WO1992019708A1 - Liquid detergents with aromatic borate ester to inhibit proteolytic enzyme - Google Patents

Abstract

Included are liquid detergent compositions comprising anionic and/or nonionic surfactant, proteolytic enzyme, second enzyme, and an aromatic borate ester.

Description

LIQUID DETERGENTS WITH AROMATIC BORATE ESTER TO INHIBIT PROTEOLYTIC ENZYME

Field of the Invention

This invention relates to liquid detergent compositions comprising anionic or nonionic surfactant, proteolytic enzyme, second enzyme, and an aromatic borate ester.

Background of the invention

A commonly encountered problem with protease-containing liquid detergents i the degradation of second enzymes in the composition by the proteolytic enzyme. The stability of the second enzyme upon storage in product and its effect on cleaning are impaired by the proteolytic enzyme.

Boric acid and boronic acids are known to reversibly inhibit proteolytic enzymes. A discussion of the inhibition of one serine protease, subtilisin by boronic acid is provided in Philipp, M. and Bender, M.L. , "Kinetics of Subtilisin and Thiosubtilisin" , Molecular & Cellular Biochemistry, vol. 51, pp. 5-32 (1983).

One type of boronic acid, peptide boronic acid, is discussed as an inhibito of trypsin-like serine proteases, especially in pharmaceuticals, in Europea Patent Application 0 293 881, Kettner et al., published December 7, 1988.

German Patent 3 918 761, published June 28, 1990 discloses liquid enzyme concentrate which is said to be usable as a raw material solution for makin liquid detergents and the like. The concentrate contains hydrolase, propylene glycol and boric acid or its salt.

U.S. Patent 4,537,707, issued August 27, 1985 describes heavy duty liqui detergents containing anionic surfactants, fatty acid, builder, proteoly enzyme, boric acid, calcium ions and sodium formate. The combination of boric acid and sodium formate is claimed to provide improved proteolytic enzyme stability in this composition, especially in the presence of a polyol. These compositions are free of lipase.

European Patent Application 0080 223, published June 1, 1983 describes detergent compositions containing a polyfunctional amino compound or a polyol together with a reducing alkali metal salt.

Similarly in GB 2 079 305, published January 20, 1982, it is disclosed th enhanced enzyme stability can be obtained in a built liquid detergent by inclusion of boric acid, a polyol in the ratio of polyol to boric acid mo than 1:1, and a cross-linked polyacrylate polymer. These compositions contain no lipase.

In European Application 0 381262, Aronson et al. , published August 8, 19 mixtures of proteolytic and lipolytic enzymes in a liquid medium have bee disclosed. The stability of lipase is claimed to be improved by the addition of boron compound and a polyol having vicinal hydroxyl groups.

It has now been found that certain aromatic borate esters are especially effective in reversibly inhibiting protease, in a HDL which also comprises detergency ingredients and a second enzyme.

Upon dilution, such as under typical wash conditions, the proteolytic enzy is no longer inhibited and can function (e.g. to remove protease-sensitive stains from fabrics in the wash) . Summary of the invention

The present invention relates to a liquid detergent composition containin a. an aromatic borate ester formed by the complexation of boric acid with an aromatic reagent of the structure:

Wherein:

-X is OH, SH, or NH₂.

_Y is CO2H, substituted or unsubstituted CH2OH,

CH SH, CH₂NH₂ or C-NH₂₎

0 -each Z is H or a substituted or unsubstituted C^-

Cg alkyl, alkenyl, alkynyl or an aryl chain, OH or -0-R, wherein R is a C^-Cg alkyl chain, or an electron withdrawing group such as CN, N0₂

CHO, SO3H, COOR wherein R is H or a C^-C alkyl chain; -i is an integer of from 1 to 4, b. from about 0.0001 to 1 % of active proteolytic enzyme; c. a performance-enhancing amount of a detergent-compatible second enzyme; d. from about 1 to 80 weight % of anionic or nonionic surfactant.

Description of the invention

The present liquid detergent compositions contain certain essential ingredients : (a) an aromatic borate ester formed by the complexation of a aromatic reagent described herein after with boric acid or its derivatives; (b) proteolytic enzyme; (c) detergent-compatible second enzyme; (d) anioni and/or nonionic detersive surfactant. These compositions will most commonly be used for cleaning of laundry, fabrics, textiles, fibers, and hard surf ces. Heavy duty liquid laundry detergents are the preferred liquid detergent compositions herein.

(a) Aromatic borate ester

The present liquid detergent compositions contain an aromatic borate est formed by the complexation of an aromatic reagent such as described herei after with boric acid or its derivatives.

The aromatic borate ester can either be formed prior to incorporation in detergent composition, or it can be formed in situ, by simply adding bori acid and the aromatic reagent in the detergent composition at any stage i its manufacturing process, or on top of the finished product.

From about 0.1 to 20 %, preferably about 0.2 to 10% weight % of the aroma borate ester can be used in the liquid detergent composition. The molar ratio of boric acid or its derivatives to aromatic reagent is preferably between about 20:1 and 1:20, more preferably between about 10:1 and 1:10, most preferably between 5:1 and 1:5.

The aromatic reagent

The aromatic reagent has the following structure:

Z

Wherein:

-X is OH, SH, or NH_2; _Y is C0₂H, substituted or unsubstituted CH 0H. CH₂SH,

CH₂NH₂ or C-NH_2;

0 -each Z is H or a substituted or unsubstituted C^-

Cg alkyl, alkenyl, alkynyl or an aryl chain, OH or -0-R wherein R is a C^-Cg alkyl chain, or an electron withdrawing group such as CN, CHO, SO3H, N0₂ or COOR wherein R is H or a C^-Cg .alkyl chain,

-i is an integer of from 1 to 4; i.e there can be up to four substituents per aromatic ring.

Preferably, there will be one substituent per aromatic ring (i.e. i=l) ; preferably, this substituent will be an electron withdrawing group, as defined hereinabove; preferably this electron withdrawing group will be in para position vs the X substituent.

Preferred aromatic reagents according to the invention are substituted or unsubstituted 2-hydroxybenzylalcohol or 2-hydroxybenzoic acid, more preferably 2-hydroxybenzylalcohol, 2,6-dihydroxybenzylalcohol, 2- hydroxybenzoic acid, 2,6- dihydroxybenzoic acid.

From about 0.05 to about 20%, most preferably about 0.2 to 10% weight % o aromatic reagent is preferred in the present liquid detergent compositions

Boric Acid

The boric acid or its derivatives used in the mixture can be boric acid, borax, boric oxide, polyborates, orthoborates, pyroborates, metaborates, mixtures thereof. Boric acid salts are of course included.

In the present liquid detergent compositions, from about 0.001 to 20, more preferably about 0.02 to 10, most preferably 0.05 to 5, weight % of boric acid or derivatives is incorporated.

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 0.5, most preferably about 0.002 to 0.1, weight % of active proteolytic enzyme. Mixtures of proteolytic enzyme are also included. The proteolyti enzyme can be of animal, vegetable or microorganism (preferred) origin. More preferred is serine proteolytic enzyme of bacterial origin. Purified or nonpurified forms of this enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included. Particularly preferred is bacterial serine proteolytic enzyme obtained f Bacillus Subtillis and/or Bacillus Licheniformis.

Suitable proteolytic enzymes include Alcalase^-, Esperase^ , Savin (preferred); Maxatase^-, Maxacal^- (preferred) , and Maxapem 15^- (protein engineered Maxacal^-) ; and subtilisin BPN and BPN' (preferred) ; which are commercially available. Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87303761.8, published April 28, 1987(particular pages 19, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 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 of Savinase^-, Maxacal*-, BPN' , Protease and Protease B, and mixtures thereof. Protease B is most preferred. C. Second Enzyme

The third essential ingredient in the present- liquid compositions a performance-enhancing amount of a detergent-compatible second enzyme. "detergent-compatible" is meant compatibility with the other ingredients a liquid detergent composition, such as detersive surfactant and detergen 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 abo so each composition herein contains at least two kinds of enzyme, includi at least one proteolytic enzyme.

The amount of second enzyme used in the composition varies accordin 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 the second enzymes are preferably used.

Mixtures of enzymes from the same class (e.g. lipase) or two or mor classes (e.g. cellulase and lipase) may be used. Purified or non-purified forms of the enzyme may be used.

Any lipase suitable for use in a liquid detergent composition can b used herein. Suitable lipases for use herein include those of bacterial a fungal origin. Second enzymes from chemically or genetically modified mutants are included.

Suitable bacterial lipases include those produced by Pseudomonas. such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034, incorporated herein by reference. Suitable lipases include tho which show a positive immunological cross-reaction with the antibody of th lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. Th lipase and a method for its purification have been described in Japanese Patent Application 53-20487, laid open on February 24, 1978, which is incorporated herein by reference. This lipase is available under the trad 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 immunodiffusion 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 fragi FERM P 133 (available under the trade name Amano-B) , lipase ex Psuedomonas nitroreducens var. lipolvticum FERM P 1338 (available under the trade na Amano-CES) , lipases ex Chromobacter viscosum. e.g. Chromobacter viscosum var. lipolvticum NRRLB 3673, and further Chromobacter viscosum lipases, an lipases ex Pseudomonas gladioli. Other lipases of interest are Amano AKG and Bacillis Sp lipase (ex. Solvay enzyme).

Suitable fungal lipases include those producible by Humicola lanuginosa and Thermomvces lanuginosus. Most preferred is lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus orvzae as described in European Patent Application 0 258 068, incorporated herein by reference, commercially available under the trade name Lipolase^.

From about 2 to 20,000, preferably about 10 to 6,000, lipase units lipase per gram (LU/g) of product can be used in these compositions. A lipase unit is that amount of lipase which produces 1 μmol of titratable butyric acid per minute in a pH stat, where pH is 9.0, temperature is 30°C, and substrate is an emulsion of 3.3wt % of tributyrin and 3.3% of gum arabic, in the presence of 2.2 μmol/1 Ca and 50μmol/l NaCl in 5μmol/l phosphate.

Any cellulase suitable for use in a liquid detergent composition can be used in these compositions. Suitable cellulase enzymes for use herein include those of bacterial and fungal origins. Preferably, they will have pH optimum of between 5 and 9.5. From about 0.0001 to 1.0, preferably 0.00 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 by referen which discloses fungal cellulase produced from Humicola insolens. Suita cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-0S

2.247.832.

Examples of such cellulases are cellulases produced by a strain o

Humicola insolens (Humicola grisea var. thermoidea) , particularly the

Humicola strain DSM 1800, and cellulases produced by a fungus of Bacillus or a cellulase 212-producing fungus belonging to the genus Aeromonas. and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabell

Auricula Solander) .

Any am lase .suitable for use in a liquid detergent composition c be used in these compositions. Amylases include, for example, amylases obtained from a special strain of B.licheniforms. described in more detai in British Patent Specification No. 1,296,839. Amylolytic proteins inclu for example, Rapidase , Maxamyl and Termamyl

From about 0.0001% to 1.0, preferably 0.0005 to 0.5, weight % on a active enz me basis of amylase can be used.

D. Detersive Surfactant

From about 1 to 80, preferably about 5 to 50, most preferably abou

10 to 30, weight % of detersive surfactant is the fourth essential ingredient in the present invention. The detersive surfactant can be selected from the group consisting of anionics, nonionics, cationics, ampholytics, zwitterionics, and mixtures thereof. Anionic and nonionic surfactants are preferred.

Heavy duty liquid laundry detergents are the preferred liquid detergent compositions herein. The particular surfactants used can vary widely depending upon the particular end-use envisioned. These compositio will most commonly be used for cleaning of laundry, fabrics, textiles, fibers, and hard surfaces.

The benefits of the present invention are especially pronounced in compositions containing ingredients that are harsh to enzymes such as certain detergency builders and surfactants. Preferably the anionic surfactant comprises C_,„to C__n alkyl ether sulfate and C- to C__ linear alkylbenzene sulfonate. Suitable surfactants are described below. Anionic Surfactants

One type of anionic surfactant which can be utilized is alkyl ester sulfonates. These are desirable because they can be made with renewable, non-petroleum resources. Preparation of the alkyl ester sulfonate surfactant component is according to known methods disclosed in the technical literature. For instance, linear esters of C„-C _n carboxylic acids can be sulfonated with gaseous S0„ according to "The Journal of th

American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starti materials would include natural fatty substances as derived from tallow, palm, and coconut oils, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprises alkyl ester sulfonate surfactants of the structural formula:

0

II _,„4 CH - C OR

S0₃M

3 wherein R is a C„-C__ hydrocarbyl, preferably an alkyl, or combination

4 thereof, R is a C.-C, hydrocarbyl, preferably an alkyl, or combination thereof, and M is a soluble salt-forming cation. Suitable salts include metal salts such as sodium, potassium, and lithium salts, and substituted unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl piperydinium, and cations derived from alkanolamines, e.g. monoethanolamin diethanolamine, and triethanolamine.

3 4

Preferably, R is C_1fi-C_lg alkyl, and R is methyl, ethyl or isopropyl.

3 Especially preferred are the methyl ester sulfonates wherein R is C - C alkyl.

Alkyl sulfate surfactants are another type of anionic surfactant of importance for use herein. In addition to providing excellent overall cleaning ability when used in combination with polyhydroxy fatty acid amid (see below) , including good grease/oil cleaning over a wide range of temperatures, wash concentrations, and wash times, dissolution of alkyl sulfates can be obtained, as well as improved formulability in liquid detergent formulations are water soluble salts or acids of the formula ROSO,M wherein R preferably is a C^-C,,, hydrocarbyl, preferably an alky hydroxyalkyl having a C^-C-- alkyl component, more preferably a C -G^.. alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal ca

(e.g., sodium, potassium, lithium), substituted or unsubstituted ammoniu cations such as methyl-, dimethyl-, and trimethyl ammonium and quaternar ammonium cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, a cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, alkyl chains of C,. . , are preferred for lower wash temperatures (e.g., below about 50"C) and C_. - _n„ alkyl chains are preferred for higher wash temperatures (e.g., above about 50^βC) .

Alkyl alkoxylated sulfate surfactants are another category of use anionic surfactant. These surfactants are water soluble salts or acids typically of the formula R0(A) S0,M wherein R is an unsubstituted C_.₀-C„, alkyl or hydroxyalkyl group having a C_._Q-C„, alkyl component, preferably

C.--C-- alkyl or hydroxyalkyl, more preferably ^ci2~^ci8 ^alky! ^or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0. and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as w as alkyl propoxylated sulfates are contemplated herein. Specific example of substituted ammonium cations include methyl-, dimethyl-, trimethyl- ammonium and quaternary ammonium cations, such as tetramethyl-ammonium, dimethyl piperdinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereo Exemplary surfactants are C_._-C_,_ alkyl polyethoxylate (1.0) sulfate, C-_-

C_._ alkyl polyethoxylate (2.25) sulfate, C_.--C_._ alkyl polyethoxylate (3.0 sulfate, and C_.„-C_,_ 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 composi .ons hereof. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C_q-C„_n linear alkylbenzenesulphonates, C„-C„„ primary or secondary alkanesulphonates, C„

C-, 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 oleyl glycerol sulf tes, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C- -C_.₀ monoesters) diesters of sulfosuccinate (especially

LΔ It- saturated and unsaturated ^C _c -C- , diesters), N-acyl sarcosinates, sulfates alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below) , branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as those of the formu R0(CH„CH₂0) CH₂C00-M wherein R is a C₈-C₂„ alkyl, k is an integer from 0

10, and M is a soluble salt-forming cation, and fatty acids esterified wi isethionic acid and neutralized with sodium hydroxide. 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 tall oil. Further examples are given in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch) . A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). Nonionic Detergent Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678, Laughlin et al. , issued December 30, 1975, at colum 13, line 14 through column 16, line 6, incorporated herein by reference. Exemplary, non-limiting classes of useful nonionic surfactants are listed below.

1. The polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in either a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available

TM nonionic surfactants of this type include Igepal CO-630, marketed by the TM GAF Corporation; and Triton X-45, X-114, X-100, and X-102, all markete the Rohm & Haas Company. These compounds are commonly referred to as al phenol alkoxylates, (e.g., alkyl phenol ethoxylates) .

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcoh l can either be straight or branched, primary or second and generally contains from about 8 to about 22 carbon atoms. Particul preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about 2 to ab

18 moles of ethylene oxide per mole of alcohol. Examples of commercially

TM available nonionic surfactants of this type include Tergitol 15-S-9

(the condensation product of C.-.-C..,. linear secondary alcohol with 9 mol

TM ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of C_.„-C primary alcohol with 6 moles ethylene oxide with a narrow molecular weigh

TM distribution) , both marketed by Union Carbide Corporation; Neodol 45-9

(the conden-sation product of C-.-C.,. linear alcohol with 9 moles of

TM ethylene oxide), Neodol 23-6.5 (the condensation product of C_.„-C_._ lin

TM alcohol with 6.5 moles of ethylene oxide), Neodol 45-7 (the condensatio product of C-.-C..,. linear alcohol with 7 moles of ethylene oxide),

TM Neodol 45-4 (the condensation product of C-.-C.,. linear alcohol with

T moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro

EOB (the condensation product of C.^-C.,. alcohol with 9 moles ethylene oxide) , marketed by The Procter & Gamble Company. This category of nonionic surfactant is referred to generally as "alkyl ethoxylates."

3. The condensation products of ethylene oxide with a hydrophob base formed by the condensation of propylene oxide with propylene glycol The hydrophobic portion of these compounds preferably has a molecular weig of from about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensati product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of t

TM commercially-available Pluronic surfactants, marketed by BASF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has molecular weight of from about 5,000 to about 11,000. Examples of this ty of nonionic surfactant include certain of the commercially available

TM Tetronic compounds, marketed by BASF.

5. Semi-polar nonionic surfactants are a special category nonionic surfactants which include water-soluble amine oxides containing on 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 atom 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 amine oxide surfactants having the formula

0

3 wherein R is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures

4 thereof containing from about 8 to about 22 carbon atoms; R is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to about 3; and each R is an alkyl or hydroxyalkyl group containing from about 1 to about carbon atoms or a polyethylene oxide group containing from about 1 to about

3 ethylene oxide groups. The R groups can be attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C_ιn-C₁₀ alkyl iU lo dimethyl amine oxides and C„-C..„ alkoxy ethyl dihydroxy ethyl amine oxides. 6. Alkylpolysaccharides disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic gr containing from about 1.3 to about 10, preferably from about 1.3 to ab 3, most preferably 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 3-, 4-, etc. positions thus giving a glucose or galactose as opposed t glucoside or galactoside.) The intersaccharide bonds can be, e.g., betwe the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.

Optionally, and less desirably, there can be a polyalkylene-oxide chain joining the hydrophobic moiety and the polysaccharide moiety. The preferred alkyleneoxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched containing from about 8 to about 18, preferably from about 10 about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and/or the polyalkyleneoxide chain can contain up to about 10, preferably less than 5, alkyleneoxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradec pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, pent and hexaglucosides, galactosides, lactosides, glucoses, fructosides, fructoses and/or galactoses. Suitable mixtures include coconut alkyl, di- tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hex glucosides.

The preferred alkylpolyglycosides have the formula R²0(C_nH_2n0)_t(glycosyl)_χ

2 wherein R is selected from the group consisting of alkyl, alkyl-phenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to abo

14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is pre- ferably derived from glucose. To prepare these compounds, the alcoh or alkylpolyethoxy alcohol is formed first and then reacted with glucos or a source of glucose, to form the glucoside (attachment at the 1- position) . The additional glycosyl units can then be attached between th 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

7. Fatty acid amide surfactants having the formula:

wherein R is an alkyl group containing from about 7 to about 21 (preferab from about 9 to about 17) carbon atoms and each R is selected from the group consisting of hydrogen, C--C, alkyl, C^ -C, hydroxyalkyl, and -

(C-H.0) H where x varies from about 1 to about 3. 2 4 x

Preferred amides are C_-C„_n ammonia amides, monoethanol- amides, diethanolamides, and isopropanolamides. Cationic Surfactants

Cationic detersive surfactants can also be included in detergent compositions of the present invention. Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula:

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N⁺ -

2 wherein R is an alkyl or alkyl benzyl group having from about 8 to abou

3 18 carbon atoms in the alkyl chain, each R is selected from the group consisting of -CH-CH- , -CH₂CH(CH_)- , -CH₂CH(CH₂0H)- , -

4 CH CH CH„-, and mixtures thereof; each R is selected from the group consisting of C. -C, alkyl, C- -C, hydroxyalkyl, benzyl, ring structures formed by joining the two R groups, -CH^CHOH-CHOHCOR CHOHCH_^OH wherein R is any hexose or hexose polymer having a molecular weight less than about

5 4

1000, and hydrogen when y is not 0; R is the same as R or is an alkyl

2 5 chain wherein the total number of carbon atoms of R plus R is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion. Other cationic surfactants useful herein are also described in Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein b reference. Other Surfactants

Ampholytic surfactants can be incorporated into the detergent compositions hereof. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight chain or branched. One of the aliphati substituents contains at least about 8 carbon atoms, typically from abou to about 18 carbon atoms, and at least one contains an anionic water- solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,678 Laughlin et al. , issued December 30, 1975 at column 19, lines 18-35 (her incorporated by reference) for examples of ampholytic surfactants.

Zwitterionic surfactants can also be incorporated into the deterge compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent 3,929,678 tc Laughlin et al., issued December 30, 1975 at column 19, line through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants.

Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants. Polyhydroxy Fatty Acid Amide Surfactant

The liquid detergent compositions hereof preferably contain an "enzyme performance-enhancing amount" of polyhydroxy fatty acid amide surfactant. By "enzyme-enhancing" is meant that the formulator of the composition can select an amount of polyhydroxy 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 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 wi comprise from about 3% to 50%, most preferably from about 3% to 30%, of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises compounds of the structural formula:

0 R¹

2 'I '

(I) R - C - N - Z

wherein: R is H, C. -C, hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, a mixture thereof, preferably C -C, alkyl, more preferably C. or C„ alkyl,

2 most preferably C. alkyl (i.e., methyl); and R is a C_t--C_₁ hydrocarbyl, preferably straight chain C₇-C-_c. alkyl or alkenyl, more preferably straig chain C„-C.₇ alkyl or alkenyl, most preferably straight chain C.-, -C_. al or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl having linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sug in a reductive amination reaction; more preferably Z will be a glycityl.

Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syru high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH₂-(CH0H) -CH₂0H, -CH(CH₂0H)-

(CHOH)_n.₁- CH₂0H, -CH₂-(CH0H)₂(CH0R')(CH0H)-CH₂0H, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive, and R'

H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, particularly -CH--(CHOH), -CH_?0H.

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.

R2-C0-N can be, for example, cocamide, stearamide, 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 w a fatty aliphatic ester or triglyceride in a condensation/amidation step form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclos for example, in G.B. Patent Specification 809,060, published February 18,

1959, U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson,

U.S. Patent 2,703,798, Anthony M. Schwartz, issued March 8, 1955, and U.S

Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference.

E. Optional Ingredients

Detergency Builders

From 0 to about 50, preferably about 3 to 30, more preferably abou to 20, weight % detergency builder can be included herein. Inorganic as well as organic builders can be used.

Inorganic detergency builders include, but are not limited to, t alkali metal, ammonium and alkanolammonium salts of polyphosphates

(exemplified by the tripolyphosphates, pyrophosphates, and glassy polymer meta-phosphates) , phosphonates, phy ic acid, silicates, carbonates

(including bicarbonates and sesquicarbonates) , sulphates, and aluminosili- cates. Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditio

(hereinaf er, collectively "borate builders"), can also be used.

Preferably, non-borate builders are used in the compositions of the invention intended for use at wash conditions less than about 50°C, especially less than about 40°C.

Examples of silicate builders are the alkali metal silicates, particularly those having a SiO„:Na„0 ratio in the range 1.6:1 to 3.2:1 an layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein reference. However, other silicates may also be useful such as for exampl magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a compone of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali aetal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultra-fine calcium 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 invention. Aluminosilicate builders are of great importance in most currently markete heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

_z(zA10₂-.ySi0₂)

wherein M is sodium, potassium, ammonium or substituted ammonium, z is fro about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO, hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicat are zeolite builders which have the formula:

Na_z[ A10₂)_z (Si0₂) ].χH₂0

wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under t designations Zeolite A, Zeolite P (B) , and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange materia has the formula:

Na₁₂[( l0₂)₁₂(Si0₂)₁₂J H₂0

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 s z of about 0.1-10 microns in diameter.

Specific examples of polyphosphates are the alkali metal tripolyphosphates. sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphat sodium polymeta phosphate in which the degree of polymerization ranges f about 6 to about 21, and salts of phytic acid.

Examples of phosphonate builder salts are the water-soluble salts ethan. 1-hydroxy-l, 1-diphosphonate particularly the sodium and potassiu salts, the water-soluble salts of methylene diphosphonic acid e.g. the trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids, such as the trisodium and tripotassium ethylidene, isopyropylidene benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforemention types are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 issued December 1, 1964 and October 19, 1965, to Diehl; U.S. Patent No. 3,422, issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 issued September 3, 1968, and January 14, 1969 to Quimby, said disclosures being incorporated herein by reference.

Organic detergent builders preferred for the purposes of the prese invention include a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.

Polycarboxylate builder can generally be added to the composition acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and La berti et al., U.S. Patent 3,635,830, issued January 18, 1972, both of which are incorporated herein by reference.

A specific type of ether polycarboxylates useful as builders in th present invention also include those having the general formula:

CH(A)(C00X)-CH(COOX)-O-CH(COOX)-CH(COOX)(B)

wherein A is H or OH; B is H or -0-CH(C00X)-CH₂(C00X) ; and X is H or a salt-forming cation. For example, if in the above general formula A and B are both H, then the compound is oxydissuccinic acid and its water-solubl salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)- CH-(COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are especially preferred for use herein. Particularly preferred are mixtures of TMS and TDS in weight ratio of TMS to TDS of from about 97:3 to about 20:80. These builders are disclosed in U.S. Patent 4,663,071, issued to Bush et al., on May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all of which ar incorporated herein by reference.

Other useful detergency builders include the ether hydroxypolycarboxylates represented by the structure:

HO-[C(R)(C0OM)-C(R)(COOM)-O] -H wherein M is hydrogen or a cation wherein the resultant salt is water- soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n averages from about 2 to about 4) and each R i the same or different and selected from hydrogen, C. , alkyl or C- , substituted alkyl (preferably R is hydrogen) .

Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, and nitrilotriacetic acid.

Also included are polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene

1,3,5-tricarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt) , are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also used in granular compositions.

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 invent 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 includ the C,.-C„_n alkyl succinic acids and salts thereof. A particularly prefe compound of this type is dodecenylsuccinic acid. Alkyl succinic acids typically are of the general formula R-CH(C00H)CH₂(C00H) i.e., derivative of succinic acid, wherein R is hydrocarbon, e.g., C_._-C₂₀ alkyl or alken preferably C_.₂-C.,. 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-dodecenylsuccinate (preferred), 2 pentadecenylsuccinate, and the like. Laurylsuc-cinates are the preferred builders of this group, and are described in European Patent Applicatio

86200690.5/0,200,263, published November 5, 1986.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxyme hyloxysuccinate, cis-cyclo-hexane- hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having molecular weights to above about

2,000 can also be effectively utilized as 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. These polyacetal carboxylates can be prepared by bringing together, under polymerization conditions, an este of glyoxylic acid and a polymerization initiator. The resulting polyaceta carboxylate ester is then attached to chemically stable end groups to 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 3,308,06 Diehl, issued March 7, 1967, incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids, and soluble salts thereof, having long chai hydrocarbyls can be utilized. These would include materials generally referred to as "soaps." Chain lengths of C_._-C_2f) are typically utilized.

The hydrocarbyls can be saturated or unsaturated. Soil Release Agent

Any soil release agents known to those skilled in the art can be employed in the practice of this invention. Preferred polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylo 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 surf ctants 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.

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are comprised of repeatin units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate units of from about 2 to about 35:65, said PEO terephthalate units containing polyethylene ox having molecular weights of from about 300 to about 2000. The molecular weight of this polymeric soil release agent is in the range of from ab 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 2 1976, which is incorporated by reference. See also U.S. Patent 3,893, to Basadur issued July 8, 1975 (incorporated by reference) which disclos similar copolymers.

Another preferred polymeric soil release agent is a polyester wit repeat units of ethylene terephthalate units containing 10-15% by weight ethylene terephthalate units together with 90-80% by weight of polyoxyethlyene terephthalate units, derived from a polyoxyethylene glyco of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate.units to polyoxyethylene terephthalate units in the polymer compound is between 2:1 and 6:1. Examples of this polymer include the commercially available material ZelconR 5126 (from Dupont) and Milease R (from ICI) . These polymers and methods of their preparation are more ful described in U.S. Patent 4,702,857, issued October 27, 1987, to Gosselink which is incorporated herein.

Other suitable polymeric soil release agents include the ethyl o methyl-capped 1,2-propylene terephthalate-polyoxy- ethylene terephthalat polyesters of U.S. Patent 4,711,730, issued December 8, 1987, to Gossel et al., the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988, to Gosselink, wherein the anionic end-caps comprise sulfo-polyethoxy groups derived from polyethylene glycol (PEG) , block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X- 0CH2CH2)_n- wherein n is from 12 to about 43 and X is a C1-C alkyl, o preferably methyl, all of these patents being incorporated herein by reference.

Additional polymeric soil release agents include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., which discloses anionic especially sulfo- aroyl, end-capped terepthalate esters, said patent being incor- porated herein by reference

The terephthalate esters contain unsymmetrically substituted oxy-1,2- alkyleneoxy units. Included among the soil release polymers of U.S. Paten 4,877.896 are materials with polyoxyethylene hydrophile components or C3 oxyalkylene terephthalate (propylene terephthalate) repeat units within th scope of the hydrophobe components of (b)(i) above. It is the polymeric soil release agents characterized by either, or both, of these criteria th particularly benefit from the inclusion of the polyhydroxy fatty acid amides hereof, in the presence of anionic surfactants.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to abou 3.0%.

Useful soil release polymers are described in U.S. Patent 4,000,093 issued December 28, 1976 to Nicol et al., European Patent Application 0 21 048, published April 22, 1987 by Kud et 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. Patent 4,702,857, issued October 27, 1987 to Gosselink, U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al., U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al. All of these patents are incorporate herein by reference.

If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi-tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to abou 3.0%. Chelating Agents

The detergent compositions herein may also optionally contain one o more iron and manganese chelating agents as a builder adjunct material. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, all as hereinafter defined. Withou intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents in compositions of the invention can have one or more, preferably at least two units of the substructure

CH

2.

"^N - (CH ) - COOM / wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e ethan mine) and x is from 1 to about 3, pref- erably 1. Preferably, t amino carboxylates do not contain alkyl or alkenyl groups with more tha about 6 carbon atoms. Operable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexa-acetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents i the compositions of the invention when at least low levels of total phosphorus are permitted in detergent composi- tions. Compounds with one more, preferably at least two, units of the substructure

CH₂

/* (CH₂)_χ P0_{3 2},

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and is from 1 to about 3, preferably 1, are useful and include ethylenediaminetetrakis (methylenephosphonates) , nitrilotris (methylenephosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Alkylene groups can be shared by substructures.

Polyfunctionally - substituted aromatic chelating agents are also useful in the compositions herein. These materials can comprise compounds having the general formula

wherein at least one R is -S0_H or -C00H or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, issued May 21, 1974, to Connor e al., incorporated herein by reference, discloses polyfunctionally - substituted aromatic chelating and sequestering agents. Preferred compoun of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydro -3,5-disulfo- benzene. Alkaline detergent compositions can contain these materials in the form of alkali metal, ammonium or substituted ammonium (e.g. mono-or triethanol-amine) salts.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi-tions herein. More preferably chelating agents will comprise from about 0.1% to about 3. by weight of such compositions. Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally conta water-soluble ethoxylated amines having clay soil removal and anti- redeposition properties. Liquid detergent compositions which contain thes compounds typically contain from about 0.01% to 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated 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 disclose in European Patent Application 111,965, Oh and Gosselink, published June 2 1984, incorporated herein by reference. Other clay soil removal/anti- redeposition agents which can be used include the ethoxylated amine polyme disclosed in European Patent Application 111,984, Gosselink, published Jun 27, 1984; the zwitterionic polymers disclosed in European Patent Applicati 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 ar incorporated herein by reference.

Other clay soil removal and/or anti redeposition agents known in th art can also be utilized in the compositions hereof. Another type of preferred anti-redeposition agent includes the carboxymethylcellulose (CMC) materials. These materials are well known in the art. Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized in the compositions hereof. These materials can aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.

Suitable polymeric dispersing agents for use herein are 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 he by reference.

Brightener

Any suitable optical brighteners or other brightening or whitenin agents known in the art can be incorporated into the detergent compositi hereof.

Commercial optical brighteners which may be useful in the 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-ring heterocycles, and other miscellaneous agents. Exampl of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the disclosure of which is incorporated herein by reference. Suds Suppressors

Compounds known, or which become known, for reducing or suppressin the formation of suds can be incorporated into the compositions of the present invention. Suitable suds suppressors are described in Kirk Othme Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-4 (John Wiley & Sons, Inc., 1979), U.S. Patent 2,954,347, issued September 1960 to St. John, U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo al., U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. an European Patent Application No. 89307851.9, published February 7, 1990, U. Patent 3,455,839, German Patent Application DOS 2,124,526, U.S. Patent 3,933,672, Bartolotta et al., and U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987. All are incorporated herein by reference.

The compositions hereof will generally comprise from 0% to about 5% of suds suppressor. Other Ingredients

A wide variety of other ingredients useful in detergent composition can be included in the compositions hereof, including 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 other solvents carriers. Low molecular weight primary or secondary alcohols exemplified methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol, 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 9.0, most preferably between 7.5 and 8.0. The compositions herein preferably have a pH in a 10% solution in water at 20°C of between about 7.0 to 11.0, 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, su as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrat with a liquid detergent composition comprising detersive surfactant, proteolytic enzyme, a detergent-compatible second enzyme, and the aryl boronic acids described above. Agitation is preferably provided for enhancing cleaning. Suitable means for providing agitation include rubbing by hand or preferably with use of a brush, sponge, cloth, mop, or other cleaning device, automatic laundry washing machines, automatic dishwashers etc.

Preferred herein are concentrated liquid detergent compositions. By "concentrated" is meant that these compositions will deliver to the wash th same amount of active detersive ingredients at a reduced dosage. Typical regular dosage of heavy duty liquids is 118 milliliters in the U.S. (about 1/2 cup) and 180 milliliters in Europe.

Concentrated heavy duty liquids herein contain about 10 to 100 weight % more active detersive ingredients than regular heavy duty liquids, and are dosed at less than 1/2 cup depending upon their active levels. Thi invention becomes even more useful in concentrated formulations because there are more actives to interfere with enzyme performance. Preferred are heavy duty liquid laundry detergent compositions with from about 30 to 90 preferably 40 to 80, most preferably 50 to 60, weight % of active detersive ingredients.

The following examples illustrate the compositions of the present invention. All parts, percentages and ratios used herein are by weight unless otherwise specified. 3o

EXAMPLES

II III

Linear alkyl benzene sulfonate

Sodium C12-15 alkyl sulfate

C14-15 alkyl 2.5 times ethoxylated sulfate

C12 glucose amide

C12-15 alcohol 7 times ethoxylated

C12-15 alcohol 5 times ethoxylated

Oleic acid

Citric acid

C12-14 alkenyl substituted succinic acid

Ethanol

1,2-propanediol

NaOH diethylene triamine penta

(methylene phosphonic acid)

Amylase (143KNU/g)

LipolaseR(100KLU/g commercial solution)

Protease B (34mg/g commercial solution)

Soil release polymer

2,6-dihydroxybenzylalcohol

CaC12

Na metaborate

Water and Minors Balance to 100%

IV VI

Linear alkyl benzene sulfonate

Sodium C12-15 alkyl sulfate

C14-15 alkyl 2.5 times ethoxylated sulfate

C12 glucose amide

C12-15 alcohol 7 times ethoxylated

C12-15 alcohol 5 times echoxylated

Oleic acid

Citric acid

C12-14 alkenyl substituted succinic acid

Ethanol

1,2-propanediol

NaOH diethylene triamine penta

(methylene phosphonic acid)

Amylase (143KNU/g)

LipolaseR(100KLU/g commercial solution)

Protease B (34mg/g commercial solution)

Soil release polymer

2-hvdroxvbenzylalcohol

ZaCΪl

"a metaborate

Vater and Minors Balance to 100% Linear alkyl benzene sulfonate

Sodium C12-15 alkyl sulfate

C14-15 alkyl 2.5 times ethoxylated sulfate

C12 glucose amide

C12-15 alcohol 7 times ethoxylated

C12-15 alcohol 5 times ethoxylated

Oleic acid

Citric acid

C12-14 alkenyl substituted succinic acid

Ethanol

1,2-propanediol

NaOH diethylene triamine penta

(methylene phosphonic acid)

Amylase (143KNU/g)

LipolaseR(100KLU/g commercial solution)

Protease B (34mg/g commercial solution)

Soil release polymer

2-hydroxybenzoic acid

CaC12

Na metaborate

Water and Minors Balance to 100%

XI XII

Linear alkyl benzene sulfonate

Sodium C12-15 alkyl sulfate

C14-15 alkyl 2.5 times ethoxylated sulfate

C12 glucose amide

C12-15 alcohol 7 times ethoxylated

C12-15 alcohol 5 times ethoxylated

Oleic acid

Citric acid

C12-14 alkenyl substituted succinic acid

Ethanol

1,2-propanediol

NaOH diethylene triamine penta

(methylene phosphonic acid)

Amylase (143KNU/g)

LipolaseR(100KLU/g commercial solution)

Protease B (34mg/g commercial solution)

Soil release polymer

2,6-dihydroxybenzoic acid

CaC12

Na metaborate

Water and Minors

Claims

A liquid detergent composition comprising : a. an aromatic borate ester formed by the complexation of boric a with an aromatic reagent of the structure:

wherein:

-X is OH, SH, or NH_2;

_Y is C02H, substituted or unsubstituted CH₂OH,

CH₂SH, CH₂NH₂ or C-NH_2;

0

-each Z is H or a substituted or unsubstituted Cl-

C6 alkyl, alkenyl, alkynyl or an aryl chain, OH or -0-R wherein R is a Cχ-Cg alkyl chain, or an electron withdrawing group such as CN, NO2

CHO, SO3H, COOR wherein R is H or a Cχ-Cg alkyl chain; -i is an integer of from 1 to 4, b. from about 0.0001 to 1 % of active proteolytic enzyme; c. a performance-enhancing amount of a detergent-compatible second enzyme; d. from about 1 to 80 weight % of anionic or nonionic surfactant;

2. A liquid detergent composition according to claim 1, wherein i is and Z is CN, N0₂, CHO, S03H or COOR, wherein R is H or a Cχ-Cg alk chain; in para position vs X;

3. A liquid detergent composition according to claim 1, wherein X is OH.

4. A liquid detergent composition according to the preceding claims, wherein the aromatic reagent is a substituted or unsubstituted 2- hydroxybenzylalcohol or 2-hydroxybenzoic acid.

5. A liquid detergent composition according to claim 4, wherein the aromatic reagent is selected from the group of 2- hydroxybenzylalcohol, 2,6-dihydroxybenzylalcohol, 2-hydroxybenzoic acid, 2,6-dihydroxybenzoic acid.

6 . A liquid detergent composition according to the preceding claims which comprises from 0.1 to 20%, preferably from 0.2 to 10% to of said aromatic borate ester.

7. A liquid detergent composition according to the preceding claims wherein the molar ratio of boric acid or its equivalent derivative to aromatic reagent is between 20:1 and 1:20, preferably 10:1 to 1:10, most preferably 5:1 to 1:5.

8. A liquid detergent composition according to the preceding claims wherein the proteolytic enzyme is a serine protease, preferably Savinase R, Maxacal R Maxapem 15 R, Protease A, ProteaseB, any chemically or genetically modified mutant thereof, and mixtures thereof.

9. A liquid detergent composition according to the preceding claims which comprises from about 0.0005 to 0.5% by weight of active proteolytic enzyme, preferably from 0.002 to 0.1% by weight.

10. A liquid detergent composition according to the preceding claims wherein said second enzyme is selected from the group consisting of lipase, amylase, cellulase, and mixtures thereof.

11. A liquid detergent composition according to claim 10 wherein said second enzyme is a lipase.

12. A liquid detergent composition according to claim 11 comprising fro about 2 to 20000, preferably 10 to 6000 lipase units per gram of detergent of said lipase product obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus orvzae.

13. A liquid detergent composition according to the preceding claims wherein said surfactant comprises an enzyme performance-enhancing amount of polyhydroxy fatty acid amine surfactant.