DETERGENT COMPOSITION

Technical Field

The present invention relates to a detergent composition comprising an aluminosilicate builder, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Background to 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, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers, all 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 different types of soils and stains. While a review of the literature would seem to indicate that a wide selection of surfactants and surfactant combinations are 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 products such as 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.

The quick and efficient removal of different types of soils and stains such as body soils, greasy/oily soils and certain food stains, can be problematic. Such soils comprise a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter and are thus notoriously difficult to remove. Low levels of hydrophobic soils and residual stains often remain on the surface of the fabric after washing.

Detergent builders are employed in the compositions described herein to assist in controlling mineral hardness, especially Ca^+ and/or Mg2+ ions, 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. Recently there has been added impetus in the development of synthetic builder compounds that provide environmental aswell as economic benefits. These builder materials are typically inorganic and insoluble/partially soluble. A particular problem associated with the use of insoluble/partially soluble, inorganic builders is the formation of insoluble complexes with hardness ions that may deposit on the surface of the washed substrate for example fabric, leaving a layer of encrusted material trapped on or within the surface of the washed substrate i.e. the fabric.

Successive washing and wearing coupled with limited removal of the soils, stains and encrusted builder material in the wash culminates in a build-up on the fabric which further entraps particulate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy appearance which is perceived as unwearable and discarded by the consumer.

The literature suggests that various nitrogen-containing cationic 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 commercial use of such materials has been limited by the difficulty encountered in the large scale manufacture of such compounds. An additional limitation has been the potential precipitation of anionic active components of the detergent composition occasioned by their ionic interaction with cationic surfactants. The aforementioned nonionic and anionic surfactants remain the major surfactant components in today's laundry compositions.

It has been discovered that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in various detergent compositions to boost detergency performance on a variety of soil and stain types, particularly the hydrophobic soil types, commonly

encountered. The bis-AQA surfactants of the present invention provide substantial benefits to the formulator, over cationic surfactants previously known in the art. For example, the bis-AQA surfactants used herein provide marked improvement in cleaning of "everyday" greasy /oily hydrophobic soils regularly encountered. Moreover, the bis-AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions such as alkyl sulfate and alkyl benzene sulfonate; incompatibility with anionic components of the detergent composition has commonly been the limiting factor in the use of cationic surfactants previously known. Low levels (as low as 3 ppm in the laundering liquor) of bis-AQA surfactants gives rise to the benefits described herein. Bis-AQA surfactants can be formulated over a broad pH range from 5 to 12. The bis-AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a manufacturing plant. Bis-AQA surfactants with degrees of ethoxylation above 5 are sometimes present in a liquid form and can therefore be provided as 100% neat materials. In addition to their beneficial handling properties, the availability of bis-AQA surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs

Furthermore, it has also been discovered that compositions containing bis-AQA surfactants and aluminosilicate builder deliver superior cleaning and whiteness performance versus products containing either technology alone. Particularly, it has been found that high levels of inorganic, insoluble or partially soluble builders can be employed in the compositions of the present invention without increasing the level of residual encrusted material remaining on the washed substrate. It is believed that insoluble inorganic builders such as aluminosilicate builders are composed of discreet units, some faces of which will be negatively charged. Bis-AQA, which has a positively charged headgroup, may interact with these faces to lift off the residual inorganic particles of builder/soil/stain from fabrics by formation of hydrophilic, charged surfactant bilayers around the inorganic particles resulting in the effective solubization of the inorganic particles in the wash water.

The present invention thus provides a detergent composition which delivers effective cleaning of everyday, especially hydrophobic soils by way of a detergent composition comprising aluminosilicate builder and a bis-AQA surfactant.

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. 2,040,990, 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 provides a composition comprising or prepared by combining an aluminosilicate builder, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein Rl is a linear, branched, substituted Cg-Ci g alkyl, alkenyl, aryl, alkaryl, eϋher or glycityl ether moiety, R^ is a C1-C3 alkyl moiety, R^ and R^ can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, and A and A' can vary independently and are each C1 -C4 alkoxy, p and q can vary independantly and are integers of from 1 to 30.

Description of the Invention

Aluminosilicate Builder

The first essential component of die composition of die present invention is an aluminosilicate builder. Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels.

Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na _z [(AlO2) _z (SiO2)y]. XH2O wherein z and y are integers of at least 6; the molar ratio of z to y is in the range of from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material can be crystalline or amporphous

but are preferably crystalline and inhydrate, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P (or Zeolite MAP), Zeolite X, Zeolite HS and mixtures thereof.

Zeolite A has the formula

Na ₁₂ [AlO ₂ ) 12 (SiO ₂ )i2j. *H ₂ O

wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x=0) may also be used. Zeolite X, a preferred aluminosilicate has me formula Nagβ [(AK>2)86(SiO2)l06]- 276 H2O. Zeolite MAP, as disclosed in EP-B-384,070 is also a preferred aluminosilicate builder herein. Preferably die aluminosilicate has a particle size of 0.1 to 10 microns in diameter.

The aluminosilicate builder is typically present at a level of from 1 % to 80% by weight, preferably from 10% to 80% by weight, most preferably from 15% to 50%or even 60% weight of the composition.

Bis-Alkoxylated Quaternary Ammonium (bis-AQA) Cationic Surfactant

Another essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:

wherein R* is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, edier, glycityl ether moiety containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms; R is an alkyl group containing from 1 to 3 carbon

atoms, preferably methyl; R^ and R ⁴ can vary independently and are selected from die group consisting of hydrogen (preferred), memyl and ethyl; X- is an anion such as chloride, bromide, methyl sulfate, sulfate, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4 and q is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably bom p and q are 1.

Bis-AQA compounds wherein me hydrocarbyl substituent R ¹ is Cg-Cj2, especially Cg- Cιo _> enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials. Accordingly, me Cg-C _j 2 bis- AQA surfactants may be preferred by some formulators. The levels of the bis-AQA surfactants used to prepare finished laundry detergent compositions can range from 0.1 % to 5% , typically from 0.45% to 2.5%, by weight. The weight ratio of bis-AQA to percarbonate bleach is in the range of from 1 : 100 to 5 : 1 , preferably from 1 : 60 to 2: 1 , most preferably from 1: 20 to 1:1.

The present invention employs an "effective amount" of the bis-AQA surfactants to improve the performance of cleaning compositions which contain other optional ingredients. By an "effective amount" of the bis-AQA surfactants herein is meant an amount which is sufficient to improve, eimer directionally or significantly at the 90% confidence level, the performance of the cleaning composition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such stains. Likewise, in a composition whose targets include clay soil, me formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such soil.

The bis-AQA surfactants may be used in combination with otiier 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 die wash water temperature, me 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 45 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 minutes and a wash water temperature of 10°C to 50°C, it is preferred to include from 2 ppm to 50 ppm, preferably from 5 ppm to 25 ppm, of me bis-AQA surfactant in the wash liquor. On die basis of usage rates of from 50 ml to 150 ml per wash load, mis translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1 % to 3.2%, preferably 0.3% to 1.5% , for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 60 g to 95 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/1) mis translates into an in-product concentration (wt.) of me bis-AQA surfactant of from 0.2% to 5.0%, preferably from 0.5% to 2.5% . On tiie basis of usage rates of from 80 g to 100 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/1), this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1 % to 3.5%, preferably from 0.3% to 1.5%.

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

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

35 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/1) this translates into an in-product concentration (wt.) of me bis-AQA surfactant of from 0.25 % to 10% , preferably from 0.5 % tol .0% . On the basis of usage rates of from 30 g to 40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/1), this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.25% tol0% , preferably from 0.5% to 1 %.

As can be seen from the foregoing, the amount of bis-AQA surfactant used in a machine- wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine. In this context, however, one heretofore unappreciated advantage of me bis-AQA surfactants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains even when used at relatively low levels with respect to die other surfactants (generally anionics or anionic/nonionic mixtures) in me finished compositions. This is to be distinguished from other compositions of the art wherein various cationic surfactants are used with anionic surfactants at or near stoichiometric levels. In general, in me practice of this invention, me weight ratio of bis-AQA: anionic surfactant in laundry compositions is in me range from 1 :70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably 1:15 to 1 :8. In laundry compositions which comprise both anionic and nonionic surfactants, the weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, preferably 1:50 to 1:8.

Various other cleaning compositions which comprise an anionic surfactant, an optional nonionic surfactant and specialized surfactants such as betaines, sultaines, amine oxides can also be formulated using an effective amount of the bis-AQA surfactants in the manner of this invention. Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and the like. Since the habits and practices of the users of such compositions show minimal variation, it is satisfactory to include from about 0.25% to about 5%, preferably from about 0.45% to about 2%, by weight, of me bis-AQA surfactants in such compositions. Again, as in the case of the granular and liquid laundry compositions, the weight ratio of me bis-AQA surfactant to omer surfactants present in such compositions is low, i.e., sub-stoichiometric in die case of anionics. Preferably, such cleaning compositions comprise bis-AQA/surfactant ratios as noted immediately above for machine-use laundry compositions.

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 top loading automatic washing machines, especially of me type used in North America, as well as under Japanese usage conditions. Typically, such compositions will comprise an anionic 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 witii 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 1:1.

The preferred emoxylated 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 of Scheme 5. Step 1 of the reaction is preferably conducted in an aqueous medium. Reaction temperatures are typically in die 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 reaction is preferably conducted using Cg-Cj4 alkyl sulfate, sodium salt. The ethoxylation and quaternization steps are carried out using conventional conditions and reactants.

Under some circumstances reaction Scheme 5 results in products which are sufficiently soluble in the aqueous reaction medium mat gels may form. While die desired product can be recovered from me gel, an alternate, two-step synthesis Scheme 6, hereinafter, may be more desirable in some commercial circumstances. The first step in Scheme 6 is conducted as in Scheme 5. The second step (edioxylation) is preferably conducted using ethylene oxide and an acid such as HC1 which provides me quaternary surfactant. As shown below, chlorohydrin i.e., chloroemanol, can also be reacted to give the desired bishydroxyemyl derivative.

For reaction Scheme 6, the following parameters summarize the optional and preferred reaction conditions for me first step. The first step is preferably conducted in an aqueous medium. Reaction temperatures are typically in me 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 me reaction, or an excess of the amine can be employed to also react wim 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, die 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 quaternization to provide bis-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, an organic base or excess amine reactant is used to neutralize generated HSO4.

Scheme 6

Scheme 7

The following further illustrates several of me above reactions solely for me convenience of me formulator, but is not intended to be limiting thereof.

Synthesis A

Preparation of N.N-Bis(2-hvdroxyemyl)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 me liquid contents of me 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 me mixture is allowed to separate. The lower chloroform layer is drained and me 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 me presence of base in the manner described in Synmesis A. The resulting 2-hydroxyethyldodecylamine is recovered and reacted wim 1-chloroethanol to prepare the title compound.

Synmesis C

Preparation of N.N-Bis(2-hvdroxyemyl)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 me liquid contents of the glass liner are poured into a 250 ml separatory funnel along wim 80 ml of chloroform. The funnel is shaken well for a few minutes and men allowed mixture to separate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted witii 1 molar equivalent of ethylene oxide in me absence of base catalyst at 120-130°C to produce me desired final product.

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

According to me foregoing, the following are nonlimiting, specific illustrations of bis-AQA surfactants used herein. It is to be understood that the degree of alkoxylation noted herein for me bis-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 etiioxylation. Thus, it is not

uncommon to report total EO values other than as whole numbers, e.g., "EO2.5", "EO3.5".

Designation E ¹ E ² ApR ³ A'qR* bis-AQA- 1 C ₁₂ -Ci4 CH3 EO EO (also referred to as Coco Methyl EO2) bis-AQA-2 ^C 12-Cl6 CH ₃ (EO) ₂ EO

bis-AQA-3 ^c 12"Cl4 CH3 (EO) ₂ (EO) ₂

(Coco Mediyl EO4) bis-AQA-4 Cl2 CH3 EO EO

bis-AQA-5 ^C 12-Cl4 CH3 (EO) ₂ (EO) ₃

bis-AQA-6 ^C 12-Cl4 CH ₃ (EO) ₂ (EO) ₃

bis-AQA-7 C8-C18 CH3 (EO) ₃ (EO) ₂

bis-AQA-8 ^C 12-Cl4 CH3 (EO) ₄ (EO) ₄

bis-AQA-9 Cl2-Cl4 C ₂ H ₅ (EO) ₃ (EO) ₃

bis-AQA- 10 C12-C18 C3H7 (EO) ₃ (EO) ₄

bis-AQA-11 C12-C18 CH3 (propoxy) (EO) ₃

bis-AQA-12 ^c 10- ^c 18 C ₂ H ₅ (iso-propoxy)2 (EO)3

bis-AQA-13 Cl0-Cl8 CH3 (EO/PO)2 (EO) ₃

bis-AQA-14 C8-C18 CH3 (EO)ι ₅ * (EO)ι _:

bis-AQA-15 ClO CH3 EO EO

bis-AQA-16 Cg-Cι ₂ CH ₃ EO EO

bis-AQA-17 Cg-C _n CH ₃ - EO 3.5 Avg. -

bis-AQA-18 C\ ₂ CH3 - EO 3.5 Avg. -

bis-AQA-19 Cg-Cι ₄ CH3 (EO) ₁₀ (EO)ιo

bis-AQA-20 ClO C ₂ H ₅ (EO) ₂ (EO) ₃

bis-AQA-21 C12-C14 C ₂ H ₅ (EO) ₅ (EO)3

bis-AQA-22 Ci2-Cι g C3H7 Bu (EO)2

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

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

wherein R* is Cg-Cig hydrocarbyl and mixtures tiiereof, preferably Cg, Cio, C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance, preferably chloride. Wim reference to the general bis-AQA structure noted above, since in a preferred compound R* is derived from coconut (C12-C14 alkyl) fraction fatty acids, R ² is methyl and ApR ³ and A'qR ⁴ are each monoetirøxy, mis preferred type of compound is referred to herein as "CocoMeEO2" or "bis-AQA- 1" in me above list.

Other bis-AQA surfactants useful herein include compounds of me formula:

wherein R ¹ is Cg-Cjg hydrocarbyl, preferably Cg-Ci4 alkyl, independently p is 1 to 3 and q is 1 to 3, R ² is C1-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of me foregoing type include those wherein me ethoxy (CH2CH2O) units (EO) are replaced by butoxy (Bu) isopropoxy [CH(CH3)CH2O] and [CH2CH(CH3θ] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Non-AQA Detersive Surfactants

In addition to me bis-AQA surfactant, die compositions of the present invention preferably further comprise a non-AQA surfactant. Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.

Anionic Surfactant

Nonlimiting examples of anionic surfactants useful herein typically at levels from 1 % to 55%, by weight, include me conventional Cj i-Ci g alkyl benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random C10-C20 alkyl sulfates, the Cjo-Cig secondary (2,3) alkyl sulfates of me formula CH3(CH2) _x (CHOSO3 ^~ M ^"f ) CH3 and CH3 (CH2)y(CHOSO3 ^_ M ⁺ ) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, me Cj2-Cιg alpha-sulfonated fatty acid esters, me Cirj-Cig sulfated polyglycosides, die Cjo-Ci g alkyl alkoxy sulfates ("AE _X S"; especially EO 1-7 ethoxy sulfates), and die CjQ-Cig alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The C12-C18 betaines and sulfobetaines ("sultaines"), Cjo-Cig amine oxides, can also be included in me overall compositions. C10-C20 conventional soaps may also be used. If high sudsing is desired, die branched-chain CJQ-CIO soaps may be used. Other conventional useful surfactants are listed in standard texts.

Nonionic Surfactants

Nonlimiting examples of nonionic surfactants useful herein typically at levels from 1 % to 55% , by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Cjø-Cig glycerol emers.

More specifically, the condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of emylene oxide (AE) are suitable for use as me 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 8 to 22 carbon atoms. Preferred are me condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon atoms, with from 1 tolO 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: TergitolTM 15-S-9 (die condensation product of C11-C15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (die condensation product of C12-C14 primary alcohol wim 6 moles ethylene oxide wim a narrow molecular weight distribution), bom marketed by Union Carbide Corporation; NeodolTM 45.9 ( _me condensation product of C14-C15 linear alcohol wim 9 moles of ethylene oxide), NeodolTM 23-3 (die condensation product of C12-C13 linear alcohol wim 3 moles of ethylene oxide), NeodolTM 45.7 ( _me condensation product of C14-C ₁ 5 linear alcohol wim 7 moles of ethylene oxide) and NeodolTM 45.5 ( _me condensation product of C14-C ₁ 5 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM £OB (me condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA O3O or O5O (me condensation product of Cl2"Ci4 alcohol with 3 or 5 moles of emylene oxide) marketed by Hoechst. The preferred range of HLB in tiiese AE nonionic surfactants is from 8-11 and most preferred from 8-10. Condensates widi propylene oxide and butylene oxides may also be used.

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

wherein R* is H, or Cι_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture mereof, R ² 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, R ² is a straight C\ ι_\ _ζ alkyl or Cj5_i7 alkyl or alkenyl chain such as coconut alkyl or mixtures tfiereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive animation reaction. Typical examples include die C^-Cjg and C12-C14 N-mefhylglucamides. 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 die nonionic surfactant in die present invention are the alkylpolysaccharides such as diose disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from 6 to 30 carbon atoms, preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 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 me glucosyl moieties (optionally me hydrophobic group is attached at me 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 die one position of die additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on me preceding saccharide units.

The preferred alkylpolyglycosides have the formula:

R2θ(C _n H ₂ nO)t(glycosyl) _x

wherein R ² is selected from die group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare tiiese compounds, me alcohol or alkylpolyethoxy alcohol is formed first and men reacted wim glucose, or a source of glucose, to form the glucoside (attachment at die 1 -position). The additional glycosyl units can tiien be attached between their 1 -position and die preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately die 2-position.

Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of die surfactant systems of die present invention, with the polyethylene oxide condensates being preferred. These compounds include me condensation products of alkyl phenols having an alkyl group containing from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in eitiier a straight-chain or branched-chain configuration with die alkylene oxide. In a preferred embodiment, me ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tol5 moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include IgepalTM CO-630, marketed by die GAF Corporation; and Triton™ X^5, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxy lates (e.g., alkyl phenol ethoxylates).

The condensation products of emylene oxide wim a hydrophobic base formed by die condensation of propylene oxide witii propylene glycol are also suitable for use as me additional nonionic surfactant in me present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 and will exhibit water insolubility. The addition of polyoxyetiiylene moieties to this hydrophobic portion tends to increase die water solubility of die molecule as a whole, and die liquid character of die product is retained up to die point where me polyoxyethylene content is 50% of die total weight of die condensation product, which corresponds to condensation witii up to 40 moles of ethylene oxide. Examples of compounds of diis type include certain of die commercially-available PluronicTM surfactants, marketed by BASF.

Also suitable for use as die nonionic surfactant of die nonionic surfactant system of the present invention, are die condensation products of etiiylene oxide wim die product resulting from die reaction of propylene oxide and etiiylenediamine. The hydrophobic moiety of tiiese products consists of me reaction product of etiiylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. This hydrophobic moiety is condensed with ethylene oxide to die extent tiiat the condensation product contains from 40% to 80% by weight of polyoxyethylene and has a molecular weight of from 5,000 to 11,000. Examples of this type of nonionic surfactant include certain of die commercially available TetronicTM compounds, marketed by BASF.

Additional Cationic surfactants

Suitable cationic surfactants are preferably water dispersible compound having surfactant properties comprising at least one ester (ie -COO-) linkage and at least one cationically charged group.

Other suitable cationic surfactants include die quaternary ammonium surfactants selected from mono Cβ-C\β, preferably C^-C\Q N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyediyl or hydroxypropyl groups. Otiier suitable cationic ester surfactants, including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Optional Detergent Ingredients

The following illustrates various otiier optional ingredients which may be used in die compositions of this invention, but is not intended to be limiting thereof.

Additional Builders

The compositions described herein, may comprise an additional builder. An additional builder may be present at a level of at least 1 % . Liquid formulations typically comprise 5% to 50%, more typically 5% to 35% of builder, a proportion of which may be comprised by additonal builder. Granular formulations typically comprise from 10% to 80%, more typically 15% to 50% builder by weight of die detergent composition, a proportion of which may be comprised by additonal builder. Lower or higher levels of builders are not excluded.

Mixed builder systems, comprising two or more builders are envisaged herein. Mixed builder systems are optionally complemented by chelants, pH-buffers or fillers, though tiiese latter materials are generally accounted for separately when describing quantities of materials herein. In terms of relative quantities of surfactant and builder in die present detergents, preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from 60:1 to 1:80. Certain preferred laundry detergents have said ratio in me range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0.

Suitable additional 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 tiiree-dimensional- structure as well as amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals otiier than sodium carbonate or sesquicarbonate; 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 die engineering of stable surfactant and/or builder-containing detergent compositions.

P-containing detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by die 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 purposes, solid hydrous 2-ratio silicates marketed by PQ Corp. under die tradename BRITESIL ^® , e.g., BRITESIL H20; 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-Na2Siθ5 morphology 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. Otiier layered silicates, such as those having the general formula NaMSi _x θ2χ+ ι VH2O 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, M' 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 otiier 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.

Suitable organic detergent builders include polycarboxylate compounds, including water- soluble nonsurfactant dicarboxylates and tricarboxylates. Mort 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 otiier 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.

Otiier suitable builders are die etiier hydroxypolycarboxylates, copolymers of maleic anhydride wim etiiylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6- trisulphonic acid; carboxymethyloxysuccimc acid; the various alkali metal, ammomum and substituted ammonium salts of polyacetic acids such as etiiylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, poly maleic acid, benzene 1 ,3,5- tricarboxylic acid, carboxymethyloxysuccinic 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 purposes, 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 die related compounds disclosed in U.S. 4,566,984, Bush, January 28, 1986. Succinic acid builders include die C5-C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986. Fatty acids, e.g., C^-Cjg monocarboxylic acids, can also be incorporated into die 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.

Otiier types of inorganic builder materials which can be used have die 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 die equation ∑j = i-is(xi multiplied by the valence of Mj) + 2y = 2z is satisfied such tiiat the formula has a neutral or "balanced" charge. These builders are referred to herein as "Mineral Builders". Waters of hydration or anions other tiian 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 die above equation. Preferably, there is present a water-soluble cation selected from me 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 tiiose selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures tiiereof. Preferred builders of this type in their simplest forms are selected from die group consisting of Na2Ca(CO3)2, K2Ca(CO ₃ )2, Na2Ca2(CO3)3, NaKCa(CO ₃ )2, NaKCa2(CO3)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, Carbocemaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Franzinite, Gaudefroyite, Gaylussite, Girvasite, Gregory ite, 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.

Bleach

The detergent compositions herein may optionally comprise a bleaching agent. When present, such bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5% to 20%, of tiie detergent composition, especially for fabric laundering.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or otiier cleaning purposes that are now known or become known. These include oxygen bleaches as well as otiier bleaching agents. Perborate bleaches, e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.

Anotiier category of bleaching agent that can be used widiout restriction encompasses percarboxylic acid bleaching agents and salts tiiereof. Suitable examples of this class of

agents include magnesium monoperoxyphthalate hexahydrate, die magnesium salt of meta- chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate 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 die range from 500 micrometers to 1,000 micrometers, not more tiian 10% by weight of said particles being smaller than 200 micrometers and not more man 10% by weight of said particles being larger than 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.

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 die sulfonated zinc and/or aluminum phthalo- cyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

Mixtures of bleaching agents can also be used.

Bleach Activators

Bleach activators are preferred components of a composition where an oxygen bleach is present. If present, the amount of bleach activators will typically be from 0.1 % to 60%,

more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The combination of peroxygen bleaching agents and bleach activators results in tiie in situ production in aqueous solution (i.e. , during the washing process) of the peroxy acid corresponding to die 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 etiiylene diamine (TAED) activators are typical, and mixtures tiiereof 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 tiiose of the formulae:

R ¹ N(R5)C(O)R ² C(O)L or RlC(O)N(R5)R2c(O)L

wherein R^.is an alkyl group containing from 6 to 12 carbon atoms, R ² is an alkylene containing from 1 to 6 carbon atoms, R^ is H or alkyl, aryl, or alkaryl containing from 1 to 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 die above formulae include (6-octanamido- caproyOoxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate, and mixtures tiiereof 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, incorporated herein by reference. A highly preferred activator of die 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 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimetiιylhexanoyl 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.

Bleach Catalyst

Bleach catalysts are optional components of die compositions of the present invention. 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. 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272A1, 544.440A2, and 544.490A1; Preferred examples of these catalysts include Mn^ ₂ (u-O)3(l,4,7- trimethyl-1 ,4,7-triazacyclononane)2(PF6)2, Mn^2( ^u_ 0)ι(u-OAc)2(l ,4,7-trimethyl-l ,4,7- triazacyclononane)2-(ClO4)2, MnHI" Mn ^rV 4(u-O)ι(u-OAc)2-(l,4,7-trimethyl-l ,4,7-triazacyclononane)2(Clθ4)3, Mn ^IV (l ,4,7- trimethyl-l, 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. 5,114,611. The use of manganese wim 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; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, die compositions and processes herein can be adjusted to provide on die 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 0.1 ppm to 700 ppm, more preferably from 1 ppm to 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 _y , wherein "OAc" represents an acetate moiety and "Ty" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH3)5OAc]Cl2; as well as [Co(NH3)5OAc](OAc)2;

[Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ ; [Co(NH ₃ ) ₅ OAc](SO ₄ ); [Co(NH3) ₅ OAc](BF ₄ ) ₂ ; and

[Co(NH3) ₅ OAc](NO ₃ )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; Inore. Chem.. 18, 1497-1502 (1979); Inorg. Chem.. 21, 2881-2885 (1982); Inorg.

Chem.. IS, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical

Chemistry. 5_6_, 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 pr vide on die order of at least one part per hundred million of the active bleach catalyst sp . αes in the aqueous washing medium, and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of die bleach catalyst species in the wash liquor. In order to obtain such levels in tiie wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions herein will

comprise from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Enzymes

Enzymes can be included in the present detergent compositions for a variety of puφoses, 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, Upases, cellulases, peroxidases, and mixtures tiiereof 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. 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.

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. In practical terms for current commercial preparations, typical amounts are up to 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 %-l % 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 die active enzyme content of die 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. Otiier 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 witii one or more amino acid residue positions equivalent to tiiose 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 die 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 die 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 60°C; or alkaline stability, e.g., at a pH from 8 to 11, measured versus die above-identified reference-point amylase. Stability can be measured using any of die 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 die Bacillus amylases, especially die Bacillus α-amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability -enhanced amylases vs. die 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 die 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. Mitcbinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases but tiiat 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 witii 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 die 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 die detergent compositions of die 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 tiie range of 8 to 10, measured by die 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 witii the amino acid sequences shown in tiie 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 die 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 9117243 to Novo.

Suitable lipase enzymes for detergent usage include tiiose 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." Otiier 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 tiie benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing die bis-AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in die range of 50 LU to 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 die wash to otiier 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 tiieir 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 tiieir 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. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Enzvme Stabilizing System

The enzyme-containing compositions herein may optionally also comprise from 0.001 % to 10%, preferably from 0.005% to 8%, most preferably from 0.01 % to 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 otiier formulation actives, or be added separately, e.g., by die 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 die 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 die 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 die 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 otiier 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 10%, preferably from 0.01 % to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating die enzymes, especially under alkaline conditions. While chlorine levels in water may be small, typically in die range from 0.5 ppm to 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 percarbonate has the ability to react with chlorine bleach 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 ammomum cations witii 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 (ME A), and mixtures tiiereof can likewise be used. Likewise, special enzyme inhibition systems can be incorporated 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 tiie 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 mat 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 tiie use of any enzyme scavenger or stabilizer which is majorly incompatible, as formulated, wim other reactive ingredients. In relation to the use of ammonium salts, such salts can be simply admixed with die 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 die 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 wweeiigehhtt., ooff ti thiee ccoommppoossiittiioonn.

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 titaniuπwTV) alkoxide. Such esters may be made using additional monomers capable of

being incoφorated into die 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 terephtiialoyl 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) ethoxy lating allyl alcohol, (b) reacting the product of (a) witii dimethyl terephthalate ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) witii sodium metabisulfite in water; the nonionic end-capped 1,2- propylene/polyoxyethylene terephthalate polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("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 etiiylene 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 me 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 die C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al. Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C^-Cg 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 togetiier with 90-80% by weight of polyoxyethylene terephthalate, derived from a polyoxyetiiylene glycol of average molecular weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Anotiier 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 wim end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyetfiyleneoxy 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 tiiereof, 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-hydroxyetiιoxy)-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 dihydroxy sulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, and combinations tiiereof; (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 ethoxy lated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures tiiereof. 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} etiianesulfonate ("SE3") and its homologs and mixtures tiiereof and the products of ethoxy lating and sulfonating ally! alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2- hydroxyethoxy)ethoxy}ethanesulfonate 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(TV) catalyst and can be designated as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -0 ₃ S[CH2CH2θ]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.

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; (IT) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. Witii a proper selection of catalyst, the trimellitic anhydride forms linkages to die terminals of the polymer through an ester of tiie 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 terephtiialate-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 botii 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 polyemylene 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.

Clav Soil Removal/ Anti-redeposition Agents

The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties. Granular detergent compositions which contain these compounds typically contain from 0.01 % to 10.0% by weight of the water-soluble etiioxylates amines; liquid detergent compositions typically contain 0.01 % to 5%.

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene- pentamine. 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 111,965, Oh and Gosselink, published June 27, 1984. Otiier clay soil removal/antiredeposition agents which can be used include die ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and die 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 die art can also be utilized in tiie 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 metiiyl cellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levels from 0.1 % to 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 polyetiiylene 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 tiieir 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 etiier, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful herein are die water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in die acid form preferably ranges from 2,000 to 10,000, more preferably from 4,000 to 7,000 and most preferably from 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, die alkali metal, ammomum and substituted ammomum salts.

Soluble polymers of tiiis 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 die dispersing/anti-redeposition agent. Such materials include die 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 2,000 to 100,000, more preferably from 5,000 to 75,000, most preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers will generally range from 30:1 to 1: 1, more

preferably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammomum 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 otiier 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 purposes range from 500 to 100,000, preferably from 1,000 to 50,000, more preferably from 1,500 to 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 10,000.

Briehtener

Any optical brighteners or otiier brightening or whitening agents known in the art can be incoφorated at levels typically from 0.01 % to 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in die 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. Otiier 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-naptho[l,2-d]triazoles; 4,4'-bis-(l,2,3-triazol-2-yl)-stilbenes; 4,4'- bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of tiiese brighteners include 4-metiιyl-7-diethyl- amino coumarin; l,2-bis(benzimidazol-2-yl)ethylene; 1,3- diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)tiιiophene; 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 die present invention may also include one or more materials effective for inhibiting die 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, manganese phthalocyanine, peroxidases, and mixtures thereof. If used, these agents typically comprise from 0.01 % to 10% by weight of the composition, preferably from 0.01 % to 5%, and more preferably from 0.05% to 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 die N-0 group can form part of the polymerizable unit or the N-0 group can be attached to botii units; A is one of the following structures: - NC(O)-, -C(0)0-, -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-0 group can be attached or die N-0 group is part of tiiese groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives tiiereof.

The N-0 group can be represented by the following general structures:

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

Any polymer backbone can be used as long as die 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 tiiereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and die otiier monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to die amine N-oxide of 10: 1 to 1 : 1 ,000,000. However, the number of amine oxide groups present in die 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, tiie average molecular weight is witiiin 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".

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

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as a class as "PVPVI") are also preferred for use herein. Preferably tiie 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 113. "Modern Methods of Polymer Characterization", the disclosures of which are incorporated 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 fro:;. ).8:1 to 0.3: 1 , most preferably from 0.6: 1 to 0.4: 1. These copolymers can be eithe: inear or branched.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to

200,000, and more preferably from 5,000 to 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 polyetiiylene glycol ("PEG") having an average molecular weight from 500 to 100,000, preferably from 1,000 to 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

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

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

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

When in the above formula, R\ 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

Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in die detergent compositions herein.

When in die above formula, R\ is anilino, R2 is N-2-hydroxyetiιyl-N-2-methylamino and M is a cation such as sodium, die 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, die 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) witii 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 tiian does either of these two detergent composition components when used alone. Witiiout being bound by theory, it is believed tiiat 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 die "exhaustion coefficient". The exhaustion coefficient is in general as die ratio of a) die brightener material deposited on fabric to b) die initial brightener concentration in tiie wash liquor. Brighteners witii 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 tiiat 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 aro- matic chelating agents and mixtures therein, all as hereinafter defined. Without intending

to be bound by tiieory, it is believed that the benefit of these materials is due in part to tiieir 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-hydroxyethylediy lenediaminetriacetates , nitrilotriacetates , etiiylenediamine tetraproprionates, triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, and etiianoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ediylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, tiiese amino phosphonates to not contain alkyl or alkenyl groups witii more than 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in tiie compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of tiiis type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy- 3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is etiiylenediamine 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.

If utilized, tiiese chelating agents will generally comprise from 0.1% to 15% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from 0.1 % to 3.0% by weight of such compositions.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can be incoφorated into die compositions of die present invention. Suds suppression can be of particular importance in the so-called "high concentration 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 die 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 tiiereof used as suds suppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammomum 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 Cιg-C40 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 witii 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 die range of -40 °C and 50°C, and a minimum boiling point not less thanllO°C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 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 12 to 70 carbon atoms. The term "paraffin," as used in tiiis 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 die silica. Silicone suds suppressors are well known in die 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)3SiOι/2 units of Siθ2 units in a ratio of from (CH3)3 SiO]/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 die preferred silicone suds suppressor used herein, the solvent for a continuous phase is made up of certain polyetiiylene glycols or polyethylene-polypropylene glycol copolymers or mixtures tiiereof (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 tiian about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyediylene/polypropylene copolymers herein have a solubility in water at room temperature of more tiian about 2 weight % , preferably more than about 5 weight % .

The preferred solvent herein is polyethylene glycol having an average molecular weight of less tiian about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol: copolymer of polyethylene- polypropylene glycol.

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

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as tiie silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a Cι-Cj6 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 or dishwashing machines, suds should not form to die extent that they either overflow the washing machine or negatively affect the washing mechanism of the dishwasher. 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 tiiis suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry or dishwashing detergents for use in automatic laundry or dishwashing machines.

The compositions herein will generally comprise from 0% to 10% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts dierein, will be present typically in amounts up to 5% , by weight, of the detergent composition. Preferably, from 0.5% to 3% of fatty monocarboxylate suds suppressor is utilized.

Silicone suds suppressors are typically utilized in amounts up to 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 witii keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing. Preferably from 0.01 % to 1 % of silicone suds suppressor is used, more preferably from 0.25% to 0.5%. As used herein, tiiese weight percentage values include any silica tiiat may be utilized in combination witii polyorganosiloxane, as well as any adjunct materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2%, by weight, of die composition. Hydrocarbon suds suppressors are typically utilized in amounts ranging from 0.01 % to 5.0%, although higher levels can be used. The alcohol suds suppressors are typically used at 0.2% -3% by weight of die finished compositions.

Alkoxylated Polycarboxylates

Alkoxylated polycarboxylates such as tiiose 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 aery late units. The side-chains are of the formula -(CH2CH2θ) _m (CH2) _n CH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to die polyacrylate "backbone" to

provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of 2000 to 50,000. Such alkoxylated polycarboxylates can comprise from 0.05% to 10%, by weight, of die compositions herein.

Fabric Softeners

Various tiirough-tiie-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 otiier softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently witii 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 and esters. 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. Finished perfumes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from 0.01 % to 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from 0.0001 % to 90% of a finished perfume composition.

The detergent compositions described herein may contain perfume ingredients. 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 l,6,10-trimethyl-2,5,9-cyclododecatrien-l-yl ketone; 7-acetyl-l, 1, 3, 4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-buty 1-1 ,1 -dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl- 1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-l,l,2,6-tetramethyl indane; 1- dodecanal , 4-(4-hydroxy-4-methy lpenty l)-3-cyclohexene- 1 -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-memyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinnamic aldehyde; 2-metiιyl-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-tetrametiιylnaphtiιo[2, lb]furan; cedrol, 5-(2,2,3-trimetiιylcyclopent- 3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-l-yl)-2-buten-l-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly preferred perfume materials are tiiose that provide die largest odor improvements in finished product compositions containing cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-metiιyl-3-(para-tert- butylphenyl)-propionaldehyde; 7-acetyl-l ,2,3,4,5 ,6,7,8-octahydro-l , 1 ,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-l, 1,3 ,4 ,4, 6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-naptiiol 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-hexametiiyl-cyclopenta-gamma-2-benzopy rane; dodecahydro- 3a,6,6,9a-tetramethylnaphtho[2,lb]furan; 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 etiiyl 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 otiier ingredients useful in detergent compositions can be included in die 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 Cιo-Cj6 alkanolamides can be incoφorated into die compositions, typically at 1%-10% levels. The C10-C ₁ 4 monoethanol and dietiianol amides illustrate a typical class of such suds boosters. Use of such suds boosters witii high sudsing adjunct surfactants such as die amine oxides, betaines and sultaines noted above is also advantageous. If desired, water-soluble magnesium and/or calcium salts such as MgCl2, MgSO4, CaCl2 CaSO4, 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, die detersive ingredient is admixed witii a surfactant before being absorbed into die porous substrate. In use, die detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

To illustrate tiiis technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%- 5% of Ci 3_i5 etiioxylated alcohol (EO 7) nonionic surfactant. Typically, tiie enzyme/surfactant solution is 2.5 X tiie 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 die final detergent matrix. By this means, ingredients such as die 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 otiier 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 tiiose containing from 2 to 6 carbon atoms and from 2 to 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, die wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between 6.8 and 9.0. Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include die use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Granules Manufacture

Adding die bis-alkoxylated cationics of tiiis 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 die alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred tiiat the particle composition not be highly alkaline. Processes for preparing high density (above 650 g/1) granules are described in U.S. Patent 5,366,652. Such particles may be formulated to have an effective pH in-use of 9, or below, to avoid die odor of impurity amines. This can be achieved by adding a small amount of acidity source such as boric acid, citric acid, or die like, or an appropriate pH buffer, to die particle. In an alternate mode, die prospective problems associated witii amine malodors can be masked by use of perfume ingredients, as disclosed herein.

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

LAS C11.5 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

NI 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 Polyetiiylene 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

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; Distyryl Biphenyl Disulfonate class; Ciba-Geigy

Brightener Y Tinopal ^® UNPA-GX; Cynauric chloride/Diamino stilbene class;

Ciba-Geigy Suds Control Silica/silicone suds suppressor

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.

Granular detergents are as follows in Examples A and B.

EXAMPLE A

INGREDIENTS % (wt.) Epm

Surfactant LAS 2 211..4477 143.20 AS 6 6..5555 43.69 NI 3 3..3300 22.01 CocoMeEO2* 0 0..4477 3.13

Builder-Alkalinity SKS-6 3 3..2299 21.94 Copolymer 7 7..1100 47.36 Zeolite 8 8..4400 56.03

PEG4000 0 0..1199 1.27 Carbonate, Na 1 177..8844 118.99 Silicate (2.0R) 1 111..4400 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 of surfactants AQA-2 through AQA-22 or other AQA surfactants herein.

EXAMPLE B

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. OR) 11.40 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 bis-AQA- 1 (CocoMeE02) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or otiier bis-AQA surfactants herein.

The following illustrates a laboratory procedure and test results, over a variety of soils and stains, using compositions witiiin 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 LAS + 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 A 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 die following sequence :

1. 78.85 gms of LAS are weighed.

2. 34.55 gms of AS are weighed into die 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 witii heating at 40 deg C for about 30 minutes until completely dissolved.

Step II:

1. 01.90 gms of the cationic are weighed into die 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 tiiis stock solution are used for per wash. This 100 ml solution when added to 49 liters of tap water gives die 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 die 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 die performance of compositions according to the present invention using CoCoMeE02 plus a mixture of LAS/ AS and Test Results II show the performance using CoCoMeEOlO* plus LAS/ AS, as compared with CoCoMeE02/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, "EOlO" indicates two poly-EO chains with an overall average of 10 EO units in tiie molecule, typically (but not restricted to) about 5 per chain.

TEST RESULTS I Premixing of CocoMeE02 Cationic witii LAS & AS (total anionic system)

Soils Test l Test fl 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 SENSπTVΕ

SOIL (Ave.) 0.27 0.49 0.38

Meat sauce 0.84 S 1.08 S 0.96

Curry 1.14 S 1.11 S 1.13

Bacon oil 0.1 0.16 0.13

DMO 0.44 -0.34 0.05

SURFACTANT SEN¬

SITIVE SOIL (Ave.) 0.63 0.5 0.57

Average (including

Socks) 0.39 0.38 0.39 Socks (before) 0.32 0.35 A 0.34 Socks (after) 0.08 0.64 A 0.36 Socks (delta) -0.24 0.28 0.02

TEST RESULTS I Premixing of CocoMeE02 Cationic with LAS alone

Soils Test I Test ll Average In-used collar 0.27 -0.73 -0.23

Insert collar -0.04 0.15 0.06

Cuffs -0.35 -0.25 -0.30

Dinginess 0.13 0.51 S 0.32

BODY SOIL (Ave.) 0.00 -0.08 -0.04 Clay C/D 0.59 0.79 S 0.69

Clay DKPE 0.04 0.66 0.35

BUILDER SENSITIVE SOIL (Ave.) 0.32 0.73 0.53

Spinach 0.07 0.58 0.33 Coffee 0.24 0.24 0.24

BLEACH SENSITIVE SOIL (Ave.) 0.16 0.41 0.29

Meat sauce -0.1 -0.08 -0.09

Curry 0.1 0.54 0.32 Bacon oil -0.53 -0.02 -0.28

DMO -0.22 0.05 -0.09

SURFACTANT SEN¬ SITIVE SOIL (Ave.) -0.19 0.12 -0.04

Average (including Socks) 0.04 0.19 0.12

Socks (before) 0.33 -0.07 0.13

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 0.11 -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) -0.11

Socks (before) 0.42 S

Socks (after) 0.64 S

Socks (delta) 0.22

Examples

In the following examples, the abbreviated component identifications have the following meanings:

LAS Sodium linear Cχ2 alkyl benzene sulfonate TAS Sodium tallow alkyl sulfate C45AS Sodium C14-C15 linear alkyl sulfate CxyEzS Sodium Cj _x -Ciy branched alkyl sulfate condensed witii z moles of ethylene oxide C45E7 A Ci4_i5 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide

C25E3 A C 12- 15 branched primary alcohol condensed witii an average of 3 moles of ethylene oxide

C25E5 A C 12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide

CocoE02 R ₁ .N+(CH3)(C ₂ H ₄ OH)2 with Ri = C ₁₂ - C14 Soap Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.

TFAA C16-C18 alkyl N-metiiyl glucamide TPKFA C12-C14 topped whole cut fatty acids STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated Sodium Aluminosilicate of formula Nai2(A102Siθ2)i2- 27H20 having a primary particle size in the range from 0.1 to 10 micrometers

NaSKS-6 Crystalline layered silicate of formula δ -Na2S-2θ5

Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm

Bicarbonate Anhydrous sodium bicarbonate with a particle size distribution between 400μm and 1200μm

Silicate Amoφhous Sodium Silicate (Siθ2:Na2θ; 2.0 ratio)

Sodium sulfate Anhydrous sodium sulfate Citrate Tri-sodium citrate dihydrate of activity 86.4% witii a particle size distribution between 425μm and 850 μm

MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average molecular weight 70,000.

CMC Sodium carboxymediyl cellulose

Protease Proteolytic enzyme of activity 4KNPU/g sold by

NOVO Industries A/S under the tradename

Savinase

Alcalase Proteolytic enzyme of activity 3 AU/g sold by

NOVO Industries A/S

Cellulase Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under die tradename Carezyme

Amylase Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under die tradename Termamyl 60T

Lipase Lipolytic enzyme of activity lOOkLU/g sold by NOVO Industries A/S under die tradename Lipolase Endolase Endoglunase enzyme of activity 3000 CEVU/g sold by NOVO Industries A/S

PB4 Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2O2

PB1 Anhydrous sodium perborate bleach of nominal formula NaBθ2-H2θ2

Percarbonate Sodium Percarbonate of nominal formula

2Na ₂ C0 ₃ .3H2θ2

NOBS Nonanoyloxybenzene sulfonate in tiie form of the sodium salt. TAED Tetraacetylethylenediamine

DTPMP Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under die

Trade name Dequest 2060

Photoactivated Sulfonated Zinc Phthalocyanine encapsulated in bleach dextrin soluble polymer

Brightener 1 Disodium 4,4 ^* -bis(2-sulphostyryl)biphenyl Brightener 2 Disodium 4,4'-bis(4-anilino-6-moφholino-1.3.5- triazin-2-y l)amino) stilbene-2 : 2 ' -disulfonate .

HEDP 1,1-hydroxyethane diphosphonic acid PVNO Polyvinylpyridine N-oxide

PVPVI Copolymer of poly vinylpyrrolidone and vinylimidazole

SRA 1 Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl backbone SRA 2 Diethoxylated poly (1, 2 propylene terephtiialate)

short block polymer

Silicone antifoam Polydimethylsiloxane foam controller wim siloxane-oxyalkylene copolymer as dispersing agent witii a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

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

In the following Examples all levels are quoted as % by weight of tiie composition.

EXAMPLE I

The following detergent formulations according to die present invention.

A B

Blown Powder

STPP 14.0 - 24.0

Zeolite A 10.0 24.0 4.0

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 - -

CocoMeE02* 1.5 1.0 2.0

Silicate 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Brightener 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

DTPMP 0.4 0.4 0.2

Spray On

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Silicone antifoam 0.3 0.3 0.3

Perfume 0.3 0.3 0.3

Dry additives

Carbonate 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photoactivated bleach 0.02 0.02 0.02

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.25 0.30 0.15

Dry mixed sodium sulfate 3.0 3.0 5.0

Balance (Moisture &

Miscellaneous) To: 100.0 100.0 100.0

Density (g/litre) 630 670 670

^♦ The bis-AQA- 1 (CocoMeE02) surfactant of die Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.

EXAMPLE II

The following nil bleach-containing detergent formulations are of particular use in washing colored clothing.

D E F

Blown Powder

Zeolite A 15.0 15.0 2.5

Sodium sulfate 0.0 5.0 1.0

LAS 2.0 2.0 -

CocoMeEO2* 1.0 1.0 1.5

DTPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.0 4.0 -

Agglomerates

C45AS - - 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

Zeolite A 10.0 15.0 13.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.0 7.0 7.0

Spray On

Perfume 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0

Dry additives

MA/AA - - 3.0

NaSKS-6 - - 12.0

Citrate 10.0 - 8.0

Bicarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Alcaiase 0.5 0.3 0.9

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Silicone antifoam 5.0 5.0 5.0

Dry additives

Sodium sulfate 0.0 9.0 0.0

Balance (Moisture &

Miscellaneous) To: 100.0 100.0 100.0

Density (g/litre) 700 700 850

*The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be re equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or < surfactants herein.

EXAMPLE III

The following detergent formulations, according to the present invention are prepared:

G H I

Blown Powder

Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

CocoMeEO2* 1.0 1.0 1.0

Silicate - 1.0 5.0

Soap - - 2.0

Brightener 1 0.2 0.2 0.2

Carbonate 8.0 16.0 20.0

DTPMP - 0.4 0.4

Spray On

C45E7 1.0 1.0 1.0

Dry additives

PVPVI/PVNO 0.5 0.5 0.5

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.1 0.1 0.1

Cellulase 0.1 0.1 0.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium sulfate - 6.0 -

Balance (Moisture

& Miscellaneous) To: 100 100 100

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

EXAMPLE IV

The following high density and bleach-containing detergent formulations, according to die present invention are prepared:

I K L

Blown Powder

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0

CocoMeEO2* 1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.0 2.0 2.0 Agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0

Spray On

Perfume 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 • _ Dry additives

Citrate 5.0 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0 PB1 13.0 7.0 10.0

Polyethylene oxide of MW 5,000,000 - - 0.2

Bentonite clay - - 10.0

Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0

Balance (Moisture &

Miscellaneous) To: 100.0 100.0 100.0 Density (g/litre) 850 850 850

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

EXAMPLE V

The following high density detergent formulations according to the present invention are prepared:

M N

Blown Powder

Zeolite A 2.5 2.5

Sodium sulfate 1.0 1.0

CocoMeEO2* 1.5 1.5

Agglomerate

C45AS 11.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.4 0.4

Spray On

C25E5 5.0 5.0

Perfume 0.5 0.5

Dry Adds

HEDP 0.5 0.3

SKS 6 13.0 10.0

Citrate 3.0 1.0

TAED 5.0 7.0

Percarbonate 15.0 15.0

SRA 1 0.3 0.3

Protease 1.4 1.4

Lipase 0.4 0.4

Cellulase 0.6 0.6

Amylase 0.6 0.6

Silicone antifoam 5.0 5.0

Brightener 1 0.2 0 Brightener 2 0.2 - Balance (Moisture &

Miscellaneous) To: 100 100 Density (g/litre) 850 850

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

Any of tiie granular detergent compositions provided herein may be tabletted using known tabletting methods to provide detergent tablets.

The manufacture of heavy duty liquid detergent compositions, especially those designed for fabric laundering, which comprise a non-aqueous carrier medium can be conducted in die manner disclosed in more detail hereinafter. In an alternate mode, such non-aqueous compositions can be prepared according to the disclosures of U.S. Patents 4,753,570;

4,767,558; 4,772,413; 4,889,652; 4,892,673; GB-A-2, 158,838; GB-A-2,195,125; GB-A-

2,195,649; U.S. 4,988,462; U.S. 5,266,233; EP-A-225,654 (6/16/87); EP-A-510,762 (10/28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (5/5/93); U.S. 4,615,820; EP-A-

565,017 (10/13/93); EP-A-030,096 (6/10/81), incoφorated herein by reference. Such compositions can contain various particulate detersive ingredients (e.g., bleaching agents, as disclosed hereinabove) stably suspended therein. Such non-aqueous compositions tiius comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references. The AQA surfactants are incorporated in the compositions at the levels and in the manner described hereinabove for the manufacture of otiier laundry detergent compositions.

LIQUID PHASE

The liquid phase will generally comprise from 35% to 99% by weight of the detergent compositions herein. More preferably, the liquid phase will comprise from 50% to 95% by weight of the compositions. Most preferably, the liquid phase will comprise from 45% to 75% by weight of the compositions herein. The liquid phase of die detergent

compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined witii a certain type of nonaqueous, liquid diluent.

(A) Essential Anionic Surfactant The anionic surfactant essentially utilized as an essential component of the nonaqueous liquid phase is one selected from die alkali metal salts of alkylbenzene sulfonic acids in which the alkyl group contains from 10 to 16 carbon atoms, in straight chain or branched chain configuration. (See U.S. Patents 2,220,099 and 2,477,383, incoφorated herein by reference.) Especially preferred are die sodium and potassium linear straight chain alkylbenzene sulfonates (LAS) in which the average number of carbon atoms in the alkyl group is from 11 to 14. Sodium C11-C14 LAS is especially preferred.

The alkylbenzene sulfonate anionic surfactant will be dissolved in the nonaqueous liquid diluent which makes up the second essential component of the nonaqueous phase. To form the structured liquid phase required for suitable phase stability and acceptable rheology, die alkylbenzene sulfonate anionic surfactant is generally present to the extent of from 30% to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulfonate anionic surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of die compositions herein. Utilization of this anionic surfactant in tiiese concentrations corresponds to an anionic surfactant concentration in die total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.

(B) Nonaqueous Liquid Diluent

To form the liquid phase of me detergent compositions, the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essential components. These two components are a liquid alcohol alkoxy late material and a nonaqueous, low-polarity organic solvent. i) Alcohol Alkoxylates

One essential component of die liquid diluent used to form tiie compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to die general formula:

R ¹ (CmH ₂ mO) _n OH wherein R* is a Cg - Ci6 alkyl group, m is from 2 to 4, and n ranges from 2 to 12.

Preferably Rl is an alkyl group, which may be primary or secondary, that contains from 9 to 15 carbon atoms, more preferably from 10 to 14 carbon atoms. Preferably also the

alkoxylated fatty alcohols will be edioxylated materials that contain from 2 to 12 ethylene oxide moieties per molecule, more preferably from 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of die liquid diluent will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17. More preferably, the HLB of this material will range from 6 to 15, most preferably from 8 to 15.

Examples of fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in tiie compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain 7 moles of emylene oxide. Such materials have been commercially marketed under die trade names Neodol 25-7 and Neodol

23-6.5 by Shell Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol averaging 11 carbon atoms in its alkyl chain with 5 moles of ethylene oxide; Neodol 23-9, an ethoxylated primary C12 - C13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C9 - Cn primary alcohol having 10 moles of ethylene oxide. Alcohol ethoxy lates of this type have also been marketed by Shell

Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated C9-C11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C15 fatty alcohol witii an average of 7 moles of ethylene oxide per mole of fatty alcohol.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 15-S-9 both of which are linear secondary alcohol etiioxylates that have been commercially marketed by Union Carbide Coφoration. The former is a mixed ethoxylation product of Cn to C15 linear secondary alkanol with 7 moles of ethylene oxide and die latter is a similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol etiioxylates useful in the present compositions are higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, with the higher fatty alcohol being of 14-15 carbon atoms and die number of ethylene oxide groups per mole being 11. Such products have also been commercially marketed by Shell Chemical Company.

The alcohol alkoxylate component which is essentially utilized as part of die liquid diluent in the nonaqueous compositions herein will generally be present to tiie extent of from 1 % to 60% of the liquid phase composition. More preferably, me alcohol alkoxylate component will comprise 5% to 40% of the liquid phase. Most preferably, the essentially utilized alcohol alkoxylate component will comprise from 5% to 30% of the detergent composition liquid phase. Utilization of alcohol alkoxylate in tiiese concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of froml% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5% to 25% by weight, of the composition.

ii) Nonaqueous Low-Polaritv Organic Solvent

A second essential component of the liquid diluent which forms part of die liquid phase of die detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s). The term "solvent" is used herein to connote tiie non-surface active carrier or diluent portion of the liquid phase of the composition. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent "-containing liquid phase, otiier components will be present as particulate material dispersed within the "solvent "-containing liquid phase. Thus the term "solvent" is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.

The nonaqueous organic materials which are employed as solvents herein are those which are liquids of low polarity. For purposes of this invention, "low-polarity" liquids are tiiose which have little, if any, tendency to dissolve one of the preferred types of particulate material used in the compositions herein, i.e., the peroxygen bleaching agents, sodium perborate or sodium percarbonate. Thus relatively polar solvents such as ethanol should not be utilized. Suitable types of low-polarity solvents useful in the nonaqueous liquid detergent compositions herein do include non-vicinal C4-C8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight polyemylene glycols, lower molecular weight methyl esters and amides.

A preferred type of nonaqueous, low-polarity solvent for use in the compositions herein comprises the non-vicinal C4-C8 branched or straight chain alkylene glycols. Materials of this type include hexylene glycol (4-methyl-2,4-ρentanediol), 1 ,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is die most preferred.

Another preferred type of nonaqueous, low-polarity solvent for use herein comprises die mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl etiiers. The specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl etiier, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl etiier and dipropylene glycol monobutyl ether are especially preferred. Compounds of die type have been commercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.

Anotiier preferred type of nonaqueous, low-polarity organic solvent useful herein comprises the lower molecular weight polyetiiylene glycols (PEGs). Such materials are those having molecular weights of at least 150. PEGs of molecular weight ranging from 200 to 600 are most preferred.

Yet anotiier preferred type of non-polar, nonaqueous solvent comprises lower molecular weight metiiyl esters. Such materials are those of the general formula: R*-C(0)-OCH3 wherein R* ranges from 1 to 18. Examples of suitable lower molecular weight metiiyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The nonaqueous, low-polarity organic solven s) employed should, of course, be compatible and non-reactive with other composition components, e.g., bleach and/or activators, used in the liquid detergent compositions herein. Such a solvent component will generally be utilized in an amount of from 1 % to 70% by weight of the liquid phase. More preferably, tiie nonaqueous, low-polarity organic solvent will comprise from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight, of the liquid phase of die composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in die total composition of from 1 % to 50% by weight, more preferably from 5% to 40% by weight, and most preferably from 10% to 30% by weight, of the composition.

iii) Alcohol Alkoxylate To Solvent Ratio

The ratio of alcohol alkoxylate to organic solvent within the liquid diluent can be used to vary die rheological properties of the detergent compositions eventually formed.

Generally, the weight ratio of alcohol alkoxylate to organic solvent will range from 50: 1 to 1:50. More preferably, this ratio will range from 3: 1 to 1 :3.

iv) Liquid Diluent Concentration As with the concentration of the alkylbenzene sulfonate anionic surfactant mixture, _t he amount of total liquid diluent in die nonaqueous liquid phase herein will be determined by the type and amounts of otiier composition components and by the desired composition properties. Generally, the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of die compositions herein. More preferably, die liquid diluent will comprise from 50% to 65% of the nonaqueous liquid phase. This corresponds to a nonaqueous liquid diluent concentration in the total composition of from 15% to 70% by weight, more preferably from 20% to 50% by weight, of the composition.

SOLID PHASE The nonaqueous detergent compositions herein also essentially comprise from 1 % to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particulate material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from 0.1 to 1500 microns. More preferably such material will range in size from 5 to 200 microns.

The particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in tiie nonaqueous liquid phase of tiie composition. The types of particulate materials which can be utilized are described in detail as follows:

COMPOSITION PREPARATION AND USE

The nonaqueous liquid detergent compositions herein can be prepared by combining tiie essential and optional components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form the phase stable compositions herein. In a typical process for preparing such compositions, essential and certain preferred optional components will be combined in a particular order and under certain conditions.

In the first step of such a typical preparation process, an admixture of the alkylbenzene sulfonate anionic surfactant and die two essential components of the nonaqueous diluent is formed by heating a combination of these materials to a temperature from 30 °C to 100°C.

In a second process step, the heated admixture formed as hereinbefore described is maintained under shear agitation at a temperature from 40°C to 100°C for a period of from 2 minutes to 20 hours. Optionally, a vacuum can be applied to die admixture at this point. This second process step serves to completely dissolve die anionic surfactant in tiie nonaqueous liquid phase.

In a third process step, this liquid phase combination of materials is cooled to a temperature of from 0°C to 35 °C. This cooling step serves to form a structured, surfactant-containing liquid base into which die particulate material of the detergent compositions herein can be added and dispersed.

Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is maintained under conditions of shear agitation. When more than one type of particulate material is to be added, it is preferred tiiat a certain order of addition be observed. For example, while shear agitation is maintained, essentially all of any optional surfactants in solid particulate form can be added in the form of particles ranging in size from 0.2 to 1,000 microns. After addition of any optional surfactant particles, particles of substantially all of an organic builder, e.g., citrate and/or fatty acid, and/or an alkalinity source, e.g., sodium carbonate, can be added while continuing to maintain tiiis admixture of composition components under shear agitation. Otiier solid form optional ingredients can then be added to die composition at this point. Agitation of the mixture is continued, and if necessary, can be increased at tins point to form a uniform dispersion of insoluble solid phase particulates within the liquid phase.

After some or all of tiie foregoing solid materials have been added to tiiis agitated mixture, the particles of the highly preferred peroxygen bleaching agent can be added to the composition, again while the mixture is maintained under shear agitation. By adding die peroxygen bleaching agent material last, or after all or most of die otiier components, and especially after alkalinity source particles, have been added, desirable stability benefits for the peroxygen bleach can be realized. If enzyme prills are incoφorated, they are preferably added to die nonaqueous liquid matrix last.

As a final process step, after addition of all of the particulate material, agitati on of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from 1 to 30 minutes.

As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more of the liquid components. Thus a premix of a small fraction of the alcohol alkoxylate and/or nonaqueous, low-polarity solvent with particles of the organic builder material and/or die particles of die inorganic alkalinity source and/or particles of a bleach activator may be separately formed and added as a slurry to the agitated mixture of composition components. Addition of such slurry premixes should precede addition of peroxygen bleaching agent and/or enzyme particles which may tiiemselves be part of a premix slurry formed in analogous fashion.

The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in tiie laundering and bleaching of fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering/bleaching solutions. The aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.

An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering/bleaching solutions can comprise amounts sufficient to form from 500 to 7,000 ppm of composition in aqueous solution. More preferably, from 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching solution.

EXAMPLE VI

A non-limiting example of a bleach-containing nonaqueous liquid laundry detergent is prepared having die composition as set forth in Table I. Table I

Component Wt. % Range (% wt.)

Liquid Phase

Na C12 Linear alkylbenzene sulfonate (LAS) 25.3 18-35 ^c 12-14> E05 alcohol ethoxylate 13.6 10-20 Hexylene glycol 27.3 20-30

Perfume 0.4 0-1.0

AQA-1* 2.0 1-3.0

Solids

Protease enzyme 0.4 0-1.0 Na3 Citrate, anhydrous 4.3 3-6

Sodium perborate 3.4 2-7

Sodium nonanoyloxybenzene sulfonate (NOBS) 8.0 2-12

Zeolite 13.9 5-20

Diethyl triamine pentaacetic acid (DTPA) 0.9 0-1.5 Brightener 0.4 0-0.6

Suds Suppressor 0.1 0-0.3

Minors Balance —

*CocoMeE02. bis-AQA-1 may be replaced by bis-AQA surfactants 2-22 or other bis- AQA surfactants herein.

The composition is prepared by mixing the bis-AQA and LAS, then the hexylene glycol and alcohol ethoxylate, together at 54°C (130°F) for 1/2 hour. This mixture is then cooled to 29°C (85°F) whereupon tiie remaining components are added. The resulting composition is tiien stirred at 29°C (85°F) for anotiier 1/2 hour.

The resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations.

The following Examples A and B further illustrate tiie invention herein with respect to a laundry bar.

EXAMPLE VII Ingredient % (wt.) Range (% wt.) A B

C12-C18 Sulfate 15.75 13.50 0-25

LAS 6.75 — 0-25

Na2Cθ3 15.00 3.00 1-20

DTPpl 0.70 0.70 0.2-1.0

Bentonite clay — 10.0 0-20

Sokolan CP-5 ² 0.40 1.00 0-2.5 bis-AQA-1 ³ 2.0 0.5 0.15-3.0

TSPP 5.00 0 0-10

STPP 5.00 15.00 0-25

Zeolite 1.25 1.25 0-15

Sodium laurate — 9.00 0-15

SRA-1 0.30 0.30 0-1.0

Protease enzyme — 0.12 0-0.6

Amylase enzyme 0.12 — 0-0.6

Lipase enzyme — 0.10 0-0.6

Cellulase enzyme — 0.15 0-0.3 Balar ιce4

1 Sodium diethylenetriamine penta (phosphonate) ^Sokolan CP-5 is maleic-acrylic copolymer ³ bis- AQA-1 ^ma y be replaced by an equivalent amount of bis-AQA surfactants bis-AQA2 through bis-AQA-22 or other bis-AQA surfactants herein.

^Balance comprises water (2% to 8%, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients.

The foregoing Examples illustrate the present invention as it relates to fabric laundering compositions, whereas the following Examples are intended to illustrate otiier types of cleaning compositions according to this invention, but are not intended to be limiting thereof.

Modern automatic dishwashing detergents can contain bleaching agents such as hypochlorite sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures tiiereof; rinse-aids, especially nonionic surfactants; builders, including zeolite and phosphate builders; low-sudsing detersive surfactants, especially ethylene oxide/propylene oxide condensates. Such compositions are

typically in the form of granules or gels. If used in gel form, various gelling agents known in the literature can be employed.

EXAMPLE VIII

The following illustrates mixtures of bis-AQA surfactants which can be substituted for the bis-AQA surfactants listed in any of die 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 bis-AQA surfactants in such mixtures differ by at least 1.5, preferably 2.5- 20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1: 10. Non- limiting examples of such mixtures are as follows.

Components Ratio (wt.) bis-AQA-1 + bis-AQA-5 1: 1 bis-AQA-1 + bis-AQA-10 1: 1 bis-AQA-1 + bis-AQA-15 1:2 bis-AQA-1 + bis-AQA-5

+ bis-AQA-20 1:1:1 bis-AQA-2 + bis-AQA-5 3:1 bis-AQA-5 + bis-AQA-15 1.5:1 bis-AQA-1 + bis-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 ethoxylated cationic surfactants of tiie formula RlN+CHsfEOlxtEOJyX" and RiN+^HstøtEOlzX-, wherein Rl and X are as disclosed above and wherein one of die cationics has (x+y) or z in the range 1-5 preferably 1-2 and die otiier 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 tiian do die cationic surfactants herein used individually. It has now been discovered that shorter EO cationics (e.g., E02) improve the cleaning performance of anionic surfactants in soft water, whereas higher EO cationics (e.g., E015) 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 die

performance "window" of anionic surfactants. Until now, however, broadening die window to encompass essentially all conditions of water hardness has been impossible to achieve.