (LU/g) of product can be used in the compositions. A lipase unit is that amount of lipase whi produces 1 mol of titratable butyric acid per minute in a stat, where pH is 7.0, temperature is 30 β C, and substrate is emulsion of tributyrin, and gum arabic, in the presence of Ca and NaCl in phosphate buffer. Any cellulase suitable for use in a liquid detergen composition can be used in these compositions. Suitable cellulas enzymes for use herein include those of bacterial and funga origins. Preferably, they will have a pH optimum of between 5 an 9.5. From about 0.0001 to 1.0, preferably 0.001 to 0.5, weight on an active enzyme basis of cellulase can be used. Suitable cellulases are disclosed in U.S. Patent 4,435,307 Barbesgaard et al ., issued March 6, 1984, incorporated herein b reference, which discloses fungal cellulase produced from Humicol insolens. Suitable cellulases are also disclosed i GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832. Examples of such cellulases are cellulases produced by strain of Humicola insolens (Humicola qrisea var. thermoidea) particularly the Humicola strain DSM 1800, and cellulases produce by a fungus of Bacillus N or a cellulase 212-producing fungu belonging to the genus Aeromonas, and cellulase extracted from th hepatopancreas of a marine mollusc (Dolabella Auricula Solander). Any amylase suitable for use in a liquid detergen composition can be used in these compositions. Amylases include for example, α-amylases obtained from a special strain o B.l icheniforms. described in more detail in British Paten Specification No. 1,296,839. Amylolytic proteins include, fo example, Rapidase™, Maxamyl™ and Termamyl™. From about 0.0001% to 1.0, preferably 0.0005 to 0.5, weigh on an active enzyme basis of amylase can be used. D. Detersive Surfactant From about 1 to 80, preferably about 5 to 50, most prefera about 10 to 30, weight % of anionic or nonionic detersi surfactant is the fourth essential ingredient in the prese invention. The detersive surfactant can be selected from t group consisting of anionics and nonionics and optional cationics, ampholytics, zwitterionics, and mixtures thereof. is preferred that no significant amounts of surfactants other th anionic and nonionic surfactants be included. Preferably the anionic surfactant is C -C20 alkyl sulfat C 2-C20 alkyl ether sulfate and/or Cg-C20 linear alkylbenze sulfonate. Preferably the nonionic surfactant is the condensati product of C10-C20 alcohol and between 2-20 moles of ethyle oxide per mole of alcohol or polyhydroxy Cιo-20 fatty acid amide Anionic Surfactants One type of anionic surfactant which can be utilized is alk ester sulfonates. These are desirable because they can be ma with renewable, non-petroleum resources. Preparation of the alk ester sulfonate surfactant component is according to known metho disclosed in the technical literature. For instance, linea esters of C8-C20 carboxylic acids can be sulfonated with gaseou SO3 according to "The Journal of the American Oil Chemist Society," 52 (1975), pp. 323-329. Suitable starting material would include natural fatty substances as derived from tallow palm, and coconut oils, etc. The preferred alkyl ester sulfonate surfactant, especiall for laundry applications, comprises alkyl ester sulfonat surfactants of the structural formula: 0 R3 . CH - C - OR 4 SO3M wherein R 3 is a C8-C20 hydrocarbyl, preferably an alkyl, o combination thereof, R 4 is a Ci-Ce hydrocarbyl, preferably a alkyl, or combination thereof, and M is a soluble salt-formin cation. Suitable salts include metal salts such as sodium potassium, and lithium salts, and substituted or unsubstitute ammonium salts, such as methyl-, dimethyl, -trimethyl, an quaternary ammonium cations, e.g. tetramethyl-ammonium an dimethyl piperydinium, and cations derived from alkanolamines e.g. monoethanolamine, diethanolamine, and triethanolamine Preferably, R 3 is C10-C16 alkyl, and R 4 is methyl, ethyl o isopropyl. Especially preferred are the methyl ester sulfonate wherein R 3 is C14-C15 alkyl. Alkyl sulfate surfactants are another type of anioni surfactant of importance for use herein. In addition to providin excellent overall cleaning ability when used in combination wit polyhydroxy fatty acid amides (see below), including goo grease/oil cleaning over a wide range of temperatures, was concentrations, and wash times, dissolution of alkyl sulfates ca be obtained, as well as improved formulabil ity in liqui detergent formulations are water soluble salts or acids of th formula ROSO3M wherein R preferably is a 10- 24 hydrocarbyl. preferably an alkyl or hydroxyalkyl having a 10-C20 alkyl component, more preferably a Cj2~ l8 alkyl or hydroxyalkyl. and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C12-16 re preferred for lower wash temperatures (e.g., below about 50 β C) and Cl6-18 lkyl chains are preferred for higher wash temperatures (e.g., above about 50 β C). Alkyl alkoxylated sulfate surfactants are another category useful anionic surfactant. These surfactants are water solubl salts or acids typically of the formula R0(A) m S03M wherein R is a unsubstituted C10-C 4 alkyl or hydroxyalkyl group having a C10-C2 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, mor preferably C12-C18 alkyl or hydroxyalkyl, A is an ethoxy o propoxy unit, m is greater than zero, typically between about 0. and about 6, more preferably between about 0.5 and about 3, and is H or a cation which can be, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), ammonium o substituted-ammonium cation. Alkyl ethoxylated sulfates as wel as alkyl propoxylated sulfates are contemplated herein. Specifi examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperydinium and cation derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are C 2-C18 alkyl polyethoxyl te (1.0) sulfate, C1 -C18 alkyl polyethoxylate (2.25) sulfate, C12-C18 alkyl polyethoxylate (3.0) sulfate. and C12-C18 alkyl polyethoxylate (4.0) sulfate wherein M is conveniently selected from sodium and potassium. Other Anionic Surfactants Other anionic surfactants useful for detersive purposes can also be included in the compositions hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesul honates, C8-C22 primary or secondary alkanesulphonates, C8-C 4 olefinsulphonates. sulphonated polycarboxylic acids prepared by sulphonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British Patent Specification No. 1,082.179, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyi glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isothionates such as the acyl isothionates, N-acyl taurates, fatty acid amides of meth tauride, alkyl succinamates and sulfosuccinates, monoesters sulfosuccinate (especially saturated and unsaturated C12-C monoesters) diesters of sulfosuccinate (especially saturated a unsaturated C6-C1 diesters), N-acyl sarcosinates, sulfates alkylpolysaccharides such as the sulfates of alkylpolyglucosi (the nonionic nonsulfated compounds being described below branched primary alkyl sulfates, alkyl polyethoxy carboxylat such as those of the formula RO(CH2CH2θ)kCH2COO-M+ wherein R is C8-C22 alkyl, k is an integer from 0 to 10, and M is a solubl salt-forming cation, and fatty acids esterified with isethioni acid and neutralized with sodium hydroxide. Resin acids a hydrogenated resin acids are also suitable, such as rosi hydrogenated rosin, and resin acids and hydrogenated resin aci present in or derived from tall oil. Further examples are give in "Surface Active Agents and Detergents" (Vol. I and II b Schwartz, Perry and Berch). A variety of such surfactants ar also generally disclosed in U.S. Patent 3,929,678, issued Decembe 30, 1975 to Laugh!in, et al . at Column 23, line 58 through Colum 29, line 23 (herein incorporated by reference). Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are generall disclosed in U.S. Patent 3,929,678, Laughlin et al . , issue December 30, 1975, at column 13, line 14 through column 16, lin 6, incorporated herein by reference. Exemplary, non-limitin classes of useful nonionic surfactants are listed below. 1. The polyethylene, polypropylene, and polybutylene oxid condensates of alkyl phenols. In general, the polyethylene oxid condensates are preferred. These compounds include th condensation products of alkyl phenols having an alkyl grou containing from about 6 to about 12 carbon atoms in either straight chain or branched chain configuration with the alkylen oxide. In a preferred embodiment, the ethylene oxide is presen in an amount equal to from about 5 to about 25 moles of ethylen oxide per mole of alkyl phenol. Commercially available nonio surfactants of this type include Igepal™ C0-630, marketed by GAF Corporation; and Triton™ X-45, X-114, X-100, and X-102, marketed by the Rohm & Haas Company. These compounds are commo referred to as alkyl phenol alkoxylates, (e.g., alkyl phe ethoxy!ates). 2. The condensation products of aliphatic alcohols with f about 1 to about 25 moles of ethylene oxide. The alkyl chain the aliphatic alcohol can either be straight or branched, prima or secondary, and generally contains from about 8 to about carbon atoms. Particularly preferred are the condensati products of alcohols having an alkyl group containing from abo 10 to about 20 carbon atoms with from about 2 to about 18 moles ethylene oxide per mole of alcohol. Examples of commercial available nonionic surfactants of this type include Tergitol 15-S-9 (the condensation product of C1 -C15 linear seconda alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (t condensation product of C12-C14 primary alcohol with 6 mol ethylene oxide with a narrow molecular weight distribution), bo marketed by Union Carbide Corporation; Neodol™ 45-9 (the conde sation product of C14-C15 linear alcohol with 9 moles of ethyle oxide), Neodol™ 23-6.5 (the condensation product of C12-C1 linear alcohol with 6.5 moles of ethylene oxide), NeodolTM 45- (the condensation product of C14-C15 linear alcohol with 7 mole of ethylene oxide), Neodol™ 45-4 (the condensation product o C14-C15 linear alcohol with 4 moles of ethylene oxide), markete by Shell Chemical Company, and Kyro™ EOB (the condensatio product of C13-C 5 alcohol with 9 moles ethylene oxide), markete by The Procter & Gamble Company. This category of nonioni surfactant is referred to generally as "alkyl ethoxylates. " 3. The condensation products of ethylene oxide with nydrophobic base formed by the condensation of propylene oxid with propylene glycol. The nydrophobic portion of these compound preferably has a molecular weight of from about 1500 to about 180 and exhibits water insolubility. The addition of polyoxyethylen moieties to this hydrophobic portion tends to increase the wate solubility of the molecule as a whole, and the liquid character o the product is retained up to the point where the polyoxyethylen content is about 50% of the total weight of the condensatio product, which corresponds to condensation with up to about 4 moles of ethylene oxide. Examples of compounds of this typ include certain of the commercially-avail ble Pluronic surfactants, marketed by BASF. 4. The condensation products of ethylene oxide with th product resulting from the reaction of propylene oxide an ethylenediamine. The hydrophobic moiety of these product consists of the reaction product of ethylenediamine and exces propylene oxide, and generally has a molecular weight of fro about 2500 to about 3000. This hydrophobic moiety is condense with ethylene oxide to the extent that the condensation produc contains from about 40% to about 80% by weight of polyoxyethylen and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain o the commercially available Tetronic™ compounds, marketed by BASF. 5. Semi-polar nonionic surfactants are a special categor of nonionic surfactants which include water-soluble amine oxide containing one alkyl moiety of 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; water-soluble phosphine oxides containing one alkyl moiety of 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; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. Semi-polar nonionic detergent surfactants include the ami oxide surfactants having the formula 0 I R (0R ) X N(R5) 2 wherein R 3 is an alkyl, hydroxyal yl, or alkyl phenyl group mixtures thereof containing from about 8 to about 22 carbon atom R 4 is an alkylene or hydroxyalkylene group containing from about to about 3 carbon atoms or mixtures thereof; x is from 0 to abou 3; and each R5 is an alkyl or hydroxyalkyl group containing fro about 1 to about 3 carbon atoms or a polyethylene oxide grou containing from about 1 to about 3 ethylene oxide groups. The R groups can be attached to each other, e.g., through an oxygen o nitrogen atom, to form a ring structure. These amine oxide surfactants in particular include C o-C alkyl dimethyl amine oxides and Cs~Ci2 alkoxy ethyl dihydrox ethyl amine oxides. 6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647 Llenado, issued January 21, 1986, having a hydrophobic grou containing from about 6 to about 30 carbon atoms, preferably fro about 10 to about 16 carbon atoms and a polysaccharide, e.g., polyglycoside, hydrophilic group containing from about 1.3 t about 10. preferably from about 1.3 to about 3, most preferabl from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties. (Optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside.) The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units. ' I 9 " Optionally, and less desirably, there can be a polyalkylen oxide chain joining the hydrophobic moiety and the polysacchari moiety. The preferred alkyleneoxide is ethylene oxide. Typic hydrophobic groups include alkyl groups, either saturated unsaturated, branched or unbranched containing from about 8 about 18, preferably from about 10 to about 16, carbon atoms Preferably, the alkyl group is a straight chain saturated alky group. The alkyl group can contain up to about 3 hydroxy group and/or the polyalkyleneoxide chain can contain up to about 10 preferably less than 5, alkyleneoxide moieties. Suitable alky polysaccharides are octyl , nonyldecyl, undecyldodecyl , tridecyl tetradecyl , pentadecyl , hexadecyl , heptadecyl , and octadecyl , di- tri-, tetra-, penta-, and hexaglucosides, galactosides lactosides, glucoses, fructosides, fructoses and/or galactoses Suitable mixtures include coconut alkyl, di-, tri-, tetra-, an pentaglucosides and tallow alkyl tetra-, penta-, and hexa glucosides. The preferred alkylpolyglycosides have the formula R 2 0(C n H2n0)t(glycosyl) x wherein R 2 is selected from the group consisting of alkyl, alkyl phenyl , hydroxyalkyl, hydroxyalkylphenyl , and mixtures thereof i which the alkyl groups contain from about 10 to about 18 preferably from about 12 to about 14, carbon atoms; n is 2 or 3 preferably 2; t is from 0 to about 10, preferably 0; and x is fro about 1.3 to about 10, preferably from about 1.3 to about 3, mos preferably from about 1.3 to about 2.7. The glycosyl is pre ferably derived from glucose. To prepare these compounds, th alcohol or alkylpolyethoxy alcohol is formed first and the reacted with glucose, or a source of glucose, to form th glucoside (attachment at the 1-position) . The additional glycosy units can then be attached between their 1-position and th preceding glycosyl units 2-, 3-, 4- and/or 6-position. preferabl predominately the 2-position. 7. Fatty acid amide surfactants having the formula: 5 wherein R 6 is an alkyl group containing from about 7 to about 2 (preferably from about 9 to about 17) carbon atoms and each R 7 i selected from the group consisting of hydrogen, C1-C4 alkyl, C1-C hydroxyalkyl, and -(C2H4θ) x H where x varies from about 1 to abou 3. 0 Preferred amides are C8-C20 ammonia amides, monoethanol amides, diethanolamides, and isopropanolamides. Polyhvdroxy Fatty Acid Amide Nonionic Surfactant The liquid detergent compositions hereof preferably contai an "enzyme performance-enhancing amount" of polyhydroxy fatty aci 15 amide surfactant. By "enzyme-enhancing" is meant that th formulator of the composition can select an amount of polyhydrox fatty acid amide to be incorporated into the composition that will improve enzyme cleaning performance of the detergent composition. In general, for conventional levels of enzyme, the incorporation 20 of about 1%, by weight, polyhydroxy fatty acid amide will enhance enzyme performance. The detergent compositions hereof will typically comprise at least about 1 weight % polyhydroxy fatty acid amide surfactant and preferably will comprise from about 3% to 50%, most preferably 25 from aoout 3% to 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula: 0 Rl 0 ( I) R 2 - C - N - Z wherein: Rl is H. C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyi , or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e.. ;5 methyl); and R 2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C1 alkyl or alkenyl, most preferably straight chain Cπ-C.15 alkyl o alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarby having a linear hydrocarbyl chain with at least 3 hydroxyl directly connected to the chain, or an alkoxylated derivativ (preferably ethoxylated or propoxylated) thereof. Z preferabl will be derived from a reducing sugar in a reductive aminatio reaction; more preferably Z will be a glycityl. Suitable reducin sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As . raw materials, high dextrose corn syrup high fructose corn syrup, and high maltose corn syrup can b utilized as well as the individual sugars listed above. Thes corn syrups may yield a mix of sugar components for Z. It shoul be understood that it is by no means intended to exclude othe suitable raw materials. Z preferably will be selected from th group consisting of -CH 2 -(CH0H) n -CH 2 0H, -CH(CH 2 0H)-(CH0H) n . 1 - CH 2 0H, -CH 2 -(CHOH)2(CHOR')(CHOH)-CH2θH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH2- (CH0H)4-CH20H. In Formula (I), R' can be, for example, N-methyl . N-ethyl , N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl . R 2 -C0-N< can be, for example, cocamide, steara ide, oleamide. lauramide, myristamide, capricamide, palmitamide, tallowamide, etc. Z can be 1-deoxyglucityl , 2-deoxyfructityl . 1-deoxymaltityl , 1-deoxylactityl , 1-deoxygalactityl , 1-deoxymannityl , 1-deoxymalto- triotityl, etc. Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkyl amine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic ester triglyceride in a condensation/amidation step to form the N-alky N-polyhydroxy fatty acid amide product. Processes for maki compositions containing polyhydroxy fatty acid amides a disclosed, for example, in G.B. Patent Specification 809,06 published February 18, 1959, U.S. Patent 2,965,576, issu December 20, 1960 to E. R. Wilson, and U.S. Patent 2,703,79 Anthony M. Schwartz, issued March 8, 1955, and U.S. Pate 1,985,424, issued December 25, 1934 to Piggott, each of which i incorporated herein by reference. E. Alphahydroxyacid Builder The last essential ingredient is from about 0.1 to 30 preferably about 1 to 20, weight % of alphahydroxy acid builder By alphahydroxy acid builder is meant that the builder salt ha one or more carboxyl groups and one or more hydroxyl groups suc that at least one hydroxyl is on the carbon alpha to the on bearing a carboxyl group. A specific class of alphahydroxy acids useful as builders i the present invention includes those having the general formula: CH(A)(C00X)-CH(C00X)-0-CH(C00X)-CH(C00X)(B) wherein A is hydroxyl; B is hydrogen or -O-CH(C00X)-CH2(C00X) ; an X is hydrogen or a salt-forming cation. If B is H. then th compound is tartrate monosuccinic acid (TMS) and its water-solubl salts. It is preferred that the above alphahydroxy acid (TMS) b mixed with tartrate disuccinate (TDS) represented by the abov chemical structure wherein A is H and B is 0-CH(C00X)-CH2(C00X) . Particularly preferred are mixtures of TMS and TDS in a weigh ratio of TMS to TDS of from about 97:3 to about 20:80. mos preferably 80 TMS:20 TDS. These builders are disclosed in U.S. Patent 4,663.071. issued to Bush et al . , on May 5, 1987. A preferred alphahydroxy acid useful in this composition is citric acid, its salt and its derivatives. Citrate builders, (particularly sodium salt), are of particular importance for heavy duty liquid detergent formulations herein. F. Optional Ingredients Other Detergency Builders In addition to the alphahydroxy acid builders describ above, the composition may contain from 0 to about 50, mo preferably about 2 to 30, weight percent of other detergen builders. Inorganic as well as organic builders can be used. Inorganic detergency builders include, but are not limite to, the alkali metal, ammonium and alkanolammonium salts o polyphosphates (exemplified by the tripolyphosphates pyrophosphates, and glassy polymeric meta-phosphates) phosphonates, phytic acid, silicates, carbonates (includin bicarbonates and sesquicarbonates) , sulphates, and aluminosili cates. Borate builders, as well as builders containin borate-forming materials that can produce borate under detergen storage or wash conditions (hereinafter, collectively "borat builders"), can also be used. Preferably, non-borate builders ar used in the compositions of the invention intended for use at was conditions less than about 50 β C, especially less than about 40"C. Examples of silicate builders are the alkali metal silicates particularly those having a Siθ :Na2θ ratio in the range 1.6:1 t 3.2:1 and layered silicates, such as the layered sodium silicate described in U.S. Patent 4,664.839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference. However, other silicate may also be useful such as for example magnesium silicate, whic can serve as a crispening agent in granular formulations, as stabilizing agent for oxygen bleaches, and as a component of sud control systems. Examples of carbonate builders are the alkaline earth an alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calciu carbonate as disclosed in German Patent Application No. 2.321,001 published on November 15, 1973, the disclosure of which is incorporated herein by reference. Aluminosilicate builders are useful in the present inventio Aluminosilicate builders are of great importance in most current marketed heavy duty granular detergent compositions, and can al be a significant builder ingredient in liquid deterge formulations. Aluminosilicate builders include those having t empirical formula: M z (zAlθ2-ySiθ2) wherein M is sodium, potassium, ammonium or substituted ammoniu z is from about 0.5 to about 2; and y is 1; this material having magnesium ion exchange capacity of at least about 50 milligra equivalents of CaC03 hardness per gram of anhydrou aluminosilicate. Preferred aluminosilicates are zeolite builder which have the formula: Na z [(A102) z (SiO∑Jy]-xH2θ wherein z and y are integers of at least 6, the molar ratio of to y is in the range from 1.0 to about 0.5, and x is an intege from about 15 to about 264. Useful aluminosilicate ion exchange materials ar commercially available. These aluminosilicates can be crystallin or amorphous in structure and can be naturally-occurrin aluminosilicates or synthetically derived. A method for producin aluminosilicate ion exchange materials is disclosed in U.S. Paten 3,985.669, Krummel , et al., issued October 12, 1976, incorporate herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: ai2[(Alθ2)l2(Siθ2)l2]-xH2θ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophospnate. sodium and potassium and ammonium pyrophosphate, sodium a potassium orthophosphate, sodium polymeta phosphate in which t degree of polymerization ranges from about 6 to about 21, a salts of phytic acid. Examples of phosphonate builder salts are the water-solubl salts of ethane 1-hydroxy-l, 1-diphosphonate particularly t sodium and potassium salts, the water-soluble salts of methylen diphosphonic acid e.g. the trisodiu and tripotassium salts an the water-soluble salts of substituted methylene diphosphoni acids, such as the trisodium and tripotassium ethylidene isopyropylidene benzylmethylidene and halo methyliden phosphonates. Phosphonate builder salts of the aforementione types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,03 issued December 1, 1964 and October 19, 1965, to Diehl; U.S Patent No. 3,422,021 issued January 14, 1969, to Roy; and U.S Patent Nos. 3,400,148 and 3,422,137 issued September 3, 1968, an January 14, 1969 to Quimby, said disclosures being incorporate herein by reference. Organic detergent builders preferred for the purposes of th present invention include a wide variety of polycarboxylat compounds. As used herein, "polycarboxylate" refers to compound having a plurality of carboxylate groups, preferably at least tw carboxylates. Polycarboxylate builder can generally be added to th composition in acid form, but can also be added in the form of neutralized salt. When utilized in salt form, alkali metals, suc as sodium, potassium, and lithium, or alkanolammonium salts ar preferred. Included among the polycarboxylate builders are a variety o categories of useful materials. One important category o polycarboxylate builders encompasses the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use a detergent builders. Examples of useful ether polycarboxylate include oxydisuccinate, as disclosed in Berg, U.S. Paten 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Pate 3,635,830, issued January 18, 1972, both of which are incorporate herein by reference. Still other ether polycarboxylates include copolymers o maleic anhydride with ethylene or vinyl methyl ether, 1, 3 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, an carboxymethyloxysuccinic acid. Organic polycarboxylate builders also include the variou alkali metal, ammonium and substituted ammonium salts o polyacetic acids. Examples include the sodium, potassium lithium, ammonium and substituted ammonium salts o ethylenediamine tetraacetic acid, and nitrilotriacetic acid. Also included are polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzen 1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, an soluble salts thereof. Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986, incorporated herein by reference. Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkyl succinic acids typically are of the general formula R-CH(C00H)CH2(C00H) i.e., derivatives of succinic acid, wherein R is hydrocarbon, e.g., C10-C20 alkyl or alkenyl, preferably C1 -C16 or wherein R may be substituted with hydroxyl , sulfo, sulfoxy or sulfone substituents, all as described in the above-mentioned patents. The succinate builders are preferably used in the form of their water-soluble salts, including the sodium, potassium. ammonium and alkanolammonium salts. Specific examples of succinate builders include: laurylsuc cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinat (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuc cinates are the preferred builders of this group, and ar described in European Patent Application 86200690.5/0,200,263 published November 5, 1986. Examples of useful builders also include sodium and potassiu carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclo hexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water soluble polyacrylates (these polyacrylates having molecula weights to above about 2,000 can also be effecitvly utilized a dispersants) , and the copolymers of maleic anhydride with vinyl methyl ether or ethylene. Other suitable polycarboxylates are the polyacetal car boxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al . , issued March 13, 1979, incorporated herein by reference. Thes polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an ester of glyoxylic acid and polymerization initiator. The resulting polyacetal carboxylat ester is then attached to chemically stable end groups t stabilize the polyacetal carboxylate against rapid depolymeriza- tion in alkaline solution, converted to the corresponding salt, and added to a surfactant. Polycarboxylate builders are also disclosed in U.S. Patent 3.308,067, Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts o homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, esaconic acid, fumaric acid, aconitic acid. citraconic acid and methylenemalonic acid. Other organic builders known in the art can also be used. For example, onocarboxylic acids, and soluble salts thereof. having long chain hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of C10-C20 are typically utilized. The hydrocarbyls can b saturated or unsaturated. Soil Release Agent Any soil release agents known to those skilled in the art ca be employed in the practice of this invention. Preferre polymeric soil release agents are characterized by having bot hydrophilic segments, to hydrophilize the surface of hydrophobi fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures. Whereas it can be beneficial to utilize polymeric soil release agents in any of the detergent compositions hereof, especially those compositions utilized for laundry or other applications wherein removal of grease and oil from hydrophobic surfaces is needed, the presence of polyhydroxy fatty acid amide in detergent compositions also containing anionic surfactants can enhance performance of many of the more commonly utilized types of polymeric soil release agents. Anionic surfactants interfere with the ability of certain soil release agents to deposit upon and adhere to hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophile segments or hydrophobe segments which are anionic surfactant-interactive. Typical polymeric soil release agents useful in this invention include those having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxy- ethylene segments with a degree of polymerization of at least 2. or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains sufficient amount of oxyethylene units such that the hydrophi component has hydrophilicity great enough to increase t hydrophilicity of conventional polyester synthetic fiber surfac upon deposit of the soil release agent on such surface, sa hydrophile segments preferably comprising at least about 2 oxyethylene units and more preferably, especially for su components having about 20 to 30 oxypropylene units, at lea about 50% oxyethylene units; or (b) one or more hydropho components comprising (i) C3 oxyalkylene terephthalate segment wherein, if said hydrophobe components also comprise oxyethyle terephthalate, the ratio of oxyethylene terephthalate: oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C alkylene or oxy C4-C6 alkylene segments, or mixtures thereo (iii) poly (vinyl ester) segments, preferably poly(vinyl acetate) having a degree of polymerization of at least 2, or (iv) C1-C alkyl ether or C4 hydroxyalkyl ether substituents, or mixture thereof, wherein said substituents are present in the form o C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives or mixtures thereof, and such cellulose derivatives ar amphiphilic, whereby they have a sufficient level of C1-C4 alky ether and/or C4 hydroxyalkyl ether units to deposit upo conventional polyester synthetic fiber surfaces and retain sufficient level of hydroxyls, once adhered to such conventiona synthetic fiber surface, to increase fiber surface hydrophilicity or a combination of (a) and (b). Useful soil release polymers are described in U.S. Paten 4,000,093. issued December 28, 1976 to Nicol et al .. Europea Patent Application 0 219 048, published April 22, 1987 by Kud e al . U.S. Patent 3,959,230 to Hays, issued May 25. 1976, U.S Patent 3,893.929 to Basadur issued July 8, 1975, U.S. Paten 4,702,857, issued October 27, 1987 to Gosselink, U.S. Paten 4,711,730, issued December 8, 1987 to Gosselink et al . , U.S Patent 4,721,580. issued January 25, 1988 to Gosselink, U.S Patent 4,702,857, issued October 27, 1987 to Gosselink, U. Patent 4,877,896, issued October 31, 1989 to Maldonado et al . A of these patents are incorporated herein by reference. If utilized, soil release agents will generally comprise fr about 0.01% to about 10.0%, by weight, of the detergent compos tions herein, typically from about 0.1% to about 5%, preferab from about 0.2% to about 3.0%. Chelating Agents The detergent compositions herein may also optionally conta one or more iron and manganese chelating agents as a build adjunct material. Such chelating agents can be selected from t group consisting of amino carboxylates, amino phosphonates polyfunctionally -substituted aromatic chelating agents an mixtures thereof, all as hereinafter defined. Without intendin to be bound by theory, it is believed that the benefit of thes materials is due in part to their exceptional ability to remov iron and manganese ions from washing solutions by formation o soluble chelates. Amino carboxylates useful as optional chelating agents i compositions of the invention can have one or more, preferably a least two, units of the substructure CH2 - (CH 2 )χ - C00M, / wherein M is hydrogen, alkali metal, ammonium or substitute ammonium (e.g. ethanolamine) and x is from 1 to about 3, pref¬ erably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitri1otriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexa- acetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof an mixtures thereof. Amino phosphonates are also suitable for use as chelatin 5 agents in the compositions of the invention when at least lo levels of total phosphorus are permitted in detergent composi tions. Compounds with one or more, preferably at least two, unit of the substructure 10 CH 2χ N (CH 2 )χ P0 3 M 2 , wherein M is hydrogen, alkali metal, ammonium or substitute ammonium and x is from 1 to about 3, preferably 1, are useful an 5 include ethylenediaminetetrakis (methylenephosphonates) nitrilotris (methylenephosphonates) and diethylenetriaminepentaki (methylenephosphonates). Preferably, these amino phosphonates d not contain alkyl or alkenyl groups with more than about 6 carbo atoms. Alkylene groups can be shared by substructures. 20 Polyfunctionally - substituted aromatic chelating agents ar also useful in the compositions herein. These materials ca comprise compounds having the general formula 0 wherein at least one R is -SO3H or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812.044, issued May 21. 1974, to Connor et al .. incorporated herein by reference, discloses polyfunctionally - substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihy- 5 droxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions can contain these materials in th form of alkali metal, ammonium or substituted ammonium (e.g ono-or triethanol-amine) salts. If utilized, these chelating agents will generally compris from about 0.1% to about 10% by weight of the detergent composi tions herein. More preferably chelating agents will comprise fro about 0.1% to about 3.0% by weight of such compositions. Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionall contain water-soluble ethoxylated amines having clay soil remova and anti-redeposition properties. Liquid detergent composition which contain these compounds typically contain from about 0.01 The most preferred soil release and anti-redeposition agen is ethoxylated tetraethylenepentamine. Exemplary ethoxylate amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986, incorporated herein by reference. Another group of preferred clay soil removal/anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984, incorporated herein by reference. Other clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111.984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4. 1984; and the amine oxides disclosed in U.S. Patent 4,548.744. Connor, issued October 22, 1985, all of which are incorporated herein by reference. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions hereof. Another type of preferred anti-redeposition agent includes the carooxymethylcellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents Polymeric dispersing agents can advantageously be utilized i the compositions hereof. These materials can aid in calcium an magnesium hardness control. Suitable polymeric dispersing agent include polymeric polycarboxylates and polyethylene glycols although others known in the art can also be used. Suitable polymeric dispersing agents for use herein ar described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967 and European Patent Application No. 66915, published December 15 1982, both incorporated herein by reference. Brightener Any suitable optical brighteners or other brightening o whitening agents known in the art can be incorporated into th detergent compositions hereof. Commercial optical brighteners which may be useful in th present invention can be classified into subgroups which include but are not necessarily limited to, derivatives of stilbene pyrazoline, coumarin, carboxylic acid, methinecyanines dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-rin heterocycles, and other miscellaneous agents. Examples of suc brighteners are disclosed in "The Production and Application o Fluorescent Brightening Agents", M. Zahradnik, Published by Joh Wiley & Sons, New York (1982), the disclosure of which incorporated herein by reference. Suds Suppressors Compounds known, or which become known, for reducing o suppressing the formation of suds can be incorporated into th compositions of the present invention. Suitable suds suppressors are described in Kirk Othmer Encyclopedia of Chemical Technology. Third Edition, Volume 7, pages 430-447 (John Wiley & Sons. Inc.. 1979), U.S. Patent 2,954,347, issued September 27, 1960 to St. John, U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., U.S. Patent 4.265,779, issued May 5, 1981 to Gandolfo et al . and European Patent Application No. 89307851.9, published Februa 7, 1990, U.S. Patent 3,455,839, German Patent Application D 2,124,526, U.S. Patent 3,933,672, Bartolotta et al . , and U. Patent 4,652,392, Baginski et al., issued March 24, 1987. All a incorporated herein by reference. The compositions hereof will generally comprise from 0% t about 5% of suds suppressor. Other Ingredients A wide variety of other ingredients useful in detergen compositions can be included in the compositions hereof, includin other active ingredients, carriers, hydrotropes, processing aids dyes or pigments, solvents for liquid formulations, bleaches bleach activators, etc. Liquid detergent compositions can contain water and othe solvents as carriers. Low molecular weight primary or secondar alcohols exemplified by methanol, ethanol, propanol, an isopropanol are suitable. Monohydric alcohols are preferred fo solubilizing surfactant, but polyols such as those containing fro 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., ethylene glycol, glycerine, and 1,2-propanediol) can also be used. Liquid Compositions Preferred heavy duty liquid laundry detergent compositions hereof will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and 11.0, preferably between about 7.0 and 8.5. The compositions herein preferably have a pH in a 10% solution in water at 20 β C of between about 6.5 and II.0, preferably 7.0 to 8.5. 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. This invention further provides a method for cleaning substrate, such as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate, with a liquid detergent composition comprising detersive surfactant, proteolytic enzyme, detergent-compatible second enzyme, and the mixture of boric ac and a polyol described above. Agitation is preferably provid for enhancing cleaning. Suitable means for providing agitati include rubbing by hand or preferably with use of a brush, spong cloth, mop, or other cleaning device, automatic laundry washi machines, automatic dishwashers, etc. Preferred herein are concentrated liquid deterge compositions. By "concentrated" is meant that these compositio will deliver to the wash the same amount of active detersi ingredients at a reduced dosage. Typical regular dosage of hea duty liquids is 118 mi11i1iters in the U.S. (about 1/2 cup) a 180 milliliters in Europe. Concentrated heavy duty liquids herein contain about 10 100 weight % more active detersive ingredients than regular hea duty liquids, and are dosed at less than 1/2 cup depending up their active levels. This invention becomes even more useful concentrated formulations because there are more actives interfere with enzyme performance. Preferred are heavy du liquid laundry detergent compositions with from about 30 to 9 preferably 40 to 80, most preferably 50 to 60, weight % of acti detersive ingredients. The following examples illustrate the compositions of t present invention. All parts, percentages and ratios used herei are by weight unless otherwise specified. EXAMPLES 1-11 A base composition is made as shown below and used i Examples 1-11. Base Matrix A INGREDIENT WT % 1) 12.3 Linear alkylbenzene sulfonic acid 8.43 2) Ci4_is Alkyl ether (2.25) sulfonic acid 3.43 3) C12-13 Alkyl ethoxylate (6.5) 3.37 4) Dodecyl trimethyl ammonium chloride 0.51 10 20 25 30 1) Base Matrix A 70.00 70.00 70.00 2) Sodium tartrate ono- and di-succinate (80:20 mix) 3.37 3.37 3.37 it> 3) Sodium formate 0.15 0.15 0.15 4) Boric acid 2.00 2.00 2.00 5) 1,2 Propanediol 4.00 6) 1,2 Butanediol -- 4.00 7) 3 Chloro 1,2 propanediol -- 8) Protease B (34g/L) 0.70 0.70 9) Lipase (100 KLU/g) 0.90 0.90 10) Water/misc. 18.88 18.88 TOTAL 100.00 100.00 (pH = 7.8 to 8.3) EX. 7 EX. 8 WT % WT % 1) Base Matrix A 70.00 70.00 64.00 2) Sodium tartrate mono- and di-succinate (80:20 mix) 3.37 3.37 3.37 3) Sodium formate 0.15 0.15 0.15 4) Boric acid 2.00 2.00 2.00 5) 2,3 Dihydroxy benzaldehyde 4.00 6) 1.2 Hexanediol -- 4.00 7) Sorbitol -- -- 4.00 8) Protease B (34g/L) 0.70 0.70 0.70 9) Lipase (100 KLU/g) 0.90 0.90 0.90 10) Water/misc. 18.88 18.88 18.88 TOTAL 100.00 100.00 100.00 (pH = 7.8 to 8.3) EX. 10 EX. 11 T WT Initial lipase activity is measured using a pH-stat compouter assisted titrimeter. Ti ration mixture is prepared using 10 M calcium chloride (CaC12), 20 mM sodium chloride (NaCl) and 5 M tris buffer at a pH of 8.5-8.8. A commercial lipase substrate containing 5.0 wt% olive oil, and an emulsifier is used. 100 microliters of the detergent composition is added to the mixture. The fatty acids formed by 1 ipase-catalysed hydrolysis are titrated against a standard sodium hydroxide solution. The slope of the titration curve is taken as the measure of lipase activity. Initial activity is measured immediately after the composition is prepared. The samples are then aged at 90 * F (32.2'C) and the residual activity is measured after two to three weeks of storage at 90 β F. The residual activity in Table 1 below is reported as the percentage of initial activity. The thermodynamic constants Ki and K2 as determined by Hβ N.M.R. have also been tabulated. , Table 1 % Residual Lipase Activity at 90°F KI K2 14 days 0 30 0 14 68 5.4 94 27 97 na 86 84 31 44 43 not provide sufficient stability to lipase in a heavy-duty liqui composition containing proteolytic enzyme. The stabiity is improved by using a mixture of boric acid and 1,2 propanediol (Example 4). Surprisingly, it is seen that by using a- mixture o boric acid and polyol . as described herein (Examples 5-8), significantly higher lipase stability is observed than with boric acid, propanediol (or a combination thereof) alone. It is concluded that for superior lipase stability, the polyol to boric acid complexation reaction should have a Ki between about 0.1 and 4001/mole and a K2 between 0 and about 1000 l 2 /mole 2 . If these values fall outside the above ranges (Examples 9-11), poor lipase stability is obtained. Other compositions of the present invention are obtained when Protease B is substituted with other proteases such as Savinase® and BPN', and/or lipase is substituted by other second enzymes such as a ylase. EXAMPLES 12-14 A base composition for a concentrated heavy-duty liαuid detergent composition is prepared as shown below and used in Examples 12-14: Base Matrix B INGREDIENT WT % 1) c 12.3 Linear alkylbenzene sulfonic acid 12.6 2) C14-15 Alkyl ether (2.25) sulfonic acid 10.6 3) C12-13 Alkyl ethoxylate (6.5) 2.4 4) Monoethanol amine 1.0 5) Sodium hydroxide 3.5 6) 1,2 propane diol 4.0 7) Ethanol 1.5 8) Sodium cumene sulfonate 6.0 9) Citric acid 4.0 10) Tetraethylene pentaamine ethoxylate 1.5 11) C12-14 fatty acid 2.0 12) Water/misc. 16.9 13) Ingredients per Examples 12-14 34.00 TOTAL 100.00 Base Matrix B is used for preparation of Examples 12-14. EX. 12 EX. 13 EX. 14 T % WT % 64.00 54.00 3.00 3.00 0.15 0.15 2.00 2.00 4.00 (pH = 7.8 to 8.3) Other compositions of the present invention are ODtained when Protease B is substituted with other proteases such as Alcalase*. Savinase*, and BPN', and/or lipase is substituted by or used in conjunction with other second enzymes such as amylase. WHAT IS CLAIMED IS:

Claims: 1. A liquid detergent composition characterized by comprising: a. a mixture of (1) from 0.1 to 30 weight % of the composition of vicina polyol of the structure where Ri is selected from the group consisting of Ci-C alkyl, aryl, substituted C1-C6 alkyl, substituted aryl, nitro, and halogen; R2, R3 and R4 are independentl selected from the group consisting of hydrogen, Cj-Cβ alkyl, aryl, substituted C1-C6 alkyl, substituted aryl, halogen, nitro, ester, amine, amine derivative, substituted amine, hydroxyl and hydroxyl derivative; R5, Rβ, R7, and Rs are independently selected from the group consisting of hydrogen, C1-C6 alkyl, aryl, substituted C1-C6 alkyl, substituted aryl, halogen, nitro, ester, amine, amine derivative, substituted amine, aldehyde, acid, sulfonate and phosphonate; and at least one R5-8 is Ri; and (2) from 0.05 to 20 weight % of the composition of boric acid or its derivative; wherein the equilibrium constants for the reaction between (1) and (2) are: Ki between 0.1 and 400 1/mole and 2 between 0 and 1000 l2/ ole 2 ; b. from 0.0001 to 1.0 weight % of active proteolytic enzyme; c. a performance-enhancing amount of a detergent-compatible second enzyme; d. from 1 to 80 weight % of anionic or nonionic surfactant; and e. from 0.1 to 30 weight % of alphahydroxyacid builder. 2. A liquid detergent composition according to Claim 1 wherein K2 is between 0.1 and 200 l 2 /mole2; and wherein said second enzyme is selected from the group consisting of lipase, amylase, cellulase, and mixtures thereof; and wherein the ratio of K2/K1 ≤ 20; and wherein said vicinal polyol is Rl - C - C - R4 OH OH where Ri is selected from the group consisting of C1-C6 alkyl, substituted C1-C6 alkyl, phenyl, and substituted phenyl, and R2, R3 and R4 are hydrogen. 3. A liquid detergent composition according to Claim 1 or 2 wherein said vicinal polyol is not catechol, 1,2 propanediol or glycerine and no other detersive surfactants are included in said composition. 4. A liquid composition according to any of the preceding claims wherein said vicinal polyol is selected from the group consisting of 1,2 butanediol, 1,2 hexanediol, 3 chloro 1,2 propanediol, propylgallate, gallic acid, 1 phenyl 1,2 ethanediol, and 1 ethoxy 2, 3 propanediol; and comprising from 0.0005 to 0.2 weight % of active proteolytic enzyme selected from the group consisting of Savinase ® , Maxacal®, BPN', Protease A, Protease B, and mixtures thereof. 5. A liquid detergent composition according to any of the preceding claims comprising from 0.2 and 20 weight % of said vicinal polyol and 0.1 to 10 weight % of boric acid; and wherein the boric/polyol molar ratio is between 20:1 and 1:20; and comprising from 5 to 50 weight % of said anionic and nonionic surfactants; and wherein said second enzyme is lipase in the amount of from 2 to 20,000 lipase units per gram. 6. A liquid laundry detergent composition according to any of the preceding claims wherein the ratio of (a) to (e) is between 10:1 and 1:10; and wherein said surfactant comprises an enzyme performance-enhancing amount of polyhydroxy fatty acid amine surfactant; and comprising from 10 to 6,000 lipase units per gram of lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Asoergillus orvzae. 7. A liquid laundry detergent composition according to any of the preceding claims wherein said anionic surfactant is C12 to C20 alkyl sulfate, C12 to 20 alkyl ether sulfate or Cg to 20 linear alkylbenzene sulfonate, and said nonionic surfactant is the condensation product of C10-C20 alcohol and between 2 and 20 moles of ethylene oxide per mole of alcohol, or polyhydroxy C10-C20 fatty acid amide. 8. A liquid laundry detergent composition according to any of the preceding claims, having a pH in a 10% solution in water at 20'C of between 6.5 and 11.0; and wherein said second enzyme comprises from 0.0001 to 1.0 weight % on an active enzyme basis of cellulase. 9. A heavy duty liquid laundry detergent composition according to any of the preceding claims, with from 30 to 90 weight % of active detergent ingredients.

Inventors: LENOIR PIERRE MARIE ALAIN, PANANDIKER RAJAN KESHAV, THOEN CHRISTIAAN ARTHUR JACQUE, LENOIR, PIERRE, MARIE, ALAIN, PANANDIKER, RAJAN, KESHAV, THOEN, CHRISTIAAN, ARTHUR, JACQUES, KAMIEL
Applicants: PROCTER & GAMBLE, THE PROCTER & GAMBLE COMPANY
Application year: 1992
Main classification: C11D3
IPC codes: C11D3