WO1997044420A2

WO1997044420A2 - Detergent composition

Info

Publication number: WO1997044420A2
Application number: PCT/US1997/008279
Authority: WO
Inventors: Kaori Asano; Stuart Clive Askew; Hajime Baba; Andre Cesar Baeck; Jean-Luc Bettiol; Thomas Anthony Cripe; John Downing Curry; Schmidt, (De Rossett), Corey, Elizabeth; Ian Martin Dodd; Richard Timothy Hartshorn; Speed, (Jones), Lynda, Anne; Rinko Katsuda; Frank Andrej Kvietok; Mark Hsiang-Kuen Mao; Michael Alan John Moss; Susumu Murata; Royohei Ohtani; Rajan Keshav Panandiker; Kakumanu Pramod; Khizar Mohamed Khan Sarnaik
Original assignee: The Procter & Gamble Company
Priority date: 1996-05-17
Filing date: 1997-05-16
Publication date: 1997-11-27
Also published as: KR20000011102A; ZA974222B; AU3068397A; HUP9902979A2; WO1997044420A3; EP0918834A2; BR9709320A; CN1225672A; CA2254955A1; JPH11511793A; AR007771A1; MX9809625A

Abstract

Alkoxylated cationic surfactants, and mixtures thereof, are used in detergent compositions comprising a mixture of alkyl sulfate and alkylbenzene sulfonate surfactants.

Description

DETERGENT COMPOSITION

TECHNICAL FIELD

The present invention relates to detergent compositions which comprise selected mixtures of anionic surfactants and selected ethoxylated quaternary ammonium compounds.

BACKGROUND OF THE INVENTION

The formulation of laundry detergents and other cleaning compositions presents a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates. Thus, laundry detergents typically require the proper selection and combination of ingredients in order to function effectively. In general, such detergent compositions will contain one or more types of surfactants which are designed to loosen and remove soils and stains. However, the removal of body soils, greasy/oily soils and certain food stains quickly and efficiently can be problematic. Indeed, while some surfactants and surfactant combinations exhibit optimal performance on certain types of soils and stains, they can actually diminish performance on other soils. For example, surfactants which remove greasy/oily soils from fabrics can sometimes be sub- optimal for removing particulate soils, such as clay. While a review of the literature would seem to indicate that a wide selection of surfactants and surfactant combinations is available to the detergent manufacturer, the reality is that many such ingredients are specialty chemicals which are not suitable in low unit cost items such as home-use laundry detergents. The fact remains that most such home-use laundry detergents still mainly comprise one or more of the conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and the need to formulate compositions which function reasonably well with a variety of soils and stains and a variety of fabrics.

Accordingly, there is a continuing search for improvements in laundry detergents; however, the challenge to the detergent manufacturer seeking improved performance has been increased by various factors. For example, some non- biodegradable ingredients have fallen into disfavor. Effective phosphate builders have been banned by legislation in many countries. Costs associated with certain classes of surfactants has impacted their use. As a result, the manufacturer is somewhat more limited than the literature would suggest in the selection of effective, yet affordable, ingredients. Still, the consumer has come to expect high quality and high performance in such compositions even when laundering fabrics under cool or cold water conditions.

The literature does suggest that various nitrogen-containing surfactants would be useful in a variety of cleaning compositions. Such materials, typically in the form of amino-, amido-, or quaternary ammonium or imidazolinium compounds, are often designed for specialty use. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide a fabric softening and anti-static benefit. For the most part, however, the use of such materials is rather limited, and the aforementioned nonionic and anionic surfactants remain the major surfactant components in today's laundry compositions.

It has now been discovered that certain alkoxylated quaternary ammonium (AQA) compounds can be used in laundry detergents to boost performance. Importantly, it has further been discovered that low levels of these AQA compounds provide superior cleaning performance when used in certain combinations with conventional alkyl sulfate and alkyl benzene sulfonate surfactants at specified ratios and proportions. Thus, the present invention provides an improvement in laundry cleaning performance without the need to develop new, expensive surfactant species.

Moreover, the AQA surfactants used in the present manner provide substantial advantages to the formulator over cationic surfactants known heretofore. For example, the AQA surfactants herein are compatible with the preferred alkyl sulfate and alkyl benzene sulfonate detersive surfactants. Moreover, the AQA surfactants are formulatable over a broad pH range from 5 to 12. The AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a manufacturing plant. AQA surfactants with degrees of ethoxylation above 5 are sometimes in a liquid form and can be provided as 100% neat materials. In addition to their handling properties, the ability of the AQA surfactants herein to be provided as high concentrate solutions provides a substantial economic advantage in transportation costs. The AQA surfactants are also compatible with various perfume ingredients, unlike other quats known in the art.

In addition to the foregoing advantages, the AQA surfactants herein appear to minimize or eliminate redeposition of fatty acids/oily materials present in an aqueous laundry liquor back onto fabrics which have been previously soiled with body soils. Accordingly, the AQA surfactants herein have now been found to prevent the redeposition of polar lipids from an aqueous laundry bath back onto fabrics from whence body soils have been removed through the laundering process. Stated otherwise, in a laundering liquor, the AQA surfactants herein remove such polar lipids and keep them suspended in the aqueous medium, rather than allowing them to redeposit onto the cleaned fabrics.

In addition to the foregoing qualities, the AQA surfactants herein are surprisingly compatible with the polyanionic materials such as polyacrylates and acrylate/maleate copolymers which are used to provide a builder and/or dispersant function with many conventional detersive surfactants. Other advantages for the AQA surfactants herein include their ability to enhance enzymatic cleaning and fabric care performance in a laundering liquor. While not intending to be limited by theory, it is speculated that enzymes may be partially denatured by conventional anionic surfactants. It is further speculated that the AQA surfactants herein somehow interact with the anionic surfactants to inhibit that degradation. An alternate theory would suggest that, even when enzymes are used to degrade soils and stains, the degraded residues must be removed from the fabric surface. It may be speculated that the improved detersive performance embodied in the mixture of AQA and anionic surfactants herein simply does a better job in removing these residues from the fabric surface. In addition to the foregoing advantages, the AQA surfactants herein provide substantial cleaning enhancement with respect to clay soil removal from fabrics, as compared with conventional detergent mixtures. Again, while not intending to be limited by theory, it may be speculated that conventional cationic surfactants associate with the clay in "close-packed" fashion and render the clay more difficult to remove. In contrast, the alkoxylated AQA surfactants are believed to provide more open associations with clays, which are then more readily removed from fabric surfaces. Whatever the reason, the compositions herein containing the AQA surfactants provide improved performance over conventional cationic surfactants with special regard to clay soil removal. Still further advantages for the AQA surfactants herein have been discovered. For example, in bleaching compositions which comprise a bleach activator (as disclosed herein) it appears that some sort of ion pair or other associative complex is formed with the per-acid released from the activator. It may be speculated that this ion pair is carried more efficiently into the soil as a new, more hydrophobic agent, thereby enhancing bleach performance associated with the use of bleach activators such as nonanoyloxy benzene sulfonate (NOBS). Quite low levels (as low as 3 ppm in the laundering liquor) of AQA surfactants gives rise to these results.

Moreover, in compositions without bleach, the formulator my choose to use somewhat higher levels of AQA to provide enhanced performance benefits. These benefits may be associated with the ability of the AQA surfactants herein to modify the solution characteristics of conventional anionic surfactants such as alkyl sulfates or alkyl benzene sulfonates to allow more of the surfactants to be available to perform their cleaning function. This is particularly true in situations faced by the formulator where the detergent composition is "underbuilt" with respect to calcium and/or magnesium water hardness ions. Under such circumstances, it is preferred to use sufficient AQA surfactant to provide from about 10 ppm to about 50 ppm of the AQA surfactants in the wash liquor. This translates into compositional usage ranges from about 1% to about 5%, by weight, in fully-formulated detergent compositions. (This concentration can vary with product usage rates and the amount of other surfactant present in the wash liquor. For high product concentrations up to about 3500 ppm, the AQA level may be as high as 100-150 ppm in solution. This still only translates to 3-4% AQA surfactant in the finished detergent composition.)

It has further been discovered that the AQA surfactants herein containing about 2 ethylene oxide (EO) groups perform extremely well under circumstances of low water hardness or when well-built detergent compositions are used. However, under circumstances of high hardness (about 170 ppm calcium carbonate, and higher) it is more preferred to use AQA surfactants with at least about 5 EO groups. Moreover, for some soils and stains, such as fecal matter, AQA surfactants having on the order of 10-20 EO groups are preferred. Accordingly, it has now been discovered that mixtures of AQA surfactants can be blended and used to provide a broad spectrum of cleaning performance over a wide variety of soils and stains and under a wide range of usage conditions. Representative, but non-limiting, examples of such combinations of AQA surfactants are disclosed in the Examples hereinafter.

Various other advantages of the AQA surfactants over cationic surfactants known in the art are described in more detail hereinafter. As will be seen from the disclosures herein, the AQA surfactants, used in the manner of the present invention, successfully address many of the problems associated with the formulation of modern, high-performance detergent compositions. In particular, the AQA surfactants allow the formulation of effective laundry compositions which can be used to remove a wide variety of soils and stains under a wide spectrum of usage conditions. These and other advantages of the present invention will be seen from the following disclosures.

BACKGROUND ART U.S. Patent 5,441 ,541 , issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/cationic surfactant mixtures. U.K. 2,040,090, issued 3 Sept. 1980, to A. P. Murphy, R.J.M. Smith and M. P. Brooks relates to ethoxylated cationics in laundry detergents.

SUMMARY OF THE INVENTION The present invention encompasses a composition of matter comprising a mixture of, or prepared by combining, a cationic surfactant and a member selected from each of two classes of anionic surfactants, said surfactants having the respective formulae:

II R O S O ₃ M ,

III R SO₃ ^"M

and, optionally, but preferably

IV a nonionic surfactant wherein R* is an alkyl or alkenyl moiety containing from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R^ is an alkyl group containing from one to three carbon atoms, preferably methyl; R^J and R^ can vary independently and are selected from hydrogen (preferred), methyl and ethyl, R is a linear or branched alkyl or alkenyl moiety having from about 10 to about 20 carbon atoms, preferably C12 to Cjg alkyl or as found in secondary alkyl sulfates; R^ is C\Q-C\β alkylbenzene, preferably C j j -C j 3 alkylbenzene; M⁺ and M'⁺ can vary independently and are selected from alkali metals, alkaline earths, alkanolammonium and ammonium; X" is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy (i.e.. -CH2CH2O-), propoxy, butoxy and mixed ethoxy/propoxy; p is from 1 to about 30, preferably 1 to about 4 and q is from 1 to about 30. preferably 1 to about 4, and most preferably to about 4; preferably both p and q are 1. The weight ratio of (I) to (II) + (III) is preferably about 1 : 100 to about

1 :7, more preferably 1 :50-1 :10. The weight ratio of (II):(III) is preferably 4: 1-1 :4, more preferably 2: 1-1 :2. The weight ratio of R^ to R^ is preferably from 1 :13-1 :5.

AQA compounds wherein the hydrocarbyl substituent R' is Cg-C_j i , especially C \ Q, enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials.

Accordingly, the Cg-Cn AQA surfactants may be preferred by some formulators. The levels of the AQA surfactants used to prepare finished laundry detergent compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.

In a preferred embodiment, the composition comprises: surfactants (I), (II) and (III) in a weight ratio of (I) to (II + III) in a weight range of at least about 1 : 10. In a preferred embodiment said anionic surfactant (II) is a C^-Cjg primary or secondary alkyl sulfate (AS) and said anionic surfactant (III) is an alkyl benzene sulfonate with cx C\ \-C\τ, branched or linear alkyl chain.

In a highly preferred embodiment, the composition also comprises a nonionic surfactant which is a member selected from the group consisting of alcohol ethoxylates, alkylphenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides, and mixtures thereof.

Specific, highly preferred compositions herein comprise: (a) from about 0.25% to about 3%, by weight, of Coco Methyl EO2 as surfactant (I); (b) from about 3% to about 40%, by weight, of straight chain or branched chain primary or secondary AS as surfactant (II);

(c) from about 6% to about 23%, by weight, of alkyl benzene sulfonate (LAS) as surfactant (III); and

(d) from about 0.5% to about 20%, by weight, of a nonionic surfactant (IV). Other embodiments comprise:

(i) from about 0.45% to about 2%, by weight, of (a);

(ii) from about 6% to about 13%, by weight, of (b);

(iii) from about 8% to about 23%, by weight, of (c); and

(iv) from about 1% to about 5%, by weight, of (d). The invention also encompasses fully formulated detergent compositions comprising adjunct ingredients and at least about 3%. by weight, of the aforesaid detersive surfactant system, said surfactant system comprising a cationic surfactant, a mixture of anionic surfactants, and optional nonionic surfactants, all as disclosed above, and adjunct ingredients including those selected from the group consisting of builders, enzymes, soil release polymers, bleaches, clay soil removal/antiredeposition agents, polymeric dispersing agents, brighteners, dye transfer inhibiting agents, suds suppressors, fabric softeners, and other adjuncts disclosed herein, as well as detersive surfactants not encompassed by surfactants (I)- (IV), e.g., a member selected from the group consisting of soaps, oleyl sulfate, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, sulfated alkyl polyglycosides, alpha- sulfonated fatty acid esters, betaines, sulfobetaines, amine oxides and mixtures thereof. Mixtures of such adjunct ingredients may be used.

The AQA surfactants used in the manner of the present invention also provide an improved method for removing the following soils and stains from fabrics: blood; greasy food stain; particulate stain; body soils (including fabric "dinginess" caused by small, but noticeable, stain/soil accumulations over time) and other stains noted herein. Such stains and soils are removed from fabrics such as cotton, polyester/cotton blends (P/C) and double-knit polyester (DKPE). The method comprises contacting fabrics in need of removal of such soils with an effective amount of the compositions herein, in the presence of water, and preferably with agitation. Various suitable usage levels and methods are disclosed hereinafter. Moreover, the AQA surfactants herein, especially the preferred CocoMeEO2

("AQA-1 " hereinafter), provide improved fabric cleaning performance in the presence of bleach. This improvement in cleaning is seen at usage levels as low as 3 parts per million (ppm) of the AQA in the laundry liquor and is believed to be associated with increased perhydrolysis. In addition, the AQA surfactants herein, especially AQA-1, provide improved (even synergistic) performance with amylase and cellulase enzymes. This improvement is seen especially in the absence of bleach.

All percentages, ratios and proportions herein are by weight of ingredients used to prepare the finished compositions, unless otherwise specified. All documents cited herein are, in relevant part, incoφorated herein by reference. DETAILED DESCRIPTION OF THE INVENTION In one of its aspects, this invention provides a means for enhancing the removal of greasy/oily soils by combining a lipase enzyme with an AQA surfactant. Greasy/oily "everyday "soils are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter. When soiled garments are stored before washing, some triglycerides are converted by bacterial action to fatty acids; lipase enzymes can be used to convert any remaining triglycerides to fatty acids through-the-wash. Generally, for formulas relying on hardness control by diffusion builders (e.g., layered silicates) pseudo unbuilt conditions will be present early a the wash which features a large intake of cold water. In these first minutes, fatty acids in the soil interact with the unbuilt hardness to form insoluble calcium lime-soaps which then hinder subsequent soil removal and cause soil residues to remain on the fabric after the wash. In unbuilt formulations this greasy/oily stain insolubilization will cause even more of a problem. Upon successive wearing/washing, residues build-up, leading to yellowing and entrapment of particulate dirt. Eventually, garments become dingy, are perceived as unwearable and are often discarded.

It has now been found that detergent compositions containing AQA surfactants and lipase enzyme deliver superior cleaning and whiteness performance vs. products containing either technology alone. These benefits appear to be the result of: (1) AQA inhibiting lime soap formation (allowing unhindered lipase access to the soil); and (2) effective lifting off of fatty acids from the soil (by AQA) to ensure maximum lipase activity (high levels of fatty acids in the soil inhibiting lipase action).

This invention also provides improved cleaning and fabric care benefits by combining a cellulytic enzyme with an AQA surfactant. In older/worn cotton fabrics or other cellulosic fabrics the sheathes around individual fibres degrade to form gelatinous/amorphous cellulose "glues" which entrap dirt. In addition, the glue acts as an ideal substrate for deposition/retention of greasy /oily body soils (e.g., on collars and pillowcases) which are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter. Removal of these hydrophobic soils from worn fabrics is thus very difficult and low levels of residual stain often remain on the fabric after washing. Again, after successive wearing/washing these soils build up, leading to yellowing and more entrapment of dirt.

Surprisingly, it has now been found that detergent compositions containing the AQA surfactants and cellulytic enzymes (e.g., cellulases and/or endoglucanases) deliver superior cleaning and whiteness performance vs. products containing either ingredient alone. These benefits appear to be the result of the effective penetration of hydrophobic body soils by the AQA surfactants. This, in turn, boosts access of the cellulytic enzymes which degrade the amorphous cellulose glue (which binds the soil on the fabric) around the fibers. As the glue dissolves, the entrapped dirt is released and whiteness is restored. In addition to cleaning benefits, the combined cellulytic/AQA system also provides softness benefits vs. the cationic or enzyme alone; effective depilling and ungluing of worn fibers leads to improved fabric softness feel.

As noted, complete removal of the very hydrophobic "everyday" or "body" soils is difficult and low levels of residual soils often remain on the fabric after washing. These residues build up and act like an amorphous glue between the fibers, entrapping particulate dirt and leading to fabric yellowing. It has now further been discovered that detergent compositions containing a combination of the water- soluble AQA surfactants herein and amylase enzymes delivers superior cleaning and whiteness performance vs. compositions containing either technology alone. These benefits appear to be the result of much improved degradation of the residual "glue" around the fibers (AQA facilitating improved amylase access to sensitive soil components through effective soil solubilization). As the glue dissolves, whiteness is restored and entrapped particulate dirt is released/made accessible to the decolorizing action of other wash actives. This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils via use of percarbonate bleach with an AQA surfactant as disclosed herein. Percarbonate, which delivers peroxide bleach into the wash, is a cornerstone technology of modern, ultra-compact granular laundry detergent formulas. Peroxide bleach is very hydrophilic and, while it cannot match the bleaching effectiveness delivered by peracids (formed for example from peroxide interaction with TAED), it is effective at decoloration of pigments (e.g., in particulates or beverage stains) and also can help remove the color from the organic residues associated with body soils. Unexpectedly, it has now been discovered that compositions containing AQA surfactants and percarbonate bleach deliver superior cleaning and whiteness performance vs. products containing either technology alone. These benefits appear to be driven by the effective solubilization of the greasy oil soils by AQA, thereby allowing access of the hydrophilic peroxide bleach to the color bodies in the soil (e.g., entrapped pigments) and resulting in improved soil decoloration. This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils by means of hydrophobic bleach activators used in combination with a water-soluble AQA surfactant of the present type. Everyday soil cleaning and whiteness benefits for hydrophobic bleach activators and peracids have already been demonstrated. Such materials are, to a limited degree, able to penetrate complex/greasy oily soils. It has now been found that detergent and bleach compositions containing AQA and hydrophobic bleach activators (including preformed peracids) deliver superior cleaning and whiteness performance vs. similar compositions containing either technology alone. It may be reasonably speculated that the benefits for the combined system are driven by: (1) AQA action on the soil surface to prevent lime soap formation and to lift off any calcium soaps present, thereby boosting hydrophobic bleach access; (2) The significantly lower surface tension at the soil/wash liquor interface (driven by AQA). As surface tension falls the hydrophobic bleach (which acts like anionic surfactant) soil penetration is boosted; and (3) Possible interaction of the hydrophobic peracid with the AQA to form a very hydrophobic ion pair, which easily penetrates deep into the greasy soil. This invention also provides compositions which deliver effective cleaning of greasy/oily soils via use of bleach catalysts using an AQA surfactant. Bleach catalysts (characterized by the presence of at least one transition metal atom) interact with peroxide to form very powerful hydrophilic bleaches. These bleaches deliver strong benefits on colored hydrophilic stains and hydrophilic everyday soils (i.e., socks). The catalysts are typically used at extremely low levels in cleaning products. As disclosed herein, products containing AQA and catalysts deliver superior cleaning and whiteness performance vs. products containing either technology alone, and are especially potent on everyday soils. These benefits are believed to be driven by effective AQA solubilization on the greasy oil soils which allow access of the hydrophilic "catalyst" bleach to the color bodies in the soil, thereby leading to effective soil decolorization. Furthermore, historical use of bleach catalysts was made difficult because of concerns about fabric damage. Using a dimanganese catalyst, known to cause fabric damage, it has now been found that the occurrence of fabric damage is much reduced when AQA cationics are present. Presumably, these cationics adsorb onto fabrics where they modify the surface charge and are available to ion-pair with the activated catalyst to minimize or prevent fabric damage.

In another aspect, this invention allows the use of high levels of insoluble inorganic builders, without fabric encrustation, using layered silicates with a water- soluble AQA surfactant. Layered silicates are composed of discreet units some faces of which are negatively charged. It may be speculated that the positively charged head-group of AQA interacts, via electrostatic bond formation, with the negatively charged face to form a surfactant monolayer upon which a second "hydrophilic" surfactant layer builds up. This drives particle lift-off from fabrics, thereby minimizing encrustation which can otherwise result in a harsh "feel to the fabrics". This invention also allows the formulation of high levels of insoluble inorganic or soluble (bi)carbonate builders in compositions containing relatively low polycarboxylate polymers, without driving fabric encrustation issues by using the different types of builder with an AQA surfactant as disclosed herein. Historically, high molecular weight polycarboxylate polymers have been used as dispersants in granular laundry detergents. These polymers are, however, generally expensive. The polymers, as well as being effective at soil suspension, also effectively control fabric encrustation by lifting off inorganics (including builders/precipitated carbonates) from fabrics. Low polymer formulations known heretofore are prone to fabric encrustation shortcomings.

It has now been found that high levels of inorganic and/or (bi)carbonate builders can be used in combination with low levels of polymers and/or lower molecular weight polymers without increasing fabric encrustation by use of the AQA surfactants in the manner disclosed herein. Fabric encrustation problems are believed to be avoided for the low polymer system by two AQA mechanisms: (1) layered silicates and zeolites are composed of discreet units, some faces of which will be negatively charged. AQA, which has a positively charged headgroup, may interact with these faces to lift off the inorganics from fabrics by formation of hydrophilic, charged surfactant bilayers around the inorganic particles; and/or (2) AQA is more fabric substantive vs. anionic/nonionic surfactants. Accordingly, low levels of these materials adsorb onto fabric surfaces where they modify surface charge. Since the degree of carbonate encrustation is dependent on negative surface charge, the AQA adsoφtion (which modifies the cotton surface charge to neutral/positive) allows less encrustation to occur. In addition, AQA can adsorb onto the "growing" faces of calcium carbonate crystals, thereby inhibiting crystal growth and minimizing encrustation on fabrics.

This invention also provides detergent compositions which deliver effective cleaning of greasy/oily "everyday" soils (and accidental soils), via use of polyethoxyated-polyamine polymers (PPP) with the AQA surfactants herein. As noted, greasy/oily "everyday" soils (e.g., on collars, pillowcases) are a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter. Complete removal of these very hydrophobic soils is difficult and low levels of residual stain often remain on the fabric after washing. To improve performance in this key area, various soil dispersant polymers have been developed. Characteristic features of these materials include: (1 ) a reasonably low molecular weight "hydrophobic" polyamine backbone (which is slightly cationic in nature providing an affinity for soils and fabrics); and (2) pendant "hydrophilic" polyethoxylate groups which provide steric stabilization and greasy soil suspension. During the wash, these polymers work at the stain/wash liquor interface.

Suφrisingly, it has now been discovered that detergent compositions containing the AQA surfactants herein and ethoxylated polyamine polymers deliver superior cleaning and whiteness performance vs. compositions containing either technology alone. Benefits for the mixed system are believed to be the result of: ( 1 ) AQA action on the stain surface to prevent lime soap formation and to lift off any calcium soaps present, thereby facilitating improved polymer deposition; (2) AQA providing solubilization deep into the soil, while the polymer acts as a "grease removal shuttle", stripping out the AQA-solubilized stain components and dispersing them into the wash liquor.

This invention also provides detergent compositions which deliver effective cleaning of greasy/oily everyday soils, by means of use of high levels of surfactant (optionally including branched surfactants) with an AQA surfactant. In view of the importance of high surfactancy in the effective removal of greasy /oily body soil, modern "ultra-compact" detergent compositions generally contain high levels of surfactants (nonionic and anionic) and are fairly effective at body soil cleaning. Unexpectedly, it has now been found that products containing AQA and high levels of anionic or mixed anionic/nonionic surfactants (optionally including branched surfactants) deliver superior cleaning performance vs. products containing either technology alone. These benefits are driven by: (1) AQA action on the soil surface to prevent lime soap formation and lift off any calcium soaps present (these soaps, if allowed to form and left at the soil-wash liquor interface, would largely prevent surfactant access); (2) AQA lowering of the surface tension between the wash liquor and the greasy/oily soil, thereby driving more effective soil penetration by surfactant (hence boosting cleaning); and (3) Possible ion pair formation between the cationic and anionic surfactant to form a very hydrophobic surfactant "pair" molecule which penetrates deep into the greasy soil.

In addition, this invention provides detergent, bleach and other compositions which deliver improved perfume residuality on fabrics after the wash, via use of perfume with a water-soluble AQA surfactant. Natural and synthetic fabrics can be characterized by the surface charge on their fibers. Cotton is hydrophilic with a net negative surface charge, whereas polyester is hydrophobic with a neutral surface charge. Perfumes are a complex mixture of hydrophobic organic actives, including esters, alcohols, ketones, aldehydes, ethers, and the like. The fabric substantivity of different perfume actives depends on: (1) functionality (how polar they are); (2) the molecular weight of the active; and (3) the charge on the fabric fibers. Most perfume actives contain electron-rich oxygen atoms which will be attracted to electron deficient molecules/surfaces.

Unexpectedly, it has now been found that the combination of AQA surfactants with perfumes (characterized as having >10% of components with molecular weight >150) provides improved perfume fabric substantivity. While not intending to be limited by theory, it appears that, as well as increasing the hydrophobicity of anionic or anionic/nonionic surfactant systems, the AQA surfactants have high fabric substantivity (especially for cotton). The AQA surfactants appear to adsorb onto the fibers where they change the surface charge from neutral/negative to positive (or electron deficient). This modified fabric surface acts like a magnet to the electron rich domains of the perfume actives, thereby drawing them onto the fabrics where they are held electrostatically. This significantly increases perfume residuality. These benefits are most pronounced for perfume components having at least one oxygen atom and a molecular weight greater than 150. The level of such perfume ingredients should account for at least about 10% of the total perfume mixture to achieve the maximum benefit of this effect.

The alkoxylated quaternary ammonium ("AQA") compounds used according to the present invention enhance the cleaning performance of fabric laundry detergent compositions which contain select amounts of certain anionic surfactants. In this context, the AQA compounds herein also have the advantage that they are commercially accessible and are compatible with the various detersive ingredients such as builders, detersive enzymes, and the like, which are used in many modern, high quality, fully-formulated laundry detergents. Moreover, the AQA compounds exhibit satisfactory stability in the presence of the bleach ingredients commonly used in laundry detergent-plus-bleach compositions. Importantly, the AQA surfactants herein exhibit superior performance with respect to the removal of body soils and everyday soils such as sock soil. The combination of the AQA surfactants with the specified anionic surfactants removes such soils from fabrics. Moreover, the specified combination of the AQA surfactants with otherwise conventional anionic surfactants provides excellent cleaning performance on a variety of other soils and stains, including food stains, particulate soils and greasy/oily stains. In short, the compositions herein provide improved performance for cleaning a broad spectrum of soils and stains including body soils from collars and cuffs, greasy soils, and enzyme/bleach sensitive stains such as spinach and coffee. The compositions herein also provide excellent cleaning on builder sensitive stains such as clay, and thus are especially useful in a nil-P context. In contrast with other cationic surfactants known in the art, the bis- alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed surfactant systems which are quite low in nonionic surfactants and which contain, for example, alkyl sulfate surfactants. This can be an important consideration for formulators of detergent compositions of the type which are conventionally designed for use in automatic washing machines, especially of the type used in Japan, as well as under North American usage conditions. Typically, such compositions will comprise an anionic (total LAS/AS) surfactant:nonionic surfactant weight ratio in the range from about 25:1 to about 1 :25, preferably about 20:1 to about 3:1. This can be contrasted with European-type formulas which typically will comprise anionic: nonionic ratios in the range of about 10:1 to 1 : 10, preferably about 5: 1 to about 1 :5.

The present invention employs an "effective amount" of the AQA surfactants to improve the performance of cleaning compositions which contain other adjunct ingredients. By an "effective amount" of the AQA surfactants and adjunct ingredients herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use sufficient AQA to at least directionally improve cleaning performance against such stains. Likewise, in a composition whose targets include clay soil, the formulator will use sufficient AQA to at least directionally improve cleaning performance against such soil. Importantly, in a fully-formulated laundry detergent the AQA surfactants can be used at levels which provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the data presented hereinafter.

As noted, the AQA surfactants are used herein in detergent compositions in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance. In the context of a fabric laundry composition, such "usage levels" can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine.

For example, in a top-loading, vertical axis U.S. -type automatic washing machine using about 45 to 83 liters of water in the wash bath, a wash cycle of about 10 to about 14 minutes and a wash water temperature of about 10°C to about 50°C, it is preferred to include from about 2 ppm to about 50 ppm, preferably from about 5 ppm to about 25 ppm, of the AQA surfactant in the wash liquor. On the basis of usage rates of from about 50 ml to about 150 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.1% to about 3.2%, preferably about 0.3% to about 1.5%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from about 60 g to about 95 g per wash load, for dense ("compact") granular laundry detergents (density above about 650 g/1) this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.2% to about 5.0%, preferably from about 0.5% to about 2.5%. On the basis of usage rates of from about 80 g to about 100 g per load for spray-dried granules (i.e., "fluffy"; density below about 650 g/1), this translates into an in- product concentration (wt.) of the AQA surfactant of from about 0.1% to about 3.5%, preferably from about 0.3% to about 1.5%.

For example, in a front-loading, horizontal-axis European-type automatic washing machine using about 8 to 15 liters of water in the wash bath, a wash cycle of about 10 to about 60 minutes and a wash water temperature of about 30°C to about 95°C, it is preferred to include from about 13 ppm to about 900 ppm, preferably from about 16 ppm to about 390 ppm, of the AQA surfactant in the wash liquor. On the basis of usage rates of from about 45 ml to about 270 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.4% to about 2.64%, preferably about 0.55% to about 1.1%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from about 40 g to about 210 g per wash load, for dense ("compact") granular laundry detergents (density above about 650 g/1) this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.5 % to about 3.5 %, preferably from about 0.7 % to about 1.5 %. On the basis of usage rates of from about 140 g to about 400 g per load for spray-dried granules (i.e., "fluffy"; density below about 650 g/1), this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.13% to about 1.8%, preferably from about 0.18% to about 0.76%.

For example, in a top-loading, vertical-axis Japanese-type automatic washing machine using about 26 to 52 liters of water in the wash bath, a wash cycle of about 8 to about 15 minutes and a wash water temperature of about 5°C to about 25°C, it is preferred to include from about 1.67 ppm to about 66.67 ppm, preferably from about 3 ppm to about 6 ppm, of the AQA surfactant in the wash liquor. On the basis of usage rates of from about 20 ml to about 30 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.25% to about 10%, preferably about 1.5% to about 2%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from about 18 g to about 35 g per wash load, for dense ("compact") granular laundry detergents (density above about 650 , , l o

g/1) this translates into an in-product concentration (wt.) of the AQA surfactant of from about 0.25% to about 10%, preferably from about 0.5% to about 1.0%. On the basis of usage rates of from about 30 g to about 40 g per load for spray-dried granules (i.e., "fluffy"; density below about 650 g/1), this translates into an in- product concentration (wt.) of the AQA surfactant of from about 0.25% to about 10%, preferably from about 0.5% to about 1%.

Cationic Surfactants - The preferred bis-ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel

Chemicals Company. Alternatively, such materials can be synthesized using a variety of different reaction schemes (wherein "EO" represents -CH2CH2O- units), as follows.

SCHEME 1

SCHEME 2

SCHEME 3

SCHEME 4

An economical reaction scheme is as follows.

SCHEME 5

The following parameters summarize the optional and preferred reaction conditions herein for Scheme 5. Step 1 of the reaction is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 140-200°C. Reaction pressures are 50-1000 psig. A base catalyst, preferably sodium hydroxide can be used. The mole ratio of reactants are 2: 1 to 1 : 1 amine to alkyl sulfate. The process herein is preferably conducted using Cg-C] 3 alkyl sulfate, sodium salt. The ethoxylation and quaternization reactions are conducted using conventional conditions and reactants.

Under some circumstances, Step 1 of reaction Scheme 5 results in products which are sufficiently soluble in the aqueous reaction medium that gels may form. While the desired product can be recovered from the gel. an alternate, two-step synthesis Scheme 6, hereinafter, may be more desirable in some commercial circumstances. The second step (ethoxylation) is preferably conducted using ethylene oxide and an acid such as HCI which provides the quaternary surfactant. As shown below, chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative. For reaction Scheme 6, the following parameters summarize the optional and preferred reaction conditions for the first step. The first step is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 100-230° C. Reaction pressures are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react with the HSO4-generated during the reaction, or an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10: 1 to 1 : 1.5; preferably from 5:1 to 1: 1.1; more preferably from 2: 1 to 1 : 1. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble. The second step of the process is conducted under conventional reaction conditions. Further ethoxylation and quatemization to provide AQA surfactants are conducted under standard reaction conditions.

Scheme 7 can optionally be conducted using ethylene oxide under standard ethoxylation conditions, but without catalyst, to achieve monoethoxylation.

The following illustrates these additional reaction schemes, wherein "EO" represents the -CH2CH2O- unit. In the reactions, either an inorganic base or an organic base or excess amine reactant is used to neutralize generated HSO4.

Scheme 6

Scheme 7

The following further illustrates several of the above reactions solely for the convenience of the formulator, but is not intended to be limiting thereof. Synthesis A Preparation ofN,N-Bis(2-hvdroxyethyl)dodecylamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of diethanolamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H2O. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then the mixture is allowed to separate. The lower chloroform layer is drained and the chloroform evaporated off to obtain product.

Synthesis B Preparation of N,N-Bis(2-hvdroxyethyl)dodecylamine 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of base in the manner described in Synthesis A. The resulting 2- hydroxyethyldodecylamine is recovered and reacted with 1 -chloroethanol to prepare the title compound.

Synthesis C Preparation of N,N-Bis(2-hvdroxyethyl)dodecylamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate

(0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H2O. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then allowed mixture to separate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120-130°C to produce the desired final product.

The bis-substituted amines prepared in the foregoing Syntheses can be further ethoxylated in standard fashion. Quatemization with an alkyl halide to form the AQA surfactants herein is routine.

According to the foregoing, the following are nonlimiting, specific illustrations of AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, following common practice for conventional ethoxylated nonionic surfactants. This is because the ethoxylation reactions typically yield mixtures of materials with differing degrees of ethoxylation. Thus, it is not uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", "EO3.5", and the like.

*Ethoxy, optionally end-capped with methyl or ethyl.

Highly preferred bis-AQA compounds for use herein are of the formula

wherein R^ is C io-Cjg hydrocarbyl and mixtures thereof, preferably C J Q, C \ J, C 14 alkyl and mixtures thereof, and X is any convenient anion to provide charge balance, preferably chloride. With reference to the general AQA structure noted above, since in a preferred compound R^ is derived from coconut (C 12-C 14 alkyl) fraction fatty acids, R2 is methyl and ApR³ and A'qR⁴ are each monoethoxy. this preferred type of compound is referred to herein as "CocoMeE02" or "AQA- 1 " in the above list. Other preferred AQA compounds herein include compounds of the formula:

wherein Rl is Cio-Cjg hydrocarbyl, preferably C 1 Q-C 14 alkyl, independently p is 1 to about 3 and q is 1 to about 3, R² is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride.

Other compounds of the foregoing type include those wherein the ethoxy

(CH2CH2O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH3)CH2θ] and [CH2CH(CH₃O] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units. Anionic Surfactants - The alkyl benzene sulfonate ("LAS") and primary (preferred; "AS") or secondary alkyl sulfate components of the present compositions are well-known and widely-used commercial surfactants. As noted above, one of the important advantages of the present invention is the discovery that the AQA surfactants, when used in the manner disclosed herein, boost the performance of these otherwise conventional materials. The LAS surfactant has an alkyl chain length typically in the Cjo-Ci 6 range, and commercially available LAS has an average alkyl chain length in the 1 1-13 range, usually around 11.5. The AS surfactant has a chain length typically in the CJ Q-C20 ^ran8^e» and many commercial sources of AS are in the 12-18 range. All such commercial LAS and AS materials may be used herein. Unsaturated sulfates such as oleyl sulfate can also be used. The branched chain C10-C20 alkyl sulfates and the secondary (2,3) alkyl sulfates of the formula CH3(CH2)_x(CHOSO₃-M⁺)CH3 and CH₃(CH2)_y(CHOSO3- M^"I")CH2CH3, wherein x and (y+1) are integers of at least about 7 and M is a water- solubilizing cation, especially sodium, may also be used. Mixtures of primary, secondary and branched may be used.

Nonionic Surfactants - Nonlimiting examples of nonionic surfactants useful herein typically at levels from about 1% to about 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), CiQ-Cj g glycerol ethers, and the like.

More specifically, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 1 to about 10 moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include: Tergitol^M 15-S-9 (the condensation product of C\ 1-C15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of Cj2-C]4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Coφoration; Neodol^M 45.9 (the condensation product of C ,4-^ 5 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12- C_j 3 linear alcohol with 3 moles of ethylene oxide), Neodol^M 45.7 (_me condensation product of CJ4-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45.5 (_me condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; Kyro^M rfOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA O3O or O5O (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred range of HLB in these AE nonionic surfactants is from 8-1 1 and most preferred from 8-10. Condensates with propylene oxide and butylene oxides may also be used.

Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.

wherein Rl is H, or C1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C5.31 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 thereof. Preferably, R^ is methyl, R2 is a straight Cl l-15 alkyl or C15.17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Typical examples include the Cj2-C j g and C₁₂-C i4 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.

Also useful as the nonionic surfactant in the present invention are the alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-. and/or 6- positions on the preceding saccharide units.

The preferred alkylpolyglycosides have the formula: R2θ(C_nH_2nO)t(glycosyl)_x wherein R2 is selected from the group consisting of alkyl, alkylphenyl. hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3. most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1 -position). The additional glycosyl units can then be attached between their 1- position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from about 2 to about 25 moles, more preferably from about 3 to about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal^M CO-630, marketed by the GAF Coφoration; and Triton™ X-45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates). The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetronic^M compounds, marketed by BASF. Additional Surfactants - Nonlimiting examples of additional surfactants useful herein with the alkyl sulfate and LAS mixture typically at levels from about 1% to about 55%, by weight, include the conventional the Cio-Cj g alkyl alkoxy sulfates ("AE_XS"; especially EO 1-7), C iQ-C j g alkyl alkoxy carboxylates (especially the EO 1-5) and Cjo-Cjg alpha-sulfonated fatty acid esters. C^-C_j g betaines and sulfobetaines ("sultaines"), Cjn-C ig amine oxides, and the like, can also be used. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain Cjo-Ciβ soaps may be used. Other conventional useful surfactants are listed in standard texts.

The following illustrates various other adjunct ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof. While the combination of the AQA and the anionic surfactants with such adjunct compositional ingredients can be provided as finished products in the form of liquids, gels, bars, or the like using conventional techniques, the manufacture of the granular laundry detergents herein requires some special processing techniques in order to achieve optimal performance. Accordingly, the manufacture of laundry granules will be described hereinafter separately in the Granules Manufacture section (below), for the convenience of the formulator.

Builders - Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned. Builder level can vary widely depending upon end use and physical form of the composition. Built detergents typically comprise at least about 1% builder. Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder. Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the detergent composition. Lower or higher levels of builders are not excluded. For example, certain detergent additive or high- surfactant formulations can be unbuilt.

Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amoφhous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water- soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid. These may be complemented by borates, e.g., for pH- buffering purposes, or by sulfates, especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or builder-containing detergent compositions.

Builder mixtures, sometimes termed "builder systems" can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein. In terms of relative quantities of surfactant and builder in the present detergents, preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1 :80. Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0. more preferably from 0.95:1.0 to 3.0:1.0. P-containing detergent builders often preferred where permitted by legislation include, but are not Hmited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.

Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a Siθ2:Na2θ ratio in the range 1.6:1 to 3.2:1, including, particularly for automatic dishwashing puφoses, solid hydrous 2-ratio silicates marketed by PQ Coφ. under the tradename BRITESIL®, e.g., BRITESIL H2O; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered aluminium-free δ -Na2SiO5 moφhology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A- 3,417,649 and DE-A-3,742,043. Other layered silicates, such as those having the general formula NaMSi_xO2_x+i yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein. Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the α, β and γ layer-silicate forms. Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

Also suitable for use herein are synthesized crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM₂θ ySiθ₂.zM'O wherein M is Na and/or K, M¹ is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.

Suitable carbonate builders include alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when anhydrous, and even calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.

Aluminosilicate builders are especially useful in granular detergents, but can also be incoφorated in liquids, pastes or gels. Suitable for the present puφoses are those having empirical formula: [M_z(AlO2)_z(SiO2)v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264. Aluminosilicates can be crystalline or amoφhous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula: Nai2[(AlO2)i2(SiO2)i2] xH2O wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Suitable organic detergent builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include the ether polycarboxylates. such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S. 3,635.830, January 18, 1972; "TMS/TDS" builders of U.S. 4,663,071 , Bush et al, May 5, 1987; and other ether carboxylates including cyclic and 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 suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymefhyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid: as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy- methyloxysuccinic acid, and soluble salts thereof.

Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.

Where permitted, and especially in the formulation of bars used for hand- laundering operations, alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- 1 -hydroxy- 1 , 1 -diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 can also be used and may have desirable antiscaling properties.

Certain detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting puφoses, when they have surfactant capability, these materials are summed up as detersive surfactants. Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l ,6- hexanedioates and the related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: laurylsuccinate. myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Fatty acids, e.g., C\2-C\g monocarboxylic acids, can also be incoφorated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S. 4,144,226, Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3.723,322.

Other types of inorganic builder materials which can be used have the formula (M_x)j Cay (CO₃)_z wherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mj are cations, at least one of which is a water- soluble, and the equation Σ\ = i-i 5(xj multiplied by the valence of Mj) + 2y = 2z is satisfied such that the formula has a neutral or "balanced" charge. These builders are referred to herein as "Mineral Builders". Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral. The charge or valence effects of such anions should be added to the right side of the above equation. Preferably, there is present a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred. Nonlimiting examples of noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof. Preferred builders of this type in their simplest forms are selected from the group consisting of Na2Ca(CO3)2, K2Ca(CO3)₂, Na₂Ca2(CO₃)3, NaKCa(CO₃)2, NaKCa₂(C0₃)₃, K₂Ca₂(CO3)3, and combinations thereof. An especially preferred material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline modifications. Suitable builders of the above-defined type are further illustrated by. and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite. Jouravskite, KamphaugiteY, Kettnerite, Khanneshite, LepersonniteGd, Liottite. MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite, Schrockingerite, Shortite, Surite, Tunisite, Tuscanite, Tyrolite, Vishnevite, and Zemkorite. Preferred mineral forms include Nyererite, Fairchildite and Shortite.

Enzymes - Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry puφoses include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.

Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsoφtion and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206. +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent applications of A. Baeck, et al, entitled "Protease-Containing Cleaning Compositions" having US Serial No. 08/322,676, and C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994. Amylases suitable herein, especially for, but not limited to automatic dishwashing puφoses, include, for example, α-amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL ® in commercial use in 1993. These preferred amylases herein share the characteristic of being "stability-enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylenediamine in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 1 1 , measured versus the above- identified reference-point amylase. Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor International. One class of highly preferred amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially in bleaching, more preferably oxygen bleaching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase according to the hereinbefore incoφorated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of the B. licheniformis alpha-amylase, known as TERMAMYL®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases herein include amylase variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL®. Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo. Other amylase enzymes include those described in WO 95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the detergent compositions of the present invention include α- amylases characterized by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase activity assay. (Such Phadebas® α-amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are α-amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incoφorated into laundry detergent compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al, March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or 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-OS-2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 91 17243 to Novo.

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 GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Coφ., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found widespread application as additive for fabric washing products. It is available from Novo Nordisk under the tradename Lipolase™, as noted above. In order to optimize the stain removal performance of Lipolase, Novo Nordisk have made a number of variants. As described in WO 92/05249. the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter). Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing the AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in the range of about 50 LU to about 8500 LU per liter of wash solution. Cutinase enzymes suitable for use herein are described in WO 8809367 A to

Genencor.

Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash io other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.

A range of enzyme materials and means for their incoφoration into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incoφoration into such formulations, are disclosed in U.S. 4,261.868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo. , ,

JO

Enzyme Stabilizing System - The enzyme-containing compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

One stabilizing approach is the use of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used. Typical detergent compositions, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incoφorated. Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson, U.S. 4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives. Stabilizing systems of certain cleaning compositions, for example automatic dishwashing compositions, may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in the range from about 0.5 ppm to about 1.75 ppm. the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dish- or fabric-washing, can be relatively large; accordingly, enzyme stability to chlorine in-use is sometimes problematic. Since perborate or percarbonate, which have the ability to react with chlorine bleach, may present in certain of the instant compositions in amounts accounted for separately from the stabilizing system, the use of additional stabilizers against chlorine, may, most generally, not be essential, though improved results may be obtainable from their use. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Likewise, special enzyme inhibition systems can be incoφorated such that different enzymes have maximum compatibility. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-containing embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, with other reactive ingredients. In relation to the use of ammonium salts, such salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.

Polymeric Soil Release Agent - Known polymeric soil release agents. hereinafter "SRA" or "SRA's", can optionally be employed in the present detergent compositions. If utilized, SRA's will generally comprise from 0.01% to 10.0%. typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition.

Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with SRA to be more easily cleaned in later washing procedures.

SRA's can include a variety of charged, e.g., anionic or even cationic (see U.S. 4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties. Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.

Preferred SRA's include oligomeric terephthalate esters, typically prepared by processes involving at least one transesterification/oligomerization, often with a metal catalyst such as a titanium(IV) alkoxide. Such esters may be made using additional monomers capable of being incoφorated into the ester structure through one, two, three, four or more positions, without of course forming a densely crosslinked overall structure.

Suitable SRA's include: a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451 , November 6, 1990 to J.J. Scheibel and E.P. Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propylene glycoi ("PG") in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,71 1,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethylenegiycol) ("PEG"); the partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26. 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8- hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink. for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate; and the anionic, especially sulfoaroyl, end-capped terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al, the latter being typical of SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see U.S. 3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et ai. Suitable SRA's characterised by poly( vinyl ester) hydrophobe segments include graft copolymers of poly( vinyl ester), e.g., C\-Cβ vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22, 1987 by Kud. et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeat units containing 10- 15% by weight of ethylene terephthalate together with 90-80% by weight of polyoxyethylene terephthalate, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having empirical formula

(CAP)2(EG/PG)5(T)5(SIP)ι which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-l ,2-propylene (EG/PG) units and which is preferably terminated with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-l,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two end-cap units derived from sodium 2-(2- hydroxyethoxy)-ethanesulfonate. Said SRA preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene- sulfonates or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate. DMT, Na- dimethyl 5-sulfoisophthalate, EG and PG.

Yet another group of preferred SRA's are oligomeric esters comprising: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1 ,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred of such esters are those of empirical formula:

{(CAP)x(EG/PG)y'(DEG)y"(PEG)y"'(T)z(SIP)z'(SEG)q(B)m} wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) represents di(oxyethylene)oxy units; (SEG) represents units derived from the sulfoethyl ether of glycerin and related moiety units; (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone; x is from about 1 to about 12; y' is from about 0.5 to about 25; y" is from 0 to about 12; y"' is from 0 to about 10; y'+y"+y*" totals from about 0.5 to about 25; z is from about 1.5 to about 25; z' is from 0 to about 12; z + z' totals from about 1.5 to about 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y', y", y"', z, z', q and m represent the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from about 500 to about 5.000.

Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3- dihydroxypropoxy)ethanesulfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxyethoxy)- ethoxyjethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)ethoxy}ethoxy]- ethanesulfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an appropriate Ti(IV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ O₃S[CH₂CH₂O]3.5)- and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis. „

41

Additional classes of SRA's include (I) nonionic terephthalates using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S. 4.240,918 Lagasse et al; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (Ill) anionic terephthalate-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly( vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters; these SRA's assertedly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF (1991); (VII) polyester- polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al, DE 2.335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Bleaching Compounds - Bleaching Agents 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 30%, more typically from about 5% to about 20%, 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 puφoses 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. Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro 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 peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 'micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

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

Highly preferred amido-derived bleach activators are those of the formulae: R!N(R5)C(O)R²C(O)L or R¹C(O)N(R⁵)R²C(O)L wherein Rl is an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms. R^ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul- fonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incoφorated herein by reference.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incoφorated herein by reference. A highly preferred activator of the benzoxazin- type is:

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

wherein R° is H or an alkyl, aryl, alkoxyaryl. or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3.5.5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incoφorated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated 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. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,1 14,606; and European Pat. App. Pub. Nos. 549,271 Al , 549.272A1 , 544,440A2, and 544.490A1 ; Preferred examples of these catalysts include Mn^IV2(u-O)3(l,4,7-trimethyl-l,4,7-triazacyclo- nonane)2(PF6)2, Mn^Iπ2(u-O) j (u-OAc)2( 1 ,4,7-trimethy 1- 1 ,4,7-triazacyclononane)2_ (ClO₄)₂, Mn^IV4(u-O)₆(l,4,7-triazacyclononane)4(ClO₄)4, Mn^πIMn^IV4(u-O)ι(u- OAc)2.(l ,4,7-trimethyl-l,4,7-triazacyclononane)2(ClO4)3, Mn^IV(1.4,7-trimethyl- 1 ,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,1 14,61 1. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,1 17; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] T_v, wherein "OAc" represents an acetate moiety and "T_y" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2; [Co(NH₃)₅OAc](PF6)2; [Co(NH3)₅OAc](SO₄); [Co(NH3)5OAc](BF₄)2; and [Co(NH₃)5OAc](NO₃)2 (herein "PAC"). These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7.1989, J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem.. _.18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952). As a practical matter, and not by way of limitation, the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, of the bleach catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Clay Soil Removal/Anti-redeposition Agents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylates 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 disclosed in European Patent Application 11 1,965, 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 1 11,984, 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. See U.S. Patent 4,891 ,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995. Another type of preferred antiredeposition 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, especially in the presence of zeolite and/or layered silicate builders. 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 methylenemalonic acid. The presence in the polymeric polycarboxylates herein or 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 acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1 : 1 , more preferably from about 10: 1 to 2: 1. Water- soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982. as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol teφolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10 teφolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol

(PEG). PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these puφoses 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. Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.

Brightener - Any optical brighteners or other brightening or whitening agents known in the art can be incoφorated at levels typically from about 0.01% 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, dibenzothiophene-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; Artie White CC and Artie White CWD, the 2-(4-styryl-phenyl)-2H-naρtho[l ,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the amino- coumarins. Specific examples of these brighteners include 4-methyl-7-diethyI- amino coumarin; l,2-bis(benzimidazol-2-yl)ethylene; 1 ,3-diphenyl-pyrazolines; 2,5- bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[l,2-d]oxazole; and 2-(stilben-4-yl)- 2H-naphtho[l ,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.

Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N- oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, _4g

manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%. and more preferably from about 0.05% to about 2%. More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general structures:

O O

I I

(R₁)_x-N-(R₂)_y; =N-(R,)_x

(R₃)z wherein R] , R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10: 1 to 1 :1 ,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1 ,000.000: more preferred 1,000 to 500.000; most preferred 5.000 to 100,000. This preferred class of materials can be referred to as "PVNO". W _ά 4_Q9

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred 5 to as a class as "PVPVI") are also preferred for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 1 13. "Modern Methods of Polymer Characterization", the 0 disclosures of which are incoφorated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 :1 to 0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1 to 0.4: 1. These copolymers can be either linear or branched.

The present invention compositions also may employ a polyvinylpyrrolidone 5 ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A-256,696, incoφorated herein by reference. Compositions containing PVP can also contain polyethylene glycol ("PEG") having 0 an average molecular weight from about 500 to about 100,000, preferably from about 1 ,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50: 1 , and more preferably from about 3: 1 to about 10: 1.

The detergent compositions herein may also optionally contain from about 5 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical brighteners.

The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

wherein R\ is selected from anilino. N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, moφhilino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, Ri is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4.4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Coφoration. Tinopal- UN PA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein. When in the above formula, R\ is anilino, R2 is N-2-hydroxyethyl-N-2- methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino- 6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Coφoration.

When in the above formula, R] is anilino, R2 is moφhilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-moφhilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Coφoration.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA- GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.

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 ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, 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 lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to 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 l,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions. Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incoφorated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration _5?

cleaning process" as described in U.S. 4,489.455 and 4,489.574 and in front-loading European-style washing machines.

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 acid 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 C]g-C4o ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl 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 50°C, and a minimum boiling point not less than about 1 10°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below about 100°C. The hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. 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 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 or 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 incoφorating 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 1,500 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)3SiO}/2 units of Siθ2 units in a ratio of from (CH3)3 SiOj/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), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked and preferably 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 about 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, 5,288.431, Huber et al., issued February 22, 1994, 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/polypropylene 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 glycolxopolymer 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 LI 01.

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, 4,075,1 18 and EP 150,872. The secondary alcohols include the C^-Ciό alkyl alcohols having a C ] -C i 6 chain. A preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 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 10% 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 primarily 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. The alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.

Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq., incoφorated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side- chains are of the formula -(CH2CH2O)_m(CH2)_nCH3 wherein m is 2-3 and n is 6- 12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the compositions herein.

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. 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.

Perfumes - Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and essences which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01% to about 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from about 0.0001% to about 90% of a finished perfume composition. Several perfume formulations are set forth in Example VIII, hereinafter.

Non-limiting examples of perfume ingredients useful herein include: 7-acetyl- l,2,3,4,5,6,7,8-octahydro-l,l,6,7-tetramethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10- trimethyl-2,5,9-cyclododecatrien-l-yl ketone; 7-acetyl- 1,1, 3, 4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl- 1,1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l,l,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l,2,6-tetramethyl indane; 1 -dodecanal, 4-(4-hydroxy- 4-methylpentyl)-3-cyclohexene-l-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-l-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-(para-tert-butylphenyl)- propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin; decalactone gamma; cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone; 1 ,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2- benzopyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetra- methylnaphtho[2,lb]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3- methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten- 1 -yl)-2-buten- 1 -ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly preferred perfume materials are those that provide the largest odor improvements in finished product compositions containing cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl)-propionaldehyde; 7-acetyl- 1,2,3 ,4,5,6,7,8-octahydro- 1,1 , 6,7- tetramethyl naphthalene; benzyl salicylate; 7-acetyl- 1,1 , 3, 4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)- propionaldehyde; 1, 3,4,6,7, 8-hexahydro-4,6,6, 7,8, 8-hexamethyl-cyclopenta- gamma-2-benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2, 1 bjfuran; anisaldehyde; coumarin; cedrol; vanillin; cyclopentadecanolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.

Other perfume materials include essential oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin. Still other perfume chemicals include phenyl ethyl alcohol, teφineol, linalool, linalyl acetate, geraniol, nerol, 2-(l ,l-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethylphthalate can be used in the finished perfume compositions.

Other Ingredients - A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C\Q-C\β alkanolamides can be incoφorated into the compositions, typically at 1%-10% levels. The C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, water-soluble magnesium and/or calcium salts such as MgCb, MgSO4, CaCl2, CaSO4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.

Various detersive ingredients employed in the present compositions optionally can be further 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 hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C 13.15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant 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 resulting 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 detergents, 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 compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.

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 1 1, preferably between about 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between about 6.8 and about 9.0. Laundry products are typically at pH 9-1 1. 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.

In the following Examples, the abbreviations for the various ingredients used for the compositions have the following meanings.

LAS Cl 1.5 average chain length alkyl benzene sulfonate anionic surfactant, preferably sodium salt AS C14-15 average chain length primary alkyl sulfate anionic surfactant, preferably sodium salt Nl C12-15 ethoxylated alcohol with an average EO9 degree of ethoxylation (nonionic surfactant) SKS-6 Layered silicate, ex. Hoechst Copolymer Copolymer of acrylic/maleic acids, sodium salt

Zeolite 1-10 Micron zeolite A

PEG4000 Polyethylene glycol; average molecular weight 4000

NOBS Nonanoyloxybenzene sulfonate bleach activator

PB- 1 Sodium perborate monohydrate Protease Proteolytic detergent enzymes as disclosed above; including

BIOSAM 3.0. Amylase Amylolytic detergent enzymes ₅

SRA-1 Soil release agent; methyl cellulose; molecular weight about

13000, degree of substitution 1.8-1.9 SRA-2 Soil release agent per U.S. Patent 5,415,807

Brightener X Tinopal® CBS-X; Disodium 4,4'-bis-(2-sulfostyryl) biphenyl; Ciba-Geigy

Brightener Y Tinopal® UNPA-6X; 4,4'-bis{ {4-anilino-6-[bis(2-hydroxy- ethyl)amino]-s-triazin-2-yl } -amino } -2,2'-stilbenedisulfonate; Ciba-Geigy Suds Control Silica/silicone suds suppressor Granules Manufacture

Adding the bis-alkoxylated cationics of this invention into a crutcher mix, followed by conventional spray drying, helps remove any residual, potentially malodorous, short-chain amine contaminants. In the event the formulator wishes to prepare an admixable particle containing the alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred that the particle composition not be highly alkaline. Processes for preparing high density (above 650 g/I) granules are described in U.S. Patent 5,366,652. Such particles may be formulated to have an effective in-use pH of 9, or below, to avoid the odor of impurity amines. This can be achieved by adding a small amount of acidity source such as boric acid, citric acid, or the like, or an appropriate pH buffer, to the particle. In an alternate mode, the prospective problems associated with amine malodors can be masked by use of perfume ingredients, as disclosed herein.

The following examples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, percentages and ratios used herein are expressed as percent weight unless otherwise specified.

Examples I and II illustrate granular detergent compositions of the invention.

EXAMPLE I

INGREDIENTS % (wt.) ppm

Surfactant LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2* 0.47 3.13

Builder-Alkalinity

SKS-6 3.29 21.94

Copolymer 7.10 47.36 Zeolite 8.40 56.03

PEG4000 0.19 1.27

Carbonate, Na 17.84 1 18.99

Silicate (2.0R) 1 1.40 76.04

Bleach

NOBS 4.05 27.01

PB-1 3.92 26.15

Enzyme

Protease 0.85 5.67

Amylase 1.20 8.00

Others SRA-1 0.26 1.73

SRA-2 0.26 1.73

Brightener X 0.21 1.40

Brightener Y 0.10 0.67

Hydrophobic silica 0.30 2.00 Suds control 0.17 1.13

Sulfate, Na 5.14 34.28

Perfume 0.25 1.67

Misc. minors and moisture 3.28 21.88

TOTAL To: 100 667.00

Dosage - 20 g/30 L

The AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.

EXAMPLE II

INGREDIENTS % (wt.) ppm

Surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2* 0.47 3.13 Builder-Alkalinity SKS-6 3.29 21.94 Copolymer 7.10 47.36 Zeolite 8.40 56.03

PEG4000 0.19 1.27 Carbonate, Na 19.04 127.00 Silicate (2.0R) 1 1.40 76.04

Bleach

NOBS 4.05 27.01 PB-1 3.92 26.15

Enzyme

Protease 0.85 5.67

Others

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Brightener X 0.21 1.40

Brightener Y 0.10 0.67

Hydrophobic silica 0.30 2.00

Suds control 0.17 1.13

Sulfate, Na 5.14 34.28

Perfume 0.25 1.67

Misc., minors and moisture 3.28 21.88

TOTAL To: 100 667.00

*The AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.

The following illustrates a laboratory procedure and test results, over a variety of soils and stains, using compositions within the scope of the invention. As will be seen from the data, overall cleaning improvements are achieved with a wide variety of soils and stains on various fabrics.

PERFORMANCE TEST PROCEDURE SAMPLE PREPARATIONS : The sample preparation basically involves following steps :

1. Preparation of premixed L AS+AS

2. Preparation of Premixed LAS+AS+Cationic

3. Preparation of stock nonionic (AE) surfactant 4. Preparation of builder solution

5. Preparation of Granules

Surfactant:

Surfactant Weight* Active Wash ems % Concentrations, ppm

LAS 78.85 44.50 143.20

AS 34.55 31.00 43.70

Cationic 01.90 40.00 3.10

AE 19.44 100.00 22.00

*(The actual weights will differ with percent active) Sequence of Product preparation for performance test : Step I:

The individual surfactants are weighed and mixed in the following sequence

1. 78.85 gms of LAS are weighed.

2. 34.55 gms of AS are weighed into the same beaker. 3. 498.10 mis of Distilled water are added to the mixture of LAS & AS.

4. LAS and AS are premixed until completely dissolved with heating at 40°C for about 30 minutes until completely dissolved. Step II:

1. 01.90 gms of the cationic are weighed into the same beaker containing LAS+AS premixed solution.

2. Total Volume of solution now is 500 mis.

This 500 ml mixture of surfactants is good for five washes, 100 mis of this stock solution are used for per wash. This 100 ml solution when added to 49 liters of tap water gives the corresponding wash concentrations for individual surfactants. Step III:

1. 19.44 gms of AE are weighed separately.

2. 900 mis of distilled water are added to the AE .

3. This 900 ml solution are good for 18 washes.

4. 50 mis of this solution are used per wash. Step IV:

Silicate: 148.32 gms per 900 ml of Distilled water; 50 mis of this solution are used per wash.

Copolymer: 92.88 gms per 900 ml of Distilled water; 50 mis of this solution are used per wash. Granules : Each granule component is weighed separately in the same beaker.

Order of addition to the washing machine : With stirring the ingredients are added in following sequence : 1. Silicate (2.0 R) 2. Copolymer (as noted above) 3. Granules

Stirring is stopped here (to avoid sudsing during surfactant addition). 4. LAS+AS+Cationic solution

5. AE solution

Stirring for 15 sec.

Hardness : No extra hardness are added on top of tap water hardness. Load : 2.4 kg of load of following composition are typically used, Cotton dress shirt ( 1 )

Worn T-shirts (from panelists) (3) Large T-shirts (11) DKPE T shirt (1) P/C Short pants (2) Cotton short pants ( 1 )

DKPE is double-knit polyester. DMO is dirty motor oil.

Test Results I, hereinafter, show the performance of compositions according to the present invention using CoCoMeEO2 plus a mixture of LAS/AS and Test Results II show the performance using CoCoMeEOlO* plus LAS/AS, as compared with CoCoMeEO2/LAS. In the Tests, performance is measured against various soil types, i.e., body soil, builder sensitive soil, bleach sensitive soil, surfactant sensitive soil and socks. *Following the "bis" terminology herein, "EO10" indicates two poly-EO chains with an overall average of 10 EO units in the molecule, typically "(but not restricted to) about 5 per chain.

TEST RESULTS I Premixing of CocoMeEO2 Cationic with LAS & AS (total anionic system) S Sooiillss T Teesstt II Test II Average

In-used collar -0.02 -0.27 -0.15

Insert collar 0.77 S 0.73S 0.75

Cuffs -0.17 0.33 0.08

Dinginess -0.1 0.17 S 0.04

BODY SOIL (Ave.) 0.12 0.24 0.18

Clay C/D 1.03 S 0.7 S 0.87

Clay DKPE 0.7 S -0.02 0.34

BUILDER SENSITIVE

SOIL (Ave.) 0.87 0.34 0.61

Spinach 0.33 0.56 0.45

Coffee 0.21 0.42 S 0.32

BLEACH SENSITIVE

SOIL (Ave.) 0.27 0.49 0.38

TEST RESULTS I Premixing of CocoMeEO2 Cationic with LAS alone

Socks (after) 0.7 S -0.05 0.33 Socks (delta) 0.36 0.02 0.19

TEST RESULTS II

Premixing of CocoMeEOlO Cationic with LAS + AS

Soils Test I Test II Average

In-used collar 0.48 -0.02 0.23

Insert collar 0.02 0.06 0.04

Cuffs 0.33 0.25 0.29 Dinginess -0.28 0.1 1 -0.09

BODY SOIL (Ave.) 0.14 0.10 0.12

Clay C/D 0.75 S 0.44 0.60

Clay DKPE 0.27 -0.47 -0.10

BUILDER SENSITIVE SOIL (Ave.) 0.51 -0.02 0.25

Spinach 0.00 0.33 0.17

Coffee 0.38 0.82 S 0.60

BLEACH SENSITIVE SOIL (Ave.) 0.19 0.58 0.39 Meat sauce 0.05 0.96 S 0.51

Curry 0.42 0.91 S 0.67

Bacon oil 0.23 -0.07 0.08

DMO 0.31 -0.13 0.09

SURFACTANT SEN- SITIVE SOIL (Ave.) 0.25 0.42 0.34

Average (including Socks) 0.2 0.26 0.23

Socks (before) 0.14 0.23 0.19

Socks (after) -0.19 0.48 S 0.15 Socks (delta) -0.32 0.25 -0.04

TEST RESULTS II Premixing of CoCoMeElO Cationic With LAS Alone

Soils In-used collar 0.17 Insert collar -0.52 Cuffs 0.19 Dinginess -0.17

BODY SOIL (Ave.) -0.08

Clay C/D -0.34

Clay DKPE 0.09

BUILDER SENSITIVE

SOIL (Ave.) -0.13

Spinach 0.06

Coffee 0.08

BLEACH SENSITIVE

SOIL (Ave.) 0.07

Meat sauce -0.20

Curry -0.38

Bacon oil -0.33

DMO -0.33

SURFACTANT SENSITIVE

SOIL (Ave.) -0.31

Average (including

Socks) -0.1 1

Socks (before) 0.42 S

Socks (after) 0.64 S

Socks (delta) 0.22

EXAMPLE III

The compositions of Examples I and II are modified by removing the bleach system (NOBS/PB_j). The AQA level is adjusted to about 1.5% of the composition (range 0.5-5%). Quite satisfactory cleaning performance on a variety of soils and stains is secured even in the absence of bleach.

The compositions of Examples I, II and III can also be provided in the form of tablets by means of standard tabletting and compaction apparatus. EXAMPLE IV

A detergent bar is prepared with the surfactant mixture is prepared using conventional extrusion techniques, and comprises the following: Ingredient % (wt.) Range (% wt.)

A B AQA-1* 2.0 0.6 0.15-3.0

C₁₂-C! ₈ Sulfate 15.75 13.50 5-25

LAS 6.75 5.5 3-25

1 Sodium diethylenetriamine penta (phosphonate) ^Sokolan CP-5 is maleic-acrylic copolymer ^Balance comprises water (about 2% to 8%, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients. *The AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any surfactants AQA-2 through AQA-22 or other AQA surfactants herein.

EXAMPLE V The following illustrates mixtures of AQA surfactants which can be substituted for the AQA surfactants listed in any of the foregoing Examples. As disclosed hereinabove, such mixtures can be used to provide a spectrum of performance benefits and/or to provide cleaning compositions which are useful over a wide variety of usage conditions. Preferably, the AQA surfactants in such mixtures differ by at least about 1.5, preferably 2.5-20, total EO units. Ratio ranges(wt.) for such mixtures are typically in the 10: 1 to 1 : 10 range. Non-limiting examples of such mixtures are as follows.

Components Ratio (wt.)

AQA-1 + AQA-5 1 1

AQA-1 + AQA- 10 1 1

AQA-1 + AQA- 15 1 2

AQA-1 + AQA-5 + AQA-20 1 1 : 1

AQA-2 + AQA-5 3 1 AQA-5 + AQA- 15 1.5: 1

AQA-1 + AQA-20 1 :3

Mixtures of the bis-AQA surfactants herein with the corresponding cationic surfactants which contain only a single ethoxylated chain can also be used. Thus, for example, mixtures of bis-ethoxylated cationic surfactants of the formula

RlN⁺CH₃[EO]_x[EO]_yX- and RlN⁺(CH₃)₂[EO]_zX-, wherein R¹ and X are as disclosed above and wherein one of the cationics has (x+y) or z in the range 1 -5 preferably 1-2 and the other has (x+y) or z in the range 3-100, preferably 10-20, most preferably 14-16, can be used herein. Such compositions advantageously provide improved detergency performance (especially in a fabric laundering context) over a broader range of water hardness than do the cationic surfactants herein used individually. It has now been discovered that shorter EO cationics (e.g., EO2) improve the cleaning performance of anionic surfactants in soft water, whereas higher EO cationics (e.g., EOI 5) act to improve hardness tolerance of anionic surfactants, thereby improving the cleaning performance of anionic surfactants in hard water. Conventional wisdom in the detergency art suggests that builders can optimize the performance "window" of anionic surfactants. Until now, however, broadening the window to encompass essentially all conditions of water hardness has been impossible to achieve. EXAMPLE VI

Having thus described various non-limiting Examples of the compositions herein and their usage, the following further illustrates the inventions encompassed herein, with particular regard to fabric laundry detergents. Granular, liquid, bar, tablet or gel-form compositions herein can comprise detersive non-AQA surfactants and optional builders at usage levels and ranges as disclosed hereinabove, said compositions also comprising an effective amount of one or more of the following combinations of ingredients:

Ingredient Weight Ratio AQA:Ingredient

Percarbonate bleach : 1 OO- 1 : 1, preferably 1 :20-1 :5 Branched alkyl sulfate 100-1 :2, preferably 1 : 10-1 :3

Bleach activator* 1-1 : 10, preferably 1 : 1-1 :5

Peracid Bleach** 10-2: 1 , preferably 1 :5-1 : 1

Photobleach 100-1 :2, preferably 1 :5-1 : 1

Layered silicate builder 300-1 :1, preferably 1 : 100-1 :5 SRA 20-1 :2, preferably 1 :10-1 : 1

Enzyme*** 10-10:1 , preferably 1 :3-3: 1

EDDS 20-10: 1 , preferably 1 :3-3:1 MGDA 1 :20-10:1, preferably 1:3-3: 1

PFAA 1 :50-1 :2, preferably 1 :25-l :3

APG 1 :50-l :2, preferably 1 :25-l :3

Ca⁺⁺ 1 :10-10:1, preferably 1 :5-5:1 Mg⁺⁺ 1 : 10-10:1, preferably 1 :5-5:1

Co catalyst 1 :10-10: 1, preferably 2:1-1:1

Mn catalyst 1 :10-10:1, preferably 2:1-1 :1

DTI agent 1 :20-20:1, preferably 1 :10-10:1

Zeolite P (MAP) 1 :300- 1 :1, preferably 1 :100-1 :5 Mineral Builder 1:300-1:1, preferably 1:100-1:5

Polymeric Dispersant**** 1 :10-10:1, preferably 1 :5-1:1

Alkoxylated Polycarboxylate 4:1-1:10, preferably 1:5-1 :1

Clay Soil Removal/ Anti¬ redeposition Agent 4:1-1:20, preferably 1 :1-1:10 Clay Softener 3:1-1 :10, preferably 2:1-1 :1 * Includes mixtures such as NOBS + TAED. ** Includes mixtures

***Ratios based on commercial enzyme preparations. This can vary, depending on the active enzyme level of the commercial enzyme product. ****Preferably polyacrylate or acrylic/maleic copolymer.

The laundry detergent compositions prepared using one or more foregoing combinations of ingredients can optionally be built with any non-phosphate or phosphate builders, or mixtures thereof, typically at levels of from 5% to about 70%, by weight of finished composition. EXAMPLE VII

The following illustrates mixtures of conventional non-AQA surfactants which can be used in combination with the AQA surfactants in any of the foregoing Examples, but is not intended to be limiting thereof. The ratios of non-AQA surfactants in the mixtures are noted in parts by weight of the surfactant mixtures. Mixtures A-C

Ingredients Ratios

ASVLAS 1 : 1

AS/LAS 10:1 (pref. 4:1)

AS/LAS 1 : 10 (pref. 1:4) *In the foregoing, the primary, substantially linear AS surfactant can be replaced by an equivalent amount of secondary AS, branched-chain AS, oleyl sulfate, and/or mixtures thereof, including mixtures with linear, primary AS shown above. The "tallow" chain length AS is particularly useful under hot water conditions, up to the boil. "Coconut" AS is preferred for cooler wash temperatures.

The mixtures of alkyl sulfate/anionic surfactants noted above are modified by incoφorating a nonionic non-AQA surfactant therein at a weight ratio of anionic (total) to nonionic in the range of about 25: 1 to about 1 :5. The nonionic surfactant can comprise any of the conventional classes of ethoxylated alcohols or alkyl phenols, alkylpolyglycosides or polyhydroxy fatty acid amides (less preferred), or mixtures thereof, such as those disclosed hereinabove.

Highly preferred combinations of the foregoing non-AQA surfactants will comprise from about 3% to about 60%, by weight, of the total finished laundry detergent composition. The finished compositions will preferably comprise from about 0.25% to about 3.5%, by weight, of the AQA surfactant.

EXAMPLE VIII This Example provides perfume formulations (A-C) for incoφoration into any of the foregoing Examples of AQA-containing detergent compositions, but is not intended to be limiting thereof. The various ingredients and levels are set forth below.

_

Vanillin - 5.0

Cyclopentadecanolide 3.0 10.0

Tricyclodecenyl acetate - 2.0

Labdanum resin - 2.0 Tricyclodecenyl propionate - 2.0

Phenyl ethyl alcohol 20.0 10.0 27.9

Teφineol 10.0 5.0

Linalool 10.0 10.0 5.0

Linalyl acetate 5.0 5.0 Geraniol 5.0 -

Nerol - 5.0

2-( 1 , 1 -dimethylethyl)-cyclohexanol acetate 5.0 -

Orange oil, cold pressed - 5.0

Benzyl acetate 2.0 2.0 Orange teφenes - 10.0

Eugenol - 1.0

Diethylphthalate - 9.5

Lemon oil, cold pressed - 10.0

Total 100.0 100.0 100.0 The foregoing perfume compositions are admixed or sprayed-onto (typically at levels up to about 2% by weight of the total detergent composition) any of the AQA surfactant-containing cleaning compositions disclosed herein. Improved deposition and/or retention of the perfume or individual components thereof on the surface being cleaned is thus secured.

Claims

WHAT IS CLAIMED IS:

1. A composition of matter comprising a mixture of, or prepared by combining, a bis-alkoxylated AQA cationic surfactant and two classes of anionic surfactants, said cationic surfactant having the formula:

and said anionic surfactants having the formulae:

II R5OSO₃-M⁺,

III R6SO₃-M^,+, and, optionally

IV a nonionic surfactant

wherein RMs an alkyl or alkenyl moiety containing from 8 to 18 carbon atoms; R² is an alkyl group containing from one to three carbon atoms; R^ and R^ can vary independently and are selected from hydrogen, methyl and ethyl; R^ is a linear or branched alkyl or alkenyl moiety having from 10 to 20 carbon atoms; R<> is Cif_j- Ci g alkylbenzene; M⁺ and M'⁺ can vary independently and are each selected from alkali metals, alkaline earths, alkanol ammonium and ammonium; X" is an anion; A and A' can vary independently and are each C 1-C4 alkoxy; p is from 1 to 30 and q is from 1 to 30; and wherein the weight ratio of (I) to (II) + (III) is 1 :100 to 1 :7; the weight ratio of (II):(III) is 4: 1 to 1 :4; and the weight ratio of R⁵ to R⁶ is from 1 :13 to 1:5.

2. A composition according to Claim 1, comprising from 0.1% to 5%, by weight, of said AQA cationic surfactant (I).

3. A composition according to Claim 2 wherein in said AQA cationic surfactant (I) R¹ is CI Q-C J S alkyl, R² is methyl, and p and q are each 1 to 4 ethoxy.

4. A composition according to Claim 3 wherein said anionic surfactant (II) is a Cj2-Ci8 primary or secondary linear or branched alkyl sulfate and wherein said anionic surfactant (III) is a Cj 1 -C13 alkyl benzene sulfonate.

5. A composition according to Claim 1 wherein said nonionic surfactant

IV is a member selected from the group consisting of alcohol ethoxylates, alkyl phenol ethoxylates, polyhydroxy fatty acid amides, alkyl polyglucosides, and mixtures thereof.

6. A composition according to Claim 1 , comprising:

(a) from 0.25% to 3%, by weight, of Coco Methyl EO2 as surfactant (I);

(b) from 3% to 40%, by weight, of straight chain or branched chain primary or secondary alkyl sulfate as surfactant (II);

(c) from 6% to 23%, by weight, of alkyl benzene sulfonate as surfactant (III); and

(d) from 0.5% to 20%, by weight, of a nonionic surfactant (IV).

7. A composition according to Claim 6, comprising: (i) from 0.45% to 2%, by weight, of (a); (ii) from 6% to 13%, by weight, of (b);

(iii) from 8% to 23%, by weight, of (c); and (iv) from 1 % to 5%, by weight, of (d).

8. A detergent composition according to Claim 1 which additionally comprises conventional adjunct ingredients, or mixtures thereof.

9. A composition according to Claim 8 wherein the adjunct ingredient is a builder.

10. A composition according to Claim 8 wherein the adjunct ingredient is an enzyme.

11. A composition according to Claim 8 wherein the adjunct ingredient is a soil release polymer.

12. A composition according to Claim 8 wherein the adjunct ingredient is bleach, a bleach activator, or mixtures thereof.

13. A composition according to Claim 8 wherein the adjunct ingredient is a clay soil removal/antiredeposition agent.

14. A composition according to Claim 8 wherein the adjunct ingredient is a polymeric dispersing agent.

15. A composition according to Claim 8 wherein the adjunct ingredient is a brightener.

16. A composition according to Claim 8 wherein the adjunct ingredient is a dye transfer inhibiting agent.

17. A composition according to Claim 8 wherein the adjunct ingredient is a suds suppressor.

18. A composition according to Claim 8 wherein the adjunct ingredient is a detersive surfactant which is a member selected from the group consisting of soaps, alkyl alkoxy sulfates, alkyl alkoxy carboxylates, sulfated alkyl polyglycosides, alpha-sulfonated fatty acid esters, betaines, sulfobetaines, amine oxides and mixtures thereof.

19. A composition according to Claim 8 wherein the adjunct ingredient is a fabric softener.

20. A composition according to Claim 8 which is substantially free of bleach.

21. A composition according to Claim 8 wherein the adjunct ingredient is a perfume.

22. A composition according to Claim 8 wherein the adjunct ingredient is a chelant.

23. A composition according to Claim 8 wherein the adjunct ingredient is a manganese^ iron or cobalt catalyst.

24. A composition according to Claim 1, comprising a mixture of AQA surfactants.

25. A composition according to Claim 1 comprising a mixture of a bis- alkoxylated AQA surfactant and a mono-alkoxylated cationic surfactant.