CA2254827A1 - Detergent composition - Google Patents

Abstract

Detergent composition comprising a peroxygen bleach, a bleach activator, a non-AQA surfactant and an alkoxylated quaternary ammonium (AQA) cationic surfactant.

Description

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97108437 DETERGENT COMPOSITON

Technir~l Field The present invention relates to a detergent bleaching composition CO111~J1 isillg a peroxygen bleach, a bleach activator, a non-AQA surfactant and an alkoxylated quaternary ammonium 10 (AQA) cationic surfactant.

Background to the Invention The formulation of laundry dele~ge.lLs and other cleaning compositions presents a 5 considerable ch~ller~e, since modern compositions are required to remove a variety of soils and stains from diverse substrates. Thus, laundry d~,rgtll~s, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing delergel1t~ 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 20 detergent compositions will contain one or more types of surfact~nr~ which are designed to loosen and remove dir~re-~l types of soils and stains. While a review of the literature would seem to inrlicat~ that a wide selection of surfactants and surfactant combinations are available to the d~te~ge.,t m~n~lf~ rer, the reality is that many such ingredients are specialty ch~mi~ which are not suitable in low unit cost items such as home-use laundry 25 del~rgel,l~. 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 surf~rt~nt~, 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 of35 hydrophobic soils and residual stains often remain on the surface of the fabric after washing. Successive washing and wearing coupled with limited hydrophobic soil removal W O 97/43389 PCTrUS97/08437 in the wash cllmlin~tes in a build up of a residual soil and stain which further entraps particluate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy appearance which is perceived as unwearable and discarded by the consumer.

5 The literature suggests that various nitrogen-cont~ining 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 4uaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits 0 to hair. Other nitrogen-cont~inin~ 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 precipation of anionic active components of the detergent composition occasioned by their 5 ionic interaction with cationic surfactants. The aforementioned nonionic and anionic surfactants remain the maJor surfactant components in today's laundry compositions.

It has now been discovered that certain alkoxylatedquaternary ammonium (AQA) compounds can be used in various detergent compositions to boost detergency performance 20 on a variety of soil and stain types, particularly the hydrophobic soil types, commonJy encountered. Unexpectedly, it has also been discovered that compositions cont~ining AQA
surfactants, peroxygen bleach and bleach activators deliver superior cleaning and whiteness performance versus products cont~ining any of the technologies alone. It is believed that an ion pair or other associative complex is forrned with the peracid released 25 from the activator. It may be speculated that this ion pair is carried more efficiently into the soil as a new, more hydrophobic agent, thereby enhancing bleach performance associated with the use of bleach activators such as nonanoyloxy benzene sulfonate (NOBS).

30 The AQA surfactants of the present invention provide substantial benefits to the formulator, over cationic surf~ctant~ previously known. For example, the AQA
surfactants used herein provide marked improvement in cleaning of "everyday" greasy/oily hydrophobic soils regularly encountered. Moreover, the AQA surfactants are compatible with anionic surfactants cornmonly used in detergent compositions such as alkyl sulfate and 35 alkyl benzene sulfonate; incompatability with anionic components of the detergent composition has commonly been the limiting factor in the use of cationic surfactants to .. . .. .

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 -date. Low levels (as low as 3 ppm in the laundering liquor) of AQA surfactants gives rise to the benefits described herein. AQA surfactants can be form~ ted over a broad pH
range from S to 12. The AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a manufacturing plant. AQA surfactants 5 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 h~n-lling plop~,Lies, the availability of AQA surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs.

0 It is believed that the greasy/oily soils are effectively solubili~ed by AQA, thereby allowing access of the ion pair derived from the bleach peracid-activator reaction, to the soil, particularly the high3y coloured hydrophillic soil, resulting in improved soil bleaching and decolouration. The present invention thus provides a detergent composition which delivers effective cleaning of both hydrophillic and hydrophobic everyday soils by way of a 5 detel~e,lL composition comprising peroxygen bleach, bleach activator and a 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 bleaching composition comprising or prepared bycombining a peroxygen bleach, a bleach activator, a non-AQA surfactant and an effective amount of an alkoxylated quaternary ammonium (AQA) cationic surfactant of 30 the formula:
R~ /ApR~
N\ X
R2' R3 wherein R1 is a linear, branched or substituted Cg-Clg alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety, R2 is a C1-C3 alkyl moiety, R3 and R4 can vary independent3y CA 022~4827 1998-11-17 W 097/43389 PCTrUS97/08437 and are selected from hydrogen, methyl and ethyl, X is an anion~ A is C1-C4 alkoxy and p is an integer in the range of from 2 to 30.

Detailed Description of the Invention Peroxygen Bleach The delergent compositions herein comprise a peroxygen bleach.
Preferred peroxygen bleach suitable for use in the present invention contain a hydrogen 0 peroxide source. Although the peroxygen bleach itself has some bleaching capability, a superior bleach exists in the peracid formed as a product of the reaction between the hydrogen peroxide and a bleach activator.

Preferred peroxygen bleaches are perhydrate bleaches. The perhydrate bleach is normally 5 incorporated in the form of the perhydrate salt, especially the sodium salt, at a level of from 1% to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5 % to 25 % by weight of the compositions.

Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, 20 persulfate and persilicate salts. The preferred perhydrate salts are norrnally the alkali metal salts. The perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
Sodium perborate can be in the form of the monohydrate of nominal formula NaB02H202 or the tetrahydrate NaBO2H202.3H20.

Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for 30 inclusion in compositions in accordance with the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, and is available commercially as a crystalline solid. Sodium percarbonate, being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise. The 35 percarbonate is most preferably incorporated into such compositions in a coated fortn which provides in-product stability.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 s A suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate. Such coatings together with coating processes have previously been described in GB-1,466,799, granted to Interox on 9th March 1977.
The weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1: 4, more preferably from 1: 99 to 1: 9, and most preferably from 1: 49 to 1:
19. Preferably, the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
Other coatings which contain silicate (alone or with borate salts or boric acids or other inorganics), waxes, oils, fatty soaps can also be used advantageously within the present invention.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from 500 micrometers tol,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more thanlO% by weight of said particles being larger than 1,250 micrometers.

Percarbonate is available from various comrnercial sources such as FMC, Solvay and Tokai Denka.

A bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphth~l~te hexahydrate, the magnesium salt of metachloro l)ell)el~oic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodec~nP~ioic acid.
Such ble~ching agents are disclosed in U.S. Patent 4,483,781, Hartrnan~ issued November 20, 1984, U.S. Patent Application 740,446, Burns et al. filed lune 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. Potassium peroxymonopersulfate is anotherinorganic perhydrate salt of utility in the compositions herein.

Mixtures of bleaching agents can also be used.

CA 022~4827 1998-11-17 W O 97143389 PCTfUS97/08437 Bleach Activators The second essential component of the composition of the present invention is a bleach activator. Bleach activators are typically present at levels of from 0.1 % to 60%, more 5 typically from 0.5% to 40% of the bleaching composition comprising the ble~c~lin~ agent-plus-bleach activator.

Peroxygen bleaching agents, the perborates, etc., are combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) 0 of the peroxy acid or peracid corresponding to the bleach activator. Various nonlirniting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene (li~min~ (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.
Highly preferred amido-derived bleach activators are those of the forrnulae:

R1N(R5)C(o)R2C(o)L or R1C(O)N(R5)R2C(O)L

wherein R1 is an alkyl group cont~ining from 6 to 12 carbon atoms, R2 is an alkylene cont~ining from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl cont~inin~ 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.

2~
Preferred examples of bleach activators of the above forrnulae include (6-oct~n~mi~lo-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate (NACA-OBS), (6-dec~n~mido-caproyl)oxybenzenesulfonate. and mixtures thereof as described in U.S.
Patent 4,634,551, incorporated 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 the benzoxazin-type is:

.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 ~N"C~

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

o R6--C--N~ ,C H2 o c c H2--f H2 R6--C--N~

0 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group con-~ining from 1 to 12 carbon atoms. Highly ~lefelled lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam. nonanoyl valerolactam, 3,5,5-trirnethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784~
issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Alkoxylated Quaternary Ammonium (AQA) Cationic Surfactant The third essential component of the present invention comprises an effective amount of an AQA surfactant of the formula:

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 R ~ ~ ApR~
~ N ~ X

wherein R1 is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety con~ining from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms; R2 and R3 are each independently 5 alkyl groups cont~ining from 1 to 3 carbon atoms, preferably methyl; R4 is selected from hydrogen (preferred), methyl and ethyl, X~ is an anion such as chloride, bromide, methylsulfate, sulfate to provide electrical neutrality; A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and p is an integer from 2 to 30, preferably 2 to 15, more preferably 2 to 8, most preferably 2 0 to4 AQA compounds wherein the hydrocarbyl substituent R1 is Cg-C12 especially Cg-1o,enhance the rate ot dissolution of laundry granules, especially under cold waterconditions, as compared with the higher chain length materials. Accordingly, the Cg-15 C12 AQA surfactants may be preferred by some formulators. The levels of the AQAsurfactants used to prepare finished laundry detergent compositions can range from 0.1% to 5%, typically from 0.45% to 2.5%, by weight.

The present invention employs an "effective amount" of the AQA surfactants to 20 improve the performance of cleaning compositions which contain other adjunct ingredients. By an "effective amount" of the AQA surfactants and adjunct ingredients herein is meant an amount which is suf~lcient to improve, either 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 25 targets include certain food stains, the formulator will use sufficient AQA to at least directionally improve cleaning performance against such stains. Lilcewise, in a composition whose targets include clay soil, the formulator will use sufficient AQA to at least directionally improve cleaning performance against such soil. Importantly, in a fully-form~ tecl laundry detergent the AQA surfactants can be used at levels which 30 provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the data presented hereinafter.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 As noted, the AQA surfactants are used herein in detergent compositions in combination with other detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance. In the context of a fabric laundry composition, such "usage levels" can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing machine.

For example, in a top-loading, vertical axis U.S.-type automatic washing machine using 45 to 83 liters of water in the wash bath, a wash cycle of 10 to 14 mim~tçs and a wash 0 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 the AQA surfactant in the wash liquor. On the basis of usage rates of from 50 ml to 150 rnl per wash load, this translates into an in-product concentration (wt.) of the 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/l) this translates into an in-product concentration (wt.) of the AQA
surfactant of from 0.2% to 5.0%, preferably from 0.5% to 2.5%. On the basis of usage rates of from 80 g to 100 g per load for spray-dried granules (i.e., "fluffy";
density below 650 g/l), this translates into an in-product concentration (wt.) of the 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 washingmachine using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60mimltes 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 AQA surfactant in the wash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this tr~n~ es into an in-product concentration (wt.) of the AQA surfactant of from 0.4% to 2.64%, preferably 0.55% to 1.1%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 40 g to 210 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.5 ~ to 3.5 %, preferably from 0.7 % to 1.5 %. On the basis of usage rates of from 140 g to 400 g per load for spray-dried granules (i.e.. "fluffy"; density below 650 g/l), this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.13% to 1.8%, preferably from35 0.18% to 0.76%.

W 097/43389 PCT~US97108437 For example, in a top-loading. vertical-axis Japanese-type automatic washing m~chine using 26 to 52 liters of water in the wash bath, 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 AQA surfactant in the wash liquor.
On the basis of usage rates of from 20 ml to 30 ml per wash load, this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.25% to 10%, preferably 1.5% to 2%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 18 g to 35 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt.) 0 of the AQA surfactant of from 0.25% to 10%, preferably from 0.5% to 1.0%. 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/l), this translates into an in-product concentration (wt.) of the AQA surfactant of from 0.25% to 10%, preferably from 0.5% to 1%.

As can be seen from the foregoing, the amount of AQA surfactant used in a m~cl-ine-wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine, and the like. In this context, however, one heretofore unappreciated advantage of the AQA surfactants is their ability to provide at least directional improvements in performance over a spectrum of soils and stains even when 20 used at relatively low levels with respect to the other surfactants (generally anionics or anionic/nonionic mixtures) in the 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 the practice of this invention, the weight ratio of AQA:anionic surfactant in laundry compositions is in the 25 range from 1:70 to 1:2, preferably from 1:40 to 1:6, more preferably from 1:30 to 1:6, most preferably from 1:15 to 1:8. In laundry compositions which comprise both anionic and nonionic surfactants, the weight ratio of AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2, preferably 1:50 to 1:8.

30 Various other cleaning compositions which comprise an anionic surfactant, an optional nonionic surfactant and specialized surfactants such as betaines, sultaines, amine oxides, and the like, can also be formulated using an effective amount of the AQA
surfactants in the manner of this invention. Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface35 cleaners~ shampoos, personal cleansing bars~ laundry bars, and the like. Since the habils and practices of the users of such compositions show minim~l variation~ it is . . .

CA 022~4827 1998-11-17 WO 97/43389 PCT/US97tO8437 satisfactory to include from 0.25% to 5%, preferably from 0.45% to 2%. by weight, of the AQA surf~t~ntc in such compositions. Again, as in the case of the granular and - liquid laundry compositions, the weight ratio of the AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionics.
5 Preferably, such cleaning compositions comprise AQA/surfactant ratios as noted imm~ tely above for m:~rhinP-use laundry compositions.

In contrast with other cationic surfactants known in the art, the alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed 0 surfactant systems which are quite low in nonionic surfact~ntc 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 m:l~hines~ especially of the type used in North America as well as under Japanese usage conditions. Typically, such compositions will 5 comprise an anionic surfactant:nonionic surfactant weight ratio in the range from 25:1 to 1:25, preferably 20:1 to 3:1. This can be contrasted with European-type formulas which typically will comprise anionic:nonionic ratios in the range of 10:1 to 1:10, preferably 5:1 to 1:1.

20 The preferred ethoxylated cationic surfactants herein can be synthesized using a variety of different reaction schemes (wherein "E0" represents -CH2CH20- units), as follows.

CA 02254827 1998-ll-17 W O 97/43389 PCT~US97/08437 R OH + C H3NH2 H21CatfHeat I ,CH3 EXCESS H

,CH3 ~ BASE Cat~ R~ N--(EO)n--H

Rl N--(EO)n--H + CH3CI HEAT~ R--Nl--(EO)n--H
CH3 Cl ,N--(EO)2H + 2 ,C~ H~ Cat , ,N--(EO)2H
"DIGLYCOLAMINE"

RlBr ~ ~N--(EO)2H ' R--Nl--(EO)2--H

CH3~ ~ BASE CAT CH
~N--(EO)H + n~ HEAT ~ ~N--(E~)n+l--RlBr + CH3'N--(EO~+l H HEAT ~ Rl I + (EO) +l H

CA 022~4827 1998-ll-17 W 097/43389PCTrUS97/08437 Cl--CH~CH,--OH + n~ ~ Cl--CH,CH,O[EO]n--H

Rl N~CH + Cl--CEI2CH2O[EO]n~R I H3CH2CH20~EO]n--H

An economical reaction scheme is as follows.

Rl OSO3 Na+ +N--CH2CH~-OH HEAT- R--N--CH2CH~-OH + Na2SO~ + H20 H
CH

3~ BASECAT. Rl N--CH CH O~EO]--H

l H3 Rl I--CH2CH~O[EO]n--H + CH3Cl ~ Rl I--CH2CH~O[EO]n--H
CH3 CH3 cr For reaction Scheme 5, the following parameters summarize the optional and preferred reaction conditions herein for step 1. Step 1 of the reaction is preferably conducted in an aqueous m~dium. Reaction temperatures are typically in the range of 100-230~C.
0 Reaction pressures are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react with the HSO4- generated during the reaction. In another mode, an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1:1.1;
more preferably from 2:1 to 1:1. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction m~d jllm in which it is insoluble . The product of step 1 is then ethoxylated and quaternized using standard reactions, as shown.

The following illustrates the foregoing for the convenience of the formulator, but is not intended to be limiting thereof.

CA 022~4827 1998-11-17 Preparation of N-(2-hydroxyethyl)-N-methyldodecylamine - To a glass autoclave liner is added 156.15 g of sodium dodecyl sulfate (0.5415 moles), 81.34 g of 2-(methylamino)ethanol (1.083 moles), 324.5 g of distilled H2O. and 44.3 g of 50 wt. %
sodium hydroxide solution (0.5538 moles NaOH). The glass liner is sealed into 3 L, 5 stainless steel, rocking autoclave, purged twice with 260 psig nitrogen and then heated to 160-180~C under 700-800 psig nitrogen for 3 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 1 L separatory funnel. The mixture is separated into a clear lower layer, turbid middle layer and clear upper layer. The clear upper layer is isolated and placed under full vacuum (<100 mm 10 Hg) at 60-65~C with mixing to remove any residual water. The clear liquid turns cloudy upon removing residual water as additional salts crystallizes out. The liquid is vacuum filtered to remove salts to again obtain a clear, colorless liquid. After a few days at room temperature, additional salts crystallize and settle out. The liquid is vacuum filtered to remove solids and again a clear, colorless liquid is obtained which 5 remains stable. The isolated clear, colorless liquid is the title product by NMR analysis and is >90% by GC analysis with a typical recovery of >90%. The amine is then ethoxylated in standard fashion. Quaternization with an alkyl halide to forrn the AQA
surfactants herein is routine.

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

Desi~nation Bl R2 g3 Alkoxylation AQA-1 Cl2-C14 CH3 CH3 EO2 AQA-2 Clo~C16 CH3 CH3 EO2 AQA-3 Cl2 CH3 CH3 EO2 CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 -AQA-6 C12-C14 C2Hs CH3 EO3-5 AQA-7 C 14-C 16 CH3 C3H7 (EO/PrO)4 AQA-8 C12-C14 CH3 CH3 (PrO)3 AQA-10 Cg-Clg CH3 CH3 EO15 AQA-l 1 Clo C2H5 C2H5 EO3.5 AQA-12 Clo CH3 CH3 EO2.5 AQA-13 Clo CH3 CH3 EO3.5 AQA-14 Clo C4Hg C4H9 EO30 AQA-16 Clo CH3 CH3 EO10 AQA-17 C12-C18 C3H9 C3H7 Bu4 AQA-l9 C8 CH3 CH3 iPr3 AQA-21 C12 CH3 CH3 EO3.5 AQA-22 C12 CH3 CH3 EO4.5 CA 022~4827 1998-11-17 WO 97/43389 PCT~US97/08437 Highly preferred AQA compound for use herein are of the formula /(C H~C H2O )2-5 H
N X
CH3/ \CH3 wherein R1 is Cg-Clg hydrocarbyl and mixtures thereof, especially Cg-C14 alkyl, 5 preferably Cg, Clo and C12 alkyl, and X is any convenient anion to provide charge balance, preferably chloride or bromide.

As noted, compounds of the foregoing type include those wherein the ethoxy (CH2CH20) units (E0) are replaced by butoxy, isopropoxy [CH(CH3)CH20] and 0 [CH2CH(CH30] units (i-Pr) or n-propoxy units (Pr), or mixtures of E0 and/or Pr and/or i-Pr units.

A highly preferred AQA compound for use in under built formulations are of the formula wherein p is an integer in the range of between 10 and 15. This compound is 5 particularly useful in laundry handwash d~tergent compositions.

Non-AQA Detersive Surfactants In addition to the AQA surfactant, the compositions of the present invention preferably 20 further comprise a non-AQA surfactant. Non-AQA surfactants may include essentially any anionic, nonionic or additional cationic surfactant.

Anionic Surfactant 25 Nonlimiting examples of anionic surfactants useful herein typically at levels from 1% to 55% . by weight, include the conventional Cl l-Clg alkyl benzene sulfonates ("LAS") and primary ("AS"), branched-chain and random C1o-C20 alkyl sulfates, the C1o-C1g secondary (2,3) alkyl sulfates of the formula CH3(CH2)x(CHOSO3 M+) CH3 and CH3 (CH2)y(CHOS03~M+) CH2CH3 where x and (y + 1) are integers of at least 7, 30 preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C12-Clg alpha-sulfonated fatty acid esters, the C1o-Clg sulfated polyglycosides, the C1~-C1g alkyl alkoxy sulfates ("AEXS"; especially E0 1-7 ethoxy sulfates), and the C10-cl8 alkyl alkoxy CA 022~4827 1998-ll-17 W O 97143389 PCT~US97/08437 carboxylates ~especially the EO 1-5 ethoxycarboxylates). The C12-Clg betaines and sulfobetaines ("sultaines"), C1o-Clg amine oxides, can also be included in the overall compositions. Clo-c2o conventional soaps may also be used. If high sudsing is desired, the branched-chain Clo-cl6 soaps may be used. Other conventional usefulsurfactants are listed in standard texts.

Nonionic Surfactants Nonlimitin~ examples of nonionic surfactants useful herein typically at levels from 1%
0 to 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Clo-Clg glycerol ethers.

More specifically. the condensation products of primary and secondary aliphatic alcohols with from 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group cont~inin~ from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon 20 atoms, with from 1 tolO moles, preferably 2 to 7, mos~ 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 (the condensation product of C1 1-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 ~MW (the condensationproduct of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow 25 molecular weight distribution), both marketed by Union Carbide Corporation;
NeodolTM 45-9 (the condensation product of C14-C1s linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C12-C13 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-Cls linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the condensation 30 product of C14-Cls linear alcohol with 5 moles of ethylene oxide) marketed by Shell Ch~mic~l Company; KyroTM EOB (the condensation product of C13-Cls alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred range of HLB in these AE
35 nonionic surfactants is from 8-11 and most preferred from 8-10. Condensates with propylene oxide and butylene oxides may also be used.

CA 022~4827 1998-11-17 W 097/43389 PCTrUS97/08437 Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formu}a.

O R

wherein R1 is H, or C14 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly conn~cted to the chain, or an 0 alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight Cl1 15 alkyl or C1s 17 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof. and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Typical examples include the C12-C1g and C12-C14 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.

Also useful as the nonionic surfactant in the present invention are the alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group cont~ining from 6 to 30 carbon atoms, 20 preferably from 10 to 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group cont~ining 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 S or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, 2s etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6- positions on the prece~ing saccharide units.

30 The preferred alkylpolyglycosides have the forrnula:

R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, 35 hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to CA 022~4827 1998-11-17 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 these compounds, the alcohol or alkylpolyethoxy alcohol is forrned first and then reacted with 5 glucose, or a source of glucose, to form the glucoside (attachrnent at the l-position).
The additional glycosyl units can then be attached between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

0 Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group con~ining from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in either a straight-5 chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tolS moles, of ethylene oxide per mole of alkyl phenol.
ConLrnercially available nonionic surfactants of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X-l 14, X-100 and X-102, all20 marketed by the Rohrn & Haas Company. These surfactants are cornmonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the 25 additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from 1500 to 1800 andwill exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the 30 polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include cerlain of the comrnercially-available PluronicTMsurfactants, marketed by BASF.

35 Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic moiety of these products consists of the reaction product of ethylen~ min~o and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000. Thishydrophobic moiety is condensed with ethylene oxide to the extent that 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 the commercially available TetronicTM compounds, marketed by BASF.

10 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 the quaternary ammonium surfact~ntc selected from mono C6-C16, preferably C6-C1o N-alkyl or alkenyl ammonium surfactants wherein the rem~ining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline 20 ester surf~t~ntc, have for exarnple been disclosed in US Patents No.s 4228042, 4239660 and 4260529.

Optional Deter~ent InPredients 25 The following illustrates various other optional ingredients which may be used in the compositions of this invention, but is not intended to be limiting thereof.

Additional Bleach 30 The compositions described herein may contain an additional bleach component to the peroxygen bleach described earlier. When present, such additional bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5 % to 20% . or even from 5% to 15% of the detergent composition, especially for fabric laundering CA 022~4827 1998-11-17 In an alternative aspect a preformed organic peracid is incorporated directly into the composition. Compositions conr~inin~ mixtures of a hydrogen peroxide source and bleach activator in combination with a preformed organic peracid are also envisaged.

Other suitable additional bleaching agents include chlorin bleach or photoactivated bleaching agents. Examples of photoactivated bleaching agents include the sulfonated zinc and/or al~mimlm phthalocyanines. 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.

Bleach Catalvst Bleach catalysts are preferred components of the compositions of the present invention. If desired, the bleaching compounds can be catalyzed by means of a m~n~n-ose compound.
Such compounds are well known in the art and include. for example, the m~n~an~se-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. 549.271Al . 549,272A1. 544,440A2, and 544,490Al; Preferred examples of these catalysts include MnIV2(u-O)3(1,4,7-trimethyl-1,4,7-triazacyclononane)2(PF6)2, MnIII2(u-O)l(u-OAc)2(1,4,7-trimethyl-1.4,7-triazacyclononane)2 (C104)2, M nIV4(u-0)6(1,4,7-triazacyclononane)4(C104)4, MnIII-MnIV4(u-O)l(u-OAc)2 (1,4,7-trimethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-"~Lhyl-1,4,7-triazacyclononane)- (OCH3)3(PF6). and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.
5,114,611. The use of m~n~n~se with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612;
5,256,779; 5,280,117; S,274,147; 5,153,161; and 5~227,084.

As a practical matter. and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from 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. Inor~. Bioinor . Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt CA 022~4827 1998-11-17 WO 97/43389 PCTrUS97108437 pen~min~o acetate salts having the formula ~Co(NH3)sOAc] Ty~ wherein "OAc"
represents an acetate moiety and "Ty" is an anion, and especially cobalt pent~min~ acetate chloride, [Co(NH3)sOAc]C12; as well as [Co(NH3)sOAc](OAc)2;
[Co(NH3)sOAc](PF6)2; [Co(NH3)sOAc](SO4); [Co(NH3)sOAc](BF4)2; and 5 [Co(NH3)sOAc](NO3)2 (herein "PAC ").

These cobalt catalysts are readily prepared by known procedures, such as taught for example in the Tobe article and the references cited therein, in U.S. Patent 4,810,410, to Diakun et al, issued March 7,1989, J. Chem. Ed. (1989), 66 (12), 104345; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inor~. Chem., 21, 2881-2885 (1982); Inor~.
Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952).

15 As a practical matter, and not by way of limitation, the automatic dishwashing compositions and cle~ning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from 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 the bleach 20 catalyst species in the wash liquor. In order to obtain such levels in the wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions herein will comprise from 0.000S% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especially m~n~n~se or cobalt catalysts, by weight of the cleaning compositions.

25 Builders Detergent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces. Builders can operate via a 30 variety of m~ch~ni.sms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of articles to be cleaned. Builder level can vary widely depending upon end use and physical form of the composition. Built detergents typically comprise at least 1 % builder. Liquid forrnulations typically comprise 5 % to 50%, more 3~ typically 5% to 35% of builder. Granular formulations typically comprise from 10% to 80%, more typically 15% to 50% builder by weight of the detergent composition. Lower CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 or higher levels of builders are not excluded. For example, certain detergent additive or high-surfactant formulations can be unbuilt.

Suitable builders herein can be selected from the group consisting of phosphates and 5 polyphosphates, especially the sodium salts; silicates including water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate;
all-minosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble 0 nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid. These may be complemented by borates, e.g., for pH-buffering purposes, or by sulfates~ especially sodium sulfate and any other fillers or carriers which may be important to the engineering of stable surfactant and/or 15 builder-cont~ining detergent compositions.

Builder mixtures, som~tim~s termed "builder systems" can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing 20 qll~ntiti~s of materials herein. In terms of relative quantities of surfactant and builder in the present detergents, preferred builder systems are typically form-ll~ted at a weight ratio of surfactant to builder of from 60:1 to 1:80. Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1Ø

25 P-cont~inin~ detelgenl builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.

30 Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na2O 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 the tradename BRITESILQ, 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-35 6", is a crystalline layered aluminium-free ~-Na2SiOs morphology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97108437 methods in German DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates. such as those having the general formula NaMSixO2x+ 1 yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, can also or alternately be used herein. Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the a, ,B and ~ layer-silicate forrns. Other silicates may also be useful, such as m~nPsium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

10 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 forrnula in an anhydride form: xM2O-ySiO2.zM'O wherein M is Na andtor 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 alk~linP earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium 20 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.

25 Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those having empirical formula: [MZ(Alo2)z(sio2)v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically 30 derived. An aluminosilicate production method is in U.S. 3,985,669, Krumrnel, et al, October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the forrnula: Na12[(AlO2)12(SiO2)12] xH2O wherein x is from 20 to 35 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter.

CA 022~4827 1998-11-17 Suitable organic detergent builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builderpolycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates.
Carboxylate builders can be forml-late~ 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.
0 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;

4,158,635; 4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic 15 anhydride with ethylene or vinyl methyl ether; 1, 3, S-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrates, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid d~Lergel-ls, 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 25 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 30 ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates, e.gthose 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 ~nti.ccaling properties.

Certain detersive surfactants or their short-chain homologs also have a builder action. For 35 unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants. Preferred types for builder functionality CA 022~4827 1998-11-17 W 097/43389 PCT~US97/08437 are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. 4,566,9~4, Bush, January 28, 1986. Succinic acid builders include the Cs-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., C12-C1g monocarboxylic acids, can also be incorporated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or the succinate builders, to provide additional builder activity. Other suitable 0 polycarboxylates are disclosed in U.S. 4,144,226~ Crutchfield et al, March 13, 1979 and in U.S. 3,308,067, Diehl, March 7, 1967. See also Diehl, U.S. 3,723,322.

Other types of inorganic builder materials which can be used have the formula (MX)i Cay (CO3)z wherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an 15 integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the equation ~ 1 1s(xi multiplied by the valence of Mi) + 2y = 2z is satisfied such that the formula has a neutral or "bal~nrecl" charge. These builders are referred to herein as "Mineral Builders". Waters of hydration or anions other than carbonate may be added provided that the overall charge is balanced or neutral. The charge or valence effects of 20 such anions should be added to the right side of the above equation. Preferably, there is present a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, amrnonium and mixtures thereof, sodium and potassium being highly preferred. Nonlimiting examples of noncarbonate 25 anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
Preferred builders of this type in their simplest forms are selected from the group consisting of Na2Ca(CO3)2, K2Ca(CO3)2, Na2Ca2(CO3)3, NaKCa(CO3)2, NaKCa2(CO3)3, K2Ca2(CO3)3, and combinations thereof. An especially preferred 30 material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline modifications. Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AshcroftineY. Beyerite, Borcarite, Burbankite,Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, 35 Ferrisurite, F~ 7i~ e, Gaudefroyite, Gaylussite~ Girvasite, Gregoryite, Jouravskite, KarnphaugiteY, Keullc,ile, Kh~nn~shite, LepersonniteGd, Liottite, MckelveyiteY, CA 022~4827 1998-11-17 Wo 97143389 PCT/US97/08437 Microsommite, Mroseite, Natrofairchildite, Nyerereite, KemonditeCe, Sacrofanite,Schrockingerite, Shortite, Surite, Tunisite~ Tllcc~nit~, Tyrolite, Vishnevite, and Zemkorite.
Preferred mineral forms include Nyererite, Fairchildite and Shortite.

5 En_ymes Enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric 0 restoration. Suitable en_ymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and 5 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 detclgellL
composition. I~rellcd detersive enzymes are hydrolases such as proteases, amylases and 20 lipases. Preferred en_ymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases.

En_ymes are normally incorporated into detergent or delergent additive compositions at 25 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 30 the d~l~rgen~ composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5 %, preferably O.Ol %-1% by weight of a commercial en_yme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0. l Anson units (AU) of activity per gram of composition. For certain d~elge~,ls, such as in automatic dishwashing, it may be desirable 35 to increase the active enzyme content of the commercial preparation in order to minimi7e the total amount of non-catalytically active materials and thereby improve spotting/filming CA 022~4827 l998-ll-l7 W 097143389 PCTrUS97/08437 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 5 of B. s~btilis and B. Iicheniforrnis. 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 preparationof this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Othersuitable proteases include ALCALASE~ and SAVINASE~ from Novo and MAXATASE~
1O 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 detelge~
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 WO9510591 A to Procter & Garnble . When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A
recombinant trypsin-like protease for detergellls suitable herein is described in WO
9425583 to Novo.
In more detail, an especially ~ler~ d protease, referred to as "Protease D" is acarbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substin-ling a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to 25 position +76, ~ ,f~ bly also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, + 101, + 103, +104, +107, +123, ~27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217? +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloli4~efaciens subtilisin, as described in the 30 patent applications of A. Baeck, et al, entitled "Protease-Conr~ining 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.

35 Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes, include, for example, a-amylases described in GB 1,296,839 to Novo;

CA 022~4827 1998-11-17 W 097/43389 PCT~US97/08437 RAPIDASE~, International Bio-Synthetics, Inc. and TERMAMYLX, Novo.
FUNGAMYL~ from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985,pp. 6518-6521. Certain preferred embodiments of the present 5 compositions can make use of amylases having improved stability in detergents such as automatic dishwashing types, especially improved oxidative stability as measured against a leference-point of TERMAMYL(~ in cornmercial use in 1993. These plef~.led arnylases herein share the characteristic of being "stability-enh:~nred" amylases, characterized, at a minimllm, by a measurable improvement in one or more of: oxidative stability, e.g., to 0 hydrogen peroxideltetraacetylethylen~ min~ in buffered solution at pH 9-10; thermal stability, e.g., at cornrnon wash temperatures such as 60~C; or ~Ik~linP stability, e.g., at a pH from 8 to 11, measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enh~nred amylases can be obtained from Novo or from 5 Genencor International. One class of highly plefelled amylases herein have thecommonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the R(7ci/1~ -amylases, regardless of whether one, two or multiple amylase strains are the imm.~ te precursors. Oxidative stability-enh~nred amylases vs. the above-identified reference amylase are preferred for use, especially in 20 ble~chin~, more preferably oxygen bleaching, as distinct from chlorine bleaclling, detergent compositions herein. Such preferred amylases include (a) an arnylase according to the hereinbefore incorporated 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, 25 known as TERMAMYL(g), or the homologous position variation of a similar parent amylase, such as B. a~tryloli4uefaciens, B. subtilis, or B. slearother~nophilus; (b) stability-enh~nred amylases as described by Genencor International in a paper entitled "Oxidatively R~si~t~nt alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in 30 automatic dishwashing d~lelge,ils inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B. Iicheniformis 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 mllt~ntc, particularly important being M197L and M197T with the M197T variant 35 being the most stable expressed variant. Stability was measured in CASCADE'~) and SUNLIGHT(~; (c) particularly preferred amylases herein include amylase variants having CA 022~4827 1998-11-17 Wo 97143389 PCT/US97/08437 additional modification in the imme~i~te parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL~. Other particularly preferred oxidative stability enhan~ed amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enh~nred amylase can be used, for example as derived by site-directed mutagenesis from Icnown 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 0 application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the de~ergent compositions of the present invention include a-arnylases characterized by having a specific activity at least 25 % higher than the specific activity of Termarnyl(~ at a temperature range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas(~ a-amylase activity assay. (Such Phadebas~) a-amylase activity assay is described at pages 9-10, WO 95/26397.) Also included herein are a-amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references. These enzymes are preferably incorporated 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 S 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 cellul:~e 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
Suitab}e 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 deLelgent usage include those produced by microor~ni~m.~ 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 "Arnano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter ,~.

W O 97/43389 PCT~US97/08437 viscosum var. Iipolylicum NRRlB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacler viscosum lipases from U.S. Biochemical Corp., 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, 5 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. Asdescribed in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase 5 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 20 the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions cont~ining the AQA surfactants in the manner disclosed herein, especially when the D96L is used at levels in the 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 the wash to other substrates present in 30 the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-cont~ining detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO
8909813 A to Novo.

35 A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor CA 022~4827 1998-ll-17 W 097/43389 PCTrUS97/08437 International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18,1978, and in U.S.4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S.
4,261,868, Hora et al, April 14,1981. Enzymes for use in d~L~lgel,Ls 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 10 described in WO 9401532 A to Novo.

Enzyme Stabilizin~ System The enZyme-co~ ng 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 other formulation actives, or be added separately, e.g., by the formulator or by a m~nllf~ rer 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 fini.~h~cl compositions which provide such ions to the enzymes.
Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used. Typical detergent compositions,especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of fni~hP-I detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. 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 exemplifled calcium salts may be used. Further increased CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing approach is by use of borate species . See Severson, U . S .4,537,706. Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced lo 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% byweight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from ~ rking and inactivating the enzymes, especially under ~lk~lin~
conditions. While chlorine levels in water may be small, typically in the 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. Sincepercarbonate 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 conl~ining arnmonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylene~i~min~tetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof 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, maJate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. In general, since the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., 3~ hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 34 an enzyme-cont~ining embodiment of the invention; even then, the scavenger is added only for optimum results. Moreover, the formulator will exercise a chemist's normal skill in avoiding the use of any enzyme scavenger or stabilizer which is majorly incompatible, as form~ ted, with other reactive ingredients. In relation to the use of ammonium salts, such 5 salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate arnmonia 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 A,eent Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be employed in the present delel~"l 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~o byweight, of the composition.
Preferred SRA's typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles thereby serving as an anchor for the hydrophilic segments. This can enable stains 20 occurring subseqllent 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 25 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 d~le~ellt or detergent additive products.

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

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97tO8437 Suitable SRA's include. a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in U.S. 4,968,451~ November 6, 1990 to J.J. Scheibel and E.P.
Gosselink: such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) reacting the product of (a) with dimethyl terephth~l~te ("DMT") and 1,2-propylene glycol ("PG") in a two-stage transesterification/ oligomerization procedure and (c) reacting the product of (b) with sodium metabisulfite in water; the nonionic end-capped 1,2-propylene/polyoxyethylene terephth~l~te polyesters of U.S. 4,711,730, December 8, 1987 o 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 ethylene glycol ("EG"), PG, DMT and Na-3~6-dioxa-8-hydroxyoct~n~sl~lfonate; 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-S-sulfoisophth~l~te; and the anionic, especially sulfoaroyl, end-capped terephth~l~te 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 20 products, an example being an ester composition made from m-sulfobenzoic acidmonosodium salt, PG and DMT optionally but preferably further comprising added PEG, e.g., PEG 3400.

SRA's also include simple copolymeric blocks of ethylene terephth~ te or propylene 25 terephth~l~t~ with polyethylene oxide or polypropylene oxide terephth~l~te, see U.S.
3,959,230 to Hays, May 25, 1976 and U.S. 3,893,929 to Basadur, July 8, 1975; cellulosic derivatives such as the hydroxyether cellulosic polymers available as METHOCEL from Dow; and the Cl-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) 30 hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Cl-C6 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.
Cornrnercially available examples include SOKALAN SRA's such as SOKALAN HP-22.
available from BASF, Germany. Other SRA's are polyesters with repeat units cont~ining 10-15% by weight of ethylene terephth~l~te together with 90-80% by weight of polyoxyethylene terephth~l~te, derived from a polyoxyethylene glycol of average molecular Wo 97/43389 PCT/US97/08437 weight 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having empirical formula 5 (CAP)2(EG/PG)s(T)s(SIP)1 which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which is preferably termin~t~d with end-caps (CAP), preferably modified isethionates, as in an oligomer comprising one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to about 10:1, and two 0 end-cap units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. Said SRA
preferably further comprises from 0.5% to 20%, by weight of the oligomer, of a crystallinity-reducing stabiliser, for example an anionic surfactant such as linear sodium dodecylbenzenesulfonate or a member selected from xylene-, cumene-, and toluene-sulfonates or mixtures thereof. these stabilizers or modifiers being introduced into the synthesis pot, all as taught in U.S. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, Na- dimethyl 5-sulfoisophth~ e, EG and PG.

Yet another group of preferred SRA ' s are oligomeric esters comprising: ~1 ) a backbone comprising ~a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxy sulfonates, a unit which is at least trifunctional whereby ester linkages are formed resulting in a branched oligomer backbone, andcombinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanP~ ulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred of such esters are those of empirical formula:
{(CAP)x(EG/PG)y'(DEG)y"(PEG)y" '(T)z(SIP)z'(SEG)~(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) represents di(oxyetnylene)oxy units; (SEG) represents units derived from the sulfoethyl e~her of glycerin and related moiety units; (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomerbackbone; 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;

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 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 rel,lesel1t 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)eth~nPslllfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products of 0 ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxyethoxy)ethoxy}eth~n~os~lfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]eth~n~sl~lfonate, DMT, sodium 2-(2.3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an ap~lopliate Ti(IV) catalyst and can be designated as (CAP)2(T)S(EG/PG)1.4(SEG)2.5(B)0.13 wherein CAP is (Na+ -O3S[CH2CH2O]3.5)-and B is a unit from glycerin and the mole ratio EG/PG is about 1.7:1 as measured by conventional gas chromatography after complete hydrolysis.

Additional classes of SRA's include (I) nonionic terephth~l~tes using diisocyanate 20 coupling agents to link up polymeric ester structures, see U.S. 4.201,824, Violland et al. and U.S. 4,240,g18 T ~g~cse et al; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxylgroups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the25 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.; (III) anionic terephth~l~te-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 30 monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graR
copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylicmonomers 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 35 Rhone-Poulenc Chemie; (VI) graRs 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) CA 022~4827 1998-11-17 WO 97/43389 PCT/USg7/08437 polyester-polyamide SRA's prepared by condensing adipic acid~ caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al, DE
2,335,044 to Unilever N. V., 1974. Other useful SRA's are described in U.S. Patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

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

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene-pent~min~. 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. Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, lg84; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Polvmeric Dispersin~e 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 polyethylene glycols~ although others known in the art can also be used. It is believed, though it is not intended to be lirnited by theory, that polymeric dispersing agents enhance overall detergent builder pelfo.lllance, when used in combination with other builders CA 022~4827 1998-ll-17 W O 97/43389 PCTrUS97/08437 (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid forrn. 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, cont~ining no carboxylate radicals such as 0 vinylmethyl ether, 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 the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the 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, the alkali metal, amrnonium and substituted ammonium salts.
Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7,1967.

Acrylic/maleic-based copolymers may also be used as a preferred component of thedispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and mali .c 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, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, ~ 1982, as well as in EP 193,360, published September 3~1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP
193,360, including, for example, the 45/45110 terpolymer of acrylic/maleic/vinyl alcohol.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 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 polyglut~m~te 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.
Bri,~htener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from 0.01 % to 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and 20 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 25 brighteners include the PHORWHITE series of brighteners from Verona. Other brigh~en~rs disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal SBM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-napthol1,2-d]triazoles; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbenes; 4,4'-bis(styryl)bisphenyls; and the aminocoumarins. Specific examples of these brighteners 30 include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(ben7imi~7ol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole;
and 2-(stilben-4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1g72 to Hamilton.

35 Dye Transfer Inhibitin~ A~ents CA 022~4827 1998-ll-17 W O 97/43389 PCT~US97/08437 The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, 5 m~n~n~Se 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 0 having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be ~tt~r~Pd or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the 15 nitrogen of the N-O group can be att~'n~d or the N-O group is part of these groups.
~lef~l~ed polyamine N-oxides are those wherein R is a heterocyclic group such aspyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

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

~l (R, )X--N--(R2~y; =N--(Rl )~
(R3)z wherein R1, R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be 25 ~ chPd or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, more preferred pKa < 6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric 30 backbones are polyvinyls, polyalKylenes, polyesters, polyethers~ polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of lO: l CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 to 1: 1.000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an a~rop~iate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of S00 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 ple~el~ed polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an 0 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 plel~lled for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is deterrnined by light scattering as described in Barth, et al., Chemical Analvsis, 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 from 0.8:1 to 20 0.3:1, most preferably from 0.6:1 to 0.4:1. These copolymers can be either linear or branched.

The present invention compositions also may employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5,000 to 400,000, preferably from 5,000 to 25 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the d~lelg~l.l field; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein by reference. Compositions cont~ining PVP can also contain polyethylene 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 30 is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

The d~lerge..l 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, the compositions herein will preferably comprise from 0.01 % to 35 1 % by weight of such optical brighteners.

. . , _ . , CA 022~4827 1998-11-17 The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

N~ ~C=C~N

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

0 When in the above fo~nula, Rl 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 comrnercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in 5 the detergent compositions herein.

When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4.4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)aminol2,2'-stilbenedisulfonic acid disodium salt. This 20 particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-25 stilbenedisulfonic acid, sodium salt. This particular brightener species is commerciallymarketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination 30 with the selected polymeric dye transfer inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal SBM-GX and/or Tinopal CA 022s4827 1998-11-17 AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without being bound by theory. it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these 5 fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be deflned by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present 1 o invention.

Of course, it will be appreciated that other, conventional optical brightener types of compounds can optionally be used in the present compositions to provide conventional fabric "brightnPcs" benefits, rather than a true dye transfer inhibiting effect. Such usage is 5 conventional and well-known to detergent forrnulations.

Chelatin~ A~ents The detergent compositions herein may also optionally contain one or more iron andlor 20 m~ng~n~se 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 theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and m~ng~n~se ions from washing solutions by 25 formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenPdi~minPtetr~cet~tes, N-hydroxyethylethylen~ minPtriacetates, nitrilotriacetates, ethylenedi~min~
telldpro~)lionates, triethylenetetr~min~hexacetates, diethylenetriaminepent~ret~tes, and 30 ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent 35 compositions, and include ethylen~ocli~minf tetrakis (methylenephosphonates) as DEQUEST.

CA 022~4827 1998-11-17 Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than

6 carbon atoms.

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

A plel~,led biodegradable chelator for use herein is ethylenP~ minP disuccinate 0 ("EDDS"). especially the [S,Sl isomer as described in U.S. Patent 4.704,233, Novem~er 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 15 builders such as zeolites, layered silicates.

If utilized, these chelating agents will generally comprise from 0.1 % to 15 % by weight of the d~leigellL 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 incorporated into the compositions of the present invention. Suds suppression can be of particular importance in 25 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 the art. See, for example, Kirk Othmer Encyclopedia of30 ChPmi~l Technology, Third Edition, Volume 7, pages 430~47 (John Wiley & Sons, Inc.~
1979). One category of suds suppressor of particular interest encompasses monocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as sudssuppressor typically have hydrocarbyl chains of 10 to 24 carbon atoms, preferably 12 to 18 35 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 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 5 C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmel~min~s or di- to tetra-alkyl(li~min~ chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ 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 0 Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of 40~C and 50~C, and a miniml-m boiling point not less thanl 10~C (atmospheric pressure~. It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100~C. The 15 hydrocarbons constitute a preferred category of suds suppressor for delelgelll 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, includealiphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor 20 discussion, is inten-led to include mixtures of true parafflns 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 25 combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming a~ueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.

35 Mixtures of silicone and sil~n~tecl silica are described, for in~t~n~e, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular CA 022~4827 l998-ll-l7 W O 97/43389 PCTrUS97/08437 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 suppressing5 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 S to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiOl/2 units of SiO2 units in a ratio of from (CH3)3 SiO1/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1;
and (iii) from about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.
In the preferred silicone suds suppressor used herein, the solvent for a 5 continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinke(l and preferably not linear.

20 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 25 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 30 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 colurnn 4, line 35.

35 The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.

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

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

Other suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include the C6-C16 alkyl alcohols having a C1-C16 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 d~l~rgel,~ compositions to be used in automatic laundry or dishwashing machines, suds should not form to the extent that they either overflow the washing machine or negatively affect the washing mechanism of the dishwasher. Suds suppressors, when utili7ed, are preferably present in a "suds suppressing amount. By "suds suppressing amount" is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry 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 therein, will be present typically in amounts up to 5 %, by weight, of the detergent composition.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 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 with keeping costs minimi7~d 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, these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any optional materials that may be utilized. Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from 0.1 % to 2 %, by 1 o weight, of the 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 the finished compositions.

Alkoxylated Polycarboxylates Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO
91/08281 and PCT 90/01815 at p. 4 et seq., incorporated herein by reference.
Chlomic~lly, these materials comprise polyacrylates having one ethoxy side-chain per every

7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The moiecular 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 the compositions herein.
Fabric Softeners Various through-the-wash fabric soRteners, especially the impalpable smectite clays of U.S.
Patent 4,062,647, Storrn and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay soReners can be used in combination with amine and cationic soReners 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 CA 022~4827 1998-11-17 W097/43389 PCTrUS97/08437 Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters. 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 0 90% of a fini.ch~cl perfume composition Non-limi~in~ examples of perfume ingredients useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetralnethyl naphthalene; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; l-dodecanal, 4-(4-hydroxy4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexyl 20 carboxaldehyde; fo~nyl tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate, condensation products of hydroxycitronellal and indol, condensation products of phenyl acet~ldehyde and indol; 2-methyl-3-~para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde; amyl cinn~mic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin; decalactone 25 ~mm~; cyclopen~dec~nolide; 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-tetramethylnaphthol2,1b]furan; cedrol, S-(2,2,3-trimethylcyclopent-3 -enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2, 2, 3 -trimethyl-3 -cyclopenten- 1-yl)-2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl 30 acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly preferred perfume materials are those that provide the largest odorimprovements in finished product compositions cont~inin~ cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-35 butylphenyl)-propionaldehyde; 7-acetyl-1,2,3 ,4,5 ,6,7,8-octahydro-1, 1 ,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyi tetralin; para-tert-butyl CA 022~4827 l998-ll-l7 W O 97/43389 PCT~US97/08437 cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro-4, 6, 6, 7, 8, 8-hexamethyl-cyclopenta-gamma-2 -benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; ~ni~ Pllyde; coumarin; cedrol; vanillin;
cyclopent~Aec~nolide; 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, Olib~mlm resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin. Still other perfume 10 chPmi~ include phenyl ethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethylphth~l~te can be used in the finished perfume compositions.

Other In~redients A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrot,opes, 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 Clo-C16 alkanol~mides can be 20 incorporated into the compositions, typically at 1%-10% levels. The Clo-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing optional surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, water-soluble magnesium and/or calcium salts such as MgC12, MgS04, CaC12 CaS04, can be added at 25 levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal pe.ro",lance.

Various detersive ingredients employed in the present compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then 30 coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.

35 To illustrate this technique in more detail, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution Cont~ining 3%-CA 022~4827 1998-11-17 W O 97143389 PCTrUS97/08437 5% of C13 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-~2,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes,bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surf~ct~ntc can be "protected" for use in detelge in~ rling liquid laundry del~lgellt compositions.

0 Li~uid detergel1t compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol,propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant. but polyols such as those cont~ining 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, the wash water will have a pH of between 6.5 and 11, 20 preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between 6.8 and 9Ø Laundry products are typically at pH 9-11. Techniques for controlling pH at recommPn~e~ usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

25 Granules l\ l~mlf~ctnre Adding the alkoxylatedcationics of this invention into a crutcher mix, followed by conventional spray drying, helps remove any residual, potentially malodorous, short-chain amine cont~min~n~c. In the event the formulator wishes to prepare an admixable particle 30 cont~ining the alkoxylated cationics for use in, for example, a high density granular detergent, it is preferred that the particle composition not be highly ~Ik~linf~. Processes for preparing high density (above 650 g/l) granules are described in U.S. Patent 5,366,652.
Such particles may be formnl~te~ to have an effective pH in-use of 9, or below, to avoid the odor of i~ ,ulily amines. This can be achieved by adding a small amount of acidity 35 source such as boric acid, citric acid, or the like, or an appropriate pH buffer, to the CA 022~4827 1998-11-17 particle. In an alternate mode, the prospective problems associated with amine malodors can be masked by use of perfume ingredients, as disclosed herein.

Examples 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 wei~ht unless otherwise specified.

0 In the following examples, the abbreviated component identifications have the following mP~nm~:
LAS : Sodium linear C12 alkyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-C1s linear alkyl sulfate CxyEzS : Sodium C1x-Cly branched alkyl sulfate condensed with z moles of ethylene oxide C45E7 : A C14 15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C25E3 : A C12 15 branched primary alcohol condensed with an average of 3 moles of elhylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CocoEO2 : Rl.N+(CH3)(c2H4OH)2 with Rl = C12 ~ C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils.
TFAA : C 16-C 1 8 alkyl N-methyl glucamide TPKFA : C12-C14 topped whole cut fatty acids STPP : Anhydrous sodium tripolyphosphate Zeolite A : Hydrated Sodium Aluminosilicate of formula Na12(A102SiO2)12. 27H20 having a primary particle size in the range t'rom 0.1 to 10 micrometers NaSKS-6 : Crystalline layered silicate of formula ~ -Na2si2~S
Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200,um and 900~m CA 022~4827 1998-11-17 Bicarbonate : Anhydrous sodium bicarbonate with a particle size distribution between 40011m and 120011m Silicate : Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio) Sodium sulfate : Anhydrous sodium sulfate Citrate : Tri-sodium citrate dihydrate of activity 86.4%
with a particle size distribution between 425~1m and 850 llm MA/AA : Copolymer of 1:4 maleic/acrylic acid, average molecular weight 70,000.
CMC : Sodium carboxymethyl cellulose Protease : Proteolytic enzyme of activity 4KNPU/g sold by NOVO Industries A/S under the tradename Savinase Alcalase : Proteolytic enzyme of activity 3AU/g sold by NOVO Industries A/S
Cellulase : Cellulytic enzyme of activity 1000 CEVU/g sold by NOVO Industries A/S under the tradename Carezyme Arnylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
Lipase : Lipolytic enzyme of activity 100kLU/g sold by NOVO Industries A/S under the 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 NaBO2.H2O2 Percarbonate : Sodium Percarbonate of nominal formula 2Na2C03 ~3H2~2 NOBS : Nonanoyloxybenzene sulfonate in the form of the sodium salt.
TAED : Tetraacetylethylenediamine CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 NACA-OBS : (6 non~n:~mi~lo caproyl) oxybenzene sulphonate DTPMP : Diethylene triamine penta (methylene phosphonate), marketed by Monsanto under the Trade name Dequest 2060 Photoactivated : Sulfonated Zinc Phthalocyanine encapsulated in bleach dextrin soluble polymer Brightener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl Brighten~r 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-0 1.3.5-triazin-2-yl)amino) stilbene-2:2'-disulfonate.
HEDP : 1,1-hydroxyethane diphosphonic acid PVNO : Polyvinylpyridine N-oxide PVPVI : Copolymer of polyvinylpyrrolidone and vinylimi~701e SRA 1 : Sulfobenzoyl end capped esters with oxyethylene oxy and terephthaloyl backbone SRA 2 : Diethoxylated poly (1, 2 propylene terephth~l~te) short block polymer Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.

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

The following dett;rgent formulations according to the present invention are prepared~
where A and C are phosphorus-cont~ining detergent compositions and B is a zeolite-cont~ining d~rgent composition.
A _ C
Blown Powder STPP 24.0 - 24.0 Zeolite A - 24.0 C45AS 8.0 5.0 11.0 MA/AA 2.0 4.0 2.0 CA 022~4827 1998-11-17 W 097/43389 PCTrUS97/08437 LAS 6.0 8.0 11.0 TAS 1.5 - -CocoMeEO2* 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 o 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 ~
TAED 3.0 - 1.0 NACA-OBS - 3.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0 4 0 4 Arnylase 0.25 0.30 0.15 Dry mixed sodium sulfate 3 .0 3 .0 5 .0 R~l~n-~e (Moisture &
Miscellaneous) To: 100.0 100.0 100.0 Density (g/litre) 630 670 670 *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 II
The following detergent forrnulations, according to the present invention are prepared:
G H
Blown Powder Zeolite A 30.0 22 0 6.0 CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 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 NACA-OBS 3.2 - -PB1 1.0 5.0 6.0 Sodium sulfate - 6.0 R~l~n~e (Moisture & Miscellaneous) To: 100 100 100 25 *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 surf~c~n~. herein.

EXAMPLE III
The following high density detergent formulations, according to the present invention are prepared:
J K
Blown Powder ZeoliteA 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 CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 DTPMP 0.4 0.40.4 CMC 0.4 0 40 4 MA/AA 4.0 2.02.0 Agglomerates LAS 5.0 5.05 0 TAS 2.0 2.01.0 Silicate 3.0 3.04 0 Zeolite A 8.0 8.08.0 Carbonate 8.0 8.04.0 0 Spray On Perfume 0.3 0.30.3 C45E7 2.0 2.02.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.010.0 TAED 6.0 2.05.0 PB1 13.0 7.010.0 Polyethylene oxide of MW 5 ,000,000 - - 0.2 Bentonite clay - - 10.0 Protease 1.0 1.01.0 Lipase 0 4 0 40 4 Amylase 0.6 0.60.6 Cellulase 0.6 0.60.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 30 R~l~n~e (Moisture &
Miscellaneous) To: 100.0 100.0100.0 Density (g/litre) 850 850 850 *The AQA -1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent 35 amount of any of surfactants AQA -2 through AQA -22 or other AQA surfactants herein.

W O 97/43389 PCTrUS97/08437 EXAMPLE IV
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 o 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 SRA1 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 0.2 Brightener 2 0 . 2 Ral~n~e (Moisture &
Miscellaneous) To: 100 100 Density (g/litre) 850 850 CA 022~4827 1998-11-17 W O 97/43389 PCTnUS97/08437 *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.

Any of the granular detelgent compositions provided herein may be tabletted using 5 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 con~llcte-l in the 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 (6/16187); EP-A-510,762 (10/28t92); EP-A-540,089 (5/5193); 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), incorporated herein by lefe~ellce. Such 5 compositions can contain various particulate detersive ingredients (e.g., bleaching agents, as disclosed hereinabove) stably suspended therein. Such non-aqueous compositions thus 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 20 the m~nllf~hlre of other laundry detergent compositions.

LIQUID PHASE

The liquid phase will generally comprise from 35% to 99% by weight of the detergent 25 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 the detergent compositions herein essentially contains relatively high concentrations of a certain type anionic surfactant combined with a certain type of nonaqueous, liquid diluent.
(A) Essential Anionic Surfactant The anionic surfactant essentially utili7~d as an essential component of the nonaqueous liquid phase is one selected from the alkali metal salts of alkylbenzene sulfonic acids in 35 which the alkyl group contains from 10 to 16 carbon atoms, in straight chain or branched chain conf1guration. (See U.S. Patents 2,220,099 and 2,477,383, incorporated herein by CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 reference.) Especially preferred are the 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 Cll-C14 LAS is especially preferred.

5 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 forrn the structured liquid phase required for suitable phase stability and acceptable rheology, the 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 o surfactant will comprise from 35% to 50% by weight of the nonaqueous liquid phase of the compositions herein. Utilization of this anionic surfactant in these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight, more preferably from 20% to 40% by weight, of the composition.

15 (B) Nonaqueous Liquid Diluent To form the liquid phase of the detelgent compositions, the hereinbefore described alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent which contains two essenti~l components. These two components are a liquid alcohol~0 alkoxylate material and a nonaqueous, low-polarity organic solvent.
i) Alcohol Alkoxylates One essential component of the liquid diluent used to form the compositions herein comprises an alkoxylated fatty alcohol material. Such materials are themselves also 25 nonionic surfactants. Such materials correspond to the general forrnula:
Rl(CmH2mO)noH
wherein Rl is a C8 - C16 alkyl group, m is from 2 to 4, and n ranges from 2 to 12.
Preferably R1 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 30 alkoxylated fatty alcohols will be ethoxylated 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 the liquid diluent will frequently have a 35 hydrophilic-lipophilic balance (HLB) which ranges from 3 to 1~. More preferably, the HLB of this material will range from 6 to 15, most preferably from 8 to 15.

CA 022~4827 1998-11-17 WO 97/43389 PCT~US97/08437 Examples of fatty alcohol alkoxylates useful as one of the essential components of the nonaqueous liquid diluent in the compositions herein will include those which are made from alcohols of 12 to 15 carbon atoms and which contain 7 moles of ethylene oxide. Such materials have been commercially marketed under the 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 Cg - C11 prirnary alcohol having 10 10 moles of ethylene oxide. Alcohol ethoxylates of this type have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol 91-5 is an ethoxylated Cg-C1 1 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C12-C1s fatty alcohol with 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 ethoxylates that have been cornmercially marketed by Union Carbide Corporation. The former is a mixed ethoxylation product of Cll to Cls linear secondary alkanol with 7 moles of ethylene oxide and the latter is a 20 similar product but with 9 moles of ethylene oxide being reacted.

Other types of alcohol ethoxylates 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 25 and the 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 the liquid diluent in the nonaqueous compositions herein will generally be present to the extent of from 1%
30 to 60% of the liquid phase composition. More preferably, the 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 these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration in the total composition of 3s from 1% to 60% by weight, more preferably from 2% to 40% by weight, and most preferably from 5 % to 25 % by weight, of the composition.

CA 022~4827 1998-11-17 W O 97/43389 PCTrUS97/08437 ii) Nonaqueous Low-Polarity OrYanic Solvent A second essential component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises nonaqueous, low-polarity organic solvent(s).
The term "solvent" is used herein to connote the 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"-cont~ining liquid phase, other components will be present as particulate material dispersed within the "solvent"-cont~ining liquid phase. Thus the term "solvent" is not meant to require that the 0 solvent material be capable of actually dissolving all of the detergent composition colnl)olle~ 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 those 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 ble~chin~ agents e.g. sodium pe,ca,bonate. Thus relatively polar solvents such as ethanol should not be utilized.
Suitable types of low-polarity solvents useful in the nona~ueous liquid detergent compositions herein do include non-vicinal C4-Cg alkylene glycols, alkylene glycol mono 20 lower alkyl ethers, lower molecular weight polyethylene 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-Cg branched or straight chain alkylene glycols. Materials of 25 this type include hexylene glycol (4-methyl-2,4-pent~n~diol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene glycol. Hexylene glycol is the most preferred.

Another prere.lcd type of nonaqueous, low-polarity solvent for use herein comprises the mono-, di-, tri-, or tetra- C2-C3 alkylene glycol mono C2-C6 alkyl ethers. The specific 30 examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are especially preferred. Compounds of the type have been comrnercially marketed under the tradenames Dowanol, Carbitol, and Cellosolve.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 Another preferred type of nonaqueous, low-polarity organic solvent useful hereincomprises the lower molecular weight polyethylene 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 another preferred type of non-polar, nonaqueous solvent comprises lower molecular weight methyl esters. Such materials are those of the general formula: Rl-C(O)-OCH3 wherein R1 ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl 0 do~lec~no~te.

The nonaqueous, low-polarity organic solvent(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, the 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 the composition. Utilization of this organic solvent in these concentrations in the liquid phase corresponds to a solvent concentration in the 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 the 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, the amount of total liquid diluent in the nonaqueous liquid phase herein will be determined by the type and amounts of other composition components and by the desired composition properties. Generally, the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the compositions herein. More preferably, the liquid diluent will comprise from 50% to 65 % of the nonaqueous liquid phase. This corresponds to a W 097/43389 PCTrUS97/08437 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.

CA 022~4827 1998-11-17 W 097/43389 PCT~US97/08437 SOLID PHASE

The nonaqueous detergent compositions herein also essentially comprise from I % to 65 %
by weight, more preferably from 5 % to 50% by weight, of a solid phase of particulate 5 material which is dispersed and suspended within the liquid phase. Generally such particulate material will range in size from 0.1 to I500 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 0 composition components which in particulate form are substantially insoluble in the nonaqueous liquid phase of the 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 the essential and optional components thereof in any convenient order and by mixing, e.g., ~git~ting, the resulting component combination to form the phase stable compositions herein. In a typical process for preparing such compositions, essential and certain 20 plcfellcd 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 the two essential components of the nonaqueous diluent is 2~ 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 m~int~in~d under shear agitation at a temperature from 40~C to 100~C for a period of from 2 mimlt~s to 20 hours. Optionally, a vacuum can be applied to the admixture at this point.
30 This second process step serves to completely dissolve the anionic surfactant in the 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, 35 surfactant-cont~ining liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 Particulate material is added in a fourth process step by combining the particulate material with the liquid base which is m~int~in~A under conditions of shear agitation. When more than one type of particulate material is to be added, it is preferred that a certain order of 5 addition be observed. For example, while shear agitation is m~int~in~, 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 subs~n~ y all of an organic builder, e.g., citrate and/or fatty acid, and/or an ~Ik~linity source, e.g., sodium carbonate, can be added while contin--ing to 0 m~inl~in this admixture of composition components under shear agitation. Other solid form optional ingredients can then be added to the composition at this point. Agitation of the mixture is contin~le~, and if n~ces~ry, can be increased at this point to form a uniform dispersion of insoluble solid phase partic~ tes within the liquid phase.

15 After some or all of the foregoing solid materials have been added to this a~it~t~ mixture, the particles of the highly p~ ed peroxygen ble~ching agent can be added to the composition, again while the mixture is rn~int~in~d under shear agitation. By adding the peroxygen bleaching agent material last, or after all or most of the other components, and especially after ~Ik~linity source particles, have been added, desirable stability benefits for 20 the peroxygen bleach can be realized. If enzyme prills are incorporated, they are preferably added to the nonaqueous liquid matrix last.

As a final process step, after addition of all of the particulate material, agitation of the mixture is continued for a period of time sufficient to form compositions having the 25 requisite viscosity and phase stability characteristics. Frequently this will involve agitation for a period of from 1 to 30 minlltec.

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 30 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 the particles of the inorganic ~Ik~liniry 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 35 premixes should precede addition of peroxygen bleaching agent and/or enzyme particles which may themselves be part of a premix slurry formed in analogous fashion.

CA 022~4827 1998-11-17 W O 97/43389 PCT~US97/08437 The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
Generally, an effective amount of such compositions is added to water, preferably in a 5 conventional fabric laundering automatic washing machine, to forn such aqueouslaundering/ble~cllin~ solutions. The aqueous washing/bleaching solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered and bleached therewith.

0 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 V
A non-limiting exarnple of a bleach-cont~ining nonaqueous liquid laundry detergent is prepared having the composition as set forth in Table I.
Table I
Component Wt. % Ran~e (% wt.) Liquid Phase Na C12 Linear alkylbenzene sulfonate (LAS) 25.3 18-35 C12 14, EO5 alcohol ethoxylate 13.6 10-20 Hexylene glycol 27.3 20-30 Perfume 0.4 0-1.0 AQA-l * 2.0 1-3.0 So 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 Sodium carbonate 13.9 5-20 Diethyl triamine pent~cetic acid (DTPA) 0.9 0-1.5 Brightener 0.4 0-0.6 Suds Suppressor 0.1 0-0.3 Minors Balance ----CA 022~4827 1998-11-17 W O 97143389 PCTrUS97/08437 *CocoMeEO2. AQA -1 may be replaced by AQA surfactants 2-22 or other AQA
surfart~ntc herein.

The composition is prepared by mixing the 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 the rem~ining components are added. The resulting composition is then stirred at 29~C (85~F) for another 1/2 hour.

The resulting composition is a stable anhydrous heavy duty liquid laundry detergent which 0 provides excellent stain and soil removal performance when used in normal fabric laundering operations.

EXAMPLE VI
The following hand wash dete~el1t formulations, according to the present invention, 15 are prepared by mixing the ingredients together in the percentage weight amounts as in~ t~ below.

A B C D
LAS 15.0 12.0 15.0 12.0 TFAA 1.0 2.0 1.0 2.0 C25E5 4.0 2.0 4.0 2.0 AQA-9* 2.0 3.0 3.0 2.0 STPP 25.0 25.0 15.0 15.0 MA/AA 3.0 3.0 3.0 3.0 CMC 0.4 0.4 0.4 0.4 DTPMP 1.0 1.6 1.6 1.6 Carbonate 2.0 2.0 5.0 5.0 Bicarbonate - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 Protease 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 Lipase 0.12 0.12 - 0.12 Photoactivated bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.2 2.2 PB1 4.0 5.4 4.0 2.3 CA 022~4827 1998-11-17 WO 97/43389 PCTrUS97/08437 NOBS 2.6 3.1 2.5 1.7 SRA 1 0.3 0.3 0.7 o 3 Brightener 1 0.15 0.15 0.15 0.15 Balance misc./water 100.0 100.0 100.0 100.0 to 100 AQA-9*; May be replaced by any AQA surfactant described herein. Preferred AQA
surfactants for use in this example are those with from 10 to 15 ethoxy groups; for example AQA-10, AQA-16.

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

Modern automatic dishwashing dete~el,~s can contain bleaching agents such as hypochlorite sources; pelbol~, pcl~all,onate or persulfate bleaches; enzymes such as proteases, lipases and amylases, or mixtures thereof; rinse-aids, especially nonionic surfactants; builders, including zeolite and phosphate builders; low-sudsing detersive 5 surfactants, especially ethylene oxide/propylene oxide contlen~t~s. 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.

The following Examples A and B further illustrate the invention herein with respect to a 20 granular phosphate-cont~ining automatic dishwashing dete.ge"l.

EXAMPLE VII

% by weight of active material INGREDIENTS A
STPP (anhydrous)1 31 26 Sodium Carbonate 22 32 Silicate (% Si~2) Surfactant (nonionic) 3 1.5 AQA-1* 0.5 1.0 CA 022~4827 1998-11-17 wo 97/43389 PCT/USg7/08437 Sodium Perborate 4.3 5 TAED 1.7 1.5 Savinase (Au/g) -- 0.04 Termamyl (Amu/g) 425 Sulfate 25 25 Perfume/Minors to 100% to 100%
1Sodium tripolyphosphate 2Sodium dichlorocyanurate *The AQA -1 surfactant can be replaced by AQA -2 through AQA -22.

EXAMPLE VIII

The following illustrates mixtures of AQA surfact~ntc which can be substituted for the AQA surf~rt~nt.c listed in any of the foregoing Examples. As disclosed hereinabove, such 5 mixtures can be used to provide a spectrum of performance benefits and/or to provide cleaning compositions which are useful over a wide variety of usage conditions.
Preferably, the AQA surfactants in such mixtures differ by at least 1.5, preferably 2.5-20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-limi~ing examples of such mixtures are as follows.
Components Ratio (wt.) AQA-l + AQA-5 1:1 AQA-1 + AQA-10 1:1 AQA-1 + AQA-15 1:2 AQA-1 + AQA-5 + AQA-20 1:1:1 AQA-2 + AQA-5 3:1 AQA-5 + AQA-15 1.5:1 AQA-1 + AQA-20 1:3 Mixtures of the 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 the formula R1N+CH3[EO]X[EO]yX~ and R1N+(CH3)2[EO]zX-, wherein R1 and X are as disclosed above and wherein one of the cationics has (x+y) or z in the range 1-5 preferably 1-2 and the other has (x+y) or z in the range 3-100, preferably 10-20, most preferably 14-16, can be used herein. Such compositions advantageously provide improved detergency performance (especially in a CA 022~4827 1998-11-17 fabric laundering context) over a broader range of water hardness than do the cationic surfactants herein used individually. It has now been discovered that shorter EO cationics (e.g., 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, 5 thereby improving the cleaning performance of anionic surfactants in hard water.
Conventional wisdom in the detergency art suggests that builders can optimize the pe,rc~ ance "window" of anionic surfact~nt~. Until now, however, broadening the window to encompass essentially all conditions of water hardness has been impossible to achieve.

EXAMPLE IX

The following illustrates a number of bleach compositions which can comprise any of the bleach activators herein or their corresponding peracids . It is plel;.-ed, but not essential, 15 that the mole ratio of AQA surfactant:activator be 1:1.
Ratio Range Composition Bleach In~redient AQA Bleach:AQA
(~vt) A TAED bis-AQAl 5:1-1:5 B NOBS bis-AQAl 5:1-1:5 C TAED/NOBS (1:1) bis-AQA15 3:1-1:3 D NACA-OBS bis-AQA1 5:1-1:5 E Oct~n~miflo oxybenzene sulfonate* bis-AQAl 5:1-1:5 F Ocl~n~ Q oxyl,enzel1e sulfonate* bis-AQA15 5:1-1:5 *As disclosed hereinabove as bleach activator.

EXAMPLE X
This Example illustrates perfume formulations (A-C) made in accordance with the invention for incorporation into any of the foregoing Examples of AQA -cont~inin,~
detelgel.~ compositions. The various ingredients and levels are set forth below. (% Wei~ht) Perfume In~redient _ B C
Hexyl ei"n~-,ic aldehyde 10.0 - 5.0 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde 5.0 5.0 CA 022~4827 1998-11-17 wo 97/43389 PCT/USg7/08437 7-acetyl-1,2,3 ,4,5,6,7,8-octahydro-1, 1,6,7-tetramethyl naphthalene 5.0 10.0 10.0 Benzyl salicylate 5 o 7-acetyl-1, 1 ,3,4,4,6-hexamethyltetralin 10.0 5.0 10.0 Para-(tert-butyl) cyclohexyl acetate 5.0 5.0 Methyl dihydro jasmonate - 5.0 Beta-napthol methyl ether o.5 Methyl beta-naphthyl ketone - o.5 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde - 2.0 O 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopyrane - 9.5 Dodecahydro-3a,6,6,9a-telld.llel}lylnaphtho-[2, lb]furan - 0.1 ~ni~ldehyde ~ ~ 0 5 Coumarin 5.0 Cedrol - o.5 Vanillin 5.0 Cyclopent~lec~n-)lide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 T ~b~l~nllm resin - - 2.0 Tricyclodecenyl propionate - - 2.0 Phenyl ethyl alcohol 20.0 10.0 27.9 Terpineol 10.0 5.0 Linalool 10.0 10.0 5.0 Linalyl acetate 5.0 - 5.0 Geraniol 5.0 Nerol - 5.0 2-(1,1-dimethylethyl)-cyclohexanol acetate 5.0 Orange oil, cold pressed - 5.0 Benzyl acetate 2.0 2.0 Orange tel~nes - 10.0 Eugenol - 1.0 Diethylphth~l~t~ 9 5 Lemon oil, cold pressed - - 10.0 Total 100.0 100.0 100.0 W 097143389 PCTrUS97/08437 The foregoing perfume compositions are admixed or sprayed-onto (typically at levels up to about 2% by weight of the total detergent composition) any of the AQA
surfactant-cont~ining cleaning (including ble~ching) compositions disclosed herein.
Improved deposition and/or retention of the perfume or individual components thereof on 5 the surface being cleaned (or bleached) is thus secured.

Claims (18)

WHAT IS CLAIMED IS:

1.A detergent composition comprising, or prepared by combining a peroxygen bleach, a bleach activator a non-AQA surfactant and an effective amount of an alkoxylated quaternary ammonium (AQA) cationic surfactant of the formula:

wherein R1 is a linear, branched or substituted C8-C18 alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety, R2 is a C1-C3 alkyl moiety, R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl, X is an anion, A is C1-C4 alkoxy and p is an integer in the range of from 2 to 30.

2. A composition according to Claim 1 wherein the peroxygen bleach is selected from the group consisting of perborate, percarbonate, perphosphate, persilicate or persulfate salts.

3. A composition according to either of Claims 1 or 2 wherein the bleach activator is selected from the group consisting of tetra acetyl ethylene diamine and (6 nonananmidocaproyl) oxybenzene sulphonate.

4. A composition according to any of Claims 1 to 3 which is prepared by mixing the non-AQA surfactant and the AQA surfactant.

5. A composition according to any of Claims 1 to 4 wherein the non-AQA surfactant is an anionic surfactant.

6. A composition according to any of Claims 1 to 5 wherein the ratio of AQA to non-AQA
surfactant is from 1:15 to 1:8.

7. A composition according to any of Claims 1 to 6 wherein, said AQA surfactant has the formula where R1 is C8-C18 alkyl, R2 is methyl, A is an ethoxy or propoxy group and p is an integer of from 2 to 8.

8. A composition according to any of Claims 1 to 7 wherein said AQA surfactant has the formula where R1 is C8-C18 alkyl, R2 is methyl, A is an ethoxy or propoxy group and p is an integer of from 2 to 4.

9. A composition according to any of Claims 1 to 8 wherein the formula of the AQA
cationic surfactant is such that p is an integer in the range of from 10 to 15.

10. A composition according to any of Claims 1 to 9, comprising two or more AQA
surfactants, or a mixture of AQA surfactant and a mono-ethoxylated cationic surfactant.

11. A composition according to any of Claims 1 to 10, comprising two or more non-AQA
surfactants and a mixture of two or more AQA surfactants.

12. A composition according to any of Claims 1 to 11 in a granular, bar, non-aqueous liquid, or tablet form.

13. A method for removing soils and stains by contacting said soils and stains with a detergent composition, or aqueous medium comprising said detergent composition, according to Claims 1 to 12.

14. A method according to Claim 13 for removing bleach sensitive soil from fabrics.

15. A method according to either Claims 13 to 14 which is conducted in an automatic machine.

16. A method according to any of Claims 13 to 15 which is conducted by hand.

17. A method for enhancing the deposition or substantivity of perfumes or perfume ingredients onto fabrics or other surfaces, comprising contacting said surfaces with a perfume or perfume ingredient in the presence of a AQA surfactant.

18. A method according to Claim 17 which is conducted using a perfume or perfumeingredient in combination with a detergent composition comprising a AQA.