DE69126880T2 - POLYHYDROXY FATTY ACID AMIDES IN POLYCARBOXYLATE AS A BUILDING DETERGENT CONTAINING - Google Patents

Abstract

Disclosed are detergent compositions containing polycarboxylate builders and one or more anionic, nonionic, or cationic detersive surfactants, or mixtures thereof, improved by the inclusion of certain polyhydroxy fatty acid amide surfactants. The compositions comprise at least 1 % by weight of polycarboxylate builder, and at least 1 % by weight of a polyhydroxy fatty acid amide of formula (I) wherein R<1> is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; and R<2> is a C5-C31 hydrocarbyl; 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.

Description

- FIELD OF INVENTION

The performance of detergent compositions containing polycarboxylate builders is enhanced by means of polyhydroxy fatty acid amide surfactants.

CROSS-REFERENCE TO A RELATED APPLICATION

This application is a continuation-in-part of co-pending application No. 589,732, filed September 28, 1990.

BASIS OF THE INVENTION

Various builder materials have been proposed for use in detergent compositions. Such materials perform a variety of functions including hardness complexation, 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 polycarboxylate builder or builder blends containing various polycarboxylate builders.

The development of phosphate-free, highly effective detergent compositions for laundry washing has presented a significant challenge to the industry. From a performance standpoint, even the best polycarboxylate builders often result in a "builder starvation" situation in hard water. In addition, simply increasing the amount of builder used can greatly increase costs and lead to solubility problems for anionic detergent surfactants in use, particularly under high water hardness conditions. Conventional nonionic surfactants, such as the alkyl ethoxylates, do not suffer from solubility problems, but on the other hand, they typically do not provide exceptional overall cleaning at low to moderate wash temperatures. Conventional nonionic surfactants can also be difficult to formulate into granular and liquid detergent formulations.

Therefore, those entrusted with the formulation of heavy-duty detergents are forced to resort to other means of performance enhancement. In order to increase the detergency performance of such compositions, experienced formulators have incorporated various detergent additives therein. Materials such as detersive enzymes, soil release polymers and bleaching agents are commonly used to increase the performance of detergent compositions containing carboxylate builders. This is particularly true in liquid detergent formulations since large amounts of builders can cause various anionic surfactants, such as alkyl sulfates and alkyl ester sulfonates, to become insoluble in the formulation.

Simply summarized, the present invention employs an improved surfactant detersive system to compensate for the reduction in cleaning performance caused by the use of polycarboxylate builders. Through the practice of this invention, certain polyhydroxy fatty acid amides are used in detergents containing polycarboxylate builders to increase detergent performance. In addition, these polyhydroxy fatty acid amides facilitate the formulation of granular and especially liquid detergents with high builder levels and anionic surfactants.

STATE OF THE ART

A variety of polyhydroxy fatty acid amides have been described in the art. For example, N-acyl,N-methylglucamides have been described by JW Goodby, MA Marcus, E. Chin and PL Finn in "The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles", Liquid Crystals, 1988, Vol. 3, No. 11, pp. 1569-1581 and by A. Muller-Fahrnow, V. Zabel, M. Steifa and R. Hilgenfeld 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 in biochemistry has recently received particular interest, for example for the dissociation of biological membranes. See for example the journal article "ND-Gluco-N-methyl-alkanamide Compounds, a New Class of Non-Ionic Detergents For Membrane Biochemistry", Biochem.J. (1982), Vol. 207, pp. 363-366, by JEK Hildreth.

The use of N-alkyl glucamides in detergent compositions has also been discussed. U.S. Patent No. 2,965,576, issued December 20, 1960, E.R. Wilson, and British Patent No. 809,060, issued February 18, 1959, assigned to Thomas Hedley & Co., Ltd., relate to detergent compositions containing anionic surfactants and certain amide surfactants, which may include N-methyl glucamide, added as a low temperature foaming agent. These compounds comprise an N-acyl residue of a higher linear fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. Generally, it is also stated that additional ingredients can also be included in the compositions to impart desirable properties to the compositions, such as fluorescent dyes, bleaching agents, perfumes, etc.

FR-A-1 580 491 relates to anionic or non-ionic detergent compositions and certain amide surfactants which have a foam-suppressing effect at high temperatures and a foam-stabilizing effect at low temperatures.

U.S. Patent No. 2,703,798, issued March 8, 1955, to A.M. Schwartz, relates to aqueous detergent compositions containing the reaction product of the condensation of N-alkylglucamine with an aliphatic fatty acid ester. This reaction product is said to be useful in aqueous detergent compositions without further purification. It is also known to prepare a sulfuric acid ester of acylated glucamine as described in U.S. Patent No. 2,717,894, issued September 13, 1955, to A.M. Schwartz.

International PCT application WO 83/04412, published on 22 December 1983, J. Hildreth, relates to amphiphilic compounds containing aliphatic groups with several hydroxyl groups which are said to be useful for a variety of purposes including use as surfactants in cosmetic products, pharmaceuticals, shampoos, lotions and eye ointments, as emulsifiers and dispersants for pharmaceuticals, and in biochemistry for solubilizing membranes, whole cells or other tissue samples and for preparing liposomes. Included in this publication are compounds of the formula R'CON(R)CH₂R" and R"CON(R)R', wherein R is hydrogen or an organic moiety, R' is an aliphatic hydrocarbon group having at least three carbon atoms and R" is the residue of an aldose.

European Patent Specification 0 285 768, published on 12 October 1988, H. Kelkenberg et al., relates to the use of N-polyhydroxyalkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R₁C(O)N(X)R₂, in which R₁ is a C₁-C₁₇-alkyl (preferably C₁-C₁₇), R₂ is hydrogen, a C₁-C₁₈-alkyl (preferably C₁-C₆), or an alkylene oxide and X is a polyhydroxyalkyl having 4 to 7 carbon atoms, e.g. N-methyl-coconut fatty acid glucamide. The thickening properties of the amides are said to be particularly useful in liquid surfactant systems containing paraffin sulfonate, although the aqueous surfactant systems may contain other anionic surfactants such as alkylaryl sulfonates, olefin sulfonates, sulfosuccinic acid half-ester salts and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, mixed polypropylene oxide-polyethylene oxide polymers, and others. Shampoo formulations of paraffin sulfonate, N-methyl coconut fatty acid glucamide and nonionic surfactant are cited as examples. In addition to the thickening properties, the N-polyhydroxyalkyl fatty acid amides are said to have the properties of better skin compatibility.

US Patent 2,982,737, published May 2, 1961, Boettner et al., relates to detergent bars containing urea, sodium lauryl sulfate as anionic surfactant and an N-alkylglucamide as nonionic surfactant selected from N-methyl,N-sorbityl auramide 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, complexing agents and washing alkalis selected from polymeric phosphates, improved by the addition of an N-acylpolyhydroxyalkylamine of the formula R₁C(O)N(R₂)CH₂(CHOH)NCH₂OH, wherein R₁ is a C₁-C₃ alkyl, R₂ is a C₁₀-C₂₂ alkyl and n is 3 or 4. The N-acylpolyhydroxyalkylamine 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 containing at least one surfactant selected from the group of anionic, zwitterionic and nonionic surfactants and as a fabric softener an N-acyl, N-alkyl polyhydroxyalkyl compound of the formula R₁N(Z)C(O)R₂, wherein R₁ is C₁₀-C₂₂ alkyl, R₂ is C₇-C₂₁ alkyl, R₁ and R₂ are have a total of 23 to 39 carbon atoms and Z is a polyhydroxyalkyl which may be -CH₂(CHOH)mCH₂OH, where m is 3 or 4.

U.S. Patent No. 4,021,539, issued May 3, 1977, H. Möller et al., relates to cosmetic compositions for skin treatment containing N-polyhydroxyalkylamines comprising compounds of the formula R1N(R)CH(CHOH)mR2, wherein R1 can be H, lower alkyl, hydroxy-lower alkyl or aminoalkyl, as well as heterocyclic aminoalkyl, R has the same meaning as R1, but neither can be H, and R2 is CH2OH or COOH.

French patent specification 1 360 018, 26 April 1963, assigned to Commercial Solvents Corporation, relates to formaldehyde solutions stabilized against polymerization by the addition of amides of the formula RC(O)N(R₁)G, in which R represents a carboxylic acid function having at least seven carbon atoms, R₁ represents hydrogen or a lower alkyl group and G represents a glycitol residue having at least 5 carbon atoms.

German Patent Specification 1 261 861, 29 February 1968, A. Heins, relates to glucamine derivatives which are useful as wetting and dispersing agents, of the formula N(R) (R₁) (R₂), in which R represents a sugar residue of glucamine, R₁ represents a C₁₀-C₂₀-alkyl residue and R₂ is a C₁₀-C₅-acyl residue.

British Patent Specification 745,036, published on 15 February 1956, assigned to Atlas Powder Company, relates to heterocyclic amides and carboxylic acid esters thereof, which are said to be useful as chemical intermediates, as emulsifiers, wetting and dispersing agents, detergents, fabric softeners, and others. The compounds are illustrated by the formula N(R)(R₁)C(O)R₂, wherein R is the residue of a hexanepentol in anhydride form or a carboxylic acid ester thereof, R₁ represents a monovalent hydrocarbon residue, and -C(O)R₂ represents the acyl residue of a carboxylic acid having 2 to 25 carbon atoms.

In U.S. Patent No. 3,312,627, issued April 4, 1967, D.T. Hooker, solid toilet bars are described which are substantially free of anionic detergents and alkaline builder materials and which contain the 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 a nonionic foaming component which may comprise a polyhydroxyamide of the formula RC(O)NR¹(R²) wherein RC(O) may have from about 10 to about 14 carbon atoms and the radicals R¹ and R² each represent H or C₁-C₆ alkyl groups, which alkyl groups contain a total of 2 to about 7 carbon atoms and have a total of 2 to about 6 hydroxyl substituent groups. A substantially similar disclosure can be found in U.S. Patent No. 3,312,626, also issued April 4, 1967, D.T. Hooker.

SUMMARY OF THE INVENTION

Improved polycarboxylate builder-containing detergent compositions are made by the inclusion of certain

Polyhydroxy fatty acid amide surfactants, and in particular one or more anionic, nonionic or cationic detersive surfactants, or mixtures thereof. Accordingly, the compositions of the present invention comprise at least 1% by weight of polycarboxylate builder and at least 1% by weight of a polyhydroxy fatty acid amide of the formula

wherein R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl (i.e. methyl); and R² is C₅-C₃₁ hydrocarbyl, preferably C₇-C₁₇ straight chain alkyl or alkenyl, more preferably C₇-C₁₇ straight chain alkyl or alkenyl, most preferably C₁₁-C₁₇ straight chain alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof (preferably an ethoxylated or propoxylated derivative). Z is preferably obtained from a reducing sugar in a 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 as well as the individual sugars listed above can be used. These corn syrups can result in a mixture of sugar components for Z. Z is therefore preferably selected from the group consisting of -CH₂-(CHOH)n-CH₂OH, -CH(CH₂OH)-(CHOH)n-1-CH₂OH, -CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, wherein n represents an integer from 3 to 5 inclusive and R' represents H or a cyclic or aliphatic monosaccharide, and the alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, especially -CH₂-(CHOH)₄-CH₂OH.

Preferably, the weight ratio of the polycarboxylate builder to the polyhydroxy fatty acid amide is from about 1:10 to about 10:1, more preferably from about 1:5 to about 7:1, most preferably from about 1:1 to about 7:1. This invention encompasses both liquid and granular detergent compositions.

This invention provides detergent compositions containing polycarboxylate builders which can exhibit improved builder performance and consequently improved cleaning performance, particularly in the area of grease/oil cleaning.

This invention further provides a method for improving the performance of detergents containing anionic, nonionic and/or cationic surfactant and polycarboxylate builder by incorporating the polyhydroxy fatty acid amide surfactant described above into such a composition such that the weight ratio of polycarboxylate to amide surfactant is from about 1:10 to about 10:1.

This invention further provides a method for cleaning substrates such as fibers, fabrics, hard surfaces, skin, and others by contacting said substrate with a detergent composition containing one or more anionic, nonionic or cationic surfactants, at least about 1% polycarboxylate builder and at least 1% polyhydroxy fatty acid amide, wherein the weight ratio of polycarboxylate builder to polyhydroxy fatty acid amide surfactant is from about 1:10 to about 10:1, in the presence of a solvent such as water or a water-miscible solvent (e.g., primary and secondary alcohols). Agitation is preferably provided to further facilitate cleaning. Suitable agitation means include rubbing by hand or, preferably, by means of a brush, sponge, mop or other cleaning device, automatic clothes washing machines, automatic dishwashers, etc.

In the above processes, the more preferred weight ratios of the polycarboxylate builder to the Polyhydroxy fatty acid amide from about 1:5 to about 7:1, most preferably from about 1:1 to about 7:1 and the preferred amounts and types of polyhydroxy fatty acid amide and polycarboxylate are as described herein.

DETAILED DESCRIPTION OF THE INVENTION Polyhydroxy fatty acid amide surfactant

The compositions of the invention 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:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl (ie methyl); and R² is C₅-C₃₁ hydrocarbyl, preferably linear C₇-C₁₇ alkyl or alkenyl, more preferably linear C₇-C₁₇ alkyl or alkenyl, most preferably linear C₁₁-C₁₇ alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain wherein at least 3 hydroxyl groups are directly attached to the chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z is preferably obtained from a reducing sugar in a 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 as well as the individual sugars listed above can be used. These corn syrups can result in a mixture of sugar components for Z. It should be understood that it is not intended to exclude other suitable raw materials. Z is preferably selected from the group consisting of -CH₂-(CHOH)n-CH₂OH, -CH(CH₂OH)-(CHOH)n-1- CH₂OH, -CH₂-(CHOH)₂(CHOR')(CHOH)-CH₂OH, wherein n is an integer from 3 to 5 inclusive and R' is H or a cyclic or aliphatic monosaccharide, and the alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, especially -CH₂-(CHOH)₄-CH₂OH.

In formula (I), R¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R²-CO-N< can mean, for example, cocoamamide, stearamide, oleamide, lauramide, myristamide, capric acid amide, palmitamide, tallowamide, etc.

Z can stand for 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl, N-1-deoxygalactityl, N-1-deoxymannityl, 1-deoxymaltotriotityl, etc.

Methods for preparing polyhydroxy fatty acid amides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkylpolyhydroxyamine with an aliphatic fatty ester or a triglyceride in a condensation/amidation step to form the N-alkyl,N-polyhydroxy fatty acid amide product. Methods for preparing compositions containing polyhydroxy fatty acid amides are described, for example, in British Patent Specification 809,060, published February 18, 1959, Thomas Hedley & Co., Ltd.; in U.S. Patent Specification 2,965,576, issued December 20, 1960, E.R. Wilson, U.S. Patent No. 2,703,798, Anthony M. Schwartz, issued May 8, 1955; and U.S. Patent No. 1,985,424, issued December 25, 1934, Piggott.

In a process for the preparation of N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides, wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl function is N-methyl, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl, the product is prepared by reacting N-alkyl or N-hydroxyalkyl glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicates, basic potassium silicates, basic sodium aluminosilicates, and basic potassium aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mole percent to about 50 mole percent, more preferably from about 2.0 mole percent to about 10 mole percent, based on the moles of N-alkyl or N-hydroxyalkyl glucamine. The reaction is preferably carried out at about 138°C to about 170°C for typically about 20 to about 90 minutes. When triglycerides are used as the fatty ester source in the reaction mixture, the reaction is also preferably carried out using from about 1% to about 10% by weight of a phase transfer agent, calculated as a weight percent of the total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkyl polyglucosides, linear glucamide surfactant, and mixtures thereof.

Preferably, this procedure is carried out as follows:

(a) preheating the fatty ester to about 138ºC to about 170ºC;

(b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester and mixing to an extent necessary to form a two-phase liquid/liquid mixture;

(c) mixing the catalyst into the reaction mixture; and

(d) Stir for the stated reaction time.

Also preferably, when the fatty ester is a triglyceride, from about 2% to about 20%, based on the weight of the reactants, of previously formed linear N-alkyl/N-hydroxyalkyl, N-linear glucosyl fatty acid amide product is added to the reaction mixture as a phase transfer agent. This establishes the reaction, thereby increasing the reaction rate A detailed experimental procedure is given below.

The polyhydroxy "fatty acid" amide materials used herein offer the detergent formulator the advantages of being able to be made wholly or predominantly from natural, renewable, non-petrochemical starting materials and of being degradable. They also exhibit low toxicity to aquatic life.

It should be noted that the processes used to prepare the polyhydroxy fatty acid amides of formula (I) will usually also provide, along with them, amounts of non-volatile by-products such as ester amides and cyclic polyhydroxy fatty acid amide. The amount of these by-products will vary depending on the particular reactants and the process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions of the invention will be provided in such a form that the composition containing the polyhydroxy fatty acid amide 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 because they can provide rather small amounts of by-products, including such cyclic amide by-product.

Polycarboxylate builder

The compositions of the invention will comprise at least about 1% polycarboxylate builder.

The amount of polycarboxylate builder can vary widely depending on the end use of the composition and its desired physical form. Liquid formulations typically contain from about 5% to about 50%, more typically from about 5% to about 30%, by weight of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight of detergent builder. However, lower or higher amounts of builder are not intended to be excluded. Preferably, the weight ratio of the polyhydroxy fatty acid amide to the Polycarboxylate builder from about 1:10 to about 10:1, more preferably from about 5:1 to about 1:7, most preferably from about 1:1 to about 1:7.

A variety of polycarboxylate compounds can be used in the compositions of the invention. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.

Polycarboxylate builders can generally be added to the composition in acid form, but they can also be added in the form of a neutralized salt. When used in the salt form, alkali metal salts such as sodium, potassium and lithium salts, especially sodium salts, or ammonium and substituted ammonium salts (e.g. alkanolammonium salts) are preferred.

The polycarboxylate builders encompass several categories of useful materials. One important category of polycarboxylate builders is the ether polycarboxylates. A number of ether polycarboxylates have been described for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinates as set forth in U.S. Patent No. 3,128,287, Berg, issued April 7, 1964, and U.S. Patent No. 3,635,830, Lamberti et al., issued January 18, 1972.

A specific type of ether polycarboxylates which are suitable as builders in the present invention also includes those of the general formula:

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

wherein A is H or OH; BH or -O-CH(COOX)-CH₂(COOX); and X is H or a salt-forming cation. For example, in the above general formula, if A and B both represent H, then the compound is oxydisuccinic acid and its water-soluble salts. If A is OH and BH is, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX)-CH₂(COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are particularly preferred for use herein. Especially 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 described in U.S. Patent No. 4,663,071, Bush et al., issued May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those listed in U.S. Patent Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergent builders include the ether hydroxypolycarboxylates, which have the structure:

HO-[C(R)(COOM)-C(R)(COOM)-O]n-H

wherein M is hydrogen or a cation, the resulting salt of which is water soluble, preferably an alkali metal, ammonium or substituted ammonium cation, n is from about 2 to about 15 (with n preferably being from about 2 to about 10, more preferably averaging from about 2 to about 4) and each R is the same or different and is selected from hydrogen, C1-4 alkyl or substituted C1-4 alkyl (with R preferably being hydrogen).

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

Organic polycarboxylate builders also include polyacetates, such as the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid builder salts include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

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

Citric acid builders, e.g. citric acid and soluble salts thereof, polycarboxylate builders are of particular importance for liquid detergent formulations, they However, they can also be used in granular compositions. Suitable salts include the metal salts such as sodium, lithium and potassium salts, as well as ammonium and substituted ammonium salts.

Other carboxylate builders include the carboxylated carbohydrates described in U.S. Patent No. 3,723,322, Diehl, issued March 28, 1973.

Also suitable for the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds set forth in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid. Typical alkyl succinic acids have the general formula R-CH(COOH)CH2(COOH), i.e. succinic acid derivatives wherein R is a hydrocarbon, e.g. C10-C20 alkyl or alkenyl, preferably C12-C16 or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents, all of which are listed in the above-mentioned patents.

The succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmitylsuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 86200690.5/0 200 263, published on November 5, 1986.

Examples of useful builders also include sodium and potassium carboxymethyloxymalonate, -carboxymethyloxysuccinate, -cis-cyclohexane-hexacarboxylate, -cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (those polyacrylates with molecular weights up to over about 2,000 can also be used effectively as dispersants) and the copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979. These polyacetal carboxylates can be prepared by contacting a glyoxylic acid ester and a polymerization initiator under polymerization conditions. 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 described in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. 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 scaffolding materials

The compositions of the present invention may comprise, in addition to the polycarboxylate builders, auxiliary builders, including both inorganic and organic builders. Typical amounts of auxiliary builder are from about 5% to about 200% by weight of the polycarboxylate builder.

Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of silicates, carbonates (including the bicarbonates and sesquicarbonates), sulfates and aluminosilicates. Borate builders and builders containing borate-forming materials capable of providing borate during storage of the detergent or under wash conditions (hereinafter collectively referred to as "borate builders") may also be used. Preferably, borate-free builders are used in the compositions of the invention intended for use at wash temperatures below about 50°C, especially below about 40°C.

Examples of silicate builders are the alkali metal silicates, especially those with a SiO₂:Na₂O ratio in the range of 1.6:1 to 3.2:1, and layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987, HP Rieck. However, other silicates may also be useful such as magnesium silicate which may serve in granular formulations as a flow aid, as a stabilizer for oxygen bleaches, and as a component of the foam control system.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate and mixtures thereof with ultrafine calcium carbonate, as described in German Patent Application No. 2 321 001, published on November 15, 1973.

Aluminosilicate builders are particularly useful for use in concentrates containing polycarboxylate builders of the present invention. Aluminosilicate builders are of paramount importance in most of the heavy-duty detergent compositions currently on the market and can also be an important builder ingredient in liquid detergent formulations. Aluminosilicate builders include those of the empirical formula:

Mz(zAlO₂.ySiO₂),

wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material has a magnesium ion exchange capacity of at least about 50 mg equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates have the formula:

Naz[(AlO₂)z(SiO₂)y].xH₂O,

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

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be naturally occurring or synthetically obtained aluminosilicates. A process for preparing aluminosilicate ion exchange materials is described in U.S. Patent No. 3,985,669, Krummel et al., issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are known as zeolites and are available under the names Zeolite A, Zeolite P (B) and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂O,

where x is from about 20 to about 30, especially about 27. This zeolite is known as zeolite A. Preferably, the aluminosilicate has a particle size in the range of 0.1 to 10 µm.

Phosphate and phosphonate builders may be added, although it is generally desirable to replace these builders with polycarboxylate or other builders. Therefore, when present, they are preferably present only in small amounts. Preferably, the phosphate builder comprises less than about 10%, more preferably less than about 5%, most preferably substantially 0% by weight of the total builder in the composition. Specific examples of polyphosphates are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate 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 salts of ethane-1-hydroxy-1,1-diphosphonate, especially the sodium and potassium salts, the water-soluble salts of methylenediphosphonic acid, e.g. the trisodium and tripotassium salts, and the water-soluble salts of substituted methylenediphosphonic acids, such as trisodium and tripotassium methylidene, isopropylidene, benzylmethylidene and halomethylidene phosphonates. Phosphonate builder salts of the types mentioned above are described in U.S. Pat. Nos. 3,159,581 and 3,213,030, issued December 1, 1964 and October 19, 1965, respectively, to Diehl; U.S. Pat. No. 3,422,021, issued January 14, 1969, to Roy; and in U.S. Pat. Nos. 3,400,148 and 3,422,137, issued September 3, 1968 and January 14, 1969, respectively, to Quimby.

A preferred builder system for granular compositions comprises a mixture of about 5% to about 50% zeolite (preferably zeolite A) and about 5% to about 50% citrate (preferably sodium citrate), which percentages are based on the total builder in the mixture calculated on an anhydrous basis.

Other organic builders known in the art may also be used. For example, monocarboxylic acids and soluble salts thereof having long hydrocarbon chains may also be used. These would include materials generally referred to as "soaps". Chain lengths of C10-C20 are typically used. The hydrocarbon moieties may be saturated or unsaturated.

Detersive surfactant system

In addition to the polyhydroxy fatty acid amide and the polycarboxylate builder, the compositions of the present invention contain one or more additional surfactants, which may be anionic, cationic or nonionic. Typically, the surfactant system will contain one or more anionic and/or nonionic surfactants in addition to the polyhydroxy fatty acid amide. The amount of additional detersive surfactant present is typically at least about 1%, preferably from about 3% to about 40%, more preferably from about 5% to about 30%, by weight of the detergent composition. The use of anionic surfactants, such as anionic sulfate or sulfonate surfactants, or mixtures thereof, is particularly contemplated. Suitable surfactants are described below.

Alkyl ester sulfonate surfactant

Herein, alkyl ester sulfonate surfactants 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 be natural fatty substances, such as those obtained from tallow, palm oil and coconut oil, among others.

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

wherein R3 is a C8-C20 hydrocarbyl, preferably an alkyl, or a combination thereof, R4 is a C1-C6 hydrocarbyl, preferably an alkyl, or a combination thereof, and M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as methyl, dimethyl, trimethyl and quaternary ammonium cations, e.g. tetramethylammonium and dimethylpiperidinium, and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine. Preferably, R³ is C₁₀-C₁₆alkyl and R⁴ is methyl, ethyl or isopropyl. Particularly preferred are the methyl ester sulfonates wherein R³ is C₁₄-C₁₆alkyl.

Alkyl sulfate surfactant

Alkyl sulfate surfactants herein are water soluble salts or acids of the formula ROSO₃M, where R is preferably a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl moiety, 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) or substituted or unsubstituted ammonium cations such as methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations, e.g. tetramethylammonium and dinethylpiperidinium cations and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and mixtures thereof, and the like. Typically, C₁₂₋₁₆ alkyl chains are preferred for lower wash temperatures (e.g., below about 50°C) and C₁₆₋₁₈ alkyl chains for higher wash temperatures (e.g., above about 50°C).

Alkoxylated alkyl sulfate surfactant

Alkoxylated alkyl sulfate surfactants herein are water-soluble salts or acids of the formula RO(A)mSO₃M, wherein R is an unsubstituted C₁₀₋₂₄ alkyl or hydroxyalkyl group having a C₁₀₋₄ alkyl moiety, preferably a C₁₂₋₂₄ alkyl or hydroxyalkyl, more preferably C₁₂₋₀₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy moiety, m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or a cation which is, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium et al.), an ammonium or substituted ammonium cation. Ethoxylated alkyl sulfates as well as propoxylated alkyl sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are C₁₂-C₁₈ alkyl polyethoxylate (1,0) sulfate, C₁₂-C₁₈ alkyl polyethoxylate (2,25) sulfate, C₁₂-C₁₈ alkyl polyethoxylate (3,0) sulfate and C₁₂-C₁₈ alkyl polyethoxylate (4,0) sulfate, wherein M is conveniently selected from sodium and potassium.

Other anionic surfactants

Other anionic surfactants suitable for detergent purposes may also be incorporated in the compositions of the invention. These may be salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soaps, linear C9-C20 alkylbenzene sulfonates, primary or secondary C8-C22 alkane sulfonates, C8-C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis product of alkaline earth metal citrates, e.g. as contained in British Patent Specification No. 1,082,179; Alkylglycerolsulfonates, fatty acylglycerolsulfonates, fatty oleylglycerolsulfates, alkylphenolethyleneoxideethersulfates, paraffinsulfonates, alkylphosphates, Isethionates such as the N-acylisethionates, acyltaurates, fatty acid amides of methyltauride, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (particularly saturated and unsaturated C₁₂-C₁₈ monoesters), diesters of sulfosuccinates (particularly saturated and unsaturated C₆-C₁₄ diesters), N-acylsarcosinates, sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic non-sulfated compounds being described below), branched primary alkyl sulfates, alkylpolyethoxycarboxylates such as those of the formula RO(CH₂CH₂O)KCH₂COO⁻M⁺, wherein R is a C₈-C₂₂ alkyl k is an integer from 1 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 hydrogenated resin acids present in or obtained from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vols. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also included in U.S. Patent 3,929,678, issued December 30, 1975, Laughlin et al., at column 23, line 58 to column 29, line 23.

Non-ionic surfactants

Suitable nonionic detergent surfactants are described in U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6. Exemplary, non-limiting classes of useful nonionic surfactants are set forth below.

1. The polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. In general, the polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group of about 6 to about 12 carbon atoms in either a linear chain or branched chain structure with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available Nonionic surfactants of this type include Igepal CO-630, which is sold by GAF Corporation, and Triton X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates, e.g., alkylphenol ethoxylates.

2. The condensation products of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be either linear or branched, primary or secondary and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols which have an alkyl group with about 10 to about 20 carbon atoms with 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 linear secondary C11-C15 alcohol with 9 moles of ethylene oxide), Tergitol 24-L-6 NMW (the condensation product of primary C12-C14 alcohol with 6 moles of ethylene oxide having a narrow molecular weight distribution), both of which are sold by Union Carbide Corporation; Neodol 45-9 (the condensation product of linear C₁₄-C₁₅ alcohol with 9 moles of ethylene oxide), Neodol 23-6.5 (the condensation product of linear C₁₂-C₁₃ alcohol with 6.5 moles of ethylene oxide), Neodol 45- 7 (the condensation product of linear C₁₄-C₁₅ alcohol with 7 moles of ethylene oxide), Neodol 45-4 (the condensation product of linear C₁₄-C₁₅ alcohol with 4 moles of ethylene oxide), which are sold by the Shell Chemical Company, and Kyro EOB (the condensation product of C₁₃-C₁₅ alcohol with 9 moles of ethylene oxide) sold by The Procter & Gamble Company. These surfactants are commonly referred to as alkyl ethoxylates.

3. The condensation products of ethylene oxide with a hydrophobic starting material which is formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is insoluble in water. The addition of polyoxyethylene groups to these hydrophobic Part tends to increase the overall water solubility of the molecule and the liquid character of the product is maintained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, corresponding to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Pluronic surfactants sold by BASF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide with ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and an excess of 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 polyoxyethylene and has a molecular weight of from about 5000 to about 11000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic compounds sold by BASF.

5. Semi-polar nonionic surfactants are a special category of nonionic surfactants which include water-soluble amine oxides containing an alkyl radical of about 10 to about 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups having about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl radical of about 10 to about 18 carbon atoms and 2 radicals selected from the group consisting of alkyl groups and hydroxyalkyl groups having about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing an alkyl radical of about 10 to about 18 carbon atoms and a radical selected from alkyl and hydroxyalkyl groups having about 1 to about 3 carbon atoms.

Semi-polar, non-ionic detergent surfactants include the amine oxide surfactants of the formula

R³(OR⁴)x (R⁵)₂,

wherein R3 represents an alkyl, hydroxyalkyl or alkylphenyl group having from about 8 to about 22 carbon atoms or mixtures thereof; R4 is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms or a mixture thereof; x is from 0 to about 3; and each R5 represents an alkyl or hydroxyalkyl group having from about 1 to about 3 carbon atoms or a polyethylene oxide group having from about 1 to about 3 ethylene oxide groups. The R5 groups may be bonded to one another, e.g., through an oxygen or nitrogen atom, to form a ring structure.

These surface-active amine oxides include in particular C₁₀-C₁₈-alkyldimethylamine oxides and C₈-C₁₂-alkoxyethyldihydroxyethylamine oxides.

6. Alkyl polysaccharides contained in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, which contain a hydrophobic group having from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide group, e.g., a hydrophilic polyglycosidic group, having 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 saccharide units. Any reducing saccharide having 5 or 6 carbon atoms can be used, e.g., the glucosyl residues can be substituted with glucose, galactose and galactosyl residues. (Optionally, the hydrophobic group may be attached at the 2-, 3-, 4- or other positions so as to give a glucose or galactose, as opposed to a glucoside or galactoside.) The intersaccharide linkages may be, e.g., between the 1-position of the additional saccharide units and the 2-, 3-, 4- and/or 6-positions of the preceding saccharide units.

Optionally and less desirably, a polyalkylene oxide chain may be present connecting the hydrophobic moiety and the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, having from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a linear, saturated alkyl group. The alkyl group may contain up to about 3 hydroxy groups and/or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide groups. Suitable alkyl polysaccharides are the octyl, nonyldecyl, undecyl, dodecyl, 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 alkyl polyglycosides have the formula

R²O(CnH2nO)t(glycosyl)x,

wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein 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 alkylpolyethoxyalcohol is first formed and then reacted with glucose or a glucose source to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the 2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position, of the preceding glycosyl units.

7. Surface-active fatty acid amides with the formula:

R6; - - N(R⁷)₂,

wherein R6 is an alkyl group having from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R7 is selected from hydrogen, C1-C4 alkyl, C1-C4 hydroxyalkyl and (C2H4O)xH, where x varies from about 1 to about 3.

Preferred amides are C8-C20 ammonia amides, monoethanol amides, diethanol amides and isopropanol amides.

In general, preferred nonionic agents for use in addition to the polyhydroxy fatty acid amides include Alkyl ethoxylates, alkyl polyglycosides and alkylphenol ethoxylates. These can be used in addition to any anionic surfactants present in the composition.

Cationic surfactants

Cationic detersive surfactants may also be included in the detergent compositions of the present invention. Cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halides and those surfactants of the formula:

[R²(OR³)y][R⁴(OR³)y]₂R⁵N⁺X⁻,

wherein R² represents an alkyl or alkylbenzyl 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 C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl, ring structures formed by the connection of the two R⁴ groups, -CH₂CHOH-CHOHCOR⁶CHOHCH⁴OH, wherein R⁴ is represents any hexose or any hexose polymer having a molecular weight of less than about 1000, and is hydrogen when y is not 0; R5 has the same meaning as R4 or represents an alkyl chain wherein the total number of carbon atoms of R2 plus R5 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 represents any compatible anion.

Other cationic surfactants useful herein are also described in U.S. Patent No. 4,228,044, Cambre, issued October 14, 1980.

Other surfactants

Ampholytic surfactants may be included in the detergent compositions herein. These surfactants may be broadly described as aliphatic derivatives of secondary or tertiary amines or as aliphatic derivatives of heterocyclic, secondary and tertiary amines, wherein the aliphatic radical is linear 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 of the aliphatic substituents has an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate. For examples of ampholytic surfactants, see U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18 to 35 (which is incorporated herein by reference).

Zwitterionic surfactants may also be included in the detergent compositions herein. These surfactants may 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. For examples of zwitterionic surfactants, see U.S. Patent No. 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 through column 22, line 48 (which is incorporated herein by reference).

Ampholytic and zwitterionic surfactants are generally used in conjunction with one or more anionic and/or nonionic surfactants.

Enzymes

Detersive enzymes may be included in the non-liquid detergent formulations for a variety of purposes including, for example, the removal of protein, carbohydrate or triglyceride based stains and the prevention of dye transfer. The enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases and mixtures thereof. Other enzymes may additionally be included. They may be of any suitable origin such as plant, animal, bacterial or fungal and yeast origin. However, their selection will be determined by several factors such as pH activity and/or stability optima, heat stability, resistance to effective detergents, to builders and the like. In this regard, 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 certain strains of B. subtilis and B. licheniformis. Another suitable protease is derived from a Bacillus strain which has its maximum activity over the pH range of 8-12, which was developed by Novo Industries A/S and is sold under the registered trade name Esperase. The production of this enzyme and analogous enzymes is described in Novo's British Patent No. 1 243 784. Commercially available proteolytic enzymes suitable for the removal of protein-based stains include those sold under the trade names ALCALASE AND SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (Netherlands).

Of interest in the category of proteolytic enzymes 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 on January 9, 1985. Protease B is a proteolytic enzyme which differs from protease A in that it has a leucine instead of tyrosine at position 217 of its amino acid sequence. Protease B is described in European Patent Application No. 87303761.8, filed on April 28, 1987, which is incorporated herein by reference. Methods for preparing protease B are also set out in EP-A-0 130 756, Bott et al., published on January 9, 1985.

Amylases include, for example, α-amylases obtained from a certain strain of B. licheniformis, which are described in more detail in British Patent Specification No. 1 296 839 (Novo). Amylolytic proteins include, for example, RAPIDASE , International Bio-Synthetics, Inc., and TERMAMYL , Novo Industries.

The cellulases usable in the present invention include both bacterial and fungal cellulases. Preferably they will have an optimum pH between 5 and 9.5. Suitable cellulases are described in US Patent 4,435,307, Barbesgoard et al., published March 6, 1984, which discloses fungal cellulase from Humicola insolens. Suitable cellulases are also described in GB-A-2 075 028; GB-A-2 095 275 and DE-OS-2 247 832.

Examples of such cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), in particular the Humicola strain DSM 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 mollusk (Dolabella auricula Solander).

Suitable lipase enzymes for use in a detergent include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas spp. ATCC 19.154, described in British Patent Specification No. 1,372,034. Suitable lipases include those which show a positive immunological cross-reaction with the antibody to the lipase produced by the microorganism Pseudomonas flurescens IAM 1057. This lipase and a process for its purification are described in Japanese Patent Application No. 53-20487, laid open 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 method of Ouchterlony (Acta. Med. Scan., 133, pp. 76-79 (1950)). These lipases and a method for their immunological cross-reaction with Amano-P are also described in U.S. Patent No. 4,707,291, Thom et al., issued November 17, 1987. Typical examples thereof are Amano-P lipase, the lipase from Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B), the lipase from Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES), lipases from Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., Netherlands, and lipases from Pseudomonas gladioli.

Peroxidase enzymes are used in conjunction with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide etc. They are used for "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from substrates during washing operations to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and halogen peroxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are contained, for example, in the International PCT application WO 89/09813 of O. Kirk, assigned to Novo Industries A/S and published on October 19, 1989 as EP-A-0 424 398.

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

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

In granular detergents, the enzymes are preferably coated with additives that are inert to the enzymes or spray crystallized to minimize dust formation and improve storage stability. to do this are well known in the art. In liquid formulations, an enzyme stabilization system is preferably used.

Bleaching compounds - bleaches and bleach activators

The detergent compositions herein may include bleaching agents or bleaching compositions comprising a bleaching agent and one or more bleach activators. When bleaching compounds are present, they will typically be present in amounts 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. When present, the amount of bleach activators will typically be from 0.1% to about 60%, 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 for fabric cleaning, hard surface cleaning, or other cleaning purposes that are already known or become known. These include oxygen bleaching agents as well as other bleaching agents. For wash conditions below about 50°C, especially below about 40°C, it is preferred that the compositions herein contain no borate or no material that can form borate in situ under detergent storage conditions or wash conditions (i.e., no borate-forming material). Therefore, under these conditions, it is preferred that a non-borate-containing and non-borate-forming bleach be used. Preferably, the detergents intended for use at these temperatures are substantially free of borate or borate-forming material of any type. As used herein, "substantially free of borate and borate-forming material" is intended to mean that the composition contains no more than about 2% by weight of borate-containing and borate-forming material, preferably no more than 1%, more preferably 0%.

One category of bleaching agents which may be used includes percarboxylic acid bleaching agents and their salts. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are described in U.S. Patent No. 4,483,781, Hartmann, issued November 20, 1984, U.S. Patent Application No. 740,446, Burns et al., filed June 3, 1985, European Patent Application No. 0,133,354, Banks et al., published February 20, 1985, and U.S. Patent No. 4,412,934, Chung et al., issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent No. 4,634,551, issued January 6, 1987, Burns et al.

Another category of bleaching agents which may be used includes the halogen bleaching agents. Examples of hypohalite bleaching agents include, for example, trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro- and N-bromoalkanesulfonamides. Such materials are usually added in amounts of from 0.5% to 10% by weight of the finished product, preferably from 1% to 5% by weight.

Peroxygen bleaches that are not boron compounds may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

Peroxygen bleaches are preferably combined with bleach activators, which in aqueous solution (i.e. during the washing process) lead to the in situ formation of the peroxyacid corresponding to the bleach activator.

Preferred bleach activators incorporated into compositions of the present invention have the general formula:

R - - L,

wherein R is an alkyl group having about 1 to about 18 carbon atoms, wherein the longest linear alkyl chain extending from carbonyl carbon, contains from about 6 to about 10 carbon atoms, and L represents a leaving group whose conjugate acid has a pKa in the range of about 4 to about 13. These bleach activators are described in U.S. Patent No. 4,915,854, issued April 10, 1990, Mao et al., and in U.S. Patent No. 4,412,934.

Bleaching agents other than oxygen bleaches are also known in the art and can be used in the present invention. One type of non-oxygen bleach of particular interest includes photoactivated bleaches such as sulfonated zinc and aluminum phthalocyanines. These materials can be deposited on the substrate during the laundering process. Upon exposure to light in the presence of oxygen, such as when hanging the garments to dry in daylight, the sulfonated zinc phthalocyanine is activated and, as a result, the substrate is bleached. A preferred zinc phthalocyanine and photoactivated bleaching process are described in U.S. Patent No. 4,033,718, issued July 5, 1977, Holcombe et al. Typically, detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Polymeric dirt solvent

Any of the soil release agents known to those skilled in the art can be used to practice this invention. Polymeric soil release agents are characterized by having both hydrophilic segments to render the surface of hydrophobic fibers, such as polyester and nylon, hydrophilic, and hydrophobic segments to deposit on hydrophobic fibers and remain bound thereto during the completion of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This can allow stains that occur following treatment with the soil release agent to be more easily removed in the subsequent laundering process.

Although it may be useful to use polymeric soil release agents in any of the detergent compositions herein, particularly those compositions used for laundry or other applications, where removal of grease and oil from hydrophobic surfaces is required, the presence of polyhydroxy fatty acid amide in detergent compositions that also contain anionic surfactants can improve the performance of many of the more commonly used types of polymeric soil release agents. Anionic surfactants interfere with the ability of certain soil release agents to deposit and bind to hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic segments or hydrophobic segments that interact with the anionic surfactant.

The compositions of the invention for which improved polymeric soil release agent performance can be achieved by the use of polyhydroxy fatty acid amide are those which contain an anionic surfactant system, a soil release agent which interacts with the anionic surfactant, and a soil release agent performance enhancing amount of polyhydroxy fatty acid amide (PFA), wherein: (I) the interaction - with the anionic surfactant - between the soil release agent and the anionic surfactant system of the detergent composition is determined by comparing the extent of deposition of the soil release agent (SRA) on hydrophobic fibers (e.g. polyester) in aqueous solution between (A) a "control experiment" wherein the deposition of the SRA of the detergent composition in aqueous solution in the absence of the other detergent ingredients and (B) a test experiment wherein "SRA and anionic surfactant" are employed, wherein the same type and amount of the anionic surfactant system used in the detergent composition is combined with the SRA in aqueous solution, in the same weight ratio of SRA to the anionic surfactant system of the detergent composition, wherein a reduced deposit in (B) as compared to (A) indicates an interaction with the anionic surfactant; and (II) whether the detergent composition contains an amount of polyhydroxy fatty acid amide which increases the performance of the soil release agent can be solved by comparing the SRA deposition of Test Run (B) employing SRA and anionic surfactant with the soil release agent deposition in (C), a Test Run employing "SRA, anionic surfactant and PFA", wherein the same type and amount of polyhydroxy fatty acid amide of the detergent composition is combined with the soil release agent and anionic surfactant system corresponding to the aforementioned Test Run employing SRA and anionic surfactant, wherein improved soil release agent deposition in Test Run (C) as compared to Test Run (B) indicates that an amount of polyhydroxy fatty acid amide is present which enhances the performance of the soil release agent. For the purposes of the invention, the tests herein should be conducted in the aqueous solution at concentrations of the anionic surfactant which are above the critical micelle concentration (CMC) of the anionic surfactant and preferably above about 100 ppm. The concentration of the polymeric soil release agent should be at least 15 ppm. A polyester fabric rag should be used as the hydrophobic fiber source. For each test, identical rags are immersed in aqueous solutions at 35°C and agitated for a period of 12 minutes, then removed and analyzed. The extent of deposition of the polymeric soil release agent can be determined by radiolabeling the soil release agent prior to treatment and then subjecting it to radiochemical analysis according to methods known in the art.

As an alternative to the radiochemical analysis method discussed above, soil release agent deposition may alternatively be determined in the above test runs (i.e., in Test Runs A, B, and C) by determining the ultraviolet (UV) light absorbance of the test solutions according to methods well known in the art. Reduced UV absorbance in the test solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition. Those skilled in the art will appreciate that UV analysis should not be used for test solutions containing types and amounts of materials that cause excessive impairment of UV absorption, such as high amounts of surfactants with aromatic groups (e.g. alkylbenzenesulfonates, etc.)

Therefore, by a "soil release agent performance enhancing amount" of polyhydroxy fatty acid amide is meant an amount of such surfactant which will increase the deposition of the soil release agent on the hydrophobic fibers as described above, or an amount at which, in the next subsequent cleaning process, an increased grease/oil cleaning performance can be achieved on the fabrics washed in the detergent composition of the invention.

The amount of polyhydroxy fatty acid amide required to increase deposition will vary with the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent selected, and the particular polyhydroxy fatty acid amide selected. Generally, the 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 the anionic surfactant. Such compositions should generally contain at least about 1%, preferably at least about 3%, of the polyhydroxy fatty acid amide, although this is not intended to be limiting.

The polymeric soil release agents for which the performance is enhanced by polyhydroxy fatty acid amide in the presence of anionic surfactant include those soil release agents which comprise: (a) one or more nonionic hydrophilic components consisting essentially of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein said hydrophilic segment does not comprise an oxypropylene moiety unless it is attached to adjacent residues 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 has a sufficient amount of oxyethylene units such that the hydrophilic component has a hydrophilicity sufficient to increase the hydrophilicity of conventional synthetic polyester fiber surfaces upon deposition of the soil release agent on such surface, which hydrophilic segments preferably contain at least about 25% oxyethylene units and more preferably, particularly for those components having from about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobic components comprising (i) C₃-oxyalkylene terephthalate segments, wherein, in the case where said hydrophobic components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate units to the C₃-oxyalkylene terephthalate units is about 2:1 or less, (ii) C₄-C₆-alkylene or oxy-C₄-C₆-alkylene segments or mixtures thereof, (iii) poly(vinyl ester) segments, preferably poly(vinyl acetate), having a degree of polymerization of at least 2, or (iv) C₁-C₄-alkyl ether or C₄-hydroxyalkyl ether substituents or mixtures thereof, wherein said substituents are 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 contain a sufficient amount of C₁-C₄-alkyl ether and/or C₄-hydroxyalkyl ether units to deposit on the conventional synthetic polyester fiber surfaces and still contain a sufficient amount of hydroxyl groups, once bound to such a conventional synthetic fiber surface, to increase the hydrophilicity of the fiber surface, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to about 200, although higher degrees of polymerization may be used, preferably from 3 to about 150, more preferably from 6 to about 100. Suitable hydrophobic oxy-C₄-C₆ alkylene segments include, but are not limited to, end groups of polymeric Soil release agents such as MO₃S(CH₂)NOCH₂CH₂O-, where M is sodium and n is an integer from 4 to 6, as described in U.S. Patent 4,721,580, issued January 26, 1988, Gosselink.

Polymeric soil release agents useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, block copolymers of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, and the like.

Cellulose derivatives that act as soil release agents are commercially available and include hydroxycellulose ethers such as Methocel (Dow).

Cellulose-based soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose, such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose. A variety of cellulose derivatives useful as soil release polymers are described in U.S. Patent No. 4,000,093, issued December 28, 1976, Nicol et al.

Soil release agents characterized by hydrophobic poly(vinyl ester) segments include graft copolymers of poly(vinyl ester), e.g. C1-C6 vinyl ester, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones. Such materials are known in the art and are described in European patent application 0 219 048, published April 22, 1987, Kud et al. Suitable commercially available soil release agents of this type include the Sokalan type material, e.g. Sokalan HP-22, available from BASF (West Germany).

One type of preferred soil release agent is formed from a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers consist of repeating units of ethylene terephthalate and PEO terephthalate in a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35:65, which PEO Terephthalate units contain 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. Reference is made to U.S. Patent No. 3,959,230, Hays, issued May 25, 1976, which is incorporated herein by reference. Reference is also made to U.S. Patent No. 3,893,929, Basadur, issued July 8, 1975, which describes similar copolymers.

Another preferred polymeric soil release agent is a polyester having repeating units of ethylene terephthalate units comprising from 10% to 15% by weight of ethylene terephthalate units together with from 90% to 80% by weight of polyoxyethylene terephthalate units derived from a polyoxyethylene glycol having an average molecular weight of from 300 to 5,000 and wherein the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymeric composition is from 2:1 to 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 making them are more fully described in U.S. Patent No. 4,702,857, issued October 27, 1987, Gosselink.

Another preferred polymeric soil release agent is formed from a sulfonated product of a substantially linear ester oligomer composed of an oligomeric ester backbone of repeating terephthaloyl and oxyalkyleneoxy units and terminal moieties covalently bonded to the backbone, which soil release agent is obtained from allyl alcohol ethoxylate, dimethyl terephthalate and 1,2-propylene diol, wherein after sulfonation the terminal moieties of each oligomer have an average total of from about 1 to about 4 sulfonate groups. These soil release agents are more fully described in U.S. Patent 4,968,451, issued November 6, 1990, J.J. Scheibel and E.P. Gosselink, and in U.S. Patent Application Serial No. 07/474,709, filed January 29, 1990.

Other suitable polymeric soil release agents include the ethyl or methyl capped 1,2-propylene terephthalate polyoxyethylene terephthalate polyesters U.S. Patent 4,711,730, issued December 8, 1987, Gosselink et al., the anionically end-capped oligomeric esters of U.S. Patent 4,721,5801, issued January 26, 1988, Gosselink, wherein the anionic end groups comprise sulfopolyethoxy groups derived from polyethylene glycol (PEG), the oligomeric block polyester compounds of U.S. Patent 4,702,857, issued October 27, 1987, Gosselink, which have polyethoxy end groups of the formula X-(OCH₂CH₂)n-, wherein n is from 12 to about 43 and X is C₁-C₄ alkyl or, preferably, methyl.

Additional polymeric soil release agents include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989, Maldonado et al., which describes terephthalate esters containing anionic end groups, particularly sulfoaroyl end groups. The terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units. Among the soil release polymers of U.S. Patent 4,877,896 are materials containing hydrophilic polyoxyethylene components or C3 oxyalkylene terephthalate (propylene terephthalate) repeating units which are within the scope of the hydrophobic components of (b) (i) above. It is the polymeric soil release agents characterized by one or both of these criteria where the inclusion of the polyhydroxy fatty acid amides therein in the presence of anionic surfactants is of particular benefit.

When employed, soil release agents will generally be from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%, by weight of the detergent compositions of the present invention.

Chelating agents

The detergent compositions herein may also optionally contain one or more iron and manganese chelating agents as a builder additive. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, all of which are defined below. Without intending to be bound by theory, It is believed that the advantage of these materials is partly due to their extraordinary ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

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

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is from 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Useful aminocarboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediaminetetrapropionates, triethylenetetraaminehexaacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium and substituted ammonium salts thereof, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when at least small amounts of total phosphorus are permitted in detergent compositions. Compounds having one or more, preferably at least two, units of the substructure

where M is hydrogen, alkali metal, ammonium or substituted ammonium, and x is from 1 to about 3, preferably 1, are suitable and include ethylenediaminetetrakis(methylenephosphonates), nitrilotris(methylenephosphonates) and diethylenetriaminepentakis(methylenephosphonates). Preferably, these aminophosphonates 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 of the invention. These materials may be compounds having the general formula

wherein at least one substituent R is -SO₃H or -COOH, or soluble salts thereof and mixtures thereof. In U.S. Patent 3,812,044, issued May 21, 1974, Connor et al., polyfunctionally substituted aromatic chelating and complexing agents are included. 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 salts (e.g., mono- or triethanolamine salts).

When used, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay soil removal/anti-settlement agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal/anti-redeposition properties. Granular detergent compositions containing these compounds preferably contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01% to about 5%. These compounds are selected from the group consisting of:

(1) ethoxylated monoamines with the formula:

(X-L-)-N-(R²)₂

(2) ethoxylated diamines with the formula:

or

(X-L-)₂-N-R¹-N-(R²)₂

(3) ethoxylated polyamines with the formula:

(4) ethoxylated amine polymers with the general formula:

and

(5) mixtures thereof;

where A¹ is

or -O-; R is H or C1-C4 alkyl or hydroxyalkyl; R1 is C2-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or a C2-C3 oxyalkylene group having from 2 to about 20 oxyalkylene units, with the proviso that no ON bonds are formed; each R2 is C1-C4 alkyl or hydroxyalkyl, the group is -LX, or two R2 together form the group (CH2)r-A2-(CH2)s-, wherein A2 is -O- 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 a mixture thereof; R³ is a substituted C₃-C₁₂ alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having p-substitution sites R4 is C1-C12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or a C2-C3 oxyalkylene group having from 2 to about 20 oxyalkylene units, with the proviso that no OO or ON bonds are formed; L is a hydrophilic chain containing the polyoxyalkylene group -{(R5O)m(CH2CH2O)n]-, wherein R5 is C3-C4 alkylene or hydroxyalkylene and m and n are numbers such that the group -(CH2CH2O)n- comprises at least about 50% by weight of said polyoxyalkylene group; for said monoamines, m is from 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 R¹ is C₂-C₃ alkylene, hydroxyalkylene or alkenylene, and is at least about 3 when R¹ 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 + z is at least 2. The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal/anti-redeposition agents is formed by the cationic compounds contained in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/anti-redeposition agents which may be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers contained in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in U.S. Patent No. 4,548,744, Connor, issued October 22, 1985.

Other clay soil removal and/or anti-redeposition agents known in the art may be included in the compositions may also be used herein. Another type of preferred anti-redeposition agent comprises the carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersants

Polymeric dispersants can be advantageously employed in the compositions of the present invention. These materials can help control calcium and magnesium hardness. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.

Polycarboxylate materials which can be employed herein as the polymeric dispersant are those polymers or copolymers which contain at least about 60% by weight of segments of the general formula

wherein X, Y and Z are each selected from 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 M 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 which 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 of monomeric segments which do not contain carboxylate radicals, such as vinyl methyl ether, styrene, ethylene, and others, in the polymeric polycarboxylates is useful herein, provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be obtained from acrylic acid. Such acrylic acid-based polymers useful in the present invention 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 preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can be, for example, the alkali metal, ammonium, and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions is described, for example, in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967.

Acrylic acid/maleic acid based copolymers can also be used as a preferred component of the dispersant. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the 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 segments 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 on December 15, 1982.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG can act as both a dispersant and a clay soil removal/anti-redeposition agent. Typical molecular weights for these purposes range 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.

Brightener

Any optical brighteners or other brightening or whitening agents known in the art may be incorporated into the detergent compositions herein.

The selection of brightener used in detergent compositions will depend on a number of factors such as the type of detergent, the nature of the other components present in the detergent composition, the temperatures of the wash water, the degree of agitation and the ratio of the material to be washed to the drum size.

The choice of brightener also depends on the type of material to be cleaned, e.g. cotton, synthetic fabrics, etc. Since most laundry detergent products are used to clean a variety of fabrics, the detergent compositions should contain a mixture of brighteners that will be effective on a variety of fabrics. It is of course necessary that the individual components of such a brightener mixture are compatible.

Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which may include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered ring heterocycles and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, published by John Wiley & Sons, New York (1982).

Stilbene derivatives which may be useful in the present invention include, but are not necessarily limited to, derivatives of bis(triazinyl)aminostilbene; 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 that may be useful in the present invention can be prepared from 4,4'-diaminostilbene-2,2'-disulfonic acid.

Coumarin derivatives that may be useful in the present invention include, but are not necessarily limited to, derivatives substituted at the 3-position, the 7-position, and 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 derivatives; naphthalenedicarboxylic 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, styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles and styrylpolyphenyls as described on page 77 of the Zahradnik reference.

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

Another class of optical brighteners which may be useful in the present invention are the derivatives of dibenzothiophene-5,5-dioxide described on pages 741-749 in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 3, pp. 737-750 (John Wiley & Son, Inc., 1962), 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 subclassified into monoazoles and bisazoles. Examples of monoazoles and bisazoles are described in the Kirk-Othmer reference.

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

In addition to the brighteners already described, various agents may also be useful as brighteners. Examples of such various agents are described on pages 93-95 of the Zahradnik reference and include 1- hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene; 4,5-diphenylimidazolonedisulfonic acid; and derivatives of pyrazolinequinoline.

Other specific examples of optical brighteners which may be useful in the present invention are those set forth in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the Phorwhite series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba-Geigy; Arctic White CC and Arctic White CWD available from Hilton-Davis, Italy; the 2-(4-styrylphenyl)-2H-naphthol[1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)stilbenes; 4,4'-bis(styryl)bisphenyls; and the γ-aminocoumarins. Specific examples of these brighteners include 4-methyl-7- diethylaminocoumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenylpyrazoline; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styrylnaphth[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 described in U.S. Patent No. 3,646,015, issued February 29, 1972, Hamilton.

Foam suppressants

Compounds known or known to reduce or suppress foam formation may be used in the compositions of the present invention. The incorporation of such materials, hereinafter referred to as "suds suppressors," may be desirable because the polyhydroxy fatty acid amide surfactants therein may increase the foam stability of the detergent compositions. Suppression of sudsing may be of particular interest when the detergent compositions contain a relatively high-sudsing surfactant in conjunction with the polyhydroxy fatty acid amide surfactant. Suds suppression is particularly desirable for compositions intended for use in automatic front-loading washing machines. These machines are typically characterized by having drums containing the laundry and wash water which have a horizontal axis and rotation about the axis. This type of agitation may result in high sudsing and, consequently, reduced cleaning performance. The use of suds suppressors may also be of particular importance under hot water wash conditions and under conditions of high surfactant concentration.

A wide variety of materials can be used as suds suppressors in the compositions of the present invention. Suds suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed., Vol. 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Patent No. 2,954,347, issued September 27, 1960, Wayne St. John. The monocarboxylic fatty acids and salts thereof for use as suds suppressors typically have hydrocarbon chains of from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include the alkali metal salts, such as sodium, potassium and lithium salts, and the ammonium and alkanolammonium salts. These Materials represent a preferred category of foam suppressors for detergent compositions.

The detergent compositions may also contain foam suppressors which are not surfactants. These include, for example: hydrocarbons with a high molecular weight such as paraffin, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀ ketones (e.g. stearone), among others. Other antifoaming agents include N-alkylated aminotriazines, such as tri- to hexaalkylmelamines or di- to tetraalkyldiaminechlorotriazines, which are formed as products of cyanuric chloride with two or three moles of a primary or secondary amine having 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate esters and monostearyl dikali metal (e.g. Na, K, Li) phosphates. The hydrocarbons such as paraffin and haloparaffin can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure and will have a pour point in the range of about -40°C to about 5°C and a boiling point minimum of not less than about 110°C (at atmospheric pressure). It is also known to use waxy hydrocarbons, preferably those having a melting point below about 100°C. The hydrocarbons represent a preferred category of suds suppressors for detergent compositions. Hydrocarbons as suds suppressors are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981, Gandolfo et al. 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 discussion of foam suppressants is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of foam suppressors which are not surfactants comprises silicones as foam 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 or supported on the silica. Silicones as foam suppressors are well known in the art and are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981, Gandolfo et al., and European Patent Application No. 89,307,785.9, published February 7, 1990, Starch, MS.

Other silicones as foam suppressors are described in US Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane oils.

Mixtures of silicone and silanized silicon dioxide are described, for example, in German patent application DOS 2 124 526. Silicones as antifoaming and anti-foaming agents in granular detergent compositions are contained in US Pat. No. 3,933,672, Bartolotta et al., and US Pat. No. 4,652,392, Baginski et al., issued March 24, 1987.

An exemplary silicone-based foam suppressor for use in the present invention is represented by a foam suppressing amount of a foam controlling agent consisting essentially of:

(i) polydimethylsiloxane oil having a viscosity of from about 2 x 10⁻⁵ m²s⁻¹ (20 cSt) to about 15 x 10⁻⁴ m²s⁻¹ (1500 cSt) at 25°C;

(ii) about 5 to about 50 parts per 100 parts by weight of (i) of a siloxane resin composed of (CH₃)₃SiO₁/₂ units and SiO₂ units in a ratio of (CH₃)₃SiO1/2 units to the SiO₂ units of about 0.6:1 to about 1.2:1; and

(iii) about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel

consists.

For any detergent composition to be used in automatic laundry washing machines, no foam will form to the extent that it will not find a place in the washing machine. Foam suppressors, when used, are preferably present in a "foam suppressing amount." The "foam suppressing amount" means that the person formulating the composition can select an amount of this foam controlling agent that will control foaming sufficiently to result in a low-foaming laundry detergent for use in automatic laundry washing machines. The amount of foam control will vary with the detergent surfactants selected. For example, with high-foaming surfactants, relatively more of the foam controlling agent will be used to achieve the desired foam control than with low-foaming surfactants. In general, a sufficient amount of suds suppressor should be incorporated in low-sudsing detergent compositions so that the suds which form during the wash cycle of the automatic washing machine (i.e., during the movement of the detergent in the aqueous solution under the intended conditions of wash temperature and concentration) do not exceed about 75% of the free volume of the washing machine drum, preferably that the suds do not exceed about 50% of said free volume, wherein the free volume is determined as the difference between the total volume of the drum and the volume of water plus laundry.

The compositions of the present invention will generally contain from 0% to about 5% suds suppressor. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof will typically be present in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% fatty monocarboxylate is used as suds suppressor. Silicones as suds suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition, although larger amounts may be used. This lower limit is primarily in view of minimizing cost and the effectiveness of lower amounts for to effectively control foaming. Preferably, from about 0.01% to about 1% of the silicone is used as a foam suppressor, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentages include any silica that may be used in combination with the polyorganosiloxane, as well as any additional materials that may be employed. Monostearyl phosphates as foam suppressors are generally used in amounts of from about 0.1% to about 2% by weight of the composition.

Hydrocarbons as foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher amounts may be used.

Other ingredients

A wide variety of other ingredients useful in detergent compositions can be included in the compositions of the invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, and others.

It is a particularly important advantage of this invention that, in addition to the improved builder-containing detergent compositions generally obtained by the combination of polycarboxylate builder and polyhydroxy fatty acid amide, heavy-duty liquid detergent compositions containing anionic surfactants and the polycarboxylate builders can be more easily formulated by including the polyhydroxy fatty acid amides described above. This invention therefore provides liquid detergent compositions comprising one or more anionic agents, polycarboxylate builder, polyhydroxy fatty acid amide and a liquid carrier. These liquid detergent compositions can contain relatively large amounts of anionic surfactants and polycarboxylate builder incorporated therein. As used herein, "large amounts of polycarboxylate builder"means Amounts of more than about 10%, especially more than about 15%, by weight of the detergent composition.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols, exemplified by methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for solubilizing the surfactant, but polyols such as those having from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerin and 1,2-propanediol) may also be used.

The detergent compositions of the invention will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of from about 6.5 to about 11, preferably from about 7.5 to about 10.5. Liquid product formulations will preferably have a pH (measured at a 10% standard dilution) of from about 7.5 to about 9.5, more preferably from about 7.5 to about 9.0. For liquids with a high builder content, the pH may be higher, preferably the pH is from 8.5 to 10.5. Methods for regulating the pH at the recommended use levels include the use of buffers, alkalis, acids, and others, and are well known to those skilled in the art.

This invention further provides a method for improving the performance of detergents containing anionic, nonionic and/or cationic surfactant and polycarboxylate builder by incorporating the above-described polyhydroxy fatty acid amide surfactant into such a composition such that the weight ratio of polycarboxylate to amide surfactant is from about 1:10 to about 10:1.

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, at least about 1% polycarboxylate builder and at least 1% of the polyhydroxy fatty acid amide, wherein the weight ratio of said polycarboxylate builder to amide surfactant is preferably from about 1:10 to about 10:1, in the presence of a solvent such as water or a water-miscible solvent (e.g., primary and secondary alcohols). Agitation is preferably provided to further facilitate cleaning. Suitable agitation means include rubbing by hand or, preferably, by means of a brush, sponge, mop or other cleaning device, automatic laundry washing machines, automatic dishwashing machines, among others.

In the above methods, the more preferred weight ratios of the polycarboxylate builder to the polyhydroxy fatty acid amide are from about 1:5 to about 7:1, most preferably from about 1:1 to about 1:7, and the preferred amounts and types of polyhydroxy fatty acid amide and polycarboxylate are as described below.

EXPERIMENTAL PART

This illustrates a process for the preparation of N-methyl 1-deoxyglucityllauramide as a surfactant for use in the present invention. Although a skilled chemist may vary the configuration of the apparatus, an apparatus suitable for use herein comprises a 3 liter four-necked flask equipped with a motor-driven paddle stirrer and a thermometer of sufficient length to come into contact with the reaction medium. The other two necks of the flask are equipped with a nitrogen purge and a large inner diameter side arm (Caution: a large inner diameter side arm is important in the case of very rapid methanol evolution) to which an efficient receiver condenser and a vacuum outlet are connected. The latter is connected to a nitrogen outlet and a vacuum gauge, then to a suction flask and a separator. A 500 watt heating mantle with a variable temperature control transformer ("Variac"), which is used to heat the reaction mixture, is thus placed on a hoist. placed so that it can be easily raised or lowered to further control the temperature of the reaction.

N-methylglucamine (195 g, 1.0 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g, 1.0 mol) are placed in a flask. The solid-liquid mixture is heated with stirring under a nitrogen purge to form a melt (approximately 25 minutes). When the melt temperature reaches 145ºC, a catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J.T. Baker) is added. The nitrogen purge is stopped and the aspirator flask and nitrogen outlet are adjusted to establish a vacuum of 16931.5 Pa (5 inches Hg or 5/31 atm.). From this point on, the reaction temperature is maintained at 150ºC by adjusting the Variac and/or by raising or lowering the jacket.

Within 7 minutes, the first methanol bubbles become visible at the meniscus of the reaction mixture. A vigorous reaction soon follows. Methanol distills over until its amount decreases. The vacuum is adjusted to achieve a vacuum of about 33863.9 Pa (10 inches Hg, 10/31 atm.). The vacuum is increased approximately as follows (in inches Hg after x minutes): to 33863.9 Pa (10) after 3, to 67727.8 Pa (20) after 7, to 84659.75 Pa (25) after 10. 11 minutes after the start of methanol formation, heating and stirring are discontinued, which coincides with some foaming. The product is cooled and solidifies.

The following examples are intended to illustrate compositions of the present invention without limiting or otherwise defining the scope of the invention, which scope is determined by the following claims.

EXAMPLES 1-12

These examples show granular heavy-duty detergent compositions containing polyhydroxy fatty acid amide and polycarboxylate builders.

Examples 1 to 3 are formulations for the preferred use of 1400 ppm by weight of wash water at temperatures below about 50°C. The above examples are prepared by combining the base granule ingredients as a slurry and spray drying to about 4-8% residual moisture. The remaining dry ingredients in granular or powder form are mixed with the spray dried granules in a rotating mixing drum and the liquid ingredients (nonionic surfactant and perfume) are sprayed on top.

Examples 4 and 5 represent compacted granular detergent compositions which are preferably used at a concentration of about 1000 ppm based on the wash water and are intended for wash temperatures of less than about 50°C. These are prepared by spray drying the base granular components to a moisture content of about 5% to 8%, admixing the granular or powdered dry ingredients and spraying the liquid components of the composition to mix in.

* TMS/TDS is tartrate monosuccinate/tartrate disuccinate.

** The foam suppressant flake is a dispersion of silica/silicone oil encapsulated in a matrix of polyethylene glycol (MW 8000) containing approximately 5% effective foam suppressant.

The compositions of Examples 6 and 7 are compacted granular formulations prepared by slurrying and spray drying the base granular ingredients to a moisture content of about 5% and mixing into the additional dry ingredients. The resulting mixture is dedusted by spraying onto the liquid ingredients. The product is intended for use at a concentration of about 1000 ppm at wash temperatures of less than about 30°C.

* 1.5 AU/g to 72 AU/g active enzyme

The compositions of Examples 8 and 9 are preferably used in concentrations of about 6000 ppm by weight of wash water at a temperature of about 30°C to 95°C. These compositions can be prepared by slurrying the base granular ingredients and spray drying to a moisture content of about 9%. The remaining dry ingredients are added in granular or powdered form and mixed in a rotating mixing drum. mixed, followed by a further addition of all the liquid components by spraying.

EXAMPLES 10-20

(which do not illustrate the present invention)

The examples show liquid heavy-duty detergent compositions containing polyhydroxy fatty acid amide and polycarboxylate builder.

Examples 10-16 are preferably used at a concentration of about 12,000 ppm by weight of wash water at temperatures of 30-95°C. They are prepared by combining the non-aqueous solvents, the aqueous surfactant pastes or solutions, the molten fatty acids, the aqueous solutions of the polycarboxylate builders and other salts, the aqueous ethoxylated tetraethylenepentamine, the buffers, the alkaline agents and the remaining water. The pH is adjusted to a pH of about 8.5 by either an aqueous citric acid solution or an aqueous sodium hydroxide solution. After the pH is adjusted, the final ingredients such as the soil release agents, enzymes, dyes and perfume are added and the mixture is stirred until a single phase is obtained.

* TMS/TDS is tartrate monosuccinate/tartrate disuccinate.

Examples 18-20 are preferably used in a concentration of about 2000 ppm, based on the weight of the wash water, used at wash temperatures below about 50°C. They are prepared by combining the non-aqueous solvents, the aqueous surfactant pastes or solutions, the molten fatty acids, the aqueous solutions of the polycarboxylate builders and other salts, the aqueous ethoxylated tetraethylenepentamine, the buffers, the alkaline agents and the remaining water. The pH is adjusted to a pH of about 8.5 using either an aqueous citric acid solution or an aqueous sodium hydroxide solution; for Examples 18 and 19, which have a higher builder content, the pH can optionally be adjusted to a pH of up to about 10.5. After the pH is adjusted, the final ingredients such as the soil release agents, enzymes, colorants and perfumes are added and the mixture is stirred until a single phase is obtained.

EXAMPLE 21

An alternative method for preparing the polyhydroxy fatty acid amides used herein is as follows. A reaction mixture is used which consists of 84.87 g of fatty acid methyl ester (source: Procter & Gamble Methyl Ester CE1270), 75 g of N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04 g of sodium methoxide (source: Aldrich Chemical Company 16,499-2) and 68.51 g of methyl alcohol. The reaction vessel comprises a standard reflux device equipped with a drying tube, condenser and stir bar. In this method, N-methylglucamine is combined with methanol by stirring under argon and heating is started with good mixing (stirring bar; reflux). After 15-20 minutes, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Periodically samples are taken to monitor the progress of the reaction, but it is found that the solution is completely clear after 63.5 minutes. It is decided that the reaction is indeed nearly complete at this point. The reaction mixture is refluxed for 4 hours. After removal of the methanol, the crude product obtained is 156.16 g. After vacuum drying and purification, a total yield of 106.92 g of purified product is obtained. However, the percent yield is not calculated on this basis because regular sampling during the course of the reaction makes an overall value for the percent yield inconclusive. The reaction can be carried out at reactant concentrations of 80% to 90% for periods of up to 6 hours to obtain products with extremely low by-product formation.

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

It will be readily appreciated that the polyhydroxy fatty acid amides exhibit some instability under highly basic or acidic conditions due to their amide linkage. Although some degradation may be tolerated, it is preferred that these materials not be subjected to pH values above about 11, preferably 10, nor below about 3 for excessively long periods of time. The pH of the final product (liquids) is typically 7.0-9.0.

During the preparation of the polyhydroxy fatty acid amides, it will usually be necessary to at least partially neutralize the basic catalyst used to form the amide bond. Although any acid may be used for this purpose, the person formulating the detergent will find it simple and convenient to use an acid which provides an anion which is otherwise useful and desirable in the final detergent composition. For example, citric acid may be used for neutralization purposes and the resulting citrate ion (about 1%) may be left in an approximately 40% polyhydroxy fatty acid amide slurry and pumped into later stages of manufacture to produce the total detergent. The acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, Tartrate/succinate and the like can be used in a similar way.

The polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C12-C14) are more soluble than their tallow alkyl counterparts (predominantly C16-C18). Therefore, the C12-C14 materials are somewhat easier to formulate into liquid compositions and are more soluble in cold water laundry wash baths. However, the C16-C18 materials are also quite useful, especially in cases where warm to hot wash water is used. In fact, the C16-C18 materials may be better detersive surfactants than their C12-C14 counterparts. Therefore, the formulator may desire to balance ease of manufacture and performance when selecting a 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 the presence of points of unsaturation and/or chain branching in the fatty acid moiety. These materials, such as the polyhydroxy fatty acid amides derived from oleic acid and isostearic acid, are more soluble than their n-alkyl counterparts.

Similarly, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, and the like will usually be greater than the solubility of their monosaccharide-derived material counterparts. This higher solubility can be particularly useful in the formulation of liquid compositions. Moreover, the polyhydroxy fatty acid amides wherein the polyhydroxy group is derived from maltose appear to function particularly well as detergents when used in conjunction with conventional alkylbenzene sulfonate surfactants ("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 higher saccharides, such as maltose, produces a significant and unexpected lowering of the interfacial tension in aqueous media, thereby increasing the wetting detergent performance. is increased. (The preparation of a polyhydroxy fatty acid amide derived from maltose is described hereinafter.)

The polyhydroxy fatty acid amides can be prepared not only from the purified sugars, but also from hydrolyzed starches, e.g. corn starch, potato starch or any other suitable plant-derived starch containing the mono-, di- and other saccharides desired by the formulator. This is particularly important from an economic point of view. Thus, "high glucose" corn syrup, "high maltose" corn syrup and others can be used conveniently and economically. Delignified hydrolyzed cellulose pulp can also be a raw material source for the polyhydroxy fatty acid amides.

As noted above, the polyhydroxy fatty acid amides obtained from the higher saccharides such as maltose, lactose, and others are more soluble than their glucose counterparts. Moreover, it appears that the more soluble polyhydroxy fatty acid amides can assist in the solubilization of their less soluble counterparts to varying degrees. Thus, the formulator may choose to use a raw material comprising a high glucose corn syrup, but select, for example, a syrup containing a small amount of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy fatty acids will generally exhibit more preferred solubility characteristics over a wider range of temperatures and concentrations than a polyhydroxy fatty acid amide obtained from "pure" glucose. Thus, in addition to any economic advantages of using sugar mixtures rather than pure sugar reactants, the polyhydroxy fatty acid amides prepared from mixed sugars can offer very substantial advantages in terms of performance and/or ease of formulation. In some cases, however, a small loss in grease removal performance (dishwashing) may be observed at fatty acid maltamide levels above about 25% and a small loss in foaming at levels above about 33% (which percentages represent the percentage of polyhydroxy fatty acid amide derived from maltamide versus the polyhydroxy fatty acid amide derived from glucose in the mixture). This may vary somewhat depending on the chain length of the fatty acid moiety. Typically, the formulator who decides to use such mixtures may find it advantageous to select polyhydroxy fatty acid amide mixtures having ratios of monosaccharides (e.g. glucose) to di- and higher saccharides (e.g. maltose) of about 4:1 to about 99:1.

The preparation of preferred non-cyclic polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures of about 30°C to 90°C, preferably about 50°C to 80°C. It has now been found that it may be convenient for the person formulating, for example, liquid detergents to carry out such processes in a 1,2-propylene glycol solvent since the glycol solvent need not be completely removed from the reaction product prior to its use in the final detergent formulation. Similarly, the person concerned with the formulation of, for example, solid, typically granular, detergent compositions may find it convenient to carry out the process at 30°C to 90°C in solvents comprising ethoxylated alcohols such as the ethoxylated (EO 3-8) C12-C14 alcohols such as those available as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they do not contain substantial amounts of non-ethoxylated alcohol and it is most preferred that they do not contain substantial amounts of mono-ethoxylated alcohol (designated "T").

Although processes for preparing the polyhydroxy fatty acid amides do not form part of the present invention per se, the formulator may also cite other syntheses for polyhydroxy fatty acid amides than those described hereinafter.

Typically, the reaction sequence for preparing the preferred acyclic polyhydroxy fatty acid amides on an industrial scale will comprise: Step 1 - preparing the N-alkylpolyhydroxyamine derivative from the desired sugar or sugar mixture by forming an adduct of the N-alkylamine and the sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by Step 2 - reacting the aforementioned polyhydroxyamine with, preferably, a fatty ester to form an amide bond. Although a variety of N-alkylpolyhydroxyamines useful in Step 2 of the reaction sequence can be prepared by various methods described in the art, the following method is convenient and uses economical sugar syrup as the raw material. It will be appreciated that to achieve the best results using such syrup raw materials, manufacturers should select syrups which are fairly light in color or, preferably, nearly colorless ("water clear").

Production of N-alkylpolyhydroxyamine from plant-derived sugar syrup

I. Adduct Formation - The following is a standard procedure wherein about 420 g of about 55% glucose solution (corn syrup - about 231 g glucose - about 1.28 moles) having a Gardner color number of less than 1 is reacted with about 119 g of about 50% aqueous methylamine solution (59.5 g methylamine - 1.92 moles). The methylamine solution (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 temperature of about 10°C to 20°C. The corn syrup is slowly added to the MMA solution at the indicated reaction temperature. The Gardner color number is determined at the approximate times indicated in minutes. TABLE 1

From the above data it can be seen that the Gardner color number for the adduct is much poorer as the temperature is increased above about 30°C, and at about 50°C the time at which the adduct has a Gardner color number below 7 is only about 30 minutes. For longer reaction times and/or longer residence times the temperature should be less than about 20°C. To obtain a glucamine with a good color the Gardner color number should be less than about 7, and preferably less than about 4.

When lower temperatures are used to form the adduct, the time to reach a substantially equilibrium concentration of the adduct is shortened by using higher ratios of amine to sugar. At the stated molar ratio of amine to sugar of 1.5:1, equilibrium is reached in about 2 hours at a reaction temperature of about 30ºC. At a molar ratio of 1.2:1, the time under the same conditions is at least about 3 hours. To achieve good color, the combination of the ratio of amine to sugar; the reaction temperature and the reaction time are selected to substantially achieve an equilibrium conversion, e.g., of greater than about 90%, preferably greater than about 95%, even more preferably greater than about 99%, based on the sugar, and a color number of less than about 7, 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 having the different Gardner color numbers indicated, the color number of the MMA adduct (after substantially equilibrium in at least about 2 hours) as indicated. TABLE 2

From the foregoing, it can be seen that the starting sugar material must be nearly colorless to consistently obtain an adduct that is acceptable. If the sugar has a Gardner color number of about 1, the adduct is sometimes acceptable and sometimes unacceptable. If the Gardner color number is above 1, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Hydrogen Reaction - The above adduct having a Gardner color number of 1 or less is hydrogenated according to the following procedure.

About 539 g of adduct in water and about 23.1 g of a United Catalyst G498 nickel catalyst are added to a 1 liter autoclave and purged twice with 1.38 x 10⁶ Pa (200 psig) H₂ at about 20°C. The H₂ pressure is increased to about 9.65 x 10⁶ Pa (1400 psi) and the temperature is increased to about 50°C. The pressure is then increased to about 11.0 x 106 Pa (1600 psig) and the temperature is maintained at about 50-55°C for about 3 hours. The product is about 95% hydrogenated at this time. The temperature is then raised to about 85ºC for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered off. The product after removal of water and MMA by evaporation is about 95% N-methylglucamine, a white powder.

The above procedure is repeated with about 23.1 g of a Raney nickel catalyst with the following changes. The catalyst is washed three times and the reactor is flushed twice with 1.38 x 10⁶ Pa (200 psig) H₂ with the catalyst already in the reactor and the reactor is pressurized with H₂ to 11.0 x 10⁶ Pa (1600 psig) for 2 hours, this is maintained during a hour and the reactor is again pressurized to 11.0 x 10⁶ Pa (1600 psig). The adduct is then pumped into the reactor at 1.38 x 10⁶ Pa (200 psig) and 20°C and the reactor is purged with 1.38 x 10⁶ Pa (200 psig) H₂, etc., as above.

In each case, the resulting product is greater than about 95% N-methylglucamine; it contains less than about 10 ppm nickel based on the glucamine; and it has a Gardner color number in solution of less than about 2.

The crude N-methylglucamine is color stable at about 140ºC for a short exposure time.

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

In another reaction, the adduct is prepared starting from about 159 g of about 50% methylamine in water, which is purged and protected with N2 at about 10-20°C. About 330 g of about 70% corn syrup (almost water clear) is degassed with N2 at about 50°C and slowly added to the methylamine solution at a temperature of less than about 20°C. The solution is mixed for about 30 minutes to obtain about 95% adduct, which is a very light yellow solution.

About 190 g of adduct in water and about 9 g of United Catalyst G498 nickel catalyst are added to a 200 mL autoclave and purged three times with H2 at about 20°C. The H2 pressure is increased to about 1.38 x 106 Pa (200 psi) and the temperature is increased to about 50°C. The pressure is increased to 1.72 x 106 Pa (250 psi) and the temperature is maintained at about 50-55°C for about 3 hours. The product, which is at this point about 95% hydrogenated, is then brought to a temperature of about 85ºC for 30 minutes, and the product, after removal of water and evaporation, is about 95% N-methylglucamine, a white powder.

It is also important to reduce the contact time between the adduct and the catalyst at an H2 pressure of less than about 6.89 x 106 Pa (1000 psig) to minimize the nickel content in the glucamine. The nickel content in the N-methylglucamine in this reaction is about 100 ppm compared to the less than 10 ppm in the above reaction.

The following reactions with H2 are performed to have a direct comparison of the effects of reaction temperature.

A 200 mL autoclave is used as a reactor, and typical procedures similar to those given above are followed to prepare the adduct and to carry out the hydrogen reaction at various temperatures.

The adduct used to prepare the glucamine is prepared by combining about 420 g of about 55% glucose (corn syrup) solution (231 g glucose; 1.28 moles) (the solution is prepared using 99DE corn syrup from Cargill, which solution has a Gardner color number of less than 1) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products).

The reaction sequence is as follows:

1. Add about 119 g of the 50% methylamine solution to a N₂ purged reactor, shield with N₂, and cool to less than about 10°C.

2. The 55% corn syrup solution is degassed and/or purged with N2 at 10-20ºC to remove oxygen in the solution.

3. The corn syrup solution is slowly added to the methylamine solution and the temperature is maintained at less than about 20ºC.

4. After all the corn syrup solution has been added, stir for 1-2 hours.

The adduct is used for the hydrogen reaction immediately after preparation or it is stored at low temperature to prevent further decomposition.

The hydrogen reactions of the adduct leading to glucamine are as follows:

1. Add about 134 g of adduct (Gardner color number below about 1) and about 5.8 g of G49B Ni to a 200 ml autoclave.

2. The reaction mixture is purged twice with about 1.38 x 10⁶ Pa (200 psi) H₂ at about 20-30°C.

3. The pressure is increased with H2 to about 2.76 x 106 Pa (400 psi) and the temperature is increased to about 50ºC.

4. The pressure is increased to about 3.45 x 10⁶ Pa (500 psi) and the reaction is allowed to proceed for about 3 hours. The temperature is maintained at about 50-55ºC. Sample 1 is taken.

5. The temperature is increased to about 85ºC for about 30 minutes.

6. Decant and filter off the nickel catalyst. Sample 2 is taken.

Conditions for reactions at constant temperature:

1. About 134 g of adduct and about 5.8 g of G49B Ni are added to a 200 ml autoclave.

2. Purge twice with approximately 1.38 x 10⁶ Pa (200 psi) H₂ at low temperature.

3. The pressure is increased with H2 to about 2.76 x 106 Pa (400 psi) and the temperature is increased to about 50ºC.

4. Increase the pressure to about 3.45 x 10⁶ Pa (500 psi) and allow the reaction to proceed for 3.5 hours. Maintain the temperature at the indicated temperature.

5. Decant and filter off the nickel catalyst. Sample 3 is obtained at about 50-55ºC; sample 4 is obtained at about 75ºC; and sample 5 is obtained at about 85ºC. (The reaction time for about 85ºC is about 45 minutes.)

All experiments give a similar purity of N-methylglucamine (about 94%); the Gardner color numbers of the experiments are similar immediately after reaction, but only the two-stage heat treatment gives good stability of the color number; and the experiment at 85ºC gives little color immediately after reaction.

EXAMPLE 22

The preparation of the hardened tallow fatty acid amide of N-methylmaltamine for use in the detergent compositions of the 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).

The reactants (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry - 50 g Raney nickel) are placed in a glass insert and placed in a 3-liter shaking autoclave which is purged with 3 x 3.45 x 10⁶ Pa (3x500 psig) nitrogen and 2 x 3.45 x 10⁶ Pa (2x500 psig) hydrogen and shaken under H₂ at room temperature over a weekend at temperatures from 28ºC to 50ºC. The crude reaction mixture is filtered twice through a glass microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The last traces of water are azeotroped by dissolving the material in methanol and then removing the methanol/water on a rotary evaporator. Final drying is done under high vacuum. The crude product is dissolved in refluxed methanol, filtered, cooled to recrystallization, filtered, and the filter cake is dried under vacuum at 35ºC. This is cut #1. The filtrate is concentrated until a precipitate begins to form and stored overnight in a refrigerator. The solid is filtered off and dried under vacuum. This is cut #2. The filtrate is again concentrated to half its volume and recrystallized. A very small amount of precipitate forms. A small amount of ethanol is added and the solution is left in the freezer over a weekend. The solid material is filtered off and dried under vacuum. The combined solids include N-methylmaltamine, which is used in step 2 of the overall synthesis.

Step 2 - Reactants: N-methylmaltamine (from step 1); hydrogenated tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); molar ratio of amine:ester 1:1; initial catalyst amount 10 mol% (weight/maltamine ratio), which is increased to 20 mol%; solvent amount 50% (weight).

In a closed bottle, 20.36 g of the tallow methyl ester is heated to its melting point (water bath) and added to a 250 mL three-necked round bottom flask with mechanical stirring. The flask is heated to approximately 70ºC to prevent solidification of the ester. Separately, 25.0 g of N-methylmaltamine is combined with 45.36 g of methanol and the resulting slurry is added to the tallow methyl ester with good mixing. 1.51 g of 25% sodium methoxide in methanol is added. After 4 hours, the reaction mixture has not cleared, so an additional 10 mol% catalyst (for a total of 20 mol%) is added and the reaction is allowed to continue overnight (at approximately 68ºC), after which time the mixture is clear. The reaction flask is then modified for distillation. The temperature is raised to 110ºC. Distillation is continued at atmospheric pressure for 60 minutes. High vacuum distillation is then initiated and continued for 14 minutes, after which time the product is very thick. The product is left in the reaction flask at 110ºC (external temperature) for 60 minutes. The product is scraped from the flask and digested in ethyl ether over a weekend. The ether is removed on a rotary evaporator and the product is stored in an oven overnight and ground to a powder. Any remaining N-methylmaltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is placed in a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) is applied to the silica gel and eluted several times using vacuum and several methanol washes. The collected eluent is evaporated to dryness (on a rotary evaporator). Any remaining tallow ester is removed by digestion in ethyl acetate overnight, followed by filtration. The filter cake is vacuum dried overnight. The product is tallow alkyl N-methylmaltamide.

In an alternative embodiment, step 1 of the above reaction sequence can be carried out using commercial corn syrup containing glucose or mixtures of glucose and typically 5% or more maltose. The resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions of the present invention.

In yet another embodiment, step 2 of the above reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, the propylene glycol or NEODOL need not be removed from the reaction product prior to its use in formulating detergent compositions. Again, at the discretion of the formulator, the methoxide catalyst can be neutralized with citric acid to yield sodium citrate which can remain in the polyhydroxy fatty acid amide.

Depending on the desires of the formulator, the compositions of the invention may contain more or less of various suds control agents. Typically, for dishwashing, high levels of sudsing are desirable, so no suds control agent will be used. For laundry washing in top-loading washing machines, some control of sudsing may be desirable, and for front-loaders, a significant 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. In fact, the selection of a suds control agent, or mixtures of such suds control agents, for any particular 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 various types of foam control agents are more efficient (ie, smaller amounts can be used) than various other types of foam control agents. The silicones available as X2-3419 and Q2-3302 (Dow Corning) are particularly useful as foam control agents herein.

The person entrusted with formulating laundry compositions, which compositions may advantageously contain a soil release agent, may select from a wide variety of known materials (see, for example, U.S. Patent Nos. 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 C1-C4 alkoxy terminated polyethoxy units (e.g., CH3[OCH2CH2]16OH); a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly(oxyethylene)oxy units (e.g., polyethylene glycol 1500); a source of oxyisopropyleneoxy units (eg 1,2-propylene glycol); and a source of oxyethyleneoxy units (eg ethylene glycol), particularly wherein the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5:1. Such nonionic soil release agents have the general formula

wherein R¹ is lower alkyl (e.g. C₁-C₄ alkyl), especially methyl ; x and y are each integers from about 6 to about 100 ; m is an integer from 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 molar ratio of oxyethyleneoxy to oxyisopropyleneoxy of at least about 0.5:1.

Another preferred type of soil release agent useful in the present invention is the general anionic type described in U.S. Patent No. 4,877,896, provided, however, that such agents are substantially free of monomers of the HOROH type, where R is propylene or higher alkyl. Thus, for example, the soil release agents of U.S. Patent No. 4,877,896 may comprise the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium sulfobenzoic acid, whereas these additional soil release agents may comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 5-sodium sulfoisophthalate and 3-sodium sulfobenzoic acid. Such agents are preferred for use in granular laundry detergents.

The formulator may also determine that it is advantageous to incorporate a non-perborate bleach, particularly in heavy-duty granular detergents. A variety of peroxygen bleaches are commercially available and may be used herein, but among these percarbonate is convenient and economical. Thus, the compositions of the invention may contain a solid percarbonate bleach, usually in the form of the sodium salt, incorporated in an amount of from 3% to 20%, more preferably from 5% to 18%, and most preferably from 8% to 15% by weight of the composition.

Sodium percarbonate is an addition compound having a formula corresponding to 2Na₂CO₃.3H₂O₂ and is commercially available as a crystalline solid. Most commercially available materials include a small amount of a heavy metal complexing agent such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or an aminophosphonate which is incorporated during the manufacturing process. For use herein, the percarbonate can be incorporated into detergent compositions without additional protection, but in preferred embodiments of the invention a stable form of the material (FMC) is used. Although a variety of coatings can be used, the most economical is sodium silicate having a SiO₂:Na₂O ratio of 1.6:1 to 2.8:1, preferably 2.0:1, which is applied as an aqueous solution and dried to give an amount of from 2% to 10% (usually from 3% to 5%) of silicate solids based on the weight of the percarbonate. Magnesium silicate may also be used and a chelating agent such as one of those mentioned above may also be included in the coating.

The particle size range of crystalline percarbonate is from 350 microns to 450 microns with a mean of about 400 microns. When coated, the crystals range in size from 400 to 600 microns.

Although the heavy metals present in the sodium carbonate used to make the percarbonate can be controlled by the inclusion of complexing agents in the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other components of the product. It has been found that the total amount of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably be less than 20 ppm to avoid an unacceptable adverse effect on the stability of the percarbonate.

A modern, compacted laundry detergent granulate is the following: EXAMPLE 23

¹ Layered silicate builders are known in the art. Sodium layered silicates are preferred. See, for example, the sodium layered silicate builders of U.S. Patent No. 4,664,859, issued May 12, 1987, HP Rieck. A suitable layered silicate builder is available as SKS-6 from Hoechst.

² Available from Novo Nordisk A/S, Copenhagen.

Highly preferred granules of the foregoing types are those containing from about 0.0001% to about 2% by weight of active 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.

The following relates to the preparation of a preferred heavy-duty liquid detergent according to the invention. It will be clear that the stability of enzymes in such compositions is considerably lower than in granular detergents. However, using typical enzyme stabilizers such as formate and boric acid, lipase and cellulase enzymes can be protected from degradation by protease enzymes. However, lipase stability is still relatively low in the presence of alkylbenzene sulfonate surfactants ("LAS"). Evidently, LAS partially denature the lipase and, furthermore, denatured lipase appears to be more vulnerable to protease attack.

In view of the above considerations, which as indicated can lead to difficulties especially in liquid compositions, one challenge is to provide liquid detergent compositions which jointly contain lipase, protease and cellulase enzymes. It is a particular challenge to combine such tertiary enzyme systems in stable liquid detergents together with an effective mixture of detersive surfactants. In addition, it is difficult to stably incorporate peroxidase and/or amylase enzymes into such compositions.

It has now been found that various mixtures of lipases, proteases, cellulases, amylases and peroxidases are sufficiently stable in the presence of certain surface-active systems which do not contain alkylbenzene sulfonate so that effective solid and even liquid heavy-duty detergents can be formulated.

In particular, prior art liquid detergent compositions typically contain LAS or LAS mixtures with surfactants of the type RO(A)mSO₃M ("AES") referred to hereinabove, i.e. LAS/AES mixtures.

In contrast, the liquid detergents of the present invention preferably comprise binary mixtures of the AES and the polyhydroxy fatty acid amides of the type described hereinabove. Although small amounts of LAS may be present, it will be appreciated that the stability of the enzymes will be reduced thereby. It is therefore preferred that the liquid compositions be substantially free of LAS (i.e., that they contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, most preferably 0%).

Such a composition (which, however, is not within the scope of the present invention) could be a liquid detergent composition which:

(a) about 1% to about 50%, preferably about 4% to about 40% of an anionic surfactant;

(b) from about 0.0001% to about 2% of an active detersive enzyme;

(c) an enzyme performance enhancing amount (preferably about 0.5% to about 12%) of a polyhydroxy fatty acid amide material of the formula

wherein R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R₂ is C₅-C₃₁ hydrocarbyl and Z is a polyhydroxylhydrocarbyl having a linear hydrocarbon chain with at least 3 hydroxyl groups directly attached to said chain or an alkoxylated derivative thereof;

and wherein the composition is substantially free of alkylbenzenesulfonate.

The water-soluble, anionic, surfactant used in the invention preferably comprises ("AES"):

RO(A)mSO₃M,

wherein R is an unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group, A is an ethoxy or propoxy moiety, m is an integer greater than 0 and M is hydrogen or a cation. Preferably, R is an unsubstituted C₁₂-C₁₈ alkyl group, A is an ethoxy moiety, m is from about 0.5 to about 6 and M is a cation. The cation is preferably a metal cation (e.g., sodium (preferred), potassium, lithium, calcium, magnesium, etc.) or an ammonium or substituted ammonium cation.

It is preferred that the ratio of the above surfactant ("AES") to the polyhydroxy fatty acid amide herein is from about 1:2 to about 8:1, preferably from 1:1 to about 5:1, most preferably from about 1:1 to about 4:1.

The liquid compositions herein may alternatively comprise polyhydroxy fatty acid amide, AES, and from about 0.5% to about 5% of the condensation product of C8-C22 linear alcohol (preferably C10-C20 alcohol) with from about 1 to about 25, preferably from about 2 to about 18 moles of ethylene oxide per mole of alcohol.

As described above, the liquid compositions herein preferably have a pH in a 10% solution in water at 20°C of from about 6.5 to about 11.0, preferably from about 7.0 to about 8.5.

The present compositions preferably further comprise from about 0.1% to about 50% of a detergent builder. These compositions preferably comprise about 0.1% up to about 20% citric acid or a water-soluble salt thereof and about 0.1% to about 20% of a water-soluble succinate tartrate, in particular the sodium salt thereof and mixtures thereof, or about 0.1% to about 20% by weight of oxydisuccinate or mixtures thereof with the aforementioned builders. 0.1% to 50% alkenyl succinate can also be used.

The preferred liquid compositions herein comprise from about 0.0001% to about 2%, preferably from about 0.0001% to about 1%, most preferably from about 0.001% to about 0.5%, of a detersive enzyme, based on the active enzyme. These enzymes are preferably selected from the group consisting of protease (preferred), lipase (preferred), amylase, cellulase, peroxidase, and mixtures thereof. Most preferred are compositions containing two or more classes of enzymes, most preferred are compositions wherein one of the enzymes is a protease.

Although various descriptions of detergent proteases, cellulases, etc. are available in the literature, detergent lipases may be somewhat less well known. Therefore, to assist the formulator, lipases of interest include Amano AKG and Bacillis Sp Lipase (e.g. Solvay Enzymes). Reference is also made to the lipases described in EP-A-0 399 681, published on 28 November 1990, EP-A-0 218 272, published on 15 April 1987 and PCT/DK 88/00177, published on 18 May 1989.

Suitable fungal lipases include those produced by Humicola lanuginosa and Thermomyces lanuginosus. Most preferred is the lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European patent application 0 258 068, which is commercially available under the trade name LIPOLASE.

From about 2 to about 20,000, preferably from about 10 to about 6,000 lipase units of lipase per gram (LU/g) can be used in these compositions. One lipase unit is that amount of lipase which in a pH-stat delivers 1 µmol of titratable butyric acid per minute, wherein the pH 7.0, the temperature is 30ºC and the substrate is an emulsion of tributyrin and gum arabic in the presence of Ca⁺⁺ and NaCl in phosphate buffer.

The following example illustrates a preferred liquid laundry detergent composition (which, however, is not within the scope of the present invention) which

(a) an enzyme selected from proteases, cellulases and lipases, or preferably a mixture thereof, typically representing from about 0.01% to about 2% by weight of the total composition, although the amounts used may be adjusted as desired by the formulator to provide an "effective" amount (i.e., a soil-removing amount) of said enzyme or enzyme mixture;

(b) a polyhydroxy fatty acid amine surfactant of the type described herein, typically representing at least about 2% by weight of the composition, and more typically from about 3% to about 15%, preferably from about 7% to about 14% by weight;

(c) a surfactant of the type RO(A)mSO₃M as described hereinbefore, preferably RO(CH₂CH₂O)mSO₃M, wherein R is (average) C₁₄-C₁₅ and m is (average) 2-3, wherein M is H or a water-soluble salt-forming cation, e.g. Na⁺, which surfactant typically represents about 5% to about 25% by weight of the composition;

(d) optionally a surfactant of the type ROSO₃M as described hereinbefore, wherein R is preferably (on average) C₁₂-C₁₄, which surfactant preferably comprises from about 1% to about 10% by weight of the compositions;

(e) a liquid carrier, in particular water or water-alcohol mixtures;

(f) optionally, but most preferably, effective amounts of enzyme stabilizers, typically from about 1% to about 10% by weight of the composition;

(g) water-soluble polycarboxylate builders, typically in an amount of from about 4% to about 25% by weight of the composition;

(h) optionally, the various detersive additives, brighteners and the like identified hereinbefore, typically (when used) in amounts of about 1% to about 10% by weight of the composition;

includes, and

(i) which composition is essentially free of LAS.

EXAMPLE 24

(which does not illustrate the present invention)

¹ Manufactured as described above

² Protease B is the modified bacterial serine protease described in European Patent Application No. 87 303 761, filed on 28 April 1987, in particular on pages 17, 24 and 98.

³ The lipase used herein is the lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae as described in European patent application 0 258 068, which is commercially available under the trade name LIPOLASE (from Novo Nordisk A/S, Copenhagen, Denmark).

&sup4; The cellulase used herein is sold under the trademark CAREZYME (Novo Nordisk A/S, Copenhagen, Denmark).

&sup5; Brightener 36 is commercially available as TINOPAL TAS 36 .

The brightener is added to the composition in the form of a separately prepared premix of brightener (4.5%), monoethanolamine (60%) and water (35.5%).

EXAMPLE 25

The following illustrates a detergent composition of the present invention containing perborate bleach and bleach activator which is prepared by mixing the listed ingredients in a mixing drum.

In the example, zeolite A refers to a hydrated crystalline zeolite A containing about 20% water and having an average particle size of from 1 to 10, preferably from 2 to 5 µ; LAS refers to sodium C12,3 linear alkylbenzenesulfonate; AS refers to sodium C14-C15 alkyl sulfate; nonionic agent refers to a coconut alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol and free of non-ethoxylated and monoethoxylated alcohol, which is also abbreviated as CDAE:6.5T; and DTPA refers to sodium diethylenetriamine pentaacetate.

¹ The base granules are produced by spray drying an aqueous crutcher mixture of the listed components.

² A freshly prepared wet NAPAA cake sample is obtained, which typically consists of about 60% water, about 2% available oxygen from peroxyacid (AvO) (corresponding to about 36% NAPAA) and the remaining unreacted starting material (about 4%). This wet cake represents the crude reaction product of NAAA (monononylamide of adipic acid), sulfuric acid and hydrogen peroxide, to which water is then added, which is then filtered, washed with distilled water and phosphate buffer, and finally subjected to suction filtration to recover the wet cake. A portion of the wet cake is air dried at 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. The pH value of the dry sample is about 4.5.

The NAPAA granules are prepared by mixing about 51.7 parts of the dried wet NAPAA cake (containing about 10% unreacted material), about 11.1 parts sodium C12-3 linear alkylbenzene sulfonate (LAS) in paste form (45% active material), about 43.3 parts sodium sulfate and about 30 parts water in a CUISINART blender. After drying, the granules (containing about 47% NAPAA) are separated by sieving through a No. 14 Tyler mesh sieve and retaining any particles that do not pass through a No. 65 Tyler mesh sieve. The mean particle size (agglomerate size) of the amide peroxyacid is about 5-40 µm and the median particle size is about 10-20 µm, which was determined by a Malvern particle size analysis.

³ The NOBS (nonanoyloxybenzene sulfonate) granules are prepared according to U.S. Patent No. 4,997,596, Bowling et al., issued March 5, 1991, which is incorporated herein by reference.

&sup4; The zeolite granules, which have the following composition, are produced by mixing zeolite A with PEG 8000 and CnAE6.5T in an energy-intensive mixer of the brand Eirich R08.

The PEG 8000 is an aqueous form containing 50% water and is maintained at a temperature of approximately 55ºF (12.8ºC). The CnAE6.5T is in a liquid state and is maintained at approximately 90ºF (32.2ºC). The two liquids are combined by pumping through a 12-element static mixer. The resulting binder material has an initial temperature of approximately 75ºF (23.9ºC) and a viscosity of approximately 5 Pa.s (5000 cps). The ratio of PEG 8000 to CnAE6.5T through the static mixer is 72:28.

The energy-intensive Eirich R08 mixer is operated in batches. First, 34.1 kg of powdered zeolite A is weighed into the pan of the mixer. The mixer is set in rotation by first rotating the pan in a counterclockwise direction at approximately 75 revolutions per minute (rpm) and then moving the rotor blade clockwise at 1800 rpm. The binder material is then fed from the static mixer directly into the energy-intensive Mixer brand Eirich R08, which contains zeolite A. The feed time of the binder material is approximately 2 minutes. Mixing in the mixer is continued for an additional minute to reach a total batch time of approximately 3 minutes. The batch is then removed and collected in a lightweight drum.

The batch step is repeated until approximately 225 kg of wet product is obtained. This withdrawn product is then dried in a fluidized bed at 240-270ºF (116-132ºC). The drying step removes much of the free water and changes the composition as described above. The total energy input by the mixer for the product in a batch operation is approximately 1.31 x 10⁵ J/kg (1.31 x 10¹² erg/kg) at a ratio of approximately 2.18 x 10⁹² J/kg-s (2.18 x 10⁹ erg/kg-s).

The resulting free-flowing agglomerates have an average particle size of about 450-500 µm.

EXAMPLE 26

(which does not illustrate the present invention)

A liquid laundry detergent composition suitable for use at the relatively high concentrations commonly used in automatic front loading machines, particularly in Europe, and over a wide temperature range is the following:

¹ As SYNPRAX 3 from ICI or as DTSA from Monsanto.

² As protease B described in EP 0342177, 15 November 1989, percentage at 40 g/l.

³ Amylase, from NOVO; percentage at 300 KNU/g.

&sup4; Lipase, from NOVO; percentage at 100 KNU/g.

&sup5; Cellulase, from NOVO; percentage at 5000 CEVU/l.

&sup6; Available from Monsanto.

&sup7; From BASF as LUTENSOL P6105.

&sup8; BLANK PHORE CPG766, Bayer.

&sup9; Silane as corrosion inhibitor, available as A1130 from Union Carbide or DYNASYLAN TRIAMINO from Hüls.

¹⁰ Polyester, according to US Patent 4,711,730.

¹¹ Silicone as a foam control agent, available as Q2-3302 from Dow Corning.

¹² Dispersant for the silicone-based foam control agent, available as DC-3225C from Dow Corning.

* The preferred fatty acids are top palm kernel fatty acids, which contain 12% oleic acid and 2% each of stearic acid and linoleic acid.

EXAMPLE 27

A granular laundry detergent composition suitable for use in the relatively high concentrations required for automatic front loading washing machines, particularly in Europe, and is suitable over a wide temperature range, is the following:

¹ SOKALAN is sodium polyacrylate/maleate, which is available from Hoechst.

² Monsanto trademark for Pentaphosphonomethyldiethylenetriamine.

³ Optical brightener available from Ciba-Geigy .

&sup4; Trade name FINNFIX, available from Metasaliton.

&sup5; LIPOLASE, lipolytic enzyme from NOVO.

&sup6; SAVINASE, protease enzyme from NOVO.

&sup7; X2-3419 is a silicone foam suppressor available from Dow Corning.

The process for producing the granules includes the following different steps, such as drying in a tower, agglomeration, dry addition, etc. The percentages are based on the final composition.

A. Crutching and guiding through the tower

Using standard procedures, the following components are subjected to crutching and tower drying.

SOKALAN CP5 3.52%

DEQUEST 2066 0.45%

TINOPAL DMS 0.28%

Magnesium sulfate 0.49%

ZEOLITE A, anhydrous 7.1%

CMC0.47%

B. Agglomerates of surfactant

B1. Agglomeration of the sodium salt of tallow alkyl sulfate and the sodium salt of C₁₂₋₁₅ EO(3) sulfate in paste form - A paste of tallow alkyl sulfate containing 50% active material and a paste of C₁₂-C₁₅ EO(3) sulfate containing 70% are agglomerated with zeolite A and sodium carbonate according to the following formulation (proportion of the detergent formulation after drying the agglomerate).

Tallow alkyl sulfate 2.82%

C₁₂₋₁₅-EO(3)-sulfate 1.18%

Zeolite A 5.3%

Sodium carbonate 4.5%

B2. Agglomerate of C₁₄-C₁₅-alkyl sulfate, C₁₂-C₁₅-alkyl ethoxy sulfate, DOBANOL C₁₂-C₁₅-EO(3) and C₁₆-C₁₈-N-methylglucosamide - The nonionic material C₁₆-C₁₈-glucosamide is synthesized with DOBANOL C₁₂₋₁₅-EO(3) which is present during the reaction with methyl ester and N-methylglucamine. The C₁₂₋₁₅-EO(3) serves as a melting point depressant, which allows the reaction to be carried out without the formation of cyclic glucosamides, which are undesirable.

A surfactant mixture of 20% DOBANOL C₁₂₋₁₅-EO(3) and 80% C₁₆-C₁₈-N-methylglucosamide is obtained and agglomerated with 10% sodium carbonate.

Second, the above particles are then coagglomerated with a high potency paste (70%) of a sodium salt of a C₁₄-C₁₅ alkyl sulfate and a C₁₂₋₁₅ EO(3) sulfate and zeolite A and an additional amount of sodium carbonate. These particles show good dispersibility of the C₁₆-C₁₈ N-methylglucosamide in cold water.

The total formulation of these particles (proportion of the detergent formulation after drying the agglomerate) is:

C₁₆₁-C₁₈-N-methylglucosamide 4.1%

DOBANOL C₁₂₋₁₅-EO(3) 0.94%

Sodium carbonate 4.94%

Zeolite A 5.3%

Na-C₁₄-C₁₅-alkyl sulfate 3.5%

Na-C₁₂₋₁₅-EO(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 phthalocyanine (photobleaching agent) 0.02%

D. Spray composition

DOBANOL C₁₂₋₁₅-EO(3) 2.60%

Perfume 0.53%

E. Foam suppressant

Dow Corning’s silicone X2-3419 (95%-97% linear high molecular weight silicone; 3%-5% hydrophobic silica) used as a foam suppressor is mixed with zeolite A (with a size of 2-5 µ), starch and stearyl alcohol as a binder. This particle has the following composition:

Zeolite A 0.22%

Strength 1.08%

X2-3419 0.22%

Stearyl alcohol 0.35%

The detergent preparation shows exceptional solubility, improved performance and exceptional foam control when used in European washing machines, e.g. using 85 g of detergent in an ABG brand washing machine at 30ºC, 40ºC, 60ºC and 90ºC cycles.

EXAMPLE 28

In any of the above examples, the fatty acid glucamide surfactant can be replaced by an equivalent amount of maltamide surfactant or mixtures of glucamide/maltamide surfactants obtained from vegetable sources. In the compositions, the use of ethanolamides appears to aid in the stability of the final formulations at cold temperatures. In addition, the use of sulfobetaine surfactants ("sultaine" surfactants) provides improved foaming.

In the event that particularly high-foaming compositions are desired, it is preferred that less than about 5%, more preferably less than about 2%, most preferably substantially no C₁₄ or higher fatty acids be present, as these can suppress foaming. Therefore, the person entrusted with the formulation of high-foaming compositions will desirably avoid incorporating foam-suppressing amounts of such fatty acids into high-foaming compositions containing the polyhydroxy fatty acid amides and/or prevent the formation of C₁₄ and higher fatty acids during storage of the finished compositions. A simple means is to use C₁₂ ester reactants to prepare the polyhydroxy fatty acid amides of the invention. Advantageously, the use of amine oxide or sulfobetaine surfactants can somewhat reduce the negative effects on foaming caused by the fatty acids.

The formulator who wishes to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% and more) of anionic or polyanionic substituents, such as the polycarboxylate builders, may find it useful to premix the brightener with water and the polyhydroxy fatty acid amide and then add the premix to the finished composition.

Polyglutamic acid or polyaspartic acid dispersants may be usefully employed with zeolite-built detergents. AE oil or flakes and DC-544 (Dow Corning) are other examples of useful foam controlling agents herein.

It will be apparent to those skilled in the art of chemistry that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein the linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein.

Claims (15)

1. A detergent composition containing a polycarboxylate builder, comprising one or more anionic, nonionic or cationic detersive surfactants or mixtures thereof, which composition contains at least 1% of a polyhydroxy fatty acid amide, optional detersive additives and optional auxiliary builders, the composition being characterized in that it (a) at least 1% by weight of a polycarboxylate detergent builder; and (b) said polyhydroxy fatty acid amide material has the formula wherein R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅-C₃₁ hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached to said chain or an alkoxylated derivative thereof, provided that in the case of liquid detergent compositions, detergent enzymes are excluded. 2. Composition according to claim 1, wherein the ratio of polycarboxylate builder to polyhydroxy fatty acid amide ranges from 1:10 to 10:1. 3. A detergent composition according to claim 2, wherein said composition contains at least 3% by weight of said polycarboxylate builder and at least 3% by weight of said polyhydroxy fatty acid amide. 4. A detergent composition according to claim 1, wherein the polycarboxylate builder is selected from the group consisting of ether polycarboxylates, ether hydropolycarboxylates, preferably oxydisuccinate, tartrate monosuccinate or tartrate disuccinate; citrates, polyacetates and succinates and mixtures thereof. 5. A detergent composition according to claim 1 comprising a phosphate or phosphonate builder in an amount of less than 10% by weight, preferably in an amount of substantially 0%, based on the total builder in said composition. 6. A composition according to claim 3, wherein with respect to said polyhydroxy fatty acid amide, R¹ is methyl, R² is C₁₁-C₁₇ alkyl or alkenyl, Z is -CH₂(CHOH)NCH₂OH, and n is an integer from 3 to 5 inclusive. 7. Composition according to claim 1, wherein with regard to said polyhydroxy fatty acid amide, Z is obtained from maltose. 8. Composition according to claim 1, wherein with regard to said polyhydroxy fatty acid amide Z is obtained from a mixture of monosaccharides, disaccharides and optionally higher saccharides, which mixture comprises at least 1% of at least one disaccharide, preferably maltose. 9. A composition according to claim 1 which is in liquid form and comprises a liquid carrier. 10. Composition according to claim 3, wherein the weight ratio of polycarboxylate to polyhydroxy fatty acid amide is in the range from 7:1 to 1:5, preferably from 7:1 to 1:1. 11. A detergent composition according to claim 1 comprising one or more anionic sulfate or sulfonate surfactants selected from the group consisting of alkyl sulfates, alkyl ester sulfonates, preferably methyl ester sulfonates, ethoxylated alkyl sulfates and alkylbenzene sulfonates. 12. A detergent composition according to claim 11 comprising more than 10% by weight of a polycarboxylate builder. 13. A process for improving the fabric cleaning performance of a detergent composition containing one or more anionic, non-ionic or cationic surfactants or mixtures thereof, at least 1% of a polycarboxylate builder, optional detersive additives and optional auxiliary builders, which process is characterized in that it incorporating at least 1% by weight of a polyhydroxy fatty acid amide material of the formula in said detergent composition, in which formula R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅-C₃₁₁ hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups, preferably a C₁₁-C₁₇-N-methylglucamide, C₁₁-C₁₇-N-methylmaltamide or mixtures of said glucamide and maltamide, or an alkoxylated derivative thereof, the ratio of polycarboxylate builder to polyhydroxy fatty acid amide being from 1:10 to 10:1; and comprising washing the fabrics with said composition in a conventional manner; provided that in the case of liquid detergent compositions, detergent enzymes are excluded. 14. The process of claim 13, wherein said Z residue in said polyhydroxy fatty acid amide is derived from mixed monosaccharides, disaccharides and polysaccharides obtainable from vegetable sources. 15. The process of claim 13, wherein said R² radical in said polyhydroxy fatty acid amide is C₁₅-C₁₇ alkyl, alkenyl or a mixture thereof.