CA2254961A1 - Detergent composition - Google Patents

Abstract

A detergent composition comprising a soil release agent, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Description

I

DETERGENT COMPOSITION
Te~hni~l Fleld The present invention relates to a del~.~ellt co...L,os;lion comprising a soil release agent, a non-AQA surfactant and a bis-alkoxylated qualeln~y ammonium (bis-AQA) cationicsurfactant.

R~rk~round to the Invention The formulAtion of laundry delelgents and other cleAning compositions p~se.,t~ acon~i~erable chAll~l-ge, since modern compositions are required to remove a variety of soils and stains from diverse sub~ tes. Thus, laundry dete.ge~ts, hard surface cleaners, cl~ oos and other ~.~onal cleAn~ing col-.pos;lic-ns, hand dishwashing detergents and d~te~ nt co-"positions suitable for use in automatic dishwashers, all require the proper selection and co---bination of ingredients in order to function effectively. In g~ rAl, such detergent compositiQns will contain one or more types of surfAct~ntc which are deci~n~d to loosen and remove dirrel~nt types of soils and stains.
While a review of the literature would seem to in~ t~ that a wide sel~tion of surf.~t~nt.c and surfactant combinations are available to the det~l~ent manufacturer, the reality is that many such ingredients are speoi~lity cherr-ic~ls which are not suitable in low unit cost items such as home-use laundry detergents. The fact remains that most such home-use ~Jl~u~ such as laundry deL~r~ents still mainly comprise one or more of the convention~l ethoxylated nonionic and/or slllfAted or sulfonated anionic surfAct~nts, plc,u~--AI-ly due to CCoilO~-,iC considerations and the need to formulate co~ ,os;tiQnc which function re~c- n~hly well with a variety of soils and stains and a variety of fabrics.

The quick and efficiPnt 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 xlule of hyd~hobic triglycerides, lipids, complex polysaccharides, inorganic salts and lho~einr ~ous matter and are thus notoriously difficult to remove. Low levels of hydr~hobic soils and residual stains often remain on the surface of the fabric after washing. Successive washing and wearing coupled with limited removal of the soils and stains in the wash culmin~tts in a build-up of remnant soils on the fabric which further CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 entrap particulate dirt leading to fabric yellowing. Eventually the fabric takes on a dingy appearance which is perceived as unwearable and discarded by the consumer.

The literature suggests that various nitrogen-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 imi-~7Olinium compounds, are often designed for speciality use. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair. Other nitrogen-cont~ining surf~rt~nts are used in some laundry detergents to provide a fabric softening and anti-static benefit. For the most part, however, the c~ e.cial use of such materials has been limited by the difficulty encountered in the large scale m~n~lf~ctllre of such compounds. An additional limitation has been the potential precipitation of anionic active components of the detergent composition occasioned by their ionic interaction with cationic surf~3~t~ntc. The aforementioned nonionic and anionic surf~ct~nt~ remain the major surfactant components in today's laundry compositions.

It has been discovered that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in various detergent compositions to boost detergency performance on a variety of soil and stain types, particularly hydrophobic soils, commonly encountered.
The bis-AQA surfactants of the present invention provide substantial benefits to the formulator, over cationic surfactants previously known in the art. For exarnple, the bis-AQA surfactants used herein provide marked improvement in cleaning of "everyday"greasy/oily hydrophobic soils regularly encountered. Moreover, the bis-AQA surfact~ntc are compatible with anionic surfart~nt~ commonly used in detergent compositions such as alkyl sulfate and alkyl benzene sulfonate; incompatibility with anionic components of the detergent composition has commonly been the limiting factor in the use of cationic surf~t~ntc to date. Low levels (as low as 3 ppm in the laundering liquor) of bis-AQA
surf~rt~nt~ gives rise to the benefits described herein. Bis-AQA surfactants can be formnl~ted over a broad pH range from 5 to l2. The bis-AQA surfactants can be prepared as 30% (wt.) solutions which are pumpable, and therefore easy to handle in a m~mlf~rtllring plant. Bis-AQA surfactants with degrees of ethoxylation above S are somPtimrs present in a liquid form and can therefore be provided as 100% neat materials.
In addition to their beneficial h~n~lling properties, the availability of bis-AQA surfactants as highly concentrated solutions provides a substantial economic advantage in transportation costs .

CA 02254961 l99X-11-17 Furthermore, it has also been discovered that compositions con~ining a soil release agent (SRA) and a bis-AQA surfactant can deliver additional superior cleaning and whiteness performance versus products cont~inin~ either technology alone SRAs are such that they have a natural affinity for fabric; during the wash the SRA adheres to and remains on the fabric. Thus soils and stains collected on wearing are left on the SRA and not the fabric itself. Subsequent washing action removes the SRA from the surface of the fabric, taking the soil/stain with it. It is believed that benefits of the bis-AQA/SRA system are the result of: (1) bis-AQA action solubilizing soil/stains; (2) solubilization of soils by bis-AQA
results in improved access of the SRA to the fabric surface; (3) removal of most recent soils by the SRA means that the bis-AQA can further solubilize built-up remnant soils. The effective removal of soils (including previously remnant soils) by this system provides improved cleaning and fabric whiteness.

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,W0,990, issued 3 Sept., 1980, to A. P.
Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry detergents.

Swnmal ~ of the Invention The present invention provides a composition comprising or prepared by combining a soil release agent (SRA), a non-AQA surfac~ant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

R~ /ApR
N X
R2/ A qR

wherein Rl is a linear, branched or substituted Cg-C1g 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, and A and A' can vary CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 independently and are each C1-C4 alkoxy, p and q can vary independantly and are integers of from 1 to 30.
D~s~ ion of the Invention Soil Release A~ent The compositions of the present invention comprise a polymeric soil release agents, hereinafter "SRA" or "SRA's". SRA's comprise from 0.01% to 10.0%, typically from0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition.

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

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

Preferred SRA's include oligomeric terephth~l~te esters, typically prepared by processes involving at least one tr~n~esterification/oligomerization, often with a metal catalyst such as a sit~ni--m(lV) 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 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) CA 022~4961 1998-11-17 W O 97144419 PCTrUS97/08317 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 te~e~h~ te polyesters of U.S. 4,711,730, December 8, 1987 to Gosselink et al, for example those produced by transesterification/oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"); the partly-and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic-capped block polyester oligomeric compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, for example produced from DMT, Me-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, Me-capped PEG and Na-dimethyl-5-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, Gosselinlc et al, the latter being typical of SRA's useful in both laundr,v and fabric conditioning products, an example being an ester composition made from m-sulfobenzoic acid monosodium salt, PG and DMT optionally but preferably further colllplishlg added PEG, e.g., PEG 3400.

SRA's also include sirnple copolymeric blocks of ethylene terephth~l~te or propylene terephth~l~te 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 C1-C4 alkylcelluloses and C4 hydroxyalkyl celluloses; see U.S. 4,000,093, December 28, 1976 to Nicol, et al. Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C1-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.
Commercially 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 weight 300-5,000. Con~nercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

CA 022C,4961 1998-ll-17 Another p-ef~lled SRA is an oligomer having empirical formula (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~tecl 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 end-cap units derived from sodium 2-(2-hydroxyethoxy)-eth~n~s~lfonate. 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, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated prop~n~s~llfonates, alkoxylated propan~i.cl~lfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred of such esters are those of empirical formula:
{(CAP)x(EG/PG)y ' (DEG)y " (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}

wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) represents di(oxyethylene)oxy units; (SEG) represents units derived from the sulfoethyl ether of glycerin and related moiety units; (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched 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; 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", CA 022~4961 1998-11-17 Wo 97/~4419 PCT/US97/08317 y"', z, z', q and m represent the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from about 500 to about 5,000.

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

Additional classes of SRA's include (I) nonionic tereph~h~l~tes using diisocyanate coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S.
4,240,918 l ~g~cse et al; (II) SRA's with carboxylate terminal groups made by adding trirnellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the t~ illals of the polymer through an ester of the isolated carboxylic acid of trirnellitic 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.; (lII) anionic terephth~l~te-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl caprolactarn~ and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including both nonionic and cationic polymers, see U.S.
4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters; these SRA'sassertedly have soil release and anti-redeposition activity similar to known cellulose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF
(1991); (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al~ DE

CA 022~4961 1998-11-17 W O 97144419 PCTrUS97/08317

2,3357044 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.

Another preferred SRA is an oligomer having empirical formula (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~ted 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 0.5:1 to 10:1, and two end-cap units derived from sodium 2-(2-hydroxyethoxy)-eth~nPs~lfonate 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~l~te, EG and PG.

Yet another group of ~ felled 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 res--lting in a branched oligomer backbone, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one unsulfonated unit which is a 1,2-oxyalkyleneoxy moiety; and (2) one or more capping units selected from nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated prop~nPs--lfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred of such esters are those of empirical formula:
{(CAP)x(EG/PG)y ' (DEG)y " (PEG)y " ' (T)z(SIP)z ' (SEG)q(B)m}
wherein CAP, EG/PG, PEG, T and SIP are as defined hereinabove, (DEG) represents di(oxyethylene)oxy units; (SEG) represents units derived from the sulfoethyl ether of glycerin and related moiety units; (B) represents branching units which are at least trifunctional whereby ester linkages are formed resulting in a branched oligomerbackbone; x is from 1 to 12; y' is from 0.5 to 25; y" is from 0 to 12; y"' is from 0 to 10;
y' +y" +y" ' totals from 0.5 to 25; z is from 1.5 to 25; z' is from 0 to 12; z + z' totals CA 022~4961 1998-11-17 from 1.5 to 25; q is from 0.05 to 12; m is from 0.01 tot 10; and x, y', y", y"', z, z', q and m represent the average number of moles of the corresponding units per mole of said ester and said ester has a molecular weight ranging from 500 to 5,000 Preferred SEG and CAP monomers for the above esters include Na-2-(2-,3-dihydroxypropoxy)eth~n~s~llfonate ("SEG"), Na-2-{2-(2-hydroxyethoxy) ethoxy}
ethanesulfonate ("SE3") and its homologs and mixtures thereof and the products of ethoxylating and sulfonating allyl alcohol. Preferred SRA esters in this class include the product of transesterifying and oligomerizing sodium 2-{2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or sodium 2-[2-{2-(2-hydroxyethoxy)-ethoxy}ethoxy]eth~nPs~lfonate, DMT, sodium 2-(2,3-dihydroxypropoxy) ethane sulfonate, EG, and PG using an app~opliate 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 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 coupling agents to link up polymeric ester structures, see U.S. 4,201,824, Violland et al. and U.S.
4,240,918 T ~g~cse et al; (II) SRA's with carboxylate terminal groups made by adding trimellitic anhydride to known SRA's to convert terminal hydroxyl groups to trimellitate esters. With a proper selection of catalyst, the trimellitic anhydride forms linkages to the terminals of the polymer through an ester of the isolated carboxylic acid of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials as long as they have hydroxyl terminal groups which may be esterified. See U.S. 4,525,524 Tung et al.; (III) anionic te.el)ht~l~late-based SRA's of the uletllallc-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl m~th~rrylate, including both nonionic and cationic polymers, see U.S.
4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters; these SRA'sassertedly have soil release and anti-redeposition activity similar to known cellulose ethers:
see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF
(1991); (VII) polyester-polyamide SRA's prepared by condensing adipic acid, caprolactam, and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al, DE

CA 022~4961 1998-11-17 W O97/44419 PCTrUS97/08317 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.

Other suitable soil release agents include materials with starch based backbones with polycarboxylic acid groups grafted thereto.

Bis-Alkoxylated Quaternary Arnmonium (bis-AQA) compound The second essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:

R~ /ApR
N X
R2/ AqR

wherein R1 is a linear, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether, glycityl ether moiety cont~ining from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably from 8 tol4 carbon atoms; R2 is an alkyl group cont~ining from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from the group consisiting of hydrogen (prefell~d), methyl and ethyl; X~ is an anion such as chloride, bromide, methyl sulfate, sulfate, sufficient to provide electrical neutrality. A and A' can vary independently and are each selected from C1-C4 alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, most preferably 1 to 4 and ~ is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, most preferably 1 to 4. Most preferably both p and q are 1.

Bis-AQA compounds wherein the hydrocarbyl substituent R1 is Cg-C12, especially Cg-C1o, enhance the rate of dissolution of laundry granules, especially under cold water conditions, as compared with the higher chain length materials. Accordingly, the Cg-C12 bis- AQA surfactants may be preferred by some formulators. The levels of the bis-AQA
surf~ct~nt.c used to prepare finich~d laundry detergent compositions can range from 0.1 % to 5%, typically from 0.45% to 2.5%, by weight. The weight ratio of bis-AQA to percarbonate bleach is in the range of from 1:100 to 5:1, preferably from 1:60 to 2:1, most preferably from 1: 20 to 1: 1.

CA 022~4961 1998-11-17 W O97144419 PCT~US97/08317 The present invention employs an "effective amount" of the bis-AQA surfactants to improve the performance of cleaning compositions which contain other optional ingredients. By an "effective amount" of the bis-AQA surfactants herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90%
confi-lenre level, the pelrolll ance of the cle:?ning composition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use sufficient bis-AQA to at least directionally irnprove cleaning performance against such stains. Likewise, in a composition whose targets include clay soil, the formulator will use sufficient bis-AQA to at least directionally improve cleaning performance against such soil.

The bis-AQA surfactants may be used in combination with other detersive surf~ct~ntc 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 t~ alure, 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 minutes and a wash water leml)eldture 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 bis-AQA surfactant in the wash li4uor. On the basis of usage rates of from 50 rnl to 150 ml per wash load, this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.1% to 3.2%, preferably 0.3% to 1.5%, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 60 g to 95 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g/l) this translates into an in-product concentration (wt. ) of the bis-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 bis-AQA surfactant of from 0.1% to

3 .5 %, preferably from 0.3 % to 1.5 % .

For example, in a front-loading, horizontal-axis European-type automatic washing machine using 8 to 15 liters of water in the wash bath, a wash cycle of 10 to 60 minutes and a wash water temperature of 30~C to 95~C, it is preferred to include from 13 ppm to .. . .. ..

CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 900 ppm~ preferably from 16 ppm to 390 ppm, of the bis-AQA surfactant in the wash liquor. On the basis of usage rates of from 45 ml to 270 ml per wash load, this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.4% to 2.64%, preferably 0.55 % to 1.1 %, for a heavy-duty liquid laundry detergent. On the basis of usage rates of from 40 g to 210 g per wash load, for dense ("compact") granular laundry d~telgellt~. (density above 650 g/l) this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.5 % to 3.5 %, preferably from 0.7 % to 1.5 %. On 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 bis-AQA surfactant of from 0.13 % to 1.8%, preferably from 0.18 % to 0.76 % .

For example, in a top-loading, vertical-axis Japanese-type automatic washing machine using 26 to 52 liters of water in the wash bath, a wash cycle of 8 to lS minutes and a wash water temperature of 5~C to 25~C, it is preferred to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the bis-AQA surfactant in the wash liquor. On 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 bis-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.) of the bis-AQA surfactant of from 0.25% to 10%, preferably from 0.5% tol.0%. On the basis of usage rates of from 30 g to 40 g per load for spray-dried granules (i.e., "fluffy"; density below 650 g/l), this translates into an in-product concentration (wt.) of the bis-AQA surfactant of from 0.25% tolO%, preferably from 0.5% to 1 %.

As can be seen from the foregoing, the amount of bis-AQA surfactant used in a m~rhin~-wash laundering context can vary, depending on the habits and practices of the user, the type of washing machine. In this context, however, one heretofore unappreciated advantage of the bis-AQA surfart~nts is their ability to provide at least directional improvements in pe.rollllallce over a spectrum of soils and stains even when used at relatively low levels wit~i respect to the other surfactants (generally anionics or anionic/nonionic mixtures) in the fini.sh~ 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 bis-AQA:anionic surfactant in laundry compositions is in the range from CA 022~4961 1998-11-17 W O97/44419 PCT~US97/08317 13 1:70 to 1:2, preferably from 1:40 to 1:6, preferably from 1:30 to 1:6, most preferably 1:15 to 1:8. In laundry compositions which comprise both anionic and nonionic surf~ct~nt.c, the weight ratio of bis-AQA:mixed anionic/nonionic is in the range from 1:80 to 1:2,preferably 1:50 to 1: 8 .

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

In contrast with other cationic surfactants known in the art, the bis-alkoxylated cationics herein have sufficient solubility that they can be used in combination with mixed surfactant systems which are quite low in nonionic surfactants and which contain, for example, alkyl sulfate surfactants. This can be an important consideration for formulators of detergent compositions of the type which are conventionally designed for use in top loading automatic washing m~ inPs, especially of the type used in North America, as well as under J~panPse usage conditions. Typically, such compositions will comprise an anionic surfactant:nonionic surfactant weight ratio in the range from about 25:1 to about 1:25, preferably about 20:1 to about 3:1. This can be contrasted with European-type formulas which typically will comprise anionic:nonionic ratios in the range of about 10:1 to 1:10, preferably about 5:1 to about 1:1.

The preferred ethoxylated cationic surfactants herein are available under the trade name ETHOQUAD from Akzo Nobel Chemicals Company. Alternatively, such materials can besynthesized using a variety of different reaction schemes (wherein "EO" represents -CH2CH2O- units~, as follows.

... .. . .. . . ~ .

CA 02254961 1998-ll-17 W O 97/44419 PCT~US97/08317 RIOH + N H3 H2/Cat/HeatRl N ~H
EXC ES S

R--N~ + 2 n~ BASECat, Rl N--~(EO)nHl2 R--N--[(EO)nH]2 + CH3CI ~Rl N--¦(Eo)nH]2 CH3 cr 'N--[(EO) Hk + C H2 Cat ~ ~N--[(Eo)2H]2 Br + N--[(EO)2H]2 HEAT, Rl N--[(EO) H]
CH3 Br [( )2 ]2 H' 'H HÉAT

R Br + N--[(EO)2H]2 HEAT ~ Rl N--[(EO) H]
CH3 Br CA 02254961 1998-ll-17 Cl--CH,CH2--OH + n~ ~ Cl--CH,CH2O[EO]n--H

R N~CH + 2 Cl--CH2CH20[EO]n--H HEAT~ RIN-[CH,CH O~EO] H]

An economical reaction scheme is as follows.

Rl OSO3~Na + H-N--[(EO)H]2 HEAT ~ R--N--[(EO)Hl2 Rl N--[(EO)H]~ + 2 n~ HEAT ~ R--N--[(EO)(EO)nHl2 Rl N--[(EO)(EO)nH]2 + CH3CI ~ R--I--[(EO)(EO)nH]2 CH3 cr The following pal~l.eters sl~mm~rize the optional and preferred reaction conditions of Scheme 5. Step 1 of the reaction is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 140-200~C. Reaction pressures are 50-1000 psig.
A base catalyst, preferably sodium hydroxide can be used. The mole ratio of react~nt.c are 2:1 to 1:1 amine to alkyl sulfate. The reaction is preferably con~ cte~l using Cg-C14 alkyl sulfate, sodium salt. The ethoxylation and quaternization steps are carried out using conventional conditions and re~ct~nt.c.

Under some circumstances reaction Sch~ S results in products which are sufficiently soluble in the aqueous reaction me~ m that gels may forrn. While the desired product can be recovered from the gel, an alternate, two-step synthesis Scheme 6, hereinafter, may be CA 022~4961 1998-11-17 W O 97/44419 PCT~US97/08317 more desirable in some commercial circumstances. The first step in Scheme 6is conducted as in Scheme 5. The second step (ethoxylation) is preferably conducted using ethylene oxide and an acid such as HCI which provides the ~uaternary surfactant. As shown below, chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative.

For reaction Scheme 6, the following parameters summarize the optional and ~lefe.led reaction conditions for the first step. The first step is preferably con~ ctec~ in an aqueous mP~ lm. Reaction temperatures are typically in the range of 100-230~C. Reaction pressures are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react with the HSO4-generated during the reaction, or an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1:1.1; more preferably from 2:1 to 1:1. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble. The second step of the process is con~uctecl under conventional reaction conditions. Further ethoxylation and quaternization to provide bis-AQA surfactants are conducted under standard reaction conditions.

Sch~-nP 7 can optionally be con~ucte~l using ethylene oxide under standard ethoxylation conditions, but without catalyst, to achieve monoethoxylation.

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

Scheme 6 H

Rl OSO3~Na+ + H,N--CH2CH2-OH~ R--N--CH2CH2-OH

IH ,CH2CH20H
R NCH2CH2OH + ClCH2CH2OH ~ R N
CH2CH,OH
Scheme 7 CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 ~ ,CH2CH~OH
Rl N--CH2CH2OH NoCatalyst ~Eot~

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

Synthesis A
Preparation of N~N-Bis(2-hydroxyethyl)dodecylamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of diethanolamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H20. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 34 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then the mixture is allowed to separate. The lower chloroform layer is drained and the chloroform evaporated off to obtain product.
Synthesis B
Preparation of N~N-Bis(2-hydroxYethyl)dodecylamine 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of base in the manner described in Synthesis A. The resulting 2-hydroxyethyldodecylamine is recovered and reacted with l-chloroethanol to prepare the title compound.

S~/nthesis C
r~ a~tion of N~N-Bis(2-hydroxyethYl)dodecYlamine To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate ~0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of flj~tillecl H20. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180~C under 300400 psig nitrogen for 34 hours. The mixture is cooled to room teln~elature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then allowed mixture to separate. The lower chloroform .. , . ..... ~

CA 022~496l l998-ll-l7 W O 97/44419 PCTrUS97/08317 layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120-130~C to produce the desired final product.

The bis-substituted amines prepared in the foregoing Syntheses can be further ethoxylated in standard fashion. Quaternization with an alkyl halide to form the bis-AQA surf~ct~ntc herein is routine.

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

Desi~nation Bl _2 ApR3 A~qR4 bis-AQA-1 C12-C14 CH3 EO EO
(also referred to as Coco Methyl EO2) bis-AQA-2 C12-C16 CH3 ~EO~2 EO

bis-AQA-3 C12-C14 CH3 ~EO~2 ~EO~2 (Coco Methyl EO4) bis-AQA4 Cl2 CH3 EO EO

bis-AQA-5 C12-C14 CH3 ~EO~2 (EO)3 bis-AQA-6 C12-C14 CH3 (EO)2 (EO)3 bis-AQA-7 Cg-Clg CH3 (EO)3 (EO)2 bis-AQA-8 C12-C14 CH3 (EO)4 (EO)4 bis-AQA-9 C12-C14 C2H5 (EO)3 (EO)3 CA 02254961 1998-ll-17 W O 97/44419 PCTrUS97/08317 bis-AQA-10 C12-C18 C3H7 (EO)3 (EO)4 bis-AQA-11 C12-C18 CH3 (propoxy) (EO)3 bis-AQA-12 C1o~C18 C2H5 (iso-propoxy)2 (EO)3 bis-AQA-13 C1o~C18 CH3 (EO/PO)2 (EO)3 bis-AQA-14 Cg-C1g CH3 (EO)15* (EO)15*

bis-AQA-15 C1o CH3 EO EO

bis-AQA-16 Cg-C12 CH3 EO EO

bis-AQA-17 Cg-C11 CH3 ~ EO 3.5 Avg. -bis-AQA-18 C12 CH3 ~ EO 3.5 Avg. -bis-AQA-19 Cg-C14 CH3 ~E~~10 (EO)1o bis-AQA-20 C1o C2H5 ~EO~2 (EO)3 bis-AQA-21 C12-C14 C2H5 (EO)5 (EO)3 bis-AQA-22 C12-C18 C3H7 Bu (EO)2 *Ethoxy, optionally end-capped with methyl or ethyl.

Highly ~lere.lcd bis-AQA compounds for use herein are of the formula;

Rl /CH2CH2OH
N X(~' CH3/ \CH2CH2OH

CA 022~4961 1998-ll-17 W O97/44419 PCTrUS97/08317 wherein Rl is Cg-C1g hydrocarbyl and mixtures thereof, preferably Cg, Clo, C12, C14 alkyl and mixtures thereof. X is any convenient anion to provide charge balance,preferably chloride. With l~felellce to the general bis-AQA structure noted above, since in a prefelled compound R1 is derived from coconut (C12-C14 alkyl) fraction fatty acids, R2 is methyl and ApR3 and A'qR4 are each monoethoxy, this preferred type of compound is referred to herein as "CocoMeE02" or "bis-AQA-l" in the above list.

Other bis-AQA surf~rt~nt~ useful herein include compounds of the forrnula:

R\ ~(CH~CH~O)pH

R (CH~CH~O)qH

wh~leh~ R1 is Cg-Clg hydrocarbyl, preferably Cg-C14 alkyl, independently p is 1 to 3 and q is 1 to 3, R2 is Cl-C3 alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

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

A highly preferred bis-AQA compound for use in under built formulations are of the forrnula wherein p and/or q are integers in the range of between 10 and 15. Thiscompound is particularly useful in laundry handwash detergent compositions.

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

Anionic Surfactant CA 022~4961 1998-ll-17 Nonlimitin~ examples of anionic surfactants useful herein typically at levels from 1% to 55%, by weight, include the conventional C11-C1g alkyl benzene sulfonates ("LAS") and prirnary ("AS"), branched-chain and random Clo-c2o alkyl sulfates, the C1o-Clg secondary (2~3) alkyl sulfates of the formula CH3(CH2)X(CHOSo3 M+) CH3 and CH3 (C~I2)y(CHOS03 M+) CH2CH3 where x and (y + 1) are integers of at least 7, preferably at least 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C12-C1g alpha-sulfonated fatty acid esters, the C1o-CIg sulfated polyglycosides, the C1o-C1g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), and the C1o-C1g alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The C12-C1g betaines and sulfobetaines ("sultaines"), C1o-C1g amine oxides, can also be included in the overall compositions. C1o-C20 conventional soaps may also be used. If high sudsin~ is desired, the branched-chain C1o-C16 soaps may be used. Other conventional useful surfactants are listed in standard texts.

Nonionic Surf~t~ntc Nonlimiting examples of nonionic surfactants useful herein typically at levels from 1% to 55%, by weight include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C1o-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 con~en~ation products of alcohols having an alkyl groupcont~ining from 8 to 20 carbon atoms, more preferably from 10 tol8 carbon atoms, with from 1 tolO moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include:
TergitolTM 15-S-9 (the condensation product of Cl 1-Cls linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of C12-C14 primary alcohol with 6 moles ethylene oxide with a narrow 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-C1s linear alcohol with 7 moles of .. .... . . .... . . . ..

CA 022~4961 1998-11-17 W O 97/44419 PCT~US97/08317 ethylene oxide) and NeodolTM 45-5 (the condensation product of C14-C1s linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 or 050 (the condensation product ofC12-C14 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst. The preferred range of HLB in these AE nonionic surfactants is from 8-11 and most preferred from 8-10.
Condensates with propylene oxide and butylene oxides may also be used.

Another class of preferred nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
R2 fi--I --z.
O R

wherein Rl is H, or Cl 4 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 connPctecl to the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a straight C11 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 ~min~tion reaction. Typical examples include the C12-C1g and C12-C14 N-methylgll-c:lmi~lec. 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, 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 cont~ining 5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl moieties can be substituted for the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, e.g., between the one position of the additional saccharide units and the 2-, 3-, 4-, and/or 6-positions on the prece~ing saccharide units.

CA 022~4961 1998-11-17 W O97/44419 PCTrUS97/08317 The preferred alkylpolyglycosides have the formula:

R20(CnH2nO)t(glycosyl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3to 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 formed first and then reacted with glucose, or a source of glucose, to form the glucoside (~tt~rhm~nt at the l-position). The additional glycosyl units can then be att~h~ cl between their 1-position and the prece~lin~ glycosyl units 2-, 3-, 4- and/or 6-position, preferably predominately the 2-position.

Polyethylene, polypropylene, and polybutylene oxide con~en.~tes 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~inin~ from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from 2 to 25 moles, more preferably from 3 tolS moles, of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfart~nt.c of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X45, X-l 14, X-100 and X-102, all marketed by the Rohm & Haas Company.
These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).

The con-tPn~a~ion products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular wei~ht of from lS00 to 1800 and will exhibit water insolubility. The addition of polyoxyethylene moieties to this hydrophobic portion tends to increase the water solubility of the molecule as a whole, and the liquid character of the product is retained up to the point where the polyoxyethylene content is 50% of the .. . .. . .. .

CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97/08317 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 certain of the commercially-available PluronicTM surfactants, marketed by BASF.

Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product re~lllting from the reaction of propylene oxide and ethylenf~ min~. The hydrophobic moiety of these products consists of the reaction product of ethylen~ minP 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. Exarnples of this type of nonionic surfactant include certain of the cornmercially available TetronicTM compounds, marketed by BASF.

Additional Cationic surfactants Suitable cationic surfart~ntc 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 surf~ct~nt~ 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 ester surfactants, have for example been disclosed in US Patents No.s 4228042,4239660 and 4260529.

Optional Dele~enL In~redients 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.

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 CA 022~4961 1998-11-17 W O 97/44419 PCT~US97108317 or to assist in the removal of particulate soils from surfaces. Builders can operate via a variety of mech~ni~m~ 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 formulations typically comprise 5% to 50%, more 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 or higher levels of builders are not excluded. For example, certain d~tel~ellt additive or high-surfactant formulations can be unbuilt.

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

Builder mixtures, som~im~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 qll~ntities of materials herein. In terms of relative qu~ntitieS of surfactant and builder in the present detergents, preferred builder systems are typically forrnl~l~te~ 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

P-cont~ining detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of .. ~ ~ ... ... . .

CA 022~496l l998-ll-l7 polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.

Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a 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 BRITESIL~, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, som~tim~s abbreviated "SKS-6", is a crystalline layered ah-rninil~m-free ~-Na2SiOs morphology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A-3,417,649 and DE-A-3,742,043. 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 ~ ,lber 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 y layer-silicate forms. Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.

Also suitable for use herein are synthesized crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM2O ySiO2.zM'O wherein M is Na and/or K, M' is Caand/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 ~Ik~linto earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicall,ollate, sodium carbonate, sodium sesquicarbonate, and other carbonate rninerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2CO3.CaCO3 when anhydrous, andeven calcium carbonates including calcite, aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be use~ul, for example as seeds or for use in synthetic detergent bars.

CA 022~4961 1998-ll-17 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 symh,oti~ y derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available as Zeolite A, Zeolite P (B), Zeolite X and, to whatever extent this differs from Zeolite P, the so-called Zeolite MAP. Natural types, including clinoptilolite, may be used. Zeolite A has the formula: Nal2[(AlO2)12(SiO2)121 xH2O wherein x is from 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in ~ m~ter.

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 form~ e~ in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithillm, or alkanolammonium salts are preferred. Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128.287, April 7, 1964, and Lamberti et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S.

4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;
4,158,635; 4,120,874 and 4,102,903.

Other suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, S-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylen~ min~ 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.

CitMtes, e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.

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

Certain detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are s--mmrcl up as detersive surfactants. Preferred types for builder functionality are illustrated by: 3,3-dicarboxy4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. 4,566,984, 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-pent~(lecenylsuccinate. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November S, 1986. Fatty acids, e.g., C12-Clg 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 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 integer from 2 to 25, Mi are cations, at least one of which is a water-soluble, and the equation ~i = 1 ls(xi multiplied by the valence of Mj) + 2y = 2z is satisfied such that the formula has a neutral or "bal~nred" charge. These builders are referred to herein as "Mineral Builders" . Waters of hydration or anions other than ~ arbonate may be added provided that the overall charge is b~l~nred or neutral. The cha.ge or valence effects of such anions should be added to the right side of the above equation. Preferably, there is present a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more CA 022~4961 1998-ll-17 W O 97/~4419 PCT~US97/08317 preferably, sodium, potassium, hydrogen, lithium, amrnonium and mixtures thereof, sodium and potassium being highly preferred. Nonlimiting examples of noncarbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate and mixtures thereof.
Preferred builders of this type in their simplest forrns 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 material for the builder described herein is Na2Ca(CO3)2 in any of its crystalline mo-lifications. Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: Afghanite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite,Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite, Fr~n7inite, Gaudefroyite, Gaylussite, Girvasite, Gregoryite, Jouravskite, KamphaugiteY, Kettnerite, E~h~nn~shite, LepersonniteGd, Liottite, MckelveyiteY, Microsommite, Mroseite, Natrofairchildite, Nyerereite, RemonditeCe, Sacrofanite,Schrockingerite, Shortite, Surite, Tunisite, T~lcc~nite, Tyrolite, Vishnevite, and Zernkorite.
Preferred mineral forrns include Nyererite, Fairchildite and Shortite.

Bleach The compositions described herein may contain a bleach. When present, such bleaching agents will typically be at levels of from 1% to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering.

In one prer~,l,ed aspect the ble~hin~ system contains a hydrogen peroxide source and a bleach catalyst. The production of the organic peroxyacid occurs by an in situ reaction of the bleach activator with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In an alternative plefcl,ed aspect a preformed peracid is incorporated directly into the composition. Compositions cont~ining mixtures of a hydrogen peroxide source and bleach activator in combination with a preformed peracid are also envisaged Preferred peroxygen bleaches are perhydrate bleaches. Although the perhydrate bleach itself has some ble~rhing capability, a superior bleach exists in the peracid forrned as a product of the reaction between the hydrogen peroxide released by the perhydrate and a ...... , . . ..... ~ ~, . .. . . . . . ... ....

CA 022~4961 1998-11-17 W 097/44419 PCT~US97/08317 bleach activator. Preformed peracids are also envisaged as a preferred peroxygen ble~hing species.
Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. The preferred perhydrate salts are normally the alkali metal salts. The perhydrate salt may be included as the crystalline solid without additional protection. For certain perhydrate salts however, the pl~r~.led 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 NaBO2H2O2 or the tetrahydrate NaBO2H2O2.3H2O.
Alkali metal percarbonates. particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available cornmercially 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 concentlations to arise. A
preferred ~,elcall,orlate bleach comprises dry particles having an average particle size in the range from 500 micrometers to 1,000 micrometers, not more than 10% by weight of said particles being smaller than 200 micrometers and not more than 10% by weight of said particles being larger than 1,250 micrometers.
The percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability. 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 morganics), waxes, oils, fatty soaps can also be used advantageously within the present lnvention.

A bleaching agent that can be used without restriction encompasses percarboxylic acid ble~ehin~ agents and salts thereof. Suitable examples of this class of agents include m~gn.osium monoperoxyphth~l~te hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino4-oxoperoxybutyric acid and diperoxydodec~n~dioic acid.
Such bleaclling agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November CA 022S4961 1998-ll-17 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985. European Patent Application 0.133,3S4, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleachinv agents also include 6-nonylarnino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634.5S1, issued January 6, 1987 to Burns et al.

Other suitable additional bleaching agents include photoactivated bleachin~ agents such as the sulfonated zinc and/or al~lmin~m 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.
Potassium peroxymonopersulfate is another inorganic perhydrate salt of utility in the compositions herein.

Mixtures of ble;~chin~ agents can also be used.

Bleach Activator Bleach activators are pre~lled components where the compositions of the present invention additionally comprise a peroxygen bleac~-ing agent. Bleach activators where present are typically at levels of from 0.1 % to 60%, more typically from 0.5 % to 40% of the ble~c~lin~ composition comprising the bleaching agent-plus-bleach activator.

Peroxygen bleachin~ agents, the perborates, etc., are preferably combined with bleach activators, which lead to the in sltu production in a~ueous solution (i.e., during the washing process) of the peroxy acid or peracid corresponding to the bleach activator.
Various nonlimitin~ 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 ~ 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 prefelled amido-derived bleach activators are those of the formulae:

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

CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 wherein R1 is an alkyl group cont~inin~ from 6 to I2 carbon atoms. R2 is an alkylene cont:~ining from 1 to 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl conr~ining from 1 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6-oct~n~mido-caproyl)oxybenzenesulfonate, (6-non~n~midocaproyl)oxybenzenesulfonate, (6-~1ec~n~mi-lo-caproyl)oxybenzenesulfonate, and mixnlres tnereof 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 ~.efel-ed activator of the benzoxazin-type is:

[~N~C~

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

O C--C H2--C H2, CH2--CH2~

R6--C--N~

W O 97/44419 PCT~US97/08317 wherein R6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group con~ining from 1 to 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoylcaprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactarn, lm~lecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium per~orate.

Bleach Catalvst Bleach catalysts are optional components of the compositions of the present invention. If desired, the bleaching compounds can be catalyzed by means of a m~ngan-~se compound.
Such compounds are well known in the art and include, for example, the rn~ng~n~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. 549,271A1, 549,272Al, 544,440A2, and544,490A1; PreferredexamplesofthesecatalystsincludeMnIV2(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, MnIV4(u-0)6(1,4,7-triazacyclononane)4(C104)4, MnIII~
MnIV4(u-O)l(u-OAc)2 (1,4,7-trirnethyl-1,4,7-triazacyclononane)2(C104)3, MnIV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat.

5,114,611. 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;
S,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, 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~e. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt . . ~

CA 022~496l l998-ll-l7 W O 97/44419 PCT~US97/08317 pent~min~ acetate salts having the formula [Co(NH3)sOAc] Ty~ wherein "OAc"
represents an acetate moiety and "Ty~ is an anion, and especially cobalt pent~mine acetate chloride, [Co(NH3)sOAc]Cl2; as well as [Co(NH3)sOAc](OAc)2;
[Co(NH3)sOAc](PF6)2; [Co(NH3)sOAc](SO4); [Co(NH3)sOAc](BF4)2; and [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),1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall; 1970),pp.461-3; Inor~. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inor~.
Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176(1960); and Journal of Physical Chemistrv, 56,22-25 (1952).

As a practical matter, and not by way of limit~rion, the automatic dishwashing compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing m.o~ -m, 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 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 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, of bleach catalyst, especially m~ng?ntose or cobalt catalysts, by weight of the cleaning compositions.

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

CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 "Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly plel~l,ed for automatic dishwashing are amylases and/or proteases.

Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware. In practical terms for current commercial preparations, typical amounts are up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5 %, preferably 0.01 %-1 % by weight of a co~ nelcial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain det~rgenls, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of the cornmercial preparation in order to minimi7~
the ~otal amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.

Suitable examples of proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. Iicheniformis. One suitable protease is obtained from a strain of A~cil/~s, having m~ximllm activity throughout the pH range of 8-12, developed and sold as ESPERASE~ by Novo Industries A/S of Denrnarlc, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE~ and SAVINASE$ from Novo and MAXATASE~ from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp~
NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in W O 97/44419 PCT~US97108317 WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A toProcter & Gamble . 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 detergents suitable herein is described in WO 9425583 to Novo.

In more detail, an especially preferred protease, referred to as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more arnino acid residue positions equivalent to those selected from the group consisting of +99, + 101, + 103, + 104, + 107, + 123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin. as described in the patent applications of A. Baeck, et al, entitled "Protease-Cont~ining Cleaning Compositions" having US Serial No. 08/322,676, and C. Ghosh, et al, "Ble~ching Compositions Comprising ProteaseEnzymes" having US Serial No. 08/322,677, both filed October 13, 1994.

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;
RAPIDASE~, International Bio-Synthetics, Inc. and TERMAMYL~9, Novo.
FUNGAMYLX from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol.
260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in de~elge~ such as automatic dishwashing types, especially improved oxidative stability as measured against a reference-point of TERMAMYL@~ in comrnercial use in 1993. These preferred amylases 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 hydrogen peroxide/tetraacetylethylenr~ min~ in buffered solution at pH 9-10; thermal stability, e.g., at common wash temperatures such as 60~C; or ~Ik~linr stability, e.g., at pH from 8 to 11, measured versus the above-identified reference-point arnylase. 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 Genencor International. One class of highly preferred arnylases herein have the W O 97/44419 PCT~US97/08317 cornmonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus a-amylases, regardless of whether one, two ot multiple amylase strains are the imme~ te precursors. Oxidative stability-enh~nrefl amylases vs. the above-identified reference amylase are preferred for use, especially in bleac~ in~, more preferably oxygen ble~ching, as distinct from chlorine bleaching, detergent compositions herein. Such preferred amylases include (a) an amylase 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, known as TERMAMYL(g), or the homologous position variation of a similar parent arnylase, such as B. anryloliquefaeiens, B. subtilis, or B. stearolhennophill~s; (b) stability-enh~nre~
amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C. Mitchinson. Therein it was noted that bleaches in automatic dishwashing detergents inactivate alpha-arnylases 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 m-lt~nt~, particularly important being M197L and M197T with the Mlg7T variant being the most stable expressed variant. Stability was measured in CASCADE~) and SUNLIGHT~'; (c) particularly pl~felled amylases herein include amylase variants having additional modification in the immPdi~t~ parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL(8;). Other particularly p~efe,l~d oxidative stability enh~n~ed arnylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enh~n~e~l amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forrns of available arnylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.

Other amylase enzymes include those described in WO 95/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056. Specific amylase enzymes for use in the detergelll compositions of the present invention include a-amylases characterized by having a specific activity at least 25 % higher than the specific activity of Termamyl(~) at a temperature range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. (Such Phadebas(~ a-amylase activity assay is CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 described at pages 9-10, WO 95/26397.) Also included herein are ~-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 deLelgelll 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
optirnum 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 cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME(~ and CELLUZYME~ (Novo) are especially useful. See also WO 9117243 to Novo.

Suitable lipase enzymes for detergent usage include those produced by microorg~ni~m.c of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB
1,372,034. See also lipases in 3apanese Patent Application 53,20487, laid open Feb. 24, 1978. This lipase is available from Amano Pharm~ce~ l Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," or "Arnano-P." Other suitable co~ elcial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;
Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE(~3) enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.

In spite of the large number of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as host has so far found widespread application as additive for fabric washing products. It is available from Novo Nordisk under the tradename LipolaseTU, as noted above. In order to optimize the stain removal performance of Lipolase, Novo Nordisk have made a number of variants. As CA 022F,4961 1998-11-17 described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter).
Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be added in an amount corresponding to 0.001-100- mg (5-500,000 LU/liter) lipase variant per liter of wash liquor. The present invention provides the benefit of improved whiteness mahllellallce on fabrics using low levels of D96L variant in detergent compositions con~ining the bis-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 ble:~chin~" or prevention of transfer of dyes or pigments removed from substrates during tne wash to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as ch~oro- 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.

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 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 detelgellt~ can be stabilised by various techni~ues. Enzyme stabilisation techniques are disclosed and exemplified in U.S.
3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S.
3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.

Enzyme Stabilizin~ System .... .... ... . .

CA 022~4961 1998-11-17 W O97/44419 PCT~US97/08317 The enZyme-con~inin~ 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~ctllrer 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 finich~l compositions which provide such ions to the enzymes. Calcium ions are generally more effective than magnesium ions and are preferred herein if only one type of cation is being used. Typical detergent compositions, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, though variation is possible depending on factors including the multiplicity, type and levels of enzymes incorporated. Preferably water-soluble calcium or magnesium salts are employed, including for example calcium chloride, calcium hydroxide, calcium forrnate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used.
Further increased levels of Calcium and/or Magnesium may of course be useful, for example for promoting the grease-cutting action of certain types of surfactant.

Another stabilizing approach is by use of borate species. See Severson, U.S. 4,537,706.
Borate stabilizers, when used, may be at levels of up to 10% or more of the composition though more typically, levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for liquid detergent use. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and reduced levels of total boron in detergent compositions may be possible though the use of such substituted boron derivatives.

Stabilizing systems of certain cleaning compositions, for example automatic dishwashing compositions, may further comprise from 0 to 10%, preferably from 0.01% to 6% by CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from ~ rking and inactivating the enzymes, especially under :~1k~1inP
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 cont~ining ammonium 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, forrnate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. ln general, since the chlorine scavenger function can be performed by ingredients separately listed under better recognized functions, (e.g., hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound performing that function to the desired extent is absent from an enzyme-cont~ining embodirnent of the invention; even then, the scavenger is added only for optimum results. Moreover, the forrnulator 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 salts can be simply admixed with the detergent composition but are prone to adsorb water and/or liberate ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in US 4,652,392, Baginski et al.

Polymeric Dispersin~ A~ents 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 CA 022~4961 1998-ll-17 and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release pe~ti;cation, and anti-redeposition.

Polymeric polycarboxylate materials can be plepared by polymeliGillg or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the polymeric polycarboxylates herein or monomeric segments, cont~ining no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitab1e 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, ammonium and substituted ammonium salts.Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.

Acrylic/maleic-based copolymers may also be used as a ~,~f~lled component of thedispelsillg/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of suchcopolymers 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 65,00(~. The ratio of acrylate to m~ t~ segments in such copolymers will generally range f.~om 30:1 tol: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/m~le~te copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97/08317 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 45/45/10 terpolymer of acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent perfo~nance 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 polygl~lt~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.

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

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene-pen~minP. 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 4,1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2, 1990 and WO 95/32272, published November 30, 1995.

., . , , _. _ .~ , . . " .. . . . ...

CA 022~496l l998-ll-l7 W O 97/44419 PCTrUS97/08317 Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.

Brightener 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. Con~,llelcial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not n~cess~rily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brightel1e.s include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, the 2-(4-styryl-phenyl)-2H-naptho[1,2-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 include 4-methyl-7-diethyl- amino coumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naptho[1,2-d]oxazole;
and 2-(stilben4-yl)-2H-naphtho[1,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton.

Dye Transfer Inhibitin~ Agents The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process.
Generally~ such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers~
polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimi-~701e, m~ng~nlose phthalocyanine, peroxidases, and mixtures thereof. If used, these agents CA 022~4961 1998-11-17 W O 97144419 PCTrUS97108317 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 l~lcfelled for use herein contain units having the following structural formula: R-AX-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and ~ is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be at~ch~d or the N-O group is part of these groups. P~efe~l~d polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

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

O O
(R~ (R2)y; --N--(Rl )x (R3)z wherein Rl, 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 alt~ch~od or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa C 10, preferably pKa < 7, more preferred pKa < 6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to CA 022~496l l998-ll-l7 W O 97/44419 PCT~US97/08317 1,000,000; more preferred 1,000 to 500,000; most plere-led 5.000 to 100,000. This preferred class of materials can be referred to as "PVNO".

The most ~lefelled polyamine N-oxide useful in the de~elgent compositions herein is poly(4-vinylpyridine-N-oxide) which has an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1 :4.

Copolymers of N-vinylpyrrolidone and N-vinylimi-1~7O1e polymers (referred to as a class as "PVPVI") are also preferred for use herein. PrefeMbly the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scattering as described in Barth, et al., Chemical Analysis, Vol 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 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 200,000, and more preferably from 5,000 to 50,000. PVP's are known to persons skilled in the de~ gel,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 is from 2:1 to 50:1, and more preferably from 3:1 to 10:1.

The de~ ge,lL 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 1 % by weight of such optical brighteners.

The hydrophilic optical brigllle~ s useful in the present invention are those having the structural formula:

CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 Rl R

R2 SO3M SO3M Rl 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.

Wherl in the above formula, R1 is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt. This particular brightener species is commercially marketed under the tra~len~mP Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergelll compositions herein.

When in the above formula, R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M
is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilbenPdic~llfonic acid disodium salt. This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.

When in the above forrnula, R1 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'-stilbenPAi~ulfonic acid, sodium salt. This particular brightener species is commercially marketed 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 with the selected polymeric dye tlal~sfel inhibiting agents hereinbefore described. The combination of such selected polymeric materials (e.g., PVNO and/or PVPVI) with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) provides si_nificantly better dye transfer inhibition in aqueous wash solutions than does either of these two detergent composition components when used alone. Without CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97/08317 being bound by theory, it is believed that such brighteners work this way because they have high affinity for fabrics in the wash solution and therefore deposit relatively quick on these fabrics. The extent to which brighteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is in general as the ratio of a) the brightener material deposited on fabric to b) the initial brightener concentration in the wash li~uor. Brighteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.

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

Chelatin~ Agents The dt:lelgellt compositions herein may also optionally contain one or more iron and/or m~n~nrse chelating agents. Such chelating agents can be selected from the group con.ci.~ting 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 formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenrf~ nillr~elldret~
N-hydroxyethylethylçnP~ minrtri~ret~tes, nitrilotriacetates, ethylenr~ minP
telldplo~lionates, triethylenet~ min~ohpx~ret~trs~ diethylenetriaminepent~ret~tes, and ethanoldiglycines, alkali metal, allllllonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelatin~ agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylen~ minptçtrakis (methylenephosphonates) as DEQUEST.
Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than

6 carbon atoms.

CA 022~4961 1998-11-17 W O 97/44419 PCT~US97/08317 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 plef~ d biodegradable chelator for use herein is ethylen~ minlo disuccinate ("EDDS"), especially the lS,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

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

If utilt7ed~ these chelating agents will generally comprise from 0.1 % to 15 % by weight of the d~lergel~l compositions herein. More preferably, if uti~i7Pd, the ch.o!~ting agents will comprise from 0.1 % to 3.0% by weight of such compositions.

Suds Suppressors Compounds for reducing or supplessillg the formation of suds can be incorporated into the compositions of the present invention. Suds suppression can be of particular importance in the so-called "high concentration cle~ning 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 ofCh~mical 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 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

.. ~ .. . .. .. . . .

CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 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 C1g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelQmin~s or di- to tetra-alkyl~ min~ chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~inin~ l to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters. The hydrocarbons such as paraffin and haloparaffm can be utilized in liquid form. The liquid hydrocarbons will be liquid at room te~ eldl~lre and atmospheric pressure, and will have a pour point in the range of 40~C and 50~C, and a ~ boiling point not less thanllO~C (atmospheric ~l.,ssule). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100~C. The hydrocarbons constitute a plefelled category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocall,ons, thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from 12 to 70 carbon atoms. The term "paraffin," as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone suds ~ essors 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 Euro~all Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.

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

Mixtures of silicone and silanated silica are described, for in.ct~nre, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 detel~,ell~ compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S.
Patent 4,652,392, R~ginc--i et al, issued March 24, 1987.

An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essen~i~lly of:
(i) polydirnethylsiloxane fluid having a viscosity of from about 20 cs. to about 1,500 cs. at 25~C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) of siloxane resin composed of (CH3)3SiO1/2 units of SiO2 units in a ratio of from (CH3)3 SiOl/2 units and to SiO2 units of from about 0.6:1 to about 1.2:1; and (iii) from about l 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 contin~lol~s phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinKed and preferably not linear.

To illustrate this point further, typical liquid laundry de~erg~l-l 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 primaryallliro~ll agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a ~mely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates;
(2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol. Similar amounts can be used in granular compositions, gels, etc. See also U.S. Patents 4,978,471, Starch, issued Dec.omber 18, 1990, and 4,983,316, Starch, issued January 8, 1991, 5.288,431, Huber et al., issued February 22, 1994, and U.S. Patents 4,639,489 and 4,749,740, Aizawa et al at column 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular ~ , CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.

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

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

Other suds su~plessors 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 suy~ressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.

For any delelgelll 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 m.och~ni~m of the dishwasher. Suds suppressors, when utili7e~, are preferably present in a "suds suppressing amount. By "suds SUppiCSSillg 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 detelgenl~ 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 su~ essors~ monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to 5 %, by weight, of the detergent composition.

CA 022~4961 1998-ll-17 W O 97/44419 PCTrUS97/08317 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.od 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 pelcen~ge values include any silica that may be utilized in conlbi~ ion with polyorganosiloxane, as well as any optional materials that may be utilized. Monostearyl phosphate suds ~u~l)ressors are generally utilized in amounts ranging from 0.1 % to 2 %, by 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 fini~h~d 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.
ChPmic~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 molecular weight can vary, but is typically in the range of 2000 to 50,000. Such alkoxylated polycarboxylates can comprise from 0.05% to 10%, by weight, of the compositions herein.

Fabric Softeners Various through-the-wash fabric softeners, especially the imr~lp~ble smectite clays of U.S.
Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from 0.5% to 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning. Clay softeners can be used in combination with amine and cationic softeners as disclosed, for exarnple, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued Sel)te.nbcr 22, 1981 ... ... . . . .

CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97/08317 Perfumes Perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chPmir~l 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, b~lc~mi~ essence, sandalwood oil, pine oil, cedar. Finished perfumes can comprise extremely complex mixtures of such ingredients.
Finished perfumes typically comprise from 0.01% to 2%, by weight, of the detergent compositions herein, and individual perfumery ingredients can comprise from 0.0001% to 90% of a finichPd perfume composition.

Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphth~le~o; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-tlilllt~hyl-2,5,9-cyclodo~3~Pc~trien-1-yl ketone; 7-acetyl-i,1,3,4,4,6-h~ m~thyl 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-t~ll al~ yl indane; 1 -dodecan~ 1, 4-(4-hydroxy4-methylpentyl)-3-cyclohexene- 1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-undecen-1-al; iso-hexenyl cyclohexyl carboxaldehyde; formyl tricyclodecane; condensation products of hydroxycitronellal and methyl anthranilate, con~lPnc~tion products of hydroxycitronellal and indol, condensation products of phenyl acet~ldPhyde and indol; 2-methyl-3-(para-tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinn~mic aldehyde; amyl cinn~mic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; coumarin; dcc~ tone g~mm~; cyclopent~ec~nolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro4,6,6,7,8,8-h.ox~m~othylcyclopenta-gamma-2-benzopyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.

Particularly plef~ d pelru,lle materials are those that provide the largest odorimprovements in fini.ch~?d product compositions cont~ining cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97/0~317 butylphenyl)-propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene; benzyl salicylate; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; para-tert-butyl cyclohexyl acetate; methyl dihydro jasmonate; beta-napthol methyl ether; methyl beta-naphthyl ketone; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-he~anletllyl-cyclopenta-gamma-2-benzopyrane; dodecahydro-3a~6~6~9a-tell~ ylnaphtho[2~lb]furan; ~ni~ Phyde; coumarin; cedrol; vanillin;
cyclopent~dec~nolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.

Other perfume materials include essenti~l oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olibanum resinoid, styrax, labdanum resin, nutmeg, cassia oil, benzoin resin, coriander and lavandin. Still other perfume chPmir~lc 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 finichlq~ perfume compositions.

Other In~redients A wide variety of other ingredients useful in del~rgell~ compositions can be included in the compositions herein, including other active ingredients, carriers, hydloL~,pes, processing aids, dyes or pigmPnt~, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C10-cl6 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C1o-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters. Use of such suds boosters with high sudsing optional surfact~nt~ such as the amine oxides, betaines and sultaines noted above is also advantageous. If desired, water-soluble m~ Psiulll and/or calcium salts such as MgC12, MgSO4, CaC12 CaS04, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enh~nre grease removal performance.

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

CA 022~4961 1998-ll-17 W O97/44419 PCT~US97/08317 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%-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 500-12,500 can be used). The res~lting silicone oil dispersion is emulsified or otherwise added to the final dc~elge~ll matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfart~nt~ can be "protected" for use in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols exemplified by m~th~nol, 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 form~ t~d such that, during use in aqueous cleaning operations, the wash water will have a pH of between 6.5 and 11, preferably between 7.5 and 10.5. Liquid dishwashing product formulations preferably have a pH between 6.8 and 9Ø Laundry products are typically at pH 9-11. Techniques for controlling pH at recomm~n~l~d usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Granules Manufacture Adding the bis-alkoxylated cationics of this invention into a crutcher mix, followed by conventional spray drying, helps remove any residual, potentially malodorous, short-chain amine cont~min~nt~. In the event the formulator wishes to prepare an admixable particle cont~ining the alkoxylated cationics for use in, for example, a high density granular de~lgellt, it is prcf~llcd that the particle composition not be highly ~Ik~lin-o. Processes for preparing high density (above 650 g/l) granules are described in U.S. Patent 5,366,652.

CA 022~4961 1998-11-17 W O 97/44419 PCT~US97/08317 Such particles may be form~ ted to have an effective pH in-use of 9, or below, to avoid the odor of impurity amines. This can be achieved ~y adding a small arnount of acidity source such as boric acid, citric acid, or the like, or an ~ppropliate pH buffer, to the particle. In an alternate mode, the prospective problems associated with amine malodors can be masked by use of perfume ingredients, as disclosed herein.

Exam~les In the following examples, the abbreviated component identifications have the following me~ning.S

LAS : Sodium linear C12 allcyl benzene sulfonate TAS : Sodium tallow alkyl sulfate C45AS : Sodium C14-Cls 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 ethylene oxide C25E5 : A C12 15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CocoEO2 : R1.N+(CH3)(C2H4OH)2 with R1 - C12 - C14 Soap : Sodium linear alkyl carboxylate derived from an 80/20 mixture of tallow and coconut oils~
TFAA : C16-C1g 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 from 0.1 to 10 miclonletels NaSKS-6 : Crystalline layered silicate of formula ~ -Na2Si2o5 . ,, ~

CA 022~4961 1998-ll-17 W O 97/44419 PCT~US97/08317 Citric acid : Anhydrous citric acid Carbonate : Anhydrous sodium carbonate with a particle size between 200,um and 900~m Bicarbonate : Anhydrous sodium bicarbonate with a particle size di~l~ibulion between 400~1m and 1200~1m 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 ~m 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 Amylase : Amylolytic enzyme of activity 60KNU/g sold by NOVO Industries A/S under the tradename Termamyl 60T
Lipase : Lipolytic enzyme of activity 100}cLU/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 PBl : Anhydrous sodium perborate bleach of nominal formula NaBO2.H2O2 Percarbonate : Sodium Percarbonate of nominal formula CA 022~4961 1998-11-17 W O 97/44419 PCT~S97/08317 2Na2C03 ~3H2~2 NOBS : Nonanoyloxyben_ene sulfonate in the forrn of the sodium salt.
TAED : Tetraacetylethylen.o(~i~min~
DTPMP : Diethylene triamine penta (methylene phosphonate), rnarketed 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 Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-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 viny~imi-1~701e 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 antifoarn: 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.

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

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

CA 022~496l l998-ll-l7 W O 97/44419 PCTrUS97/08317 EXAMPLE I

The following detergent formulations according to the present invention are prepared, where A and C are phosphorus-cont~ining detergent compositions and B is a zeolite-cont~inin~ detel~ellt composition.
B 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 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 SRA1 0.3 0 3 0-5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray On C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 ~lrullR 0 3 0 3 0 3 Dry additives Carbonate 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PB1 4.0 4.0 0 TAED 3.0 3.0 1.0 Photoactivated bleach 0.02 0.02 0.02 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 Dry mixed sodium sulfate 3.0 3.0 5.0 CA 02254961 1998-ll-17 nre (Moisture &
Miscellaneous) To: 100.0 100.0 100.0 Density (g/litre) 630 670 670 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surf~rt~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfactants herein.

EXAMPLE II

The following nil bleach-cont~ining detergent formulations are of particular use in washing colored clothing.
D E F
Blown Powder Zeolite A 15.0 15.0 2.5 Sodium sulfate 0.0 5.0 1.0 LAS 2.0 2.0 CocoMeEO2* 1.0 1.0 1.5 DTPMP 0.4 0.5 CMC 0.4 0.4 MA/AA 4.0 4.0 Agglomerates C45AS - - g.o LAS 6.0 5.0 2.0 TAS 3.0 2.0 Silicate 4.0 4.0 Zeolite A 10.0 15.0 13.0 CMC - ~ 0 5 SRA 1 0.3 0.2 0.4 MA/AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray On Perfume 0-3 0 3 0 5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry additives ._,. . ,~

CA 022~496l l998-ll-l7 W O97/44419 PCT~US97/08317 MA/AA - 3 o NaSKS-6 - - 12 .0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI/PVNO 0.5 0 5 0 5 Alcalase 0.5 0 3 0 9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 9.0 0.0 Ral~nre (Moisture &
Miscellaneous) To:100.0 100.0 100.0 Density (g/litre) 700 700 850 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA
surf~rt~ntc herein.

EXAMPLE III

The following detergent forrnulations, according to the present invention are ple~dled:
G H
Blown Powder Zeolite A 30.0 22.0 6.0 Sodium sulfate 19.0 5.0 7.0 MA/AA 3.0 3.0 6.0 LAS 13.0 11.0 21.0 C45AS 8.0 7.0 7.0 CocoMeEO2* 1.0 1.0 1.0 Silicate - 1.0 5.0 Soap - - 2.0 SRA 2 0.1 0.05 0.14 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 PBl 1.0 5.0 6.0 Sodium sulfate - 6.0 R~l~nre (Moisture & Miscell~n~ollc) To: 100 100 100 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfact~ntc herein.

EXAMPLE IV
The following high density and bleach-cont~ining detergent formulations, according to the present invention are prepared:
J K L
Blown Powder Zeolite A 15.0 15.0 15.0 Sodium sulfate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 bis-AQA-1 * 1.0 1.5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 SRA 2 0.3 0.15 0.35 MA/AA 4.0 2.0 2.0 Agglomerates TAS 2.0 2.0 1.0 .. ... . ..... . ... .

CA 02254961 1998-ll-17 W O 97/44419 PCT~US97/08317 Silicate 3 0 3.0 4 0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray On ulllC 0.3 0.3 0 3 C45E7 2.0 2.0 2.0 C25E3 2.0 - -Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 Carbonate 8.0 15.010.0 TAED 6.0 2.0 5.0 PB1 13.0 7.0 10.0 Polyethylene oxide of MW 5,000,000 - - 0.2 BeIILO11iI~ clay - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 R2l~nre (Moisture &
Miscellaneous) To: 100.0 100.0100.0 Density (g/litre) 850 850 850 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfart~ntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfa~tantc herein.

EXAMPLE V

The following high density det~.ge--l formulations according to the present invention are ~,le~ d:

W O 97/44419 PCT~US97/08317 M N
Blown Powder Zeolite A 2.5 2.5 Sodium sulfate 1.0 1.0 CocoMeEO2* 1.5 1.5 Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0 4 Spray On C25E5 5.0 5.0 Perfume 0.5 0 5 Dry Adds HEDP 0.5 0.3 SKS6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 15.0 15.0 SRA 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Rql~n~e (Moisture &
- Miscellaneous) To: 100 I00 Density (g/litre) 850 850 *The bis-AQA-1 (CocoMeEO2) surfactant of the Example may be replaced by an equivalent amount of any of surfqcPntc bis-AQA-2 through bis-AQA-22 or other bis-AQA
surfactants herein.

.. . .. .
.. _ .. . . .

CA 022~496l l998-ll-l7 W O 97/44419 PCTn3S97/08317 Any of the granular detergent compositions provided herein may be tabletted using known tabletting methods to provide detergent tablets.

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

EXAMPLE VI

In~redient % (wt.) Ran~e (% wt.) A B
C12-C18 Sulfate 15.75 13.50 0-25 LAS 6.75 --- 0-25 Na2C~3 15.00 3.00 1-20 DTPP1 0.70 0.70 0.2-1.0 Bentonite clay --- 10.0 0-20 Sokolan CP 52 0.40 1.00 0-2.5 bis-AQA-13 2.0 0.5 0.15-3.0 TSPP 5.00 0 0-10 STPP 5.00 15.00 0-25 Zeolite 1.25 1.25 0-15 Sodium laurate --- 9.00 0-15 SRA-1 0.30 0.30 0-1.0 Protease enzyme --- 0.12 0-0.6 Amylase enzyme 0.12 --- 0-0.6 Lipase enzyme --- 0.10 0-0.6 Cellulase enzyme --- 0.15 0-0.3 --Ral~n~e4--------~
1Sodium diethylenetriamine penta (phosphonate) 2Sokolan CP-5 is maleic-acrylic copolymer 3bis-AQA-1 may be replaced by an equivalent amount of Bis-AQA surfactants bis-AQA-2 through bis-AQA-22 or other bis-AQA surfactants herein.
4R~l~nre comprises water (2% to 8~, including water of hydration), sodium sulfate, calcium carbonate, and other minor ingredients.

CA 022~4961 1998-11-17 W O 97/44419 PCTrUS97108317 EXAMPLE VII
The following hand wash detergent forrnulations, according to the present invention, are prepared by mixing the ingredients together in the percentage weight amounts as indicated 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 C M C 0.4 0.4 0.4 o 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 PBl 4.0 5.4 4.0 2.3 N O BS 2.6 3.1 2.5 1.7 SRA 1 0.3 0.3 0.7 0.3 Brightener 1 0.15 0.15 0.15 0.15 nre 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 but are not intended to be limiting thereof. It is also envisaged that the combination of bis-AQA surfactants and soil release agents may also be useful when formul~tecl into hard surface cleaners, personal cleansing bars or gels, shampoos, hand and automatic dishwashing detergents etc.

.. . .

CA 022~4961 1998-ll-17 The following Example further illustrates the invention herein with respect to a hand dishwashing liquid.

EXAMPLE VIII
In~redient % (wt.) Range (% wt.) bis-AQA-1* 2.0 0.15-3 Ammonium C12 13 alkyl sulfate 7.0 2-35 C12-C14 ethoxy(l) sulfate 20.5 5-35 Coconut amine oxide 2.6 2-5 Betaine/Tetronic 7040 0.87-0.10 0-2 (mix) Alcohol Ethoxylate C8E11 5 0 2-10 Ammonium xylene sulfonate 4.0 1-6 Ethanol 4.0 0-7 Ammonium citrate 0.06 0-1.0 Magnesium chloride 3.3 0-4.0 Calcium chloride 2.5 04.0 Amrnonium sulfate 0.08 0-4.0 Hydrogen peroxide 200 ppm 0-300 ppm SRA 1 0.2 0.4 Perfume 0.18 0-0.5 Maxatase~ proteasc 0.50 0-1.0 Water and minors R~l~nt~e *May be replaced bis-AQA-2 - bis-AQA-22 or other bis-AQA surf~t~ntc herein.
**Cocoalkyl betaine.

The following E~ample further illustrates the invention herein with respect to hard surface cleaners.
EXAMPLE IX
In~redient % (wt.) Ran~e (% wt.) bis-AQA-1* 2.0 0.25-5 3-(N-dodecyl-N ,N-dimethyl)-2-hydroxy-propane- 1 -sulfonate 2.0 1-5 Octyl polyethoxylate (2.5) 1.1 1-5 Octyl polyethoxylate (6.0) 2.9 1-5 Butoxy propoxy propanol 5.0 0-10 Succinic acid 10.0 2-12 Sodium cumene sulfonate 4.2 1-5 SRA 2 0.2 0.2 Water. buffering agents, and minors R~l~nre pH 3.0 *May be replaced by bis-AQA2-bis-AQA-22 or other bis-AQA surf~ct~ntc herein.

The following Example further illusll~tes the invention herein with respect to a personal cl~ g bar or gel.

EXAMPLE X

In~redient % (wt.) Range (% wt.) bis-AQA-1* 1.5 1.0-3.0 Coconut soap, Na** 80.0 70-99 C12-C14 methyl gl~ mi~1e 4.0 0-10 Carboxymethyl cellulose 2.0 0-5 SRA 1 0.4 0.12 ~.runle 0.1 Optional Moisture and Minors R~l~nre *May be replaced by bis-AQA2-bis-AQA-22 or other bis-AQA surfactants herein.
$*Soap may be replaced wholly or in part by synthetic anionic surfact:ln~ such as C12-C14 aL~cyl sulfates or C12-C16 alkyl ethoxy sulfates.

The following Examples A and B further illustrate the invention herein with respect to a granular phosphate-con~ining automatic dishwashing de~elg.,nl.

EXAMPLE XI
% by weight of active material INGREDIENTS A B
STPP (anhydrous)1 31 26 ~o~ -m Carbonate 22 32 Silicate (~0 SiO2) CA 022~496l l998-ll-l7 W O 97/44419 PCT~US97/08317 Surfactant (nonionic) 3 1.5 NaDCC Bleach2 2 --bis-AQA-1* 0.5 1.0 Sodium Perborate -- 5 TAED -- 1.5 Savinase (Au/g) -- 0.04 Te~ ullyl (Amu/g) 425 SRA2 0.3 0.4 Sulfate 25 25 ~e.rullle/Minors to 100% to 100%
lSodium tripolyphosphate 2Sodium dichlorocyanurate *The bis-AQA-1 surfactant can be replaced by bis-AQA-2 through bis-AQA-22.

EXAMPLE xn The following illustrates mixtures of bis-AQA surfart~ntc which can be substituted for the bis-AQA surf. t~nt~ listed in any of the foregoing Examples. As disclosed hereinabove, such mixtures can be used to provide a spectrum of p~l ro~ ance benefits and/or to provide cle~ning conI~)o~iliol~s which are useful over a wide variety of usage conditions.
Preferably, the bis-AQA sulr.~ in such ~ ures differ by at least 1.5, preferably 2.5-20, total EO units. Ratio ranges (wt.) for such mixtures are typically 10:1-1:10. Non-limiting examples of such mixtures are as follows.
Components Ratio (wt.) bis-AQA-1 + bis-AQA-5 1:1 bis-AQA-1 + bis-AQA-10 1:1 bis-AQA-l + bis-AQA-15 1:2 bis-AQA-1 + bis-AQA-5 + bis-AQA-20 1:1:1 bis-AQA-2 + bis-AQA-5 3:1 bis-AQA-5 + bis-AQA-15 1.5:1 bis-AQA-l + bis-AQA-20 1:3 Mixtures of the bis-AQA surf~t~ntc herein with the col~csponding cationic surfactants which contain only a single ethoxylated chain can also be used. Thus, for example, llli~lUlCS of ethoxyla~ed cationic surfa~t~ntc of the formula RlN+CH3[EO]x[EO]yX~ and , . . . .

CA 0225496l l998-ll-l7 WO 97/44419 PCTrUS97/08317 R1N+(CH3)2[Eo]zx-~ wherein Rl 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 det~.ge.l~,y pe,roll.lance (especially in a fabric laundering context) over a broader range of water hardness than do the cationic surfactants herein used individually. It has now been discovered that shorter EO catiQnirs (e.g., EO2) improve the cle~nin~ perfo~ ce of anionic surfa~t~nt~ in soft water, whereas higher EO cationics (e.g., EO15) act to improve har~ ess tolerance of anionic surf~rt~nts, thereby improving the cle~nin~ pclrorl.,al~ce of anionic surfactants in hard water.
Conventional wisdom in the detergen.;y art suggests that builders can O~ c the ~cl r~ lance "window " of anionic surfactants. Until now, however, bro~denin~ the window to encoll~ass essentially all conditions of water hardness has been illlpossible to achieve.

EXAMPLE XIII
This Exarnple illustrates ~l~lle formulations (A-C) made in accordal1ce with theinvention for incorporation into any of the foregoing Examples of bis-AQA-cont~inin~
det. ~gcnl compositions. The various ingredients and levels are set forth below. (% Weight) .rullle In~redient _ B C
Hexyl cin,u ~ir aldehyde 10.0 - 5 .0 2-methyl 3-(para-tert-blllyl~hel~yl)-propionaldehyde 5.0 5.0 7-acetyl-1 ,2,3,4,5,6,7,8-octahydro-1,1 ,6,7-~ell,tullclllyl nap~ .on.o 5 o 10.0 10.0 Benzyl salicylate 5.0 7-acetyl-1, 1 ,3,4,4,6-h~ m~thyltetralin 10.0 5.0 10.0 Para-(tert-butyl) cyclohexyl acetate 5.0 5.0 Methyl dihydro jasmonate - 5.0 Beta-napthol methyl ether - 0.5 Methyl beta-naphthyl ketone - 0.5 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde - 2.0 1,3 ,4,6,7,8-hexahydro4,6,6,7,8 ,8-hP,Y~mPthyl-cyclopenta-~amma-2-bel~yrane - 9.5 Dodecahydro-3a,6,6,9a-tell~n~ ylnaphtho-[2, lb]furan - - 0.1 W O 97/44419 PCT~US97/08317 ~Ani.~ lehyde ~ ~ 0 5 Counlalin - - 5.0 Cedrol 0.5 Vanillin - - 5.0 Cyclopent~-1ec~nolide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 T q~n--m 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 S.0 - 5.0 Geraniol 5.0 Nerol - 5.0 2-(1,1-dimethylethyl)-cycl-)hPY~m l acetate 5.0 Orange oil, cold pressed - 5.0 Benzyl acetate 2.0 2.0 Orange te.~ s - 10.0 F.l)g~
Diethylphth~l~te - 9.5 Lemon oil, cold pressed - - 10.0 Total 100.0 100.0 100.0 The foregoing ~,~.rullR compositions are ~miYPtl or sprayed-onto (typically at levels up to about 2% by weight of the total dete~ge.ll composition) any of the bis-AQA surfactant-co..~ g cle~ning (including ble~ching) compositions disclosed herein. Improved deposition and/or retention of the p~,lrullle or individual collll)ol~.ll~ thereof on the surfacebeing rle~ned (or bleached) is thus secured.

Claims (23)

WHAT IS CLAIMED IS:

1. A composition comprising or prepared by combining a soil release agent, a non-AQA
surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-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, and A and A' can vary independently and are each C1-C4 alkoxy, p and q can very independently and are integers in the range of from 1 to 30.

2. A composition according to Claim 1 wherein said soil release agent is a sulfobenzoyl end capped ester with a sulfonated endcapped polyethylene terephthaloyl copolymer with 5 sulfoisophthaloyl units.

3. A composition according to either of Claims 1 or 2 which is prepared by mixing the non-AQA surfactant and the AQA surfactant.

4. A composition according to any of Claims 1 to 3 wherein the non-AQA surfactant is an anionic surfactant.

5. A composition according to any of Claims 1 to 4 wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1:8.

6. A composition according to any of Claims 1 to 5 wherein said bis-AQA surfactant of the formula where R1 is C8-C18 alkyl, R2 is methyl A and A' are ethoxy and propoxy groups and p and q are each integers of from 1 to 8.

7. A composition according to any of Claims 1 to 6 wherein said bis-AQA surfactant of the formula where R1 is C8-C18 alkyl, R2 is methyl A and A' are ethoxy and propoxy groups and p and q are each integers of from 1 to 4.

8. A composition according to any of Claims 1 to 7 wherein the formula of the bis-AQA
cationic surfactant is such that p and/or q are integers in the range of from 10 to 15.

9. A composition according to any of Claims 1 to 8 comprising two or more bis-AQA
surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

10. A composition according to any of Claims 1 to 9 comprising two or more non-AQA
surfactants and a mixture of two or more bis-AQA surfactants.

11. A composition according to any of Claims 1 to 10 in a granular, bar, aqueous liquid or non-aqueous liquid, or tablet form.

12. 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 any of Claims 1 to 11.

13. A method according to Claim 12 for removing body soils, builder sensitive soils, bleach sensitive soils or surfactant sensitive soils from fabrics.

14. A method according to either of Claims 12 or 13 for cleaning dishware or other hard surfaces.

15. A method according to any of Claims 12 to 14 which is conducted in an automatic machine.

16. A method according to any of Claims 12 to 15 which is conducted by hand.

17. A method according to any of Claims 12 to 16 additionally comprising amylase, protease, lipase or cellulase or cellulytic enzymes, or mixtures thereof.

18. A method according to any of Claims 12 to 17 which employs high levels of non-AQA
surfactants.

19. A method according to any of Claims 12 to 18 which employs an ethoxylated polyamine surfactant.

20. A method according to any of Claims 12 to 19 wherein the detergent composition comprises a mixture of two or more bis-AQA surfactants, or a mixture of a bis-AQA
surfactant and a mono-ethoxylated cationic surfactant.

21. A method according to any of Claims 12 to 20 wherein the detergent composition comprises a mixture of two or more bis-AQA surfactants, or a mixture of a bis-AQA
surfactant and a mono-ethoxylated cationic surfactant.

22. 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 bis-AQA surfactant.

23. A method according to Claim 22 which is conducted using a perfume or perfumeingredient in combination with a detergent composition comprising a bis-AQA.