NZ240024A - Built detergent containing zeolite or layered silicate detergency builder and polyhydroxy fatty acid amide - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £40024 24 0 0 24 ri'iuiu/ .. ?■; ft ; 5.1.'. flQ* ..6.2:9/ Comptsio Specilica'.icn Filed: i Clans: Publication Date: ... 2 7.JUM.J9S5....

! P.O. Jourrm!, Nc: I.v/. .'.tv NO DRAWB85S " No.: Date: NEW ZEALAND PATENTS ACT, 1953 COMPLETE SPECIFICATION ri.Z. PATENT OFFICE IG SEP 1997 POLYHVDROXY FATTY ACID AMIDES IN ZEOLITE/LAYERED SILICATE BUILT DETERGENTS We, THE PROCTER & GAMBLE COMPANY, a corporation organized and existing under the laws of the State of Ohio, United States of America, located at One Procter & Gamble Plaza, Cincinnati, Ohio 45202, United States of America, hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- (followed by page la) - la - FIELD OF THE INVENTION Zeolite or layered silicate detergency builders, or mixtures thereof, are combined with polyhydroxy fatty acid amides to assist in detergent formulations.

BACKGROUND OF THE INVENTION Various builder materials have been suggested for use in detergent compositions. Such materials serve a variety of functions, including hardness sequestration, peptization, pH control, and the like. For many years, sodium tripolyphosphate was the builder of choice, but recent developments in the field include builder materials such as zeolites, various polycarboxylates, and the like. Currently, many fully-formulated detergent compositions contain a zeolite builder or a carboxylate builder, or mixtures thereof.

The development of high performance laundry detergent compositions without phosphates has been a considerable challenge to the industry. From the performance standpoint, even the best zeolite builders often result in an "under-built" situation in hard water. Moreover, commonly available zeolite builders handle calcium hardness, but are not particularly effective against magnesium hardness. Layered silicate builders have been more recently discovered for use as detergent builders. However the layered silicates handle magnesium hardness, but are somewhat less adept at controlling calcium hardness.

At present, almost all phosphate-free heavy duty granular detergents contain a zeolite builder. While zeolite-built laundry detergents are in broad commercial use, their shortcomings are well-known to formulators. In order to enhance the detergency performance of zeolite or layered silicate compositions, sophisticated formulators would need to incorporate various detergency adjuncts into detergent compositions. Materials such as detersive enzymes, soil release polymers, bleaches and bleach activators are commonly used to enhance the performance of built detergent compositions.

Furthermore, whereas for a number of years new detergent formulators have strived to replace phosphate-built detergents with equally effective phosphate-free detergents, there has recently developed interest in formulating detergents with decreased reliance upon surfactants derived from petroleum or other non-renewable resources.

It has now been found that of certain polyhydroxy fatty acid amide detergent compositions can provide excellent overall cleaning performance in full or partial replacement of commonly used petroleum-derived surfactants, such as linear alkyl benzene sulfonates. These polyhydroxy fatty acid amides can be obtained mainly, or even entirely, from natural renewable raw materials and, furthermore, are degradable and exhibit low toxicity to aquatic life. These polyhydroxy fatty acid amides can enhance solubility and dissolution of surfactant and auxiliary builder salts during use of the detergent compositions. Furthermore, these polyhydroxy fatty acid amides can surprisingly enhance zeolite and layered silicate builder performance in underbuilt wash conditions.

Simply stated, the present invention employs an improved detersive surfactant system containing zeolite and/or layered silicate builders. By the practice of this invention, polyhydroxy fatty acid amides are used in zeolite and/or layered silicate built detergents to provide enhanced detergency performance.

BACKGROUND ART A variety of polyhydroxy fatty acid amides have been described in the art. N-acyl, N-methyl glucamides, for example, are disclosed by J. W. Goodby, M. A. Marcus, E. Chin, and P. L. Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles," Liquid Crystals, 1S88, Volume 3, No. 11, pp 1569-1581, and by A. Muller-Fahrnow, V. Zabel, M. Steifa, and R. Hi 1genfeld in "Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methylglucamide," J. Chem. Soc. Chem. Commun., 1986, pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has been of substantial interest recently for use in biochemistry, for example in the dissociation of biological membranes. See, for 0 " •-> r i ♦ i 3 - example, the journal article "N-D-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry," Biochem. J. (1982), Vol. 207, pp 363-366, by J. E. K. Hildreth.

The use of N-alkyl glucamides in detergent compositions has also been discussed. U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson, and G.B. Patent 809,060, published February 18, 1959, assigned to Thomas Hedley & Co., Ltd. relate to detergent compositions containing anionic surfactants and certain amide 10 surfactants, which can include N-methyl glucamide, added as a low temperature suds enhancing agent. These compounds include an N-acyl radical of a higher straight chain fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates, and 15 carbonates. It is also generally indicated that additional constituents to impart desirable properties to the composition can also be included in the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.

U.S. Patent 2,703,798, issued March 8, 1955 to A. M. Schwartz, relates to aqueous detergent compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid. The product of this reaction is said to be useable in aqueous detergent compositions without further purification. It is also known to prepare a sulfuric ester of acylated glucamine as disclosed in U.S. Patent 2,717,894, issued September 13, 1955, to A. M. Schwartz.

PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth, relates to amphiphilic compounds containing polyhydroxyl aliphatic groups said to be useful for a variety of purposes including use as surfactants in cosmetics, drugs, shampoos, lotions, and eye ointments, as emulsifiers and dispensing agents for medicines, and in biochemistry for solubilizing membranes, whole cells, or other tissue samples, and for preparing liposomes. Included in this disclosure are compounds ^ of the formula R'C0N(R)CH2R" and R"C0N(R)R' wherein R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms, and R" is the residue of an aldose.

European Patent 0 285 768, published October 12, 1988, H. Kelkenberg, et al., relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula RiC(0)N(X)R2 wherein Rj is a Cj-Cj 7 (preferably C7-C17) alkyl, R2 is hydrogen, a Ci-C1 s (preferably Cj-Cg) alkyl, or an alkylene oxide, and X is a polyhydroxy alkyl having four to seven carbon atoms, e.g., N-methyl, coconut fatty acid glucamide. The thickening properties of the amides are indicated as being of particular use in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems can contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymers, etc. Paraffin sulfonate/N-methyl coconut fatty acid glucamide/nonionic surfactant shampoo formulations are exemplified. In addition to thickening attributes, the N-polyhydroxy alkyl fatty acid amides are said to have superior skin tolerance attributes.

U.S. Patent 2,982,737, issued May 2, 1961, to Boettner, et al., relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactant, and an N-alkylglucamide nonionic surfactant which is selected from N-methyl, N-sorbityl lauramide and N-methyl, N-sorbityl myristamide.

Other glucamide surfactants are disclosed, for example, in DT 2,226,872, published December 20, 1973, H. W. Eckert, et al., which relates to washing compositions comprising one or more surfactants and builder salts selected from polymeric phosphates, sequestering agents, and washing alkalis, improved by the addition of an N-acylpolyhydroxy- alkyl-amine of the formula RjC(0)N(R2)CH2(CH0H)nCH20H, wherein Ri is a C1-C3 alkyl, R2 is a C10-C22 alkyl, and n is 3 or 4. The N-acylpolyhydroxyalkyl-amine is added as a soil suspending agent.

U.S. Patent 3,654,166, issued April 4, 1972, to H. W. Eckert, et al., relates to detergent compositions comprising at least one surfactant selected from the group of anionic, zwitterionic, and nonionic surfactants and, as a textile softener, an N-acyl, N-alkyl polyhydroxy1alkyl compound of the formula R]N(Z)C(0)R2 wherein Rj is a C10-C22 alkyl, R2 is a C7-C21 alkyl, Rj and R2 total from 23 to 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2(CH0H)mCH20H where m is 3 or 4.

U.S. Patent 4,021,539, issued May 3, 1977, to H. Moller, et al., relates to skin treating cosmetic compositions containing N-polyhydroxy!alkyl-amines which include compounds of the formula RlN(R)CH(CH0H)mR2 wherein Rj is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as ^ Rj but both cannot be H, and R2 is CH2OH or C00H.

French Patent 1,360,018, April 25, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stabilized against polymerization with the addition of amides of the formula RC(0)N(Ri)G wherein R is a carboxylic acid functionality having at least seven carbon atoms, Rj is hydrogen or a lower alkyl group, and G is a glycitol radical with at least 5 carbon atoms.

German Patent 1,261,861, February 29, 1968, A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of the formula N(R)(Ri)(R2) wherein R is a sugar residue of glucamine, ^ Rj is a C10-C20 alkyl radical, and R2 is a Cj-C5 acyl radical.

G.B. Patent 745,036, published February 15, 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic esters thereof that are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc. The compounds are expressed by the formula N(R)(Rl)C(0)R2 wherein R is the residue of an anhydrized hexane pentol or a carboxylic acid ester thereof, Ri is a monovalent hydrocarbon radical, and -C(0)R2 is the acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.

U.S. Patent 3,312,627, issued April 4, 1967 to D. T. Hooker, discloses solid toilet bars that are substantially free of anionic detergents and alkaline builder materials, and which contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylene oxide-ethylenediamine-ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates, and polymerized ethylene glycol, and also contain a nonionic lathering component which can include polyhydroxyamide of the formula RC(0)NRl(R2) wherein RC(0) contains from about 10 to about 14 carbon atoms, and Rl and R? each are H or Cj-C6 alkyl groups, said alkyl 24 0C2 4 groups containing a total number of carbon atoms of from 2 to about 7 and a total number of substituent hydroxyl groups of from 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626, also issued April 4, 1967 to D. T. Hooker.

SUMMARY OF THE INVENTION A built detergent composition, comprising one or more anionic, nonionic or cationic detersive surfactants, or mixtures thereof, optional detersive adjuncts, and optional auxiliary builders, wherein the composition contains (a) at least about 1% by weight of a zeolite or layered silicate detergency builder, or mixture thereof; and (b) at least about 1% by weight of a polyhydroxy fatty acid amide material of the formula 0 Rl 11 1 R2 - C - N - Z wherein: Rl is H, Ci-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C1 -C4 alkyl, more preferably Cj or C2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-Cjg alkyl or alkenyl, more preferably straight chain Cg-C17 alkyl or alkenyl, most preferably straight chain Cj1-Ci7 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Preferably the weight ratio of zeolite, layered silicate, or mixture thereof, to polyhydroxy fatty acid amide is from about 1:10 to about 20:1, more preferably from about 1:5 to about 15:1, most preferably from about 1:3 to about 10:1.

DETAILED DESCRIPTION OF THE INVENTION Polyhydroxy Fatty Acid Amide Surfactant The compositions hereof will comprise at least about 1%, typically from about 3% to about 50%, preferably from about 3% to about 30%, of the polyhydroxy fatty acid amide surfactant described below.

The polyhydroxy fatty acid amide surfactant component of the present invention comprises compounds of the structural formula: 0 Rl -j " 1 (I) R2 - C - N - Z wherein: Rl is H, Ci-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, preferably C j-C4 alkyl, more preferably Cj or C2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-Cj7 alkyl or alkenyl, most preferably straight chain C1j-C17 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl having a 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 sugar in reductive amination reaction; more preferably Z is a glycityl. Suitable reducing 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 be utilized as well as the individual sugars listed above. These corn syrups may yield a 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 -CHZ-(CHOH)n-CH2OH, -CH(CH20H)-(CH0H)n-1-CH20H, -CH2-(CHOH)2(CHOR')(CHOH)-CH2OH, 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), Rl 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, N-l-deoxygalactityl, N-l-deoxymannityl, 1-deoxymaltotriotityl, 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 or triglyceride in a condensation/amidation step to form the N-alkyl, ^ ^ J O L i N-polyhydroxy fatty acid amide product. Processes for making compositions containing polyhydroxy fatty acid amides are disclosed, for example, in G.B. Patent Specification 809,050, published February 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Patent 5 2,955,576, issued December 20, 1960 to E. R. Wilson, and 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.

In one process for producing N-alkyl or N-hydroxyalky1, 10 N-deoxyglycityl fatty acid amides wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl glucamine with a fatty ester selected from fatty 15 methyl esters, fatty ethyl esters, and fatty triglycerides in the presence of a catalyst selected from the group consisting of tri-lithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, 20 lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, sodium basic silicates, potassium basic silicates, sodium basic aluminosilicates, and potassium basic aluminosilicates, and mixtures thereof. The amount of catalyst is 25 preferably from about 0.5 mole % to about 50 mole %, more preferably from about 2.0 mole % to about 10 mole %, on an N-alkyl or N-hydroxyalkyl-glucamine molar basis. The reaction is preferably carried out at from about 138*C to about 170*C for typically from about 20 to about 90 minutes. When glycerides are utilized in the 30 reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10 weight % of a phase transfer agent, calculated on a weight percentage basis of the total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkylpolyglycosides, linear glycamide surfactant, 35 and mixtures thereof.

Preferably, this process is carried out as follows: (a) preheating the fatty ester to about 138°C to about 170°C; 2 4 (b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to the extent needed to form a two-phase liquid/liquid mixture; (c) mixing the catalyst into the reaction mixture; and 5 (d) stirring for the specified reaction time.

Also preferably, from about 2% to about 20% of preformed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product is added to the reaction mixture, by weight of the reactants, as the phase transfer agent if the fatty ester is a triglyceride. This 10 also seeds the reaction, thereby increasing reaction rate. A detailed experimental procedure is provided below.

The polyhydroxy "fatty acid" amide materials used herein also offer the advantages to the detergent formulator that they can be prepared wholly or primarily from natural, renewable, 15 non-petrochemical feedstocks and are degradable. They also exhibit low toxicity to aquatic life.

It should be recognized that along with the polyhydroxy fatty acid amides of Formula (I), the processes used to produce them will also typically produce quantities of nonvolatile by-product such as 20 esteramides and cyclic polyhydroxy fatty acid amide. The level of these by-products will vary depending upon the particular reactants and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions hereof will be provided in a form such that the polyhydroxy fatty acid 25 amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, of cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they can yield rather low levels of by-products, including such cyclic amide by-product.

Zeolite and Layered Silicate Builders The compositions hereof contain zeolite or layered silicate builder, or a mixture thereof.

The level of zeolite and/or layered silicate builder can vary widely depending upon the end use of the composition and its desired 35 physical form. The detergent compositions will comprise at least about 1% of such builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight of the builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about •< -• ■; C 2 50% by weight of the builder. Lower or higher levels of builder, however, are not meant to be excluded. Preferably the weight ratio of zeolite or layered silicate builder, or mixture thereof, to polyhydroxy fatty acid amide is from about 1:10 to about 20:1, more preferably from about 1:5 to about 15:1, most preferably from about 1:3 to about 10:1.

Zeolite builders are a category of aluminosilicate builders that have attained importance in the formulation of present day heavy duty detergents, particularly granular formulations. The zeolite builders hereof can be crystalline or amorphous in structure and can be naturally-occurring or synthetically derived. Methods for producing zeolite materials are well known in the art. See, for example, U.S. Patent 3,985,669, Krummel, et al., issued October 12, 1976, incorporated herein by reference. Preferred synthetic zeolite ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In general, the zeolite builders hereof include those having the formula: Naz[(A102)z (Si02)y]-x^O 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, and this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosi1icate. In an especially preferred embodiment, the crystalline aluminosi1icate ion exchange material has the formula: Nai2[(A102)i2(Si02)l2]-xH20 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A.

Layered silicate builders are also known in the art. Preferred are the layered sodium silicates. See, for example, the layered sodium silicate builders of U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference.

Preferably, detergents to be used at these temperatures below about 50*C, especially below about 40*C, are substantially free of borate-containing and borate-forming builders. As used herein, "substantially free of borate-containing and borate-forming builder" shall mean that the composition contains not more than about 2%, by weight, of borate-containing and borate-forming builder, preferably, no more than 1%, more preferably no more than about 0.5%, most preferably essentially 0%.

Detersive Surfactant System In addition to the polyhydroxy fatty acid amide and zeolite builder, the compositions hereof contain one or more additional surfactants which can be anionic, cationic or nonionic. Typically the surfactant system will include one or more anionic and/or nonionic surfactants in addition to the polyhydroxy fatty acid amide. It is especially preferred to include an anionic surfactant for effective overall cleaning under a wide variety of wash conditions. In particular, the benefits of this invention are especially realized when the compositions hereof include hardness sensitive surfactants such as alkyl sulfates, alkyl ester sulfonates (e.g., methyl ester sulfonates), alkyl alkoxylated sulfonates (e.g., alkyl ethoxylated sulfonates), and alkyl benzene sulfonates (e.g., linear alkyl benzene sulfonate). The further inclusion of a conventional nonionic surfactant, such as an alkyl ethoxylate or an alkyl polyglycoside, as described below, is further desirable. Typically, the amount of additional detersive surfactant present is from about 1% to about 50%, by weight, of the detergent composition, preferably from about 3% to about 40%, more preferably from about 5% to about 30%. Suitable surfactants are described below.

Alkyl Ester Sulfonate Surfactant Alkyl ester sulfonate surfactants hereof include linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society," 52 (1975), pp. 323-329. Suitable starting 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, comprise alkyl ester sulfonate surfactants of the structural formula: O R3 - CH - C - OR4 SO3M wherein R^ is a C8-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R4 is a C1 -C5 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salts would include metal salts such as sodium, potassium, and lithium salts, and substituted or unsubstituted ammonium salts, such as methyl-, dimethyl, -trimethyl, and quaternary ammonium cations, e.g. tetramethyl-ammonium and dimethyl piperdinium, and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine. Preferably, is Cjo-Cig alkyl, and R4 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R^ is C14-C16 alkyl.

Alkyl Sulfate Surfactant Alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20 alkyl component, more preferably a C12-C18 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 are preferred for lower wash temperatures (e.g., below about 50*C) and C15-18 alkyl chains are preferred for higher wash temperatures (e.g., above about 50*C).

Alkyl Alkoxylated Sulfate Surfactant Alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula R0(A)mS03M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a Cjo-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more preferably Cj2-C18 alkyl 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 0.5 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 well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof. Exemplary surfactants are Cl2"C18 alkyl polyethoxylate (1.0) sulfate, C j 218 alkyl polyethoxylate (2.25) sulfate, Ci2"Cl8 alkyl polyethoxylate (3.0) sulfate, and Cj218 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 alkylbenzenesulphonates, C8-C22 primary or secondary alkanesulphonates, C8-C24 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 sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the N-acyl isethionates, acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12 ~ C18 monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C6~ Cj 4 diesters), N-acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsul fated compounds being described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as those of the formula R0(CH2CH20)^CH2C00-M+ wherein R is a Cs-C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation, and fatty acids esterified with 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 hydrcgenated resin acids present in or derived from tall oil. Further examples are described 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, Laugh!in et al., issued December 30, 1975, at column 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 nonionic surfactants of this type include Igepal™ C0-630, marketed by the GAF Corporation; and Triton™ X-45, X-114, X-100, and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkyl 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 alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly 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 about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol™ 15-S-9 (the condensation product of Cji-C15 linear secondary alcohol with 9 moles ethylene oxide), Tergitol™ 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; Neodol™ 45-9 (the condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol™ 23-6.5 (the condensation product of Cj2"C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol™ 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide), Neodol™ 45.4 (the condensation product of Cj4-C15 linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro^M EOS (the condensation 24 0 C ^ product of C]3-C]5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. These surfactants are commonly referred to as alkyl ethoxylates. 3. The condensation products of ethylene oxide with a 5 hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight 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 10 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 condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the 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 a 25 molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic™ compounds, marketed by BASF.

. Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine 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; 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 2 4 J C 2 4 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 5 oxide surfactants having the formula 0 R3(OR4)xN(R5)2 wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; 10 r4 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 R5 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R5 groups can be 15 attached to each other, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include Cjo-Ci8 alkyl dimethyl amine oxides and Cs-Ci2 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 from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilic group containing from about 1.3 to about 25 10, preferably from about 1.3 to about 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 2-, 30 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.

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 to 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, 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-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

The preferred alkylpolyglycosides have the formula R20(CnH2n0)t(glycosyl)x wherein r2 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 about 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 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 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: 0 R6 - C - N(R7)2 wherein R& is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R? is selected from the group consisting of hydrogen, C1-C4 alkyl, (4-C4 hydroxyalkyl, and -(C2H4O)XH where x varies from about 1 to about 3.

Preferred amides are C8-C20 ammonia amides, monoethanolamides, diethanolamides, and isopropanolamides.

Cationic Surfactants Cationic detersive surfactants can also be included in detergent compositions of the present invention. Cationic surfactants / v r* o / ■ 18 - include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula: [R2(0R3)y][R4(0R3)y]2R5N+X-wherein R^ is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from the group consisting of -CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures thereof; each R4 is selected from the group consisting of Cj-C4 alkyl, C4-C4 hydroxyalkyl, benzyl, ring structures formed by joining the two R4 groups, -CH2CHOH-CH0HC0R6CHOHCH2OH wherein R5 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of carbon atoms of R2 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 U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by 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 ? ^ aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 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 to Laughlin et al., issued December 30, 1975 at column 19, lines 18-35 (herein incorporated by reference) for examples of ampholytic surfactants.

Zwitterionic surfactants can also be incorporated into the detergent 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 No. 3,929,678 to Laughlin et al., issued December 30, 1975 at column 19, line 38 through column 22, line 48 (herein incorporated by reference) for examples of zwitterionic surfactants. 240024 Ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and/or nonionic surfactants. Auxiliary Builders Detergent compositions of the present invention can also 5 comprise auxiliary builders, including both inorganic and organic detergent builders, to assist in mineral hardness control. Typical amounts of auxiliary builder are from about 5% to about 200% of the weight of the zeolite/layered silicate builder.

Inorganic detergent builders include, but are not limited to, 10 the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluninsilicates. Borate builders, 15 as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions (hereinafter, collectively "borate builders"), can also be used. Preferably, non-borate builders are used in the compositions of the invention intended for use at wash temperatures below about 50*C, 2° especially below about 40*C.

Examples of silicate builders are the alkali metal silicates, particularly those having a Si02:Na20 ratio in the range 1.6:1 to 3.2:1. However, other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in 25 granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Aluminosi1icates other than zeolites can also be used. In general, the aluminosilicates will have the empiracal formula Mz(zA102*ySi02) wherein M is sodium, potassium, ammonium or *3 A substituted ammonium, z is from about 0.5 to about 2, and y is 1, '1 although not necessarily falling within the scope of formulas set forth above describing zeolites.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and OC sesquicarbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in u.s. Patent no. 4,174,291.-—- the disclosure of which is incorporated herein by reference.

Phosphate and phosphonate builders can be added, although it is generally desired to replace these builders with zeolite/layered silicate and, optionally, other auxiliary builders and detergent adjuncts. Thus, if present they preferably are included only at low 5 levels. Preferably, the phosphate builder comprises less than about 10%, more preferably less than about 5%, most preferably essentially zero percent, by weight, of total builder in the composition.

Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, 10 sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta phosphate in which the degree of polymerization ranges from about 6 to about 21, and salts of phytic acid.

Examples of phosphonate builder salts are the water-soluble 15 salts of ethane 1-hydroxy-l, 1-diphosphonate particularly the sodium and potassium 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 20 benzylmethylidene and halo methylidene phosphonates. Phosphonate builder salts of the aforementioned 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. 3,422,021 issued January 14, 1969, to Roy; and U.S. Patent Nos. 3,400,148 and 3,422,137 25 issued September 3, 1968, and January 14, 1969 to Quimby, said disclosures being incorporated herein by reference.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" 30 refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.

Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized soluble salt. When utilized in salt form, alkali metals 35 (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 2 4 >3 C 2 4 - 21 number of ether polycarboxylates have been disclosed for use as detergent builders. Examples of useful ether polycarboxyl ates include oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, 5 issued January 18, 1972, both of which are incorporated herein by reference.

A specific type of ether polycarboxylates useful as builders in the present invention also include those having the general formula: CH(A)(C00X)-CH(COOX)-0-CH(COOX)-CH(COOX)(B) 10 wherein A is H or OH; B is H or -O-CH(COOX)-CH2(COOX); 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-soluble salts. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A 15 is H and B is -0-CH(COOX)-CH2(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 a weight ratio of TMS to TDS of from about 97:3 to about 20:80. These builders are 20 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 a1ieyelie 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 are incorporated herein by reference.

Other useful detergency builders include the ether hydroxypolycarboxylates represented by the structure: H0-[C(R)(COOM)-C(R)(C00M)-0]n-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 is the same or different and selected from hydrogen, Ci-4 alkyl or Cj-4 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. r ? v L 22 - 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, 5 and nitrilotriacetic acid.

Also included are polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof 10 (especially sodium), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations, but can also be used in granular compositions.

Other carboxylate builders include the carboxylated carbohydrates disclosed in U.S. Patent 3,723,322, Diehl, issued 15 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 20 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, 25 preferably C12-C15 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 30 alkanolammonium salts.

Specific examples of succinate builders include: lauryl succinate, myristylsuccinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis- cyclohexane-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 carboxylates 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 ester of glyoxylic acid and a polymerization 10 initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a surfactant.

Polycarboxylate builders are also disclosed in U.S. Patent 15 3,308,067, 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 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 be saturated 25 or unsaturated.

Enzymes Enzymes can be included in the detergent formulations for a variety of purposes including removal of protein-based, carbohydrate-based, or triglyceride-based stains, for example, and prevention of refugee dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as ^ pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed 5 and sold by Novo Industries A/S under the registered trade name Esperase®. The preparation of this enzyme and analogous enzymes is described in British patent specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradenames 10 ALCALASE™ and SAVINASE™ by Novo Industries A/S (Denmark) and MAXATASE™ by International Bio-Synthetics, Inc. (The Netherlands).

Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B. Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference. Protease B is a proteolytic enzyme which differs from Protease A in that it has a leucine substituted for tyrosine in position 217 in its amino acid sequence. Protease B is described in European Patent 20 Application Serial No. 87303761.8, filed April 28, 1987, incorporated herein by reference. Methods for preparation of Protease B are also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985, incorporated herein by reference.

Amylases include, for example, a-amylases obtained from a special strain of B.licheniforms, described in more detail in British patent specification No. 1,296,839 (Novo), previously incorporated herein by reference. Anxiolytic proteins include, for example, RAPIDASE™, International Bio-Synthetics, Inc. and 30 TERMAMYL™, Novo Industries.

The cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH ! optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al., issued March 6, 1984, incorporated herein by reference, which discloses fungal cellulase ^ produced from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and u.s. 3,844,890.

I J L. i ; i 'J Cj -r Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSH 1800, and cellulases produced by a fungus of Bacillus N or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusc (Dolabella Auricula Solander).

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent No. 1,372,034, incorporated herein by reference. Suitable lipases include those which show a positive immunoligical cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and a method for its purification have been described in Japanese Patent Application No. 53-20487/ laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P." Such lipases of the present invention 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 1339 (available under the trade name Amano-B), lipase ex Psuedomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. 1ipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.

Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, iv.i i 1 .ihl n on rpnur";f . 24 0 0 2 4 ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S, 5 incorporated herein by reference.

A wide range of enzyme materials and means for their incorporation into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. (incorporated herein by reference). Enzymes are further disclosed 10 in U.S. Patent No. 4,101,457, Place et al., issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both incorporated herein by reference. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al., 15 issued April 14, 1981, also incorporated herein by reference.

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition.

For granular detergents, the enzymes are preferably coated or 20 prilled with additives inert toward the enzymes to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art. In liquid formulations, an enzyme stabilization system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique for enzyme stabilization in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions can be used in combination with short chain carboxylic acid salts, perferably formates. See, for example, U.S. Patent 4,318,818, Letton, et al., issued March 9, 1982, incorporated herein by reference. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy-alcohol s, dialkylglycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine, etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are additionally disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al., U. S. Hatent 3,600,319, issued August 17, 1971 to Gedge, et al., both incorporated herein by 24 00c reference, and European Patent Application Publication No. 0 199 405, Application No. 85200586.5, published October 29, 1986, Venegas. Non-boric acid and borate stabilizers are preferred. Enzyme stabilization systems are also described, for example, in 5 U.S. Patents 4,261,868, 3,600,319, and 3,519,570.

Bleaching Compounds - Bleaching Agents and Bleach Activators The detergent compositions hereof may contain bleaching agents or bleaching compositions containing bleaching agent and one or more bleach activators. When present bleaching compounds will typically 10 be present at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition. In general, bleaching compounds are optional components in non-liquid formulations, e.g., granular detergents. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, 15 more typically from about 0.5% to about 40% of the bleaching composition.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. For wash conditions below about 50*C, especially below about 40*C, it is preferred that the compositions hereof not contain borate or material which can form borate in situ (i.e. borate-forming material) under detergent storage or wash conditions. Thus it is preferred under these conditions that a non-borate, non-borate-forming bleaching agent is used. Preferably, detergents to be used at these temperatures are substantially free of borate and borate-forming material. As used herein, "substantially free of borate and borate-forming material" shall mean that the composition contains not more than about 2% by weight of borate-containing and borate-forming material of any type, preferably, no more than 1%, more preferably 0%. j One category of bleaching agent that can be used encompasses j percarboxylic acid bleaching agents and salts thereof. Suitable 35! examples of this class of agents include magnesium monoperoxyphthal-i ate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid, j Such bleaching agents are disclosed in U.S. Patent 4,483,781, j Hartman, issued November 20, 1984, U.S. Patent 4,<s3-?,v>i, -V 0 0 Burns et al., filed June 3, 1985, European Patent Application 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, all of which are incorporated by reference herein. Highly preferred bleach-5 ing agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns, et al., incorporated herein by reference.

Another category of bleaching agents that can be used encompasses the halogen bleaching agents. Examples of hypohalite 10 bleaching agents, for example, include trichloro isocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such materials are normally added at 0.5-10% by weight of the finished product, preferably 1-5% by weight.

Peroxygen bleaching agents can also be used. Suitable peroxy- gen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.

Peroxygen bleaching agents are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.

Preferred bleach activators incorporated into compositions of the present invention have the general formula: 25 0 ii R - C - L wherein R is an alkyl group containing from about 1 to about 18 carbon atoms wherein the longest linear alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 Of) carbon atoms and L is a leaving group, the conjugate acid of which has a pKa in the range of from about 4 to about 13. These bleach activators are described in U.S. Patent 4,915,854, issued April 10, 1990 to Mao, et al., incorporated herein by reference, and U.S. Patent 4,412,934, which was previously incorporated herein by reference.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated / ... ' ■ - 1 - c bleaching agents such as sulfonated zinc and aluminum phthalocya-nines. These materials can be deposited upon the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, such as by hanging clothes out to dry in the daylight, 5 the sulfonated zinc phthalocyanine is activated and, consequently, the substrate is bleached. Preferred zinc phthalocyanine and a photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Hoi combe et al., incorporated herein by reference. Typically, detergent compositions will contain 10 about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.

Polymeric Soil Release Agent Any polymeric soil release agents known to those skilled in the art can be employed in the practice of this invention. Polymeric 15 soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic 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 20 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 25 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 3° 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.

The compositions hereof for which improved polymeric soil release agent performance can be obtained through the use of polyhydroxy fatty acid amide are those which contain an anionic surfactant system, an anionic surfactant-interactive soil release agent and a soil release agent-enhancing amount of the polyhydroxy fatty acid amide (PFA), wherein: (I) anionic surfactant-interaction between the soil release agent and the anionic surfactant system of the detergent composition can be shown by a comparison of the level of soil release agent (SRA) deposition on hydrophobic fibers (e.g., 5 polyester) in aqueous solution between (A) a "Control" run wherein deposition of the SRA of the detergent composition in aqueous solution, in the absence of the other detergent ingredients, is measured, and (B) an "SRA/Anionic surfactant" test run wherein the same type and amount of the anionic surfactant system utilized in 10 detergent composition is combined in aqueous solution with the SRA, at the same weight ratio of SRA to the anionic surfactant system of the detergent composition, whereby reduced deposition in (B) relative to (A) indicates anionic-surfactant interaction; and (II) whether the detergent composition contains a soil release 15 agent-enhancing amount of polyhydroxy fatty acid amide can be determined by a comparison of the SRA deposition of the SRA/Anionic surfactant test run of (B) with soil release agent deposition in (C) an "SRA/Anionic surfactant/PFA test run" wherein the same type and level of polyhydroxy fatty acid amide of the detergent composition 20 is combined with the soil release agent and anionic surfactant system corresponding to said SRA/Anionic surfactant test run, whereby improved deposition of the soil release agent in test run (C) relative to test run (B) indicates that a soil release agent-enhancing amount of polyhydroxy fatty acid amide is present. For 25 purposes hereof, the tests hereof should be conducted at anionic surfactant concentrations in the aqueous solution that are above the critical micelle concentration (CMC) of the anionic surfactant and preferably above about 100 ppm. The polymeric soil release agent concentration should be at least 15 ppm. A swatch of polyester ^ fabric should be used for the hydrophobic fiber source. Identical swatches are immersed and agitated in 35"C aqueous solutions for the respective test runs for a period of 12 minutes, then removed, and analyzed. Polymeric soil release agent deposition level can be determined by radiotagging the soil release agent prior to treatment and subsequently conducting radiochemical analysis, according to techniques known in the art.

As an alternative to the radiochemical analytical methodology discussed above, soil release agent deposition can alternately be determined in the above test runs (i.e., test runs A, B, and C) by 2 determination of ultraviolet light (UV) absorbance of the test solutions, according to techniques well known in the art. Decreased UV absorbance in the test solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition. As will be 5 understood by those skilled in the art, UV analysis should not be utilized for test solutions containing types and levels of materials which cause excessive UV absorbance interference, such as high levels of surfactants with aromatic groups (e.g., alkyl benzene sulfonates, etc.).

Thus by "soil release agent-enhancing amount" of polyhydroxy fatty acid amide is meant an amount of such surfactant that will enhance deposition of the soil release agent upon hydrophobic fibers, as described above, or an amount for which enhanced grease/oil cleaning performance can be obtained for fabrics washed 15 in the detergent composition hereof in the next subsequent cleaning operation.

The amount of polyhydroxy fatty acid amide needed to enhance deposition will vary with the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent 20 chosen, as well as the particular polyhydroxy fatty acid amide chosen. Generally, compositions will comprise from about 0.01% to about 10%, by weight, of the polymeric soil release agent, typically from about 0.1% to about 5%, and from about 4% to about 50%, more typically from about 5% to about 30% of anionic surfactant. Such ^5 compositions should generally contain at least about 1%, preferably at least about 3%, by weight, of the polyhydroxy fatty acid amide, though it is not intended to necessarily be limited thereto.

The polymeric soil release agents for which performance is enhanced by polyhydroxy fatty acid amide in the presence of anionic on surfactant include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene 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 a sufficient amount of oxyethylene units such that the hydrophile component has 24 0 c hydrophilicity great enough to increase the hydrophi1icity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more 5 preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene 10 terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C5 alkylene or oxy C4-C6 alkylene segments, or mixtures thereof, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate), having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, 15 or mixtures thereof, wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellulose derivatives, or mixtures thereof, and such cellulose derivatives are amphiphilic, whereby they have a sufficient level of C1 -C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon 20 conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a 25 degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as MO3S(CH2)nOCH2CH20-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, incorporated herein by reference.

Polymeric soil release agents useful in the present invention include cellulosic derivatives such as hydroxyether cellulosic ^ polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. 2 4 C C 2 4 Cellulosic derivatives that are functional as soil release agents are commercially available and include hydroxyethers of cellulose such as Methocel^ (Dow).

Cellulosic soil release agents for use herein also include 5 those selected from the group consisting of Cj-C4 alkyl and C4 hydroxyalkyl cellulose such as methyl cellulose, ethylcellulose, hydroxypropyl methyl cellulose, and hydroxybutyl methylcellulose. A variety of cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to 10 Nicol, et al., incorporated herein by reference.

Soil release agents characterized by polyvinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C6 vinyl esters, preferably polyvinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide 15 backbones. Such materials are known in the art and are described in European Patent Application 0 219 048, published April 22, 1987 by Kud, et al. Suitable commercially available soil release agents of this kind include the Sokalan™ type of material, e.g., Sokalan™ HP-22, available from BASF (West Germany).

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 repeating units of ethylene terephthalate and PEO terephthalate in a mole ratio of ethylene terephthalate units to PEO terephthalate 25 units of from about 25:75 to about 35:65, said PEO terephthalate units containing polyethylene oxide 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 about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976, 30 which is incorporated by reference. See also U.S. Patent 3,893,929 to Basadur issued July 8, 1975 (incorporated by reference) which discloses similar copolymers.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% 35 by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000, and the mole ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric compound is between 2:1 and -3~ C. ** cr c 6:1. Examples of this polymer include the commercially available material Zelcon^ 5126 (from Dupont) and Milease^ T (from ICI). These polymers and methods of their preparation are more fully described in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, 5 which is incorporated herein by reference.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone, 10 said soil release agent being derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2 propylene diol, wherein after sulfonation, the terminal moieties of each oligomer have, on average, a total of from about 1 to about 4 sulfonate groups. These soil release agents are described fully in U.S. Patent 4,968,451, 15 issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink, incorporated herein by reference.

Other suitable polymeric soil release agents include the ethyl -or methyl-capped 1,2-propylene terephthalate-polyoxyethylene 20 terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink 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), the block polyester 25 oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, having polyethoxy end-caps of the formula X-(OCH2CH2)n" wherein n is from 12 to about 43 and X is a C1 -C4 alkyl, or 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 sulfoaroyl, end-capped terephthalate esters, said patent being incorporated j herein by reference. The terephthalate esters contain unsymmetric-3!j ally substituted oxy-1,2-alkyleneoxy units. Included among the soil release polymers of U.S. Patent 4,877,896 are materials with polyoxyethylene hydrophile components or C3 oxyalkylene terephthalate 1 (propylene terephthalate) repeat units within the scope of the hydrophobe components of (b)(i) above. It is the polymeric soil J '•< <"> o -j c release agents characterized by either, or both, of these criteria that 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 5 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 about 3.0%.

Chelating Agents The detergent compositions herein may also optionally contain 10 one or ra0re 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. Without 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 CH2 ^ N - (CH2)x - C00M, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 25 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-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexaacetates, diethylenetri-aminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions. Compounds with one or more, preferably at least two, units of the substructure CH2 (CH2)X P03M2, wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, are useful and include etnylenediaminetetrakis (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 oh wherein at least one R is -so3h or -COOH or soluble salts thereof and mixtures thereof. U.S. Patent 3,812,044, issued Hay 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 dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene. 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 compositions herein. More preferably chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clav Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions, typically about 0.01% to about 5%. These compounds are selected preferably from the group consisting of: 2/i n C 2 4 (1) ethoxylated monoamines having the formula: (X-L-)-N-(R2)2 (2) ethoxylated diamines having the formula: r2-N-R1-N-R2 (R2)2-N-R1-N-(R2)2 L L I i i i XX X or (X-L-)2-N-R1-N-(R2)z (3) ethoxylated polyamines having the formula: R2 R3-[(Al)q-(R«)t-N-l-X]p (4) ethoxylated amine polymers having the general formula: R2 [(R2)2-N]w[Rl-N)x[Rl-NJyfRl-N-L-X)2 L i X and (5) mixtures thereof; wherein A* is 0 0 0 0 0 1 II 11 II » -NC-, -NC0-, -NCN-, -CN-, -0CN-, ii ill i R R R R R R 0 0 0 0 0 U II I II II -CO-, -OCO-, -0C-, -CNC-, i R or -0-; R is H or Cj-c4 alkyl or hydroxyalkyl; Rl is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a c2-c3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-N bonds are formed; each R2 is Cj-c4 or hydroxyalkyl, the moiety -L-X, or two R2 together form the moiety -(CH2)r> -A2-(ch2)s~» wherein A2 is -0- or -CH2-, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixture thereof; R3 is a substituted c3-c12 alkyl, hydroxyalkyl, alkenyl, aryl, or alkaryl group having substitution sites; R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a c2-c3 oxyalkylene moiety having from 2 to about 20 oxyalkylene units provided that no 0-0 or 0-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety -[(R50)m(CH2CH20)n]-, wherein R^ is c3-c4 alkylene or hydroxyalkylene and m and n are numbers such that the moiety a 0 02 -(CH2CH20)n- comprises at least about 50% by weight of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, and n is at least about 12; for said diamines, m is from 0 to about 3, and n is at least about 6 when Rl is C2-C3 alkylene, 5 hydroxyalkylene, or alkenylene, and at least about 3 when Rl is other than c2-c3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers, m is from 0 to about 10 and n is at least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, provided that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y 10 + z is at least 2. 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 15 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.

OC 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 carboxy methyl cellulose (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. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower ~ 2 molecular weight polycaroxylates) by crystal growth inhibition, particulate soil peptization, and anti-redeposition.

Polymeric dispersing agents are generally used at levels of about 0.5% to about 5%, by weight, of the detergent composition, more generally from about 1.0% to about 2.0%.

Polycarboxylate materials which can be employed as the polymeric dispersing agent herein are these polymers or copolymers which contain at least about 60% by weight of segments with the general formula X Z c - c COOM wherein X, Y, and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; a salt-forming cation and n is from about 30 to about 400. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen and H is hydrogen, alkali metal, ammonia or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxyl ates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most prefereably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can 0 0 2 4 include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent No. 3,308,067, issued 5 March 7, 1967. This patent is incorporated herein by reference.

Acryl ic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the 10 acid form preferably ranges from about 2,000 to 100,000, preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982, which publication is incorporated herein by 20 reference.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal/anti-redeposition agent. Typical molecular weight ranges for these purposes range ^5 from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000. Briqhtener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions hereof.

The choice of brightener for use in detergent compositions will depend upon a number of factors, such as the type of detergent, the nature of other components present in the detergent composition, the temperatures of wash water, the degree of agitation, and the ratio of the material washed to tub size.

The brightener selection is also dependent upon the type of material to be cleaned, e.g., cottons, synthetics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners ^ - j 2 which will be effective for a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible.

Commercial optical brighteners which may be useful in the 5 present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of st i1 bene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such 10 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.

Stilbene derivatives which may be useful in the present 15 invention include, but are not necessarily limited to, derivatives of bis(triazinyl)amino-stilbene; bisacylamino derivatives of stilbene; triazole derivatives of stilbene; oxadiazole derivatives of stilbene; oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Certain derivatives of bis(triazinyl)aminostilbene which may be useful in the present invention may be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives 25 substituted in the 3-position, in the 7-position, and in the 3- and 7-positions.

Carboxylic acid derivatives which may be useful in the present invention include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid 30 derivatives; naphthalenedicarboxyl ic acid derivatives; heterocyclic acid derivatives; and cinnamic acid derivatives.

Cinnamic acid derivatives which may be useful in the present invention can be further subclassified into groups which include, but are not necessarily limited to, cinnamic acid derivatives, 35 styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles, and styrylpolyphenyls, as disclosed on page 77 of the Zahradnik reference.

The styrylazoles can be further subclassified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles, as -J L disclosed on page 78 of the Zahradnik reference. It will be understood that these three identified subclasses may not necessarily reflect an exhaustive list of subgroups into which styrylazoles may be subclassified.

Another class of optical brighteners which may be useful in the present invention are the derivatives of dibenzothiophene-5,5-dioxide disclosed at page 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology. Volume 3, pages 737-750 (John Wiley & Son, Inc., 1962), the disclosure of which is incorporated herein by reference, and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid 5,5 dioxide.

Another class of optical brighteners which may be useful in the present invention include azoles, which are derivatives of 5-membered ring heterocycles. These can be further subcategorized into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk-Othmer reference.

Another class of brighteners which may be useful in the present invention are the derivatives of 6-membered-ring hetero- cycles disclosed in the Kirk-Othmer reference. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminonaphthalamide.

In addition to the brighteners already described, miscellaneous agents may also be useful as brighteners. Examples of such miscellaneous agents are disclosed at pages 93-95 of the Zahradnik reference, and include l-hydroxy-3,6,8-pyrenetri- sulphonic acid; 2,4-dimethoxy-l,3,5-triazin-6-yl-pyrene; 4,5-di- phenylimidazolone-disulphonic acid; and derivatives of pyrazoline- quinoline.

Other specific examples of optical brighteners which may be useful in the present invention are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988, the disclosure of which is incorporated herein by reference. These brighteners include the PhorwhiteTM series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artie White CWD, available from Hilton-Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[1,2-d]triazoles; 4,4'-bi s- (1,2,3-triazol-2-yl)-st i1 - benes; 4,4'-bis(styryl)bis-phenyls; and the y-aminocoumarins. Specific examples of these r\ L brighteners include 4 - methyl-7-diethyl - amino coumarin; 1,2-bis-(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazol ines; 2,5-bis-(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[1,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [1,2-d]triazole.

Other optical brighteners which may be useful in the present invention include those disclosed in U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton, the disclosure of which is incorporated herein by reference.

Suds Suppressors Compounds known, or which become known, for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. The incorporation of such materials, hereinafter "suds suppressors," can be desirable because the polyhydroxy fatty acid amide surfactants hereof can increase 15 suds stability of the detergent compositions. Suds suppression can be of particular importance when the detergent compositions include a relatively high sudsing surfactant in combination with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in front 20 loading automatic washing machines. These machines are typically characterized by having drums, for containing the laundry and wash water, which have a horizontal axis and rotary action about the axis. This type of agitation can result in high suds formation and, consequently, in reduced cleaning performance. The use of suds 25 suppressors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.

A wide variety of materials may be used as suds suppressors in the compositions hereof. Suds suppressors are well known to those ^ skilled in the art. They are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John, said patent being incorporated herein by reference. The monocarboxylic fatty acids, and salts thereof, for use as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanol ammoniurn salts. These materials are a preferred category of suds suppressor for detergent compositions.

The detergent compositions may also contain non-surfactant suds suppressors. These include, for example, list: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18_C40 ketones (e.g. stearone), etc. Other suds 10 inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyl diamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl 15 alcohol phosphate ester and monostearyl di-alkali metal (e.g., Na, K, Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of 20 about -40"C and about 5'C, and a minimum boiling point not less than about 110'C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100'C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors ^ are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo, et al., incorporated herein by reference. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this OA suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et u al. and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S., both incorporated herein by reference.

Other silicone suds suppressors are disclosed in U.S. Patent 5 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydi-methylsiloxane fluids.

Mixtures of silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526. Silicone 10 defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and in U.S. Patent 4,652,392, Baginski et al., issued March 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting 15 essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25*C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 SiOj/2 units of 20 Si02 units in a ratio of from (CH3)3 Si0i/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel; For any detergent compositions to be used in automatic laundry 25 washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount." By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will ^0 sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines. The amount of suds control will vary with the detergent surfactants selected. For example, with high sudsing surfactants, relatively more of the suds controlling agent is used to achieve the desired suds control 35 than with lesser foaming surfactants. In general, a sufficient amount of suds suppressor should be incorporated in low sudsing detergent compositions so that the suds that form during the wash cycle of the automatic washing machine (i.e., upon agitation of the detergent in aqueous solution under the intended wash temperature u and concentration conditions) do not exceed about 75% of the void volume of washing machine's containment drum, preferably the suds do not exceed about 50% of said void volume, wherein the void volume is determined as the difference between total volume of the containment 5 drum and the volume of the water plus the laundry.

The compositions hereof will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts thereof, will be present typically in amounts up to about 5%, by weight, of the detergent 10 composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about .01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in 20 combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphates are generally used at levels ranging from about 0.1% to about 2%, by weight, of the composition.

Hydrocarbon suds suppressors are typically utilized in amounts 25 ranging from about .01% to about 5.0%, although higher levels can be used.

Other Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the compositions hereof, including 30 other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol 35 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. n ■ 47 - The 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 about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably 5 have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. 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 improving the 10 performance of detergents containing anionic, nonionic, and/or cationic surfactant and zeolite or layered silicate builder, or mixture thereof, by incorporating into such composition the polyhydroxy fatty acid amide surfactant described above, such that the weight ratio of zeolite and/or layered silicate to the 15 polyhydroxy fatty acid amide surfactant is from about 1:10 to about 20:1.

This invention further provides a method for cleaning substrates, such as fibers, fabrics, hard surfaces, skin, etc., by contacting said substrate with a detergent composition comprising one or more anionic, nonionic, or cationic surfactants, zeolite or layered silicate builder, or a mixture thereof, and the polyhydroxy fatty acid amide, wherein the weight ratio of said builder:polyhy-droxy fatty acid amide surfactant is from about 1:10 to about 20:1, in the presence of a solvent such as water or water-miscible solvent (e.g., primary and secondary alcohols). Agitation is preferably provided to further facilitate cleaning. Suitable agitation means include providing agitation by hand, or with cleaning devices such as brushes, cloths, sponges, mops, etc., automatic dishwashing machines, automatic washing machines for cleaning of textiles (e.g., clothing), etc.

In the above methods, the more preferred zeolite and/or layered silicate builder: polyhydroxy fatty acid amide weight ratios are from about 1:5 to about 15:1, most preferably from about 1:3 to about 10:1.

EXPERIMENTAL This exemplifies a process for making a N-methyl, 1-deoxyglucityl lauramide surfactant for use herein. Although a skilled chemist can vary apparatus configuration, one suitable apparatus for use herein comprises a three-liter four-necked flask fitted with a motor-driven paddle stirrer and a thermometer of length sufficient to contact the reaction medium. The other two necks of the flask are fitted with a nitrogen sweep and a wide-bore side-arm (caution: a wide-bore side-arm is important in case of 5 very rapid methanol evolution) to which is connected an efficient collecting condenser and vacuum outlet. The latter is connected to a nitrogen bleed and vacuum gauge, then to an aspirator and a trap. A 500 watt heating mantle with a variable transformer temperature controller ("Variac") used to heat the reaction is so placed on a 10 lab-jack that it may be readily raised or lowered to further control temperature of the reaction.

N-methylglucamine (195 g., 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter 4 Gamble CE 1270, 220.9 g., 1.0 mole) are placed in a flask. The solid/liquid mixture is heated with stirring 15 under a nitrogen sweep to form a melt (approximately 25 minutes). When the melt temperature reaches 145* C, catalyst (anhydrous powdered sodium carbonate, 10.5 g., O.l mole, J. T. Baker) is added. The nitrogen sweep is shut off and the aspirator and nitrogen bleed are adjusted to give 5 inches (5/31 atm.) Hg. vacuum. From this 20 point on, the reaction temperature is held at 150* C by adjusting the Variac and/or by raising or lowering the mantle.

Within 7 minutes, first methanol bubbles are sighted at the meniscus of the reaction mixture. A vigorous reaction soon follows. Methanol is distilled over until its rate subsides. The vacuum is 25 adjusted to give about 10 inches Hg. (10/31 atm.) vacuum. The vacuum is increased approximately as follows (in inches Hg. at minutes): 10 at 3, 20 at 7, 25 at 10. 11 minutes from the onset of methanol evolution, heating and stirring are discontinued coincident with some foaming. The product is cooled and solidifies. 30 The following examples are meant to exemplify compositions of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention, said scope being determined according to claims which follow.

EXAMPLES 1-12 These examples show heavy duty granular detergent compositions containing polyhydroxy fatty acid amide and zeolite and/or layered silicate builders.

Base Granule JL _2_ _3_ _4_ C14-15 Alkyl Sulfate 16, .9 . ,1 11. ,3 C14-15 Alkyl Ethoxy (2.25) Sulfate . 6 Cl2-18 Alkyl Sulfate 16. .9 Linear Ci2 Alkylbenzene Sulfonate . .1 N-Methyl N-l-Deoxyglucityl Cocoamide , .6 2. ,4 . ,6 , .6 Zeolite A , .1 18. 8 18. ,8 . ,1 Sodium Citrate 6. ,3 6. .3 Sodium Carbonate 16, .9 21. .9 21. .9 16, .9 Sodium Silicate , ,6 . ,6 . ,6 , ,6 Sodium Sulfate , ,0 . .0 . .1 . ,1 Sodium Polyacrylate (4500 MW) 1, ,1 1. .1 1. ,1 1. 1 Polyethylene Glycol (8000 MW) 1. ,1 1. .1 1. ,1 1. 1 Tallow Fatty Acid 1. ,1 1. .1 1. .1 1. ,1 Brightener 0. 2 0. ,2 0. ,2 0. 2 Admix and SDrav-on Protease (1.4% active enzyme) 0, .9 0. .9 0. .9 0. ,9 Perfume 0. ,3 0. .3 0. .3 0. ,3 Cl2-13 Alkyl Ethoxylate (6.5 mole)l. ,1 1. ,1 1. .1 1. 1 Water 3. .8 3. .8 3, .8 3. ,8 100. ,0 100. .0 100, .0 100. ,0 Examples 1-4 are formulations for preferred use of about 1400 ppm, wash water weight basis, for temperatures below about 50*C. The above examples are made by combining the base granule ingredients as a slurry, and spray drying to about 4-8% residual moisture. The remaining dry ingredients are admixed in granular or powder form with the spray dryed granule in a rotary mixing drum, and the liquid ingredients (nonionic surfactant and perfume) sprayed on.

Base Granule 6 7 Linear C\2 Alkylbenzene Sulfonate 8.6 C14-15 Alkyl Sulfate 12.6 C16-18 Fatty Acid 2.2 2.2 Zeolite 7.0 7.0 .4 Polyacrylate (4500 MW) 3.3 3.3 3.5 Polyethylene Glycol (8000 MW) 1.3 1.3 1.5 Sodium Carbonate .7 .7 Sodium Sulfate .0 .0 .0 * "» ■J \J Sodium Silicate (Si02/Na20=2) 5.0 5.0 3.0 Miscellaneous 7.1 7.1 7.9 Admix Zeolite 5.0 5.0 5.0 N-Methyl N-l-Deoxyglucityl Cocoamide 6.4 6.4 3.2 Cl6-18 Methyl Ester Sulfate 19.1 C12-18 Alkyl Sulfate 19.1 Miscellaneous (bleach, builder, salts, filler salts, etc) 17.2 17.2 20.4 Spray-on C12-13 Alkyl Ethoxylate (6.5 mole) 2 .0 2, .0 2, .0 Perfume 0 .5 0, .5 0, .5 Water and Miscellaneous 8, ,2 8, ,3 6. ,4 Totals 100, .0 100, .0 100. ,0 The compositions of Examples 5-7 represent condensed granular formulations prepared by slurrying and spray drying the base granule ingredients to a moisture of about 5%, and admixing the additional granular or powdered dry ingredients. The powder is dedusted by spraying on the liquid ingredients. The product is intended for use 20 about 1050 ppm concentration, at wash temperatures less than about 50"C.

Base Granule 8 9 10 11 Linear Cj2 Alkylbenzene Sulfonate 6.8 ^14-15 Alkyl Sulfate 4.6 7.6 7.6 Ci6-i8 Alkyl Sulfate 2.4 2.4 2.4 2.2 C16-I8 Alkyl Ethoxylate (11 mole) 1.1 1.1 1.1 Zeolite 22.0 24.7 21.3 13.0 3Q Acrylate/maleate copolymer (60000 MW) 4.3 5.6 4.3 Polyacrylate (4500 MW) 5.0 Water and Optional ingredients 9.4 9.2 10.1 10.2 Admi x N-methyl N-l-Deoxyglucityl Cocoamide 7.0 4.0 N-Methyl N-l-Deoxyglucityl Tallow Fatty Amide 4.0 6.0 Sodium Citrate 8.0 - 4 : 1 w Sodium Carbonate 17.5 17.3 17.5 17.0 Sodium Sil icate 3.5 3.0 3.5 3.0 Layered Silicate 11.0 Miscellaneous (bleach, filler 5 salts, etc) 27.3 24.1 19.4 24.8 Spray-on Perfume 0.4 0.4 0.4 0.5 Silicone Fluid 0.5 0.5 0.5 0.5 Total 100.0 100.0 100.0 100.0 The compositions of Examples 8-10 are preferably utilized at concentrations of about 6000 ppm, wash water weight basis, at temperature of from about 30"C to 95'C. These compositions are made by slurrying the base granule ingredients and are spray dried to about 9% moisture content. Remaining dry ingredients are added 15 and mixed in a rotary mix drum, followed by spray on addition of the final liquid ingredients.

Base Granule 12 13 14 Linear C12 Alkylbenzene Sulfonate 5.9 5.9 N-Methyl N-l-Deoxyglucityl Lauramide 5.9 c14-15 Alkyl Sulfate 5.9 C16-18 Alkyl Sulfate 2.5 2.5 2.5 Zeolite 23.5 14.0 20.5 Polyacrylate (4500 MW) 3.9 3.9 3.9 Sodium Citrate 6.0 Sodium Carbonate 12.7 16.0 12.7 Water and Miscellaneous 8.1 8.2 8.7 Admix and Spray-on N-Methyl N-l-Deoxyglucityl Cocoamide 5.9 N-Methyl N-l-Deoxyglucityl Tallow Fatty Amide 5.6 Miscellaneous (bleach, builder salts, filler salts, etc) 37.5 37.9 39.9 Totals 100.0 100.0 100.0 Examples 12-14 show standard density heavy duty granular detergent compositions for wash temperatures between about 30-95*C, at concentrations of about 8000 ppm, wash water weight basis. The compositions are prepared by spray drying a slurry of the base granule ingredients to about 10-13% moisture, adding additional dry powdered ingredients, such as bleach, activators, and other adjuncts, and spraying on liquids such as perfume, nonionics, or suds suppressor fluids.

EXAMPLE 15 An alternate method for preparing the polyhydroxy fatty acid 5 amides used herein is as follows. A reaction mixture consisting of 84,87g. fatty acid methyl ester (source: Procter & Gamble methyl ester CE1270), 75g. N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04g. sodium methoxide (source: Aldrich Chemical Company 16,499-2), and 68.51g. methyl alcohol is used. The reaction 13 vessel comprises a standard reflux set-up fitted with a drying tube, condenser and stir bar. In this procedure, the N-methyl glucamine is combined with methanol with stirring under argon and heating is begun with good mixing (stir bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and 15 sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction, but it is noted that the solution is completely clear by 63.5 minutes. It is judged that the reaction is, in fact, nearly complete at that point. The reaction mixture is maintained at reflux for 4 hours. After removal of the 20 methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, an overall yield of 106.92 grams purified product is recovered. However, percentage yields are not calculated on this basis, inasmuch as regular sampling throughout the course of the reaction makes an overall percentage yield value 25 meaningless. The reaction can be carried out at 80% and 90% reactant concentrations for periods up to 6 hours to yield products with extremely small by-product formation.

The following is not intended to limit the invention herein, but is simply to further illustrate additional aspects of the 30 technology which may be considered by the formulator in the manufacture of a wide variety of detergent compositions using the polyhydroxy fatty acid amides.

It will be readily appreciated that the polyhydroxy fatty acid amides are, by virtue of their amide bond, subject to some 35 instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that these materials not be subjected to pH's above about 11, preferably 10, nor below about 3 for unduly extended periods. Final product pH (liquids) is typically 7.0-9.0.

During the manufacture of the polyhydroxy fatty acid amides it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. While any acid can be used for this purpose, the detergent formulator will recognize that 5 it is a simple and convenient matter to use an acid which provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, citric acid can be used for purposes of neutralization and the resulting citrate ion (ca. 1%) be ID allowed to remain with a ca. 40% polyhydroxy fatty acid amide slurry and be pumped into the later manufacturing stages of the overall detergent-manufacturing process. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate/succinate, and the like, can be used similarly. 15 The polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly Ci2-C14) are more soluble than their tallow alkyl (predominantly C16-C18) counterparts. Accordingly, the C i r "C14 materials are somewhat easier to formulate in liquid compositions, and are more soluble in cool-water laundering baths. 23 However, the C16-Clg materials are also quite useful, especially under circumstances where warm-to-hot wash water is used. Indeed, the C16-C18 materials may be better detersive surfactants than their C12-C14 counterparts. Accordingly, the formulator may wish to balance ease-of-manufacture vs. performance when selecting a 25 particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amides can be increased by having points of unsaturation and/or chain branching in the fatty acid moiety. Thus, 33 materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.

Likewise, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., will ordinarily 35 be greater than the solubility of their monosaccharide-derived counterpart materials. This higher solubility can be of particular assistance when formulating liquid compositions. Moreover, the polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function especially well as ■'} detergents when used in combination with conventional alkylbenzene sulfonate ("LAS") surfactants. While not intending to be limited by theory, it appears that the combination of LAS with the polyhydroxy fatty acid amides derived from the higher saccharides such as 5 maltose causes a substantial and unexpected lowering of interfacial tension in aqueous media, thereby enhancing net detergency performance. (The manufacture of a polyhydroxy fatty acid amide derived from maltose is described hereinafter.) The polyhydroxy fatty acid amides can be manufactured not only 10 from the purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch, or any other convenient plant-derived starch which contains the mono-, di-, etc. saccharide desired by the formulator. This is of particular importance from the economic standpoint. Thus, "high glucose" corn syrup, "high maltose" corn 15 syrup, etc. can conveniently and economically be used. De-1ignified, hydrolyzed cellulose pulp can also provide a raw material source for the polyhydroxy fatty acid amides.

As noted above, polyhydroxy fatty acid amides derived from the higher saccharides, such as maltose, lactose, etc., are more soluble 20 than their glucose counterparts. Moreover, it appears that the more soluble polyhydroxy fatty acid amides can help solubilize their less soluble counterparts, to varying degrees. Accordingly, the formulator may elect to use a raw material comprising a high glucose corn syrup, for example, but to select a syrup which contains a 25 modicum of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy fatty acids will, in general, exhibit more preferred solubility properties over a broader range of temperatures and concentrations than would a "pure" glucose-derived polyhydroxy fatty acid amide. Thus, in addition to any economic advantages for using 30 sugar mixtures rather than pure sugar reactants, the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages with respect to performance and/or ease-of-formulation. In some instances, however, some loss of grease removal performance (dishwashing) may be noted at fatty acid 35 maltamide levels above about 25% and some loss in sudsing above about 33% (said percentages being the percentage of maltamide-derived polyhydroxy fatty acid amide vs. glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary somewhat, depending u on the chain length of the fatty acid moiety. Typically, then, the formulator electing to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures which contain ratios of monosaccharides (e.g., glucose) to di- and higher saccharides (e.g., 5 maltose) from about 4:1 to about 99:1.

The manufacture of preferred uncyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures from about 30*C-90"C, preferably about 50*C to 80*C. It has now been determined that it may be 13 convenient for the formulator of, for example, liquid detergents to conduct such processes in 1,2-propylene glycol solvent, since the glycol solvent need not be completely removed from the reaction product prior to use in the finished detergent formulation. Likewise, the formulator of, for example, solid, typically granular, 15 detergent compositions may find it convenient to run the process at 30*C-90*C in solvents which comprise ethoxylated alcohols, such as the ethoxylated (E0 3-8) C12-C14 alcohols, such as those available as NE0D0L 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they not contain substantial amounts of unethoxylated 20 alcohol and, most preferably, not contain substantial amounts of mono-ethoxylated alcohol. ("T" designation.) While methods for making polyhydroxy fatty acid amides per se form no part of the invention herein, the formulator can also note other syntheses of polyhydroxy fatty acid amides as described 25 hereinafter.

Typically, the industrial scale reaction sequence for preparing the preferred acyclic polyhydroxy fatty acid amides will comprise: Step 1 - preparing the N-alkyl polyhydroxy amine derivative from the desired sugar or sugar mixture by formation of an adduct of the 30 N-alkyl amine and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Step 2 - reacting the aforesaid polyhydroxy amine with, preferably, a fatty ester to form an amide bond. While a variety of N-alkyl polyhydroxy amines useful in Step 2 of the reaction sequence can be prepared by various 35 art-disclosed processes, the following process is convenient and makes use of economical sugar syrup as the raw material. It is to be understood that, for best results when using such syrup raw materials, the manufacturer should select syrups that are quite light in color or, preferably, nearly colorless ("water-white"). 2 -4 0 0 Preparation of N-Alkyl Polyhydroxy Amine From Plant-Derived Sugar Syrup I. Adduct Formation - The following is a standard process in which about 420 g of about 55% glucose solution (corn syrup - about 5 231 g glucose - about 1.28 moles) having a Gardner Color of less than 1 is reacted with about 119 g of about 50% aqueous methylamine (59.5 g of methylamine - 1.92 moles) solution. The methylamine (MMA) solution is purged and shielded with N2 and cooled to about 10*C, or less. The corn syrup is purged and shielded with N2 at a 10 temperature of about 10*-20*C. The corn syrup is added slowly to the MMA solution at the indicated reaction temperature as shown. The Gardner Color is measured at the indicated approximate times in minutes.

TABLE 1 Time in Minutes: 10 30 60 120 180 240 Reaction Temp. *C Gardner Color (Approximate) 1 1 1 1 1 1 2 4 5 As can be seen from the above data, the Gardner Color for the adduct is much worse as the temperature is raised above about 30'C and at about 50'C, the time that the adduct has a Gardner Color below 7 is only about 30 minutes. For longer reaction, and/or holding times, the temperature should be less than about 20*C. The Gardner Color should be less than about 7, and preferably less than about 4 for good color glucamine.

When one uses lower temperatures for forming the adduct, the time to reach substantial equilibrium concentration of the adduct is shortened by the use of higher ratios of amine to sugar. With the 1.5:1 mole ratio of amine to sugar noted, equilibrium is reached in about two hours at a reaction temperature of about 30*C. At a 1.2:1 mole ratio, under the same conditions, the time is at least about three hours. For good color, the combination of amine:sugar ratio; reaction temperature; and reaction time is selected to achieve substantially equilibrium conversion, e.g., more than about 90%, preferably more than about 95%, even more preferably more than about 99%, based upon the sugar, and a color that is less than about 7, 0 1 1 1 1 1 1 1 1 2 50 4 6 - 57 ■ preferably less than about 4, more preferably less than about 1, for the adduct.

Using the above process at a reaction temperature of less than about 20'C and corn syrups with different Gardner Colors as 5 indicated, the MMA adduct color (after substantial equilibrium is reached in at least about two hours) is as indicated.

TABLE 2 Gardner Color (Approximate) Corn syrup 1111+000+ Adduct 3 4/5 7/8 7/8 12 1 As can be seen from the above, the starting sugar material must be very near colorless in order to consistently have adduct that is acceptable. When the sugar has a Gardner Color of about 1, the adduct is sometimes acceptable and sometimes not acceptable. When 15 the Gardner Color is above 1 the resulting adduct is unacceptable. The better the initial color of the sugar, the better is the color of the adduct.

II. Hydrogen Reaction - Adduct from the above having a Gardner Color of 1 or less is hydrogenated according to the following 20 procedure.

About 539 g of adduct in water and about 23.1 g of United Catalyst G49B Ni catalyst are added to a one liter autoclave and purged two times with 200 psig H2 at about 20*C. The H2 pressure is raised to about 1400 psi and the temperature is raised to about 25 50*C. The pressure is then raised to about 1600 psig and the temperature is held at about 50-55'C for about three hours. The product is about 95% hydrogenated at this point. The temperature is then raised to about 85*C for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered out. The product, 30 after removal of water and MMA by evaporation, is about 95% N-methyl glucamine, a white powder.

The above procedure is repeated with about 23.1 g of Raney Ni catalyst with the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged ^5 twice with 200 psig H2 and the reactor is pressurized with H2 at 1600 psig for two hours, the pressure is released at one hour and the reactor is repressurized to 1600 psig. The adduct is then pumped into the reactor which is at 200 psig and 20*C, and the reactor is purged with 200 psig Hz, etc., as above.

The resulting product in each case is greater than about 95% N-methyl glucamine; has less than about 10 ppm Ni based upon the glucamine; and has a solution color of less than about Gardner 2.

The crude N-methyl glucamine is color stable to about 140*C for 5 a short exposure time.

It is important to have good adduct that has low sugar content (less than about 5%, preferably less than about 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1).

In another reaction, adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and shielded with N2 at about 10-20'C. About 330 g of about 70% corn syrup (near water-white) is degassed with N2 at about 50*C and is added slowly to the methylamine solution at a temperature of less than about 15 20'C. The solution is mixed for about 30 minutes to give about 95% adduct that is a very light yellow solution.

About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20*C. The H2 pressure is raised to about 200 20 psi and the temperature is raised to about 50°C. The pressure is raised to 250 psi and the temperature is held at about 50-55'C for about three hours. The product, which is about 95% hydrogenated at this point, is then raised to a temperature of about 85°C for about 30 minutes and the product, after removal of water and evaporation, 25 is about 95% N-methyl glucamine, a white powder.

It is also important to minimize contact between adduct and catalyst when the H2 pressure is less than about 1000 psig to minimize Ni content in the glucamine. The nickel content in the N-methyl glucamine in this reaction is about 100 ppm as compared to 30 the less than 10 ppm in the previous reaction.

The following reactions with H2 are run for direct comparison of reaction temperature effects.

A 200 ml autoclave reactor is used following typical procedures similar to those set forth above to make adduct and to run the 35 hydrogen reaction at various temperatures.

Adduct for use in making glucamine is prepared by combining about 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 moles) (the solution is made using 99DE corn syrup from CarGill, the solution having a color less than Gardner 1) and 2 /. f ( 'J U about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).

The reaction procedure is as follows: 1. Add about 119 g of the 50% methylamine solution to a N2 purged 5 reactor, shield with N2 and cool down to less than about 10*C. 2. Degas and/or purge the 55% corn syrup solution at 10-20'C with N2 to remove oxygen in the solution. 3. Slowly add the corn syrup solution to the methylamine solution and keep the temperature less than about 20*C. 4. Once all corn syrup solution is added in, agitate for about 1-2 hours.

The adduct is used for the hydrogen reaction right after making, or is stored at low temperature to prevent further degradation.

The glucamine adduct hydrogen reactions are as follows: 1. Add about 134 g adduct (color less than about Gardner 1) and about 5.8 g G49B Ni to a 200 ml autoclave. 2. Purge the reaction mix with about 200 psi H2 twice at about 20-30'C. 3. Pressure with H2 to about 400 psi and raise the temperature to about 50*C. 4. Raise pressure to about 500 psi, react for about 3 hours. Keep temperature at about 50-55*C. Take Sample 1.

. Raise temperature to about 85*C for about 30 minutes. 25 6. Decant and filter out the Ni catalyst. Take Sample 2.

Conditions for constant temperature reactions: 1. Add about 134 g adduct and about 5.8 g G49B Ni to a 200 ml autoclave. 2. Purge with about 200 psi H2 twice at low temperature. 3. Pressure with H2 to about 400 psi and raise temperature to about 50*C. 4. Raise pressure to about 500 psi, react for about 3.5 hours. Keep temperature at indicated temperature.

. Decant and filter out the Ni catalyst. Sample 3 is for about ^5 50-55*C; Sample 4 is for about 75*C; and Sample 5 is for about 85*C. (The reaction time for about 85*C is about 45 minutes.) All runs give similar purity of N-methyl glucamine (about 94%); the Gardner Colors of the runs are similar right after reaction, but "> L L ~t only the two-stage heat treatment gives good color stability; and the 85"C run gives marginal color immediately after reaction. example 16 The preparation of the tallow (hardened) fatty acid amide of 5 N-methyl maltamine for use in detergent compositions according to this invention is as follows.

Step 1 - Reactants: Maltose monohydrate (Aldrich, lot 01318KW); methylamine (40 wt% in water) (Aldrich, lot 03325TM); Raney nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW). 10 The reactants are added to glass liner (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry - 50 g Raney Ni) and placed in 3 L rocking autoclave, which is purged with nitrogen (3X500 psig) and hydrogen (2X500 psig) and rocked under H2 at room temperature over a weekend at temperatures ranging from 28*C to 15 50*C. The crude reaction mixture is vacuum filtered 2X through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are azetroped off by dissolving the material in methanol and then removing the methanol/water on a rotary evaporator. Final drying is 20 done under high vacuum. The crude product is dissolved in refluxing methanol, filtered, cooled to recrystal1ize, filtered and the filter cake is dried under vacuum at 35*C. This is cut #1. The filtrate is concentrated until a precipitate begins to form and is stored in a refrigerator overnight. The solid is filtered and dried under 25 vacuum. This is cut *2. The filtrate is again concentrated to half its volume and a recrystal1ization is performed. Very little precipitate forms. A small quantity of ethanol is added and the solution is left in the freezer over a weekend. The solid material is filtered and dried under vacuum. The combined solids comprise 30 N-methyl maltamine which is used in Step 2 of the overall synthesis.

Step 2 - Reactants: N-methyl maltamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); mole ratio 1:1 amine:ester; initial catalyst level 10 mole % (w/r maltamine), raised to 20 mole %; solvent level 35 50% (wt.).

In a sealed bottle, 20.36 g of the tallow methyl ester is heated to its melting point (water bath) and loaded into a 250 ml 3-neck round-bottom flask with mechanical stirring. The flask is "40 0 2 4 heated to ca. 70°C to prevent the ester from solidifying. Separately, 25.0 g of N-methyl maltamine is combined with 45.36 g of methanol, and the resulting slurry is added to the tallow ester with good mixing. 1.51 g of 25% sodium methoxide in methanol is added. 5 After four hours the reaction mixture has not clarified, so an additional 10 mole % of catalyst (to a total of 20 mole %) is added and the reaction is allowed to continue overnight (ca. 68"C) after which time the mixture is clear. The reaction flask is then modified for distillation. The temperature is increased to 110'C. 13 Distillation at atmospheric pressure is continued for 60 minutes. High vacuum distillation is then begun and continued for 14 minutes, at which time the product is very thick. The product is allowed to remain in the reaction flask at 110"C (external temperature) for 60 minutes. The product is scraped from the flask and triturated in 15 ethyl ether over a weekend. Ether is removed on a rotary evaporator and the product is stored in an oven overnight, and ground to a powder. Any remaining N-methyl maltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol. A 23 concentrated sample of the product (20 g in 100 ml of 100% methanol) is loaded onto the silica gel and eluted several times using vacuum and several methanol washes. The collected eluant is evaporated to dryness (rotary evaporator). Any remaining tallow ester is removed by trituration in ethyl acetate overnight, followed by filtration. 25 The filter cake is vacuum dried overnight. The product is the tallowalkyl N-methyl maltamide.

In an alternate mode. Step 1 of the foregoing reaction sequence can be conducted using commercial corn syrup comprising glucose or mixtures of glucose and, typically, 5%, or higher, maltose. The 33 resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.

In still another mode, Step 2 of the foregoing reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, the propylene glycol or NEODOL 35 need not be removed from the reaction product prior to its use to formulate detergent compositions. Again, according to the desires of the formulator, the methoxide catalyst can be neutralized by citric acid to provide sodium citrate, which can remain in the polyhydroxy fatty acid amide. :: ? 4 J ! "T Depending on the desires of the formulator, the compositions herein can contain more or less of various suds control agents. Typically, for dishwashing high sudsing is desirable so no suds control agent will be used. For fabric laundering in top-loading 5 washing machines some control of suds may be desirable, and for front-loaders some considerable degree of suds control may be preferred. A wide variety of suds control agents are known in the art and can be routinely selected for use herein. Indeed, the selection of suds control agent, or mixtures of suds control agents, 13 for any specific detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide used therein, but also on the other surfactants present in the formulation. However, it appears that, for use with polyhydroxy fatty acid amides, silicone-based suds control agents of various types are more 15 efficient (i.e., lower levels can be used) than various other types of suds control agents. The silicone suds control agents available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful herein.

The formulator of fabric laundering compositions which can advantageously contain soil release agent has a wide variety of 23 known materials to choose from (see, for example, U.S. Patents 3,962,152; 4,116,885; 4,238,531; 4,702,857; 4,721,580 and 4,877,896). Additional soil release materials useful herein include the nonionic oligomeric esterification product of a reaction mixture comprising a source of Cj-C4 alkoxy-terminated polyethoxy units 25 (e.g., CH3[0CH2CH2]160H), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(oxyethylene)oxy units (e.g., polyethylene glycol 1500); a source of oxyiso-propyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol) especially wherein the mole ratio of 30 oxyethyleneoxy unitsroxyiso-propyleneoxy units is at least about 0.5:1. Such nonionic soil release agents are of the general formula R10-(CH2CH20)x 0 , , O ii /—\ H 0 0 c-u /Vco-ch-ch2o R2 0 0 C-C /Vc0(CH2CH20)y CA^/-C - 0 (CH2CH20)x-R1 wherein R1 is lower (e.g., Cj-C4) alkyl, especially methyl; x and y are each integers from about 6 to about 100; m is an integer of from 0 , r / about 0.75 to about 30; n is an integer from about 0.25 to about 20; and R2 is a mixture of both H and CH3 to provide a mole ratio of oxyethyleneoxy:oxyisopropyleneoxy of at least about 0.5:1.

Another preferred type of soil release agent useful herein is 5 of the general anionic type described in U.S. Patent 4,877,896, but with the condition that such agents be substantially free of monomers of the HOROH type wherein R is propylene or higher alkyl. Thus, the soil release agents of U.S. Patent 4,877,896 can comprise, for example, the reaction product of dimethyl terephthalate, -3 ethylene glycol, 1,2-propylene glycol and 3-sodiosulfobenzoic acid, whereas these additional soil release agents can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. Such agents are preferred for use in granular laundry detergents. 15 The formulator may also determine that it is advantageous to include a non-perborate bleach, especially in heavy-duty granular laundry detergents. A variety of peroxygen bleaches are available, commercially, and can be used herein, but, of these, percarbonate is convenient and economical. Thus, the compositions herein can 23 contain a solid percarbonate bleach, normally in the form of the sodium salt, incorporated at a level of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8% to 15% by weight of the composition.

Sodium percarbonate is an addition compound having a formula 25 corresponding to 2NazC03. 3H202, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxy-ethylidene 1,1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process. For use 33 herein, the percarbonate can be incorporated into detergent compositions without additional protection, but preferred embodiments of the invention utilize a stable form of the material (FMC). Although a variety of coatings can be used, the most economical is sodium silicate of Si02:Na20 ratio from 1.6:1 to 2.8:1, preferably 2.0:1, 35 applied as an aqueous solution and dried to give a level of from 2% to 10% (normally from 3% to 5%), of silicate solids by weight of the percarbonate. Magnesium silicate can also be used and a chelant such as one of those mentioned above can also be included in the coating. 2 4 The particle size range of the crystalline percarbonate is from 350 micrometers to 450 micrometers with a mean of approximately 400 micrometers. When coated, the crystals have a size in the range from 400 to 600 micrometers.

While heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction, mixture, the percarbonate still requires protection from heavy metals present as impurities in other ingredients of the product. It has been found that the total level 10 of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm in order to avoid an unacceptably adverse effect on percarbonate stability.

A modern, condensed laundry detergent granule is as follows.

EXAMPLE 17 Ingredient Wt.% C14-15 alkyl alcohol sulfonic acid 13 C j 4 - j 5 alkyl polyethoxy (2.25) sulfonic acid 5.60 C j j-j 3 alkyl polyethoxylate (6.5) 1.45 Cw.14 fatty acid N-methyl glucamide 2.50 23 Sodium aluminosilicate (as hydrated Zeolite A) 25.2 Crystalline layered silicate builder1 23.3 Citric acid 10.0 Sodium carbonate To get wash pH » 9.90 Sodium polyacrylate (m.w. 2000-4500) 3.2 Diethylenetriamine pentaacetic acid 0.45 Savinase2 0.70 6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40 Sodium perborate monohydrate 2.10 Nonanoyloxybenzene sulfonic acid 5.00 Brightener 0.10 layered silicate builders are known in the art. Preferred are the layered sodium silicates. See, for example, the layered sodium silicate builders of U.S. Patent 4,664,859, issued May 12, 1987 to H. P. Rieck, incorporated herein by reference. A suitable layered 35 silicate builder is available as SKS-6 from Hoechst.

Available from Novo Nordisk A/S, Copenhagen.

Highly preferred granules of the foregoing types are those which comprise from about 0,0001% to about 2% by weight of active 1 - \J ■ 65 enzyme and at least about 1% by weight of said polyhydroxy fatty acid amide, and, most preferably, wherein the anionic surfactant is not an alkylbenzene sulfonate surfactant.

EXAMPLE 18 The following illustrates a perborate bleach-plus-bleach activator detergent composition of the present invention which is prepared by admixing the listed ingredients in a mixing drum.

In the example, Zeolite A refers to hydrated crystalline Zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 3 to 5, microns; LAS refers to sodium Cj2.3 linear alkylbenzene sulfonate; AS refers to sodium Cl4-C15 alkyl sulfate; nonionic refers to coconut alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol and stripped of unethoxylated and monoethoxylated alcohol, also abbreviated as CnAE6.5T.; and DTPA refers to sodium diethylenetriamine pentaacetate.

Parts by Weight of Final Composition 51.97 Base Granules1 AS LAS Moisture Sodium silicate (1.6 ratio) Sodium sulfate Sodium polyacrylate (4500 MW) PEG 8000 Nonionic Sodium carbonate Brightener Sodium aluminosi1icate DTPA Perfume NAPAA Granules2 NAPAA LAS Sulfate and Misc.

NOBS Granules3 NOBS LAS % of Granules 100.00 6.09 3.88 9.44 2.92 4.47 1.35 6.47 2.61 1.18 0.46 13.29 0.20 9.11 0.27 0.20 2.86 0.30 2.93 3.15 0.12 100.00 100.00 18.16 5.62 8.60 2.60 12.45 5.02 2.27 0.89 25.57 0.38 17.53 0.52 0.38 46.96 4.93 48.11 81.19 3.09 : 0 2 66 - PEG 8000 0.19 4.90 Misc. 0.42 10.82 Zeolite Granules4 12.00 100.00 Sodium aluminosilicate 7.39 61.58 PEG 8000 1.50 12.47 Nonionic 1.16 9.70 Moisture 1.66 13.83 Misc. 0.29 2.42 Admi x Sodium SKS-6 layered silicate 15.84 Protease (0.078 mg/g activity) 0.52 Sodium perborate 15 monohydrate 1.33 Citric acid 6.79 Ciz"Cm N-methyl glucamide 1.58 Total of final composition 100.00 lThe base granules are produced by spray drying an aqueous 20 crutcher mix of the listed ingredients.

*A freshly-prepared sample of NAPAA wet cake, which typically consists of about 60% water, about 2% peroxyacid available oxygen (AvO) (corresponding to about 36% NAPAA), and the rest (about 4%) unreacted starting material, is obtained. This wet cake is the 25 crude reaction product of NAAA (monononyl amide of adipic acid), sulfuric acid, and hydrogen peroxide which is subsequently quenched by addition to water followed by filtration, washing with distilled water, phosphate buffer washing and final suction filtration to recover the wet cake. A portion of the wet cake is air-dried at 30 room temperature to obtain a dry sample which typically consists of about 5% AvO (corresponding to about 90% NAPAA) and about 10% unreacted starting material. When dry, the sample pH is about 4.5.

NAPAA granules are prepared by mixing about 51.7 parts of the dried NAPAA wet cake (containing about 10% unreacted), about 11.1 35 parts of sodium C12>3 linear alkyl benzene sulfonate (LAS) paste (45% active), about 43.3 parts of sodium sulfate, and about 30 parts of water in a CUISINART mixer. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 14 Tyler mesh sieve and retaining all particles not passing through a No. 65 Tyler mesh. The average amide peroxyacid particle (agglomerate) size is about 5-40 microns and the median particle size is about 10-20 microns, as determined by Malvern particle size analysis. 3The NOBS (nonanoyloxybenzene sulfonate) granules are prepared 5 according to U.S. Patent 4,997,596, Bowling et al, issued March 5, 1991, incorporated herein by reference.

'Zeolite granules having the following composition are made by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich R08 energy intensive mixer.

Parts by Weight Before Drying After Drying Zeolite A (includes bound water) 70.00 76.99 PEG 8000 10.80 12.49 CnAE6.5T 8.40 9.72 Free water 10.80 0.80 The PEG 8000 is in an aqueous form containing 50% water and is at a temperature of approximately 55"F (12.8'C). The CnAE6.5T is in a liquid state and is held at approximately 90"F (32.2*C). The two liquids are combined by pumping through a 12 element static mixer. 20 The resulting binder material has an outlet temperature of approximately 75°F (23.9'C) and a viscosity of approximately 5000 cps. The ratio of PEG 8000 and CnAE6.5T through the static mixer is 72:28 respectively.

The Eirich R08 energy intensive mixer is operated in a batch 25 type mode. First, 34.1 kg of powdered Zeolite A is weighed into the pan of the mixer. The mixer is started by first rotating the pan in a counterclockwise direction at approximately 75 rotations per minute (rpm), and then rotating the rotor blade in a clockwise direction at 1800 rpm. The binder material is then pumped from the 39 static mixer directly into the Eirich R08 energy intensive mixer which contains Zeolite A. The feed rate of the binder material is about 2 minutes. The mixer continues to mix for an additional 1 minute for a total batch time of approximately 3 minutes. The batch is then discharged and collected in a fiber drum.

The batch step is repeated until approximately 225 kg of wet product has been collected. This discharged product is then dried in a fluid bed at 240-270"F (116-132"C). The drying step removes most of the free water and changes the composition as described above. The total energy input by the mixer to the product in a 2-;: o24 batch mode is approximately 1.31X1012 erg/kg. at a rate of approximately 2.18X109 erg/kg-s.

The resulting free flowing agglomerates have a mean particle size of about 450-500 microns. 5 EXAMPLE 19 A granular laundry detergent composition suitable for use at the relatively high concentrations common to front-loading automatic washing machines, especially in Europe, and over a wide range of temperatures is as follows.

Ingredient Wt. % SOKALAN CP5 (100% active as Na salt)1 3.52 DEQUEST 2066 (100% as acid)2 0.45 TINOPAL DMS3 0.28 MgSO« 0.49 Zeolite A (anhydrous 2-5 /j) 17.92 CMC (100% active)4 0.47 Na2C03 9.44 Citric acid 3.5 Layered Silicate SKS-6 12.9 Tallow alkyl sulfate (100% active; Na salt) 2.82 C]4-C15 alkyl sulfate (100% active; Na salt) 3.5 C12-Cj5 alkyl EO(3) sulfate 1.76 Cie"CiB N-methyl glucamide 4.1 DOBANOL C,2-Cls E0(3) 3.54 LIPOLASE (100,000 LU/g)5 0.42 SAVINASE (4.0 KNPU)6 1.65 Perfume 0.53 X2-34197 0.22 Starch 1.08 Stearyl alcohol 0.35 Sodium percarbonate (coated) 22.3 Tetraacetylethylenediamine (TAED) 5.9 Zinc phthalocyanin 0.02 Water (ex zeolite) Balance 35 ^OKALAN is sodium poly-acrylate/maleate available from Hoechst. 2Monsanto brand of pentaphosphonomethyl diethylenetriamine. 30ptical brightener available from Ciba Geigy. 4Trade name FINNFIX available from Metasaliton. 5LIPOLASE lipolytic enzyme from NOVO. 6SAVINASE protease enzyme from NOVO. 7X2-3419 is a silicone suds suppressor available from Dow Corni ng.

The procedure for preparing the granules comprises various tower-drying, agglomerating, dry-additions, etc., as follows. The percentages are based on the finished composition.

A. Crutched and Blown Through the Tower Using standard techniques the following components are crutched and tower-dried.

SOKALAN CP5 3.52% DEQUEST 2066 0.45% TINOPAL DMS 0.28% Magnesium sulfate 0.49% ZEOLITE A as anhydrous 7.1% CMC 0.47% B. Surfactant Agglomerates Bl. Agglomeration of Sodium Salt of Tallow Alkyl Sulfate and Sodium Salt of EO(3) Sulfate Pastes - A 50% active paste of tallow alkyl sulfate and a 70% paste of CirC15 EO(3) sulfate are agglomerated with Zeolite A and sodium carbonate according to the following formula (contribution to the detergent formulation after the drying of the agglomerate).

Tallow alkyl sulfate 2.82% C12-15 E0(3) sulfate 1.18% Zeolite A 5.3% Sodium carbonate 4.5% B2. Agglomerate of the C-,-Clc Alkyl Sulfate. C,,-C,t Alkyl Ethoxy Sulfate. DOBANOL C17-C,„ E0(3) and C1f-C,„ N-methyl glucose amide - The C16-C1B glucose amide nonionic material is synthesized with DOBANOL C12.15E0(3) present during the reaction of methyl ester and N-methyl glucamine. The C12.15EO(3) acts as a melting point depressor which allows the reaction to be run without forming cyclic glucose amides which are undesirable.

A surfactant mixture of 20% DOBANOL Ca2-15 EO(3) and 80% Cie'Cia N-methyl glucose amide is obtained and coagglomerated with 10% sodium carbonate.

Second, the above particle is then coagglomerated with a high active paste (70%) of a sodium salt of C14-C15 alkyl sulfate and Cj2-15 EO(3) sulfate and Zeolite A and extra sodium carbonate. This particle evidences a good dispersibility in cold water of the 5 C1S-C1B N-methyl glucose amide.

The overall formulation of this particle (contribution to the detergent formulation after the drying of the agglomerate) is: Ci6"Cib N-methyl glucose amide 4.1% DOBANOL C12.1S EO(3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% Na C14-C15 alkyl sulfate 3.5% Na C j j-!5 E0(3) sulfate 0.59% C. Dry Additives The following ingredients are added.

Percarbonate 22.3% TAED (tetraacetylethylenediamine) 5.9% Layered silicate SKS 6 from Hoechst 12.90% Citric acid 3.5% Lipolase 0.42% 100,000 LU/g SAVINASE 4.0 KNPU 1.65% Zinc phthalocyanin (photobleach) 0.02% D. Spray on DOBANOL C12.15 EO(3) 2.60% Perfume 0.53% E. Suds Suppressor The silicone suds suppressor X2-3419 (95%-97% high molecular weight linear silicone; 3%-5% hydrophobic silica) ex Dow Corning is 30 coagglomerated with Zeolite A (2-5 ^ size), starch and stearyl alcohol binder. This particle has the following formulation: Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% The detergent preparation exhibits excellent solubility, superior performance and excellent suds control when used in European washing machine, e.g., using 85 g detergent in an AEG-brand washing machine in 30'C, 40*C, 60"C and 90*C cycles.

Claims (20)

2*0024 71 - In any of the foregoing examples, the fatty acid glucamide surfactant can be replaced by an equivalent amount of the maltamide surfactant, or mixtures of glucamide/maltamide surfactants derived 5 from plant sources. In the compositions the use of ethanolamides appears to help cold temperature stability of the finished formulations. Moreover, the use of amine oxide and/or sulfobetaine (aka "sultaine") surfactants provides superior sudsing. In the event that especially high sudsing compositions are 10 desired, it is preferred that less than about 5%, more preferably less than about 2%, most preferably substantially no Cu or higher fatty acids be present, since these can suppress sudsing. Accordingly, the formulator of high sudsing compositions will desirably avoid the introduction of suds-suppressing amounts of such fatty 15 acids into high sudsing compositions with the polyhydroxy fatty acid amides, and/or avoid the formation of C14 and higher fatty acids on storage of the finished compositions. One simple means is to use Cl2 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine 20 surfactants can overcome some of the negative sudsing effects caused by the fatty acids. The formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and greater) of anionic or polyanionic substituents such as the 25 polycarboxylate builders may find it useful to pre-mix the brightener with water and the polyhydroxy fatty acid amide, and then to add the pre-mix to the final composition. Polyglutamic acid or polyaspartic acid dispersants can be usefully employed with zeolite-built detergents. AE fluid or flake 30 and DC-544 (Dow Corning) are other examples of useful suds control agents herein. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in 35 the formation of polyhydroxy fatty acid amides wherein linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein and do not depart from the scope of the invention as disclosed and claimed. WHAT&WE CLAiM IS: - 72 - 'HOO 24

1. A built detergent composition, comprising one or ^ore anionic, nonionic or cationic detersive surfactants, or a mixture thereof, optional detersive adjuncts, and optional auxiliary builders, said composition containing: (a) at least l'i by weight of a zeolite or layered silicate detergency builder, or a mixture thereof; and (b) at least 1% by weight of a polyhydroxy fatty acid amide material of the formula 0 Rl R2 - c - N - Z wherein Rl is H. Cj-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, is C5-C31 hydrocarbyl. and Z is a polyhyaroxyhydrocarbyl having a linear hydrocarbyl cnain with at least 3 hydroxyls directly connected to said chain, or an alkoxylated derivative thereof.

2. A detergent composition according to Claim 1, wherein the zeolite builder of (a) is Zeolite A.

3. A detergent composition according to Claim 2, which is a granular composition.

4. A composition according to Claim 1. wherein Z of the polyhydroxy fatty acid amide material is derived from a reducing sugar. Rl is methyl, and R^ is Cg-Cj7 alkyl or alkenyl.

5. A composition according to Claim 4, wherein Z represents -CH2(CH0H)4CH20H.

6. A composition as in Claim 1 wherein, with respect to the polyhydroxy fatty acid amide, Z is derived from glucose or maltose Or a mixture thereof.

7. A composition as in Claim 1 wherein Z is derived from a mixture of monosaccharides, disaccharides and, optionally, polysaccharides comprising at least 1% by weight of disaccharides, said mixture being available from plant sources. 240024

3. A detergent composition as in Claim 1. -vnerein tne '"atio of zeolite, laye>-od silicate, or mixture thereof to polyhydroxy fattv acid anido is fron 1:10 to 20:1.

9. A detergent composition as in Claim 8, wherein the ratio of zeolite, layered silicate, or mixture thereof to polyhydroxy fatty acid amide is from 1:5 to 15:1.

10. A detergent composition as in Claim 9, wherein said ratio is from 1:3 to about 10:1.

11. A detergent composition as in Claim 1. comprising one or more anionic surfactants selected from the group consisting of alkyl sulfates, alkyl ethoxylated sulfates, alkyl ester sulfonates, and alkyl benzene sulfonates.

12. A detergent composition as in Claim 11, further comprising an alkyl ethoxylate or alkyl polyglycoside nonionic surfactant, or a mixture thereof.

13. A composition as in Claim 1 additionally comprising a polycarboxylate builder.

14. A method for improving cleaning performance of a detergent composition comprising: one or more anionic, nonionic, or cationic surfactants, or a mixture thereof: zeolite or layered silicate builder, or a mixture thereof; optional detergent adjuncts, and optional auxiliary builder; wherein the improvement comprises incorporating into said detergent composition at least \/o by weight of a polyhydroxy fatty acid amide material of the formula 0 Rl R2 - C - N - Z wherein Rl is h, Cx-C4 hydrocarbyl, 2-hydroxy ethyl, 2—hydroxy propyl, or a mixture thereof, r2is c5-c31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl with at leas£-3-hydroxyls, or an alkoxylated derivative thereof, wherein thp'ratio of zeolite, layered silicate, or mixture thereof to polyhydroxy fatty acid amide is from 1:10 to 20:1. - 74 -

15. A method as in Claim 14 wherein R2 in the polyhydroxy fatty acid arrnde is Cu-C17 alkyl or alkenyl and wherein Z is derived from glucose, maltose or a mixture thereof available from plant sources.

16. A method as in Claim 14, wherein said detergent composition comprises one or more anionic surfactants.

17. A method as in Claim 16 wherein said anionic surfactant is not an alkyl-benzene sulfonate surfactant.

18. A built detergent composition substantial]y as herein described with reference to any embodiment disclosed in the examples.

10. A method according to claim 14 and substantially as herein described with reference to any embodiment disclosed.

20. A detergent composition wherein its cleaning performance has been improved by the method of any one of claims 14 to 17 and 19. By the authorised agents A. J. park & son. PerJ^^C ^ i, DEC 1994