WO1994012598A1

WO1994012598A1 - Cleaning with low-sudsing mixed polyhydroxy fatty acid amide nonionic/anionic surfactants

Info

Publication number: WO1994012598A1
Application number: PCT/US1993/011451
Authority: WO
Inventors: Jean-Pol Boutique; Athanasios Surutzidis; Daniel Stedman Connor; Jeffrey John Scheibel
Original assignee: The Procter & Gamble Company
Priority date: 1992-11-30
Filing date: 1993-11-24
Publication date: 1994-06-09
Also published as: JPH08503986A; MX9307508A; AU5678294A; EP0670875A1; CN1090880A; CA2148097A1

Abstract

Mixed nonionic/anionic surfactants which comprise polyhydroxy fatty acid amides and their sulfated analogs are used in various cleaning functions where low sudsing is desired. Thus, C10-C22 fatty acid N-alkyl glucamides are partly sulfated to form mixtures of the nonionic glucamide and the anionic glucamide sulfate. The resulting mixtures exhibit good cleaning of fabrics, dishware, skin and hair.

Description

CLEANING WITH LOW-SUDSING MIXED POLYHYDROXY FATTY ACID AMIDE NONIONIC/A IONIC SURFACTANTS

FIELD OF THE INVENTION The present invention relates to cleaning compositions an methods which employ low-sudsing detergent mixtures comprising nonionic surfactant and an anionic surfactant, both of which ar prepared from mainly renewable resources such as fatty esters an reducing sugars.

BACKGROUND OF THE INVENTION Most conventional detergent compositions contain mixtures o various detersive surfactants in order to remove a wide variety o soils and stains from surfaces. For example, various anioni surfactants, especially the alkyl benzene sulfonates, are useful for removing particulate soils, and various nonionic surfactants such as the alkyl ethoxylates and alkylphenol ethoxylates ar useful for removing greasy soils. Accordingly, mixtures o anionic and nonionic surfactants are used in many modern detergen compositions. Unfortunately, many such surfactants are prepare mainly from petrochemical feedstocks.

While a review of the l terature would seem to suggest that wide selection of surfactants is available to the detergen manufacturer, the reality is that many such materials ar specialty chemicals which are not suitable for routine use in lo unit cost items such as home laundering compositions. The fac remains that most home-use detergents still comprise one or mor of the conventional ethoxylated nonionic and sulfated o sulfonated anionic surfactants, presumably due to the economic an performance considerations noted below.

Considerable attention has lately been directed to nonioni surfactants which can be prepared using mainly renewabl resources, such as fatty acid esters and sugars. One such clas of surfactants comprises the polyhydroxy fatty acid amides Moreover, the combination of such nonionic surfactants wit conventional anionic surfactants such as the alkyl sulfates, alky benzene sulfonates, alkyl ether sulfates, and the like, has also been studied.

The formulation of mixed nonionic/anionic surfactant systems generally requires quite different raw materials, with attendant extra costs in storage, handling and manufacturing with respect to the individual nonionic and anionic surfactant components. Accordingly, once capital has been invested to manufacture and handle a given type of surfactant system, it may become economic¬ ally unattractive to change to a different surfactant system, even in the face of other advantages that the new system might afford.

In light of the foregoing, it would be advantageous to provide surfactant systems which comprise a mixture of nonionic and anionic surfactants, both of which can be prepared from renewable, non-petrochemical resources. It would additionally be advantageous to devise such surfactant systems which provide good detergency performance, as compared with current formulations. It would be of considerable additional economic advantage for such mixed nonionic/anionic surfactant systems to be manufactured mainly from the same basic feedstock materials. An additional factor to be considered is that the formulation of detergent compositions containing typical detersive surfactants usually results in products which have, to a more or less degree, the inherent tendency to form suds when the compositions are agitated in an aqueous medium. In many circumstances the formation of suds is desirable, and consumers have come to expect high, rich suds in various shampoo, personal cleansing and hand dishwashing compositions. On the other hand, in certain other compositions the presence of suds can be problematic. For example, most hard surface cleansers are designed to have low suds levels, thereby obviating the need for extensive rinsing of the surfaces after the cleanser has been applied. Likewise, some washing machines, especially European-style front-loading machines which are designed to use substantially less water than the more familiar American style top-loading machines, typically employ higher concentrations of detersive surfactants. Suds levels must be kept low or else the suds can actually spill from such machines. A similar situation occurs with most automatic dishwashing machines where surfactant levels are kept very low and suds controlling agents are used extensively to provide a nearly sudsless cleaning of dishware. Low sudsing can also be advantageous in concentrated laundering processes such as those described in U.S. Patents 4,489,455 and 4,489,574. Unfortunately, many of the polyhydroxy fatty acid amide surfactants are suds boosters and stabilizers, especially when used in combination with conventional anionic surfactants. Accordingly, the formulator of low sudsing detergent compositions either must curtail the use of this desirable class of surfactants when formulating low sudsing detergents, or must use relatively high amounts of suds controlling agents in such compositions.

It has now been discovered that the combination of properly selected nonionic polyhydroxy fatty acid amides with their anionic sulfated analogs quickly and easily provides superior mixed nonionic/anionic surfactant systems which are low-sudsing, which are derivable from the same feedstocks, thereby affording the manufacturing advantages noted above, and which are available from renewable resources such as plants.

BACKGROUND ART A method for preparing crude polyhydroxy fatty acid amides (glucamides) is described in U.S. Patent 1,985,424, Piggott, and in U.S. Patent 2,703,798, Schwartz. The use of such glucamides with various synthetic anionic surfactants is described in U.S. Patent 2,965,576, corresponding to G.B. Patent 809,060. The sulfuric esters of acylated glucamines are disclosed in U.S. Patent 2,717,894, Schwartz.

SUMMARY OF THE INVENTION The present invention encompasses a method for cleaning surfaces with low sudsing, comprising contacting the surface to be cleaned with an aqueous medium containing a low-sudsing mixed surfactant system which comprises: (a) a nonionic polyhydroxy fatty acid amide of the formula:

0 Rl R2 - C - N - Z (I) wherein R¹ is C2-C8 hydrocarbyl, especially when R¹ is n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, and the like, or a mixture thereof, R² is C5-C32 hydrocarbyl, especially C12-C18 hydrocarbyl, and Z is a polyhy- droxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two (in the case of glyceraldehyde), or at least three (in the case of other reducing sugars), hydroxyls directly connected to the chain; and (b) an anionic surfactant which is a member selected from the group consisting of the sulfated reaction products of said polyhydroxy fatty acid amides of formula (a), at a weight ratio of (a):(b) of from about 10:1 to about 1:10, preferably from about 1:3 to about 3:1, most preferably about 1:1. The invention also encompasses the mixture of said nonionic and anionic compounds (a) and (b) in the proportions indicated in the above method.

The method herein is suitable for a variety of cleaning purposes, including but not limited to: laundering fabrics; washing eating and cooking utensils, glassware and dishes in automatic washing machines; cleaning other hard surfaces, such as walls, floors, and other environmental surfaces including automo¬ biles, windows and the like; if low sudsing is desired, for personal cleansing such as cleaning skin or shampooing hair; or any other use where low sudsing is desired, or for other circumstances where a low interfacial tension is required, e.g., oil recovery.

Methods for cleaning wherein low sudsing is required prefer¬ ably uses compounds (both nonionic and the corresponding sulfated compound) wherein Rl is C3-C8 alkyl, especially C3 (i.e., n-propyl or iso-propyl) or C4 (n-butyl or iso-butyl), or C (n-hexyl) and without hydroxyalkyl, and especially where Rl + R² totals no more than about 20 carbon atoms so as to ensure good solubility even in liquid formulations. Such methods are particularly useful in automatic washing machines for fabric laundering.

The invention also provides a low-sudsing composition of matter which is especially adapted for use as the surfactant mixture in a fully-formulated detergent composition comprising said nonionic surfactant (a) and said sulfated nonionic surfactant (b) at a weight ratio of from about 1:10 to about 10:1, preferably about 1:3 to about 3:1, most preferably about 1:1.

The invention also encompasses fully-formulated low-sudsing detergent compositions comprising from about 2% to about 60% of such mixture of surfactants (a) and (b), together with various detersive adjuncts such as builders, enzymes, bleaches and the like.

All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION While the polyhydroxy fatty acid amides used herein can be prepared, for example, by the methods disclosed in the Schwartz or Piggott references above, this invention most preferably employs high quality polyhydroxy fatty acid amide surfactants which are substantially free of cyclized by-products.

As an overall proposition, the preparative methods described in WO-9,206,154 and W0-9,206,984 will afford high quality poly- hydroxy fatty acid amides. The methods comprise reacting N-alkylamino polyols with, preferably, fatty acid methyl esters in a solvent using an alkoxide catalyst at temperatures of about 85^*C to provide high yields (90-98%) of polyhydroxy fatty acid amides having desirable low levels (typically, less than about 1%) of sub-optimally degradable cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2. Use of N-C2-C8 alkylamino polyols yields low-sudsing compounds of the type employed herein. (With some of the low sudsers, e.g., n-butyl, iso-butyl, n-hexyl, the methanol introduced via the catalyst or generated during the reaction provides sufficient fluidization that the use of additional reaction solvent may be optional.) If desired, any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, to minimize the overall level of amines in the product.

By "cyclized by-products" herein is meant the undesirable reaction by-products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures which may not be readily biodegradable. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substituents) is naturally "capped" by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein.

By "low sudsing" herein is meant a suds height or suds volume for the low sudsing detergent compositions herein containing the C3-C8 N-alkyl polyhydroxy fatty acid amide surfactant which is substantially less than that which is achieved in comparable compositions containing the N-methyl polyhydroxy fatty acid amide surfactant. Typically, the compositions herein provide sudsing which is no greater, on average, than about 70%, preferably no greater than about 50%, of that produced with the N-methyl surfactants. Of course, the sudsing can be still further reduced by means of standard suds control agents such as the silicones, various fatty materials and the like.

For the convenience of the foπnulator, a useful test procedure for comparing the sudsing of the low-suds compositions herein is provided hereinafter. The test comprises agitating aqueous solutions containing the detergent being tested in a standardized fashion and comparing sudsing against equivalent detergents containing the N-methyl polyhydroxy fatty acid amide. This particular test is run at ambient temperature (ca. 23*C) and at 60^*C, and at water hardness (3:1 Ca:Mg) levels of 10.4 gr/gal (179 ppm) and 25 gr/gal (428 ppm) to mimic a wide variety of prospective usage conditions. Of course, the formulator may modify the test conditions to focus on prospective usage conditions and user habits and practices throughout the world.

Sudsing Test Suds cylinders having the dimensions 12 inch (30.4 cm) height and 4 inch (10.16 cm) diameter are releasably attached to a machine which rotates the cylinders 360^* around a fixed axis. A typical test uses four cylinders, two for the standard comparison detergent product and two for the low sudsing detergent test product.

In the test, 500 mL of aqueous solution of the respective detergents is placed in the cylinders. Conveniently, the solutions comprise 3 g of the detergent, but other amounts can be used. The temperature of the solutions and their hardness are adjusted as noted above. Typically, CaCl2 and MgCl2 salts are used to supply hardness. The cylinders are sealed and the 500 ml level marked with tape. The cylinders are rotated through two complete revolutions, stopped and vented.

After the foregoing preparatory matters have been completed, the test begins. The cylinders are allowed to rotate 360* on the machine at a rate of 30 revolutions per minute. The machine is stopped at one minute intervals, the suds height from the top of the solution to the top of the suds is measured, and the machine is restarted. The test proceeds thusly for 10 minutes. A suds "volume" is calculated by taking the average suds height over the test time (10 minutes) and can be expressed as suds volume per minute (cm), which conforms with: suds volume per minute - sum of suds height at each time of measurement divided by total time (10 minutes).

It is to be understood that the foregoing test provides a relative comparison between low sudsing detergent compositions of the type provided herein vs. standard comparison products. Stated otherwise, absolute values of suds heights are meaningless, since they can vary widely with solution temperature and water hardness. To Illustrate this point further, an N-n-propyl polyhydroxy fatty acid amide (low sudser) exhibits suds volumes per minute in the above test of: 0.5 cm at T-ambient, hardness 10.4; 2.1 cm at T-amblent, hardness 25. In comparison, the respective figures for a tallowalkyl N-methyl glucamide (high sudser) are 1 cm and 3.3 cm.

Ingredients More specifically, the compositions and processes herein use low-sudsing polyhydroxy fatty acid amide surfactants of the formula:

0 Rl (I) R2 - C - N - Z

(and their corresponding sulfated reaction products) wherein: R is C2-C8 hydrocarbyl, especially C3-C6 alkyl; and R² is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C19 alkyl or alkenyl, or mixtures thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde which can be considered to be a sugar for the present purposes) or 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety. Suitable reducing sugars include glucose, fructose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be understood that it is by no means intended to exclude other suitable raw materials. Z preferably will be selected from the group consisting of -CH2~(CHOH)_n-CH20H, -CH(CH2θH)-(CHOH)_n-i-CH2θH, -CH2-(CHOH)2(CHOR')(CHOH)-CH2θH, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CH0H)4-CH20H.

In Formula (I), Rl can be, for example, N-n-propyl, N-iso- propyl, N-n-butyl, N-1sobutyl, N-n-hexyl, or N-2-ethyl hexyl.

R²-CO-N< can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxyxylityl, 1-deoxymaltityl, l-deoxylact1tyl, 1-deoxygalactityl, 1-deoxyman- nityl, 1-deoxymaltotriotityl, 2,3-dihydroxypropyl (from glyceral- dehyde), etc.

It will be appreciated that the polyhydroxy fatty acid amide surfactants used herein as the nonionic surfactant component can be mixtures of materials having various substituents Rl and R².

SULFATION REACTION It is to be understood that the anionic sulfation products used herein are believed to be mainly mono-sulfates on the ter¬ minal hydroxyl substituent of the polyhydroxy fatty acid amides. However, since the amides do contain multiple hydroxyl groups where sulfation can occur, the di-, tri-, tetra-, etc. sulfates can be formed in varying amounts and be co-present in the composi¬ tions. Indeed, it appears that using the syntheses disclosed herein, approximately 10% di-sulfation can routinely occur. The presence of such poly-sulfated materials does not detract from the performance herein, and no special purification steps need be used to remove them.

Coconut Glucose Amide Sulfate - One mole of coconut N-n- propyl glucose amide (mainly CnH23C0N(n-C3H7)CH2[CH0H]4CH20H, made from 95% C12 methyl ester), is dissolved in dry chloroform. (Note: chloroform is passed through silica gel to -dry and to remove ethanol). Dry apparatus is used. One mole of chlorosul- fonic acid is dissolved in chloroform and the acid solution is dripped into the glucose amide solution at 54*C (15 minutes) with stirring under a nitrogen blanket. The solution is stirred an additional 45 minutes with a nitrogen sweep at 50^*C to evaporate off about half of the chloroform and cooled below 30^*C. The acid solution is slowly poured into a vigorously stirred, ice cooled base solution. The pH is monitored to assure that it remains basic at all times. A mixture with a final pH of 9.0 is achieved with IN sodium hydroxide. The mixture is evaporated at ambient in a dish in hood-air stream for one week with occasional stirring to remove chloroform.

In an alternative process, the coconut N-n-propyl glucose amide sulfate is made in ^' multi-step process, as follows. Step 1 - 0.5 moles of said glucose amide are dissolved in methylene chloride in a reaction flask. Step 2 - 0.5 moles of a 1:1 (mole basis) pyridine/S03 complex obtained from Aldrich Chemical Company are added to the reaction flask. The reaction is allowed to proceed at room temperature for three days (a matter of conveni¬ ence; other reaction times can be used, depending on temperature, etc.). Step 3 - Sodium carbonate is dissolved in water and added to the reaction flask with mixing for four hours. Step 4 - The crude reaction mixture is evaporated and the residue taken up in ethanol . Step 5 - The methanol is dried over MgSθ4 and the solids removed by vacuum filtration. Step 6 - The methanol solution is decolorized with charcoal; the charcoal is removed by filtration through a Celite bed. Step 7 - Excess methanol is evaporated on a rotary evaporator (60^*C; vacuum). The residue is slurried with ethyl acetate (slightly warm). Step 8 - The ethyl acetate slurry is cooled to room temperature and the solids allowed to settle. The ethyl acetate containing the desired sulfated glucamide surfactant is decanted from the solids and the solvent removed by evaporation. Step 9 - The solids remaining after evaporation of the ethyl acetate are ground by mortar and pestle and dried in a vacuum oven (25^*C; 20 mm pressure).

The aforesaid sulfated product is mixed with the unsulfated C12-C14 N-(n-C3H7) glucamide at any desired ratio to provide the mixed nonionic/anionic surfactants of the invention. In an alternate mode, the sulfation reaction uses one-half the stated amount of pyridine/S03 to provide a 1:1 mixture of nonionic/ani¬ onic without further work-up. Tallow (Ci6-Ci8) N-n-hexylglucamide, C1 -C14 N-iso-propyl glucamide C12-C14 N-n-butyl glucamide, C12-C14 N-isobutyl glucamide and C12- 14 N-n-hexyl fructamide are each sulfated similarly to the above-noted multi-step process, except that pyridine is used in place of methylene chloride as the solvent in the first step. The respective sulfated products are used to prepare the mixed compositions of this invention.

The sulfated polyhydroxy fatty acid amides used herein as the anionic surfactant component can also comprise the sulfated reaction product of polyhydroxy fatty acid amides having a mixture of Rl and R² substituents.

Mo/Ca Salts The sulfated polyhydroxy fatty acid amide surfactants used herein are conventionally prepared in their acid or alkali metal (e.g., Na, K) salt forms, or as ammonium or alkanolammonium salts, e.g., triethanolammonium. These counterion salts are non-limiting examples of typical sulfated detergents. However, in circum¬ stances where high grease removal performance is of particular importance, the formulator may find it advantageous to incorporate at least about 0.5%, preferably from about 0.6% to about 2%, by weight of magnesium ions, calcium ions, or mixtures thereof, into the finished detergent composition. This can be done by simply adding various water-soluble salts such as the chlorides, sul- fates, acetates, formates, malates, maleates, etc. of magnesium or calcium to the compositions. (Preferably, if such compositions contain builders, they will be selected from non-phosphate builders, especially citrate, zeolite and layered silicate.) It is also useful to generate the magnesium and/or calcium salts of the sulfated polyhydroxy fatty acids herein by reacting Mg(0H)2 or Ca(0H)2 with the acid form of the sulfated polyhydroxy fatty acid amide, and this can conveniently be done in situ during the formulation of the finished detergent compositions or as a separ¬ ate step during the manufacture of the sulfated surfactant, itself.

The aforesaid nonionic/anionic mixtures can be. used with conventional "detersive adjunct" materials to provide fully- formulated detergent compositions. The "detersive adjunct" materials will vary, depending on the intended end-use of the final compositions. The following are intended only to be nonlimiting illustrations of such adjuncts, more examples of which will readily come to mind of the skilled formulator.

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

Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition. Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade nam ESPERASE. The preparation of this enzyme and analogous enzymes i described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stain that are commercially available include those sold under th tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (Th Netherlands). Other proteases include Protease A (see Europea Patent Application 130,756, published January 9, 1985) an Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).

Amylases include, for example, α-amylases described i British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulases usable in the present invention include bot bacterial or fungal cellulase. Preferably, they will have a p optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2.247.832.

Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also lipases in Japanese Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from A ano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafter referred to as "Amano- ." Other commercial lipases include Amano-CES, lipases ex Chromobacter viscosυm, e.g. Chromobacte viscosum var. l ipolyticum NRRLB 3673, commercially available fro Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosu lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladiol i . Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution. Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorp¬ oration into synthetic detergent granules is also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al (). Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. Patent 4,261,868, Hora et al, issued April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued August 17, 1971 to Gedge, et al, and European Patent Application Publication No. 0 199405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.

In addition to enzymes, the compositions herein can option- ally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbon- ates), sulphates, and aluminosilicates. However, non-phosphate builders are required in some locales. Importantly, the composi¬ tions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders. Moreover, the polyhydroxy fatty acid amides herein actually seem to perform best in the presence of weak, nonphosphate builders wherein some free Ca++ or Mg++ is present.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 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 to H. P. Rieck. However, other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Aluminosilicate builders are especially useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent composi¬ tions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula: M_z(zAlθ2-ySiθ2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2; and y is 1; this material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaC03 hardness per gram of anhydrous aluminosili- cate. Preferred aluminosilicates are zeolite builders which have the formula:

Na_z[(A10₂)_z (Si0₂)y]-xH₂0 wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commer¬ cially available.- These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosili¬ cates or synthetically derived. A method for producing alumino- silicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Kru mel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Nai2[(A10₂)l2(Siθ2)i2]-xH₂0 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarbox late compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al , U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.

Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxy- polycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, poly aleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular composi¬ tions, especially in combination with zeolite and/or layered silicate builders. Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5- 20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuc- cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al , issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.

Fatty acids, e.g., C12-C18 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, the various alkali metal phosphates such as the well known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1,1- diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Bleaching Compounds - Bleaching Aoents and Bleach Activators

The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more .bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein, but, under some conditions, may undesirably interact with the polyol nonionic surfactant.

One category of bleaching agent that can be used without restriction encompasses percarboxylic ("percarbonate") acid bleaching agents and salts therein. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application.0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxy- hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

Mixtures of bleaching agents can also be used. Peroxygen bleaching agents and the perborates are preferably combined with bleach activators, which lead to the in situ produc- tion in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al , and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non- oxygen bleaching agent of particular interest includes photo- activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al . Typically, detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zin phthalocyanine.

Polymeric Soil Release Agent - Any polymeric soil releas agent known to those skilled in the art can optionally be employe in the compositions and processes of this invention. Polymeri soil release agents are characterized by having both hydrophili segments, to hydrophilize the surface of hydrophobic fibers, suc as polyester and nylon, and hydrophobic segments, to deposit upo hydrophobic fibers and remain adhered thereto through completio of washing and rinsing cycles and, thus, serve as an anchor fo the hydrophilic segments. This can enable stains occurrin subsequent to treatment with the soil release agent to be mor easily cleaned in later washing procedures.

The amount of mixed nonionic/anionic surfactant needed t enhance deposition will vary with the particular soil releas agent chosen, the optional presence or absence of other anioni surfactants, and their type, as well as the particula nonionic/anionic chosen. Generally, compositions will compris from about 0.01% to about 10%, by weight, of the polymeric soi release agent, typically from about 0.1% to about 5%, and fro about 4% to about 50%, more typically from about 5% to about 30 of anionic surfactant. Such compositions should generally contai at least about 1%, preferably at least about 3%, by weight, of th mixed nonionic/anionic surfactant of this invention, though it i not intended to necessarily be limited thereto.

The polymeric soil release agents for which performance i enhanced herein especially include those soil release agent having: (a) one or more nonionic hydrophile components consistin essentially of (i) polyoxyethylene segments with a degree o polymerization of at least 2, or (ii) oxypropylene or polyoxy propylene segments with a degree of polymerization of from 2 t 10, wherein said hydrophile segment does not encompass an oxypropylene unit unless it is bonded to adjacent moieties a each end by ether linkages, or (iii) a mixture of oxyalkylen units comprising oxyethylene and from 1 to about 30 oxypropylen units wherein said mixture contains a sufficient amount o oxyethylene units such that the hydrophile component has hydro philicity great enough to increase the hydrophilicity o conventional polyester synthetic fiber surfaces upon deposit o the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkyl¬ ene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate:C3 oxyalkylene terephthalate units is about 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (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 substitu- ents, or mixtures therein, wherein said substituents are present in the form of C1-C4 alkyl ether or C4 hydroxyalkyl ether cellu¬ lose derivatives, or mixtures therein, and such cellulose deriva¬ tives are amphiphilic, whereby they have a sufficient level of C1-C4 alkyl ether and/or C4 hydroxyalkyl ether units to deposit upon conventional polyester synthetic fiber surfaces and retain a sufficient level of hydroxyls, once adhered to such conventional synthetic fiber surface, to increase fiber surface hydrophilicity, or a combination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(1) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150, more prefer¬ ably from 6 to about 100. Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as Mθ3S(CH2)nOCH2CH2θ-, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.

Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METH0CEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al .

Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-Cδ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud, et al . Commercially available soil release agents of this kind include the S0KALAN type of material, e.g., S0KALAN HP-22, available from BASF (West Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. The molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.

Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELC0N 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone. These soil release agents are described fully in U.S. Patent 4,968,451, issued November 6, 1990 to J. J. Scheibel and E. P. Gosselink.

Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink. Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo- aroyl, end-capped terephthalate esters. If utilized, soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi¬ tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydroxyethylethylenedi- aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri- onates, triethylenetetraaminehexaacetates, diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein. Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephos- phonates), nitrilotris (methylenephosphonates) and diethylenetri- aminepentakis (methylenephosphonates). Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethyl- enediamine disuccinate ("EDDS"), as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi¬ tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.

Clay Soil Re oval/Anti-redeposition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-nedeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986. Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds dis¬ closed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. Another type of preferred anti- redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein. These materials can also aid in calcium and magnesium hardness control. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

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

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of aerylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982.

Another polymeric material which can be included is poly¬ ethylene glycol (PEG). PEG can exhibit dispersing agent perform¬ ance as well as act as a clay soil removal/antiredeposition agent. Typical molecular weight ranges 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.

Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.

Brightener - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley. & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the present compositions are those identified 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 disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba- Geigy; Arctic White CC and Artie White CWD, available from Hilton- Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l,2- d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis- (styryl)bisphenyls; and the y-aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.

Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention. The incorporation of such materials, herein¬ after "suds suppressors," can be desirable to further reduce the already-low sudsing of the mixed nonionic/anionic surfactants herein. Additional suds suppression can be of particular importance when the detergent compositions herein optionally include a relatively high sudsing surfactant in combination with the low-sudsing mixed nonionic/anionic surfactants of this invention.

A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. The detergent compositions herein may also contain non- surfactant suds suppressors. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkyl elamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanurie chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and onostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40^*C and about 5^*C, and a minimum boiling point not less than about 110'C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about lOO'C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al . The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, and heterocyelic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

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

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

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

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs. at 25^*C; (ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3 Si0ι 2 units of Siθ2 units in a ratio of from (CH3)3 Si0ι/2 units and to Siθ2 units of from about 0.6:1 to about 1.2:1; and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel; In the preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and not linear.

To illustrate this point further, typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from abut 0.05 to about 0.5, weight

% of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents

4,978,471, Starch, issued December 18, 1990, and 4,983,316,

Starch, issued January 8, 1991, and U.S. Patents 4,639,489 and 4,749.740, Aizawa et al at column 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/poly- propylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %. The preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol .

The preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-Ci6 alkyl alcohols having a Cj-Cje chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark IS0F0L 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washing machines, suds should not form to the extent that they overflow the washing machine. Suds suppressors, when utilized, are preferably present in a "suds suppressing amount." By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.

The compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition. Preferably, from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized. Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from about 0.01% to about 1% of silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. As used herein, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging- from about 0.01% to about 5.0%, although higher levels can be used.

In addition to the foregoing ingredients, the surfactant compositions herein can also be used with a variety of other adjunct ingredients which provide still other benefits in various compositions within the scope of this invention. The following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.

Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. The polyhydroxy fatty acid amides of the present invention cause less interference with the softening performance of the clay than do the common polyethylene oxide nonionic surfactants of the art. Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.

Optional Additional Surfactants - The compositions herein are designed to provide good cleaning with quite low sudsing. Accord¬ ingly, if the formulator wishes to incorporate additional high sudsing surfactants into the compositions to provide various auxiliary cleaning benefits, it is preferred that such surfactants be used at levels less than about 10% by weight. If levels up to 30% by weight are used, then it is preferable to also employ one or more of the suds suppressors noted above to help maintain low sudsing.

Nonlimiting examples of optional (albeit high sudsing) surfactants useful herein include the conventional Cπ-Ci6 alkyl benzene sulfonates, the C12-C18 primary and secondary alkyl sulfates and C12-C18 unsaturated (alkenyl) sulfates such as oleyl sulfate, the Cio-Ciβ alkyl alkoxy sulfates (especially ethoxy sulfates), the Cιo^-C18 alkyl polyglycosides and their correspond¬ ing sulfated polyglycosides, C12-C18 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C1 -C18 bataines and sulfobetaines, Cio-Cjβ amine oxides, and the like, having due regard for the effects on sudsing noted above. Polyhydroxy fatty acid amides wherein Rl is methyl can also be used. Other conven- tional useful surfactants are listed in standard texts.

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

Various detersive ingredients employed in the present compo¬ sitions advantageously can be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate this technique in more detail, a porous hydro- phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 ethoxylated alcohol E0(7) nonionic surfactant. Typically, the enzyme/surfact¬ ant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The result¬ ing silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in deter¬ gents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine,, and 1,2- propanediol) can also be used.

The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

The following are typical, nonlimiting examples which illustrate the use of the mixed nonionic/anionic surfactant systems provided by this invention to prepare fully-formulated detergent compositions.

EXAMPLE I

A liquid detergent composition herein comprises the following.

Ingredient % (wt.)

Nonionic/anionic* 15.0

Sodium citrate 1.0

Cio alcohol ethoxylate (3) 13.0

Monoethanolamine 2.5

Water/propylene glycol/ethanol (100:1:1) Balance

*1:1 mixture of coconutalkyl N-n-propyl glucamide and its sulfated counterpart surfactant, Na salt. EXAMPLE u A granular detergent herein comprises the following. Ingredient % (wt.)

Nonionic/anionic* 10.0 Zeolite A (1-10 micrometer) 30.0

Sodium citrate 10.0

Sodium carbonate 20.0

Optical brightener 0.1

Detersive enzyme** 1.0 Ci4-i6 fatty acid 5.0

Sodium sulfate 15.0

Water and minors Balance

*1:1 mixture of tallowalkyl N-n-hexyl glucamide and its sul¬ fated counterpart surfactant, Na salt. **Lipolytic enzyme preparation (LIPOLASE).

EXAMPLE III The compositions of Example II and III are modified by including 0.5% of a commercial proteolytic enzyme preparation (ESPERASE) therein. Optionally, 0.5% of a commercial amylase preparation (TERMAMYL) and 0.5% of a commercial lipolytic enzyme preparation (LIPOLASE) can be co-incorporated in such detergent compositions.

EXAMPLE IV A washing composition with high grease removal properties is as follows.

Ingredient % (wt.)

Nonionic/anionic* 20.0

Coconut monoethanolamine 1.0

Water Balance *Cl2-Cl4 fatty acid amide of N-n-propyl glucamine or N-ethyl fructamine, sulfated to provide a 3:1 nonionic:sulfated anionic mixture and neutralized partly with MgSθ4 and partly with NaOH to provide a Mg content in finished detergent compositions of 1.6%.

EXAMPLE V A stable, clear, transparent liquid heavy duty laundry detergent suitable for use in European-style front-loading washing machines is as follows. Ingredient % (wt.)

C12-14 N-n-propyl glucamide 8.0

C12-14 N-n-propyl glucamide sulfate 8.0

Ci2-14 ethoxylated alcohol (E07) 2.5 Palm kernel fatty acids 6.0

Citric acid (as anhydrous) 3.0

Ethanol 3.0

1,2-propanediol 4.0

Monoethanolamine/NaOH to 7.8-8.0 Water and minors Balance

EXAMPLE VI A heavy duty laundry granule suitable for use in a European washing machine is as follows.

Ingredient % (wt.) 12-I8 N-n-propyl glucamide sulfate 9.0

C12-I8 N-n-propyl glucamide 6.0

Zeolite A (1-10 microns) 20.0

Sodium silicate 4.0

Sodium carbonate 10.0 Polyacrylate-maleate copolymer* 4.0

Diethylene triamine pentakis (methylene phosphonic acid) 0.4

Tetraacetylethylenediamine 5.0

Sodium citrate 7.0 Sodium perborate-IH2O 16.0

Water and minors Balance

^♦Available from BASF Corp. under the trade name S0KALAN CP5.

EXAMPLE VII The compositions of Examples V and VI are, respectively, modified by replacing the nonionic and anionic N-n-propyl polyhy¬ droxy fatty acid amides with their respective N-n-butyl, N-isobutyl and N-n-hexyl counterpart compounds to secure low- sudsing compositions.

The foregoing disclosure and Examples illustrate the practice of this invention in considerable detail. It is to be appreci¬ ated, however, that the advantages afforded by the compositions and processes of this invention are broadly useful with a variety of other technologies which have been developed for use in a wide variety of modern, fully-formulated cleaning compositions, espe¬ cially laundry detergents. The compositions herein will typically be used in aqueous media at concentrations of at least about 200 ppm, e.g., for lightly-soiled fabrics and/or hand dishwashing. Higher usage concentrations in the range of 1,000 ppm to 8,000 ppm, and higher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user, soil loads, soil types, and the like. Wash temperatures can range from 5^*C to the boil. As disclosed hereinabove, the mixed nonionic/anionic composi¬ tions herein can also comprise mixtures of nonionic compounds of formula I, wherein Rl is C -C8 alkyl with their anionic, sulfated counterpart compounds wherein Rl is methyl. Likewise, the mixed nonionic compositions can comprise mixtures of nonionic compounds of formula I wherein Rl is methyl and their anionic, sulfated compounds wherein Rl are C2-C8 alkyl. In such mixtures, the weight ratio of .the nonionic:anionic compounds typically ranges from about 10:1 to about 1:10.

Claims

1. A method for cleaning surfaces with low sudsing, character¬ ized in that it comprises contacting the surface to be cleaned with an aqueous medium containing a mixed nonionic/anionic sur¬ factant system which comprises a polyhydroxy fatty acid amide (a) of the formula:

0 Rl

- •» ' R² - C - N - Z wherein Rl is C2-C8 hydrocarbyl, R² is C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and

(b) an anionic surfactant which is a member selected from the group consisting of sulfated polyhydroxy fatty acid amides of said formula (a), at a weight ratio of (a):(b) of from 10:1 to 1:10.

2. A method according to Claim 1 which comprises laundering fabrics.

3. A method according to Claim 1 wrierein a secondary (2,3) alkyl sulfate is also present in the aqueous medium.

4. A method according to Claim 1 which comprises washing eating utensils or other hard surfaces.

5. A method according to Claim 1 which comprises cleansing skin or shampooing hair.

6. A method according to Claim 1 wherein Rl is n-propyl, n-butyl, isobutyl or n-hexyl, whereby cleaning is achieved with low sudsing.

7. A method for laundering fabrics in an automatic washing machine according to Claim 6.

8. A method for washing eating utensils in an automatic dish¬ washer according to Claim 6.

9. A method for cleaning hard surfaces according to Claim 6.

10. A composition of matter which is especially adapted for use as the surfactant mixture in a detergent composition, character¬ ized in that it comprises (a) a polyhydroxy fatty acid amide of the formula:

0 Rl

- ⁿ i R² - C - N - Z wherein Rl is C2-C8 hydrocarbyl, or a mixture thereof, R² is

C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and

11. A low sudsing composition according to Claim 10 wherein Rl is selected from n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl and n-hexyl, and wherein R² is C12-C18 hydrocarbyl.

12. A low-sudsing composition according to Claim 10 wherein Rl is C3-C8 hydrocarbyl and the combination of Rl and R² comprises a total of no more than 20 carbon atoms.

13. A composition of matter, characterized in that it comprises: (a) a polyhydroxy fatty acid amide of the formula:

0 Rl R² - C - N - Z wherein Rl is C2-C8 hydrocarbyl, or mixture thereof, R² is C5-C32 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two hydroxyls directly connected to the chain; and (b) a sulfated reaction product of the foregoing polyhydroxy acid amide having Rl as methyl; at a weight ratio of (a):(b) of from 1:10 to 10:1.

14. A composition of matter, characterized in that it comprises:

(a) a polyhydroxy fatty acid amide of the formula:

0 Rl R² - C - N - Z wherein Rl is methyl, R² is C5-C32 hydrocarbyl and Z is a polyhydroxyhydrocarbyl moiety having a linear hydro¬ carbyl chain with at least two hydroxyls directly connected to the chain; and

(b) a sulfated reaction product of the foregoing polyhydroxy fatty acid amide having Rl as C2-C8 alkyl; at a weight ratio (a):(b) of from 1:10 to 10:1.