CA2252852A1 - Liquid detergent compositions comprising specially selected modified polyamine polymers - Google Patents

Abstract

Laundry detergent compositions that provide fabric appearance benefits to all fabric comprising modified polyamine agents and other selected fabric appearance agents, and a method for providing these benefits to fabric by contacting fabric articles with a water soluble and/or dispersible, modified polyamine having functionalized backbone moieties.

Description

CA 022~28~2 1998-10-29 LIQUID DETERGENT COMPOSITIONS COMPRISING SPECIALLY SELECTED
MODIFIED POLYAMINE POLYMERS

PRIOR HISTORY
This application claims priority to the following pending applications: U.S.
Serial No. 60/016,527, filed May 3, 1996; U.S. Serial No. 60/017,062, filed May 3, 1996;
U.S. Serial No. 60/016,525, filed May 3, 1996; U.S. Serial No. 60/017,059, filed May 3, 1996; U.S. Serial No. 60/017,060, filed May 3, 1996; U.S. Serial No. 60/016,526, filed May 3, 1996; U.S. Serial No. 60/016,531, filed May 3, 1996; U.S. Serial No. 60/016,528, filed May 3, 1996; U.S. Serial No. 60/027,902, filed October 7, 1996; and U.S. Serial No. 60/027,899, filed October 7, 1996.
FIELD OF THE INVENTION
The present invention relates to liquid laundry detergent compositions that provide fabric appearance benefits to fabric under a variety of soil conditions. The compositions herein comprise specially selected modified polyamine fabric ap~e~dnce agents. The present invention also relates to a method for providing fabric appe~lce benefits to fabrics by cont~ting fabric articles with a water soluble and/or dispersible, modified polyamine.
BACKGROUND OF THE rNVENTION
A wide variety of fabric appearance agents for use in domestic and industrial fabric tre~tmtont processes such as laundering, fabric drying in hot air clothes dryers, and the like are known in the art. Various fabric apl~e~ce agents, including soil release agents, di~ all~" surf~ct~nt~, fabric softeners, and dye transfer inhibitors, have been commercialized and are currently used in detergent compositions and fabric softener/~nti~t~tic articles and compositions.
Extensive research in this area has yielded significant improvements in the effectiveness of the various fabric appearance agents, providing el h~n.~ed product performance and form~ t~hility. However, no one single compound has been identifed which can perform a number of these fabric appearance enh~ncement~ Thus, formulators must pick and choose among several technologies to achieve the overall performance expected by consumers in a cost effective manner. The problem is compounded in liquid detergents because of the potential interactions of the various agents in an aqueous solution.
Moreover, many of these conventional fabric appearance agents do not provide enhanced perfomance on both hydrophobic and hydrophilic soils and stains. Tea stains are hydrophilic. Dirt and tomato stains are hydrophobic.

CA 022~28~2 1998-10-29 W O 97/42287 PCTrUS97/06989 Thus, until now the development of an effective, all-around fabric appearance agent for use in a laundry detergent has been elusive. Attempts by others to apply theparadigm of matching the structure of a polymer with the structure of the fabric, a method successful in the polyester soil release polymer field, has nevertheless yielded marginal results.
It has now been surprisingly discovered that effective fabric appearance agents can be pl~pa~ed from certain modified polyamines. This unexpected result has yieldedcompositions that are key to the present method for providing several fabric appearance benefits, i.e., soil removal, dispersal of soils, and dye transfer inhibition, once available to only with the use of several individual laundry additives. The process or method of the present invention also provides benefits on all types of soils and stains.
The process or method of the present invention is especially effective when the laundry detergent compositions disclosed herein are liquid. The liquid detergents can have a wide range of viscosity and may include heavy concentrates, pourable "ready"
detergents, or light duty fabric pre-tre~tm~nt~
The modified polyamines disclosed in the present method are compatible with other laundry d~ gent additives and adjuncts. In fact, it is believed that the polyarnines of this invention actually compliment and enh~n..e the perforrnance of other detergent additives, such as surf~ct~nt~ and additives that before now can cause negative dye transfer problems.
BACKGROUND ART
U.S. Patent 4,548,744, Connor, issued October 22, 1985; U.S. Patent 4,597,898, Vander Meer, issued July 1, 1986; U.S. Patent 4,877,896, Maldonado, et al., issued October 31, 1989; U.S. Patent 4,891,160, Vander Meer, issued January 2, 1990; U.S.
Patent 4,976,879, Maldonado, et al., issued December 11, 1990; U.S. Patent 5,415,807, Gosselink, issued May 16,1995; U.S. Patent 4,235,735, Marco, et al., issued November 25, 1980; WO 95/32272, published November 30, 1995; U.K. Patent 1,537,288, published December 29, 1978; U.K. Patent 1,498,520, published January 18, 1978;
German Patent DE 28 29 022, issued January 10, 1980; J~p~nese Kokai JP 06313271,published April 27, 1994. See also U.K. 1,314,897; U. S. Patent No. 3,897,026; U.S.
Patent No. 3,912,681; U.S. Patent No. 3,948,838 issued to Hinton, et alia describes high molecular weight (500,000 to 1,500,000) polyacrylic polymers for soil release; U.S.
Patent4,559,056; U.S. PatentNo. 4,579,681; U.S. PatentNo. 4,614,519.
Examples of alkoxylated polyarnines and quaternized alkoxylated polyamines are disclosed in European Patent Application 206,513 as being suitable for use as soil dispersents, however their possible use as a cotton soil release agent is not disclosed.

CA 022~28~2 1998-10-29 SUMMARY OF THE INVENTION
Submitted herein are liquid laundry detergent compositions comprising:
a) at least about 0.1% by weight, of a detersive surfactant selected from anionic surfactants, nonionic surfactants, or mixtures thereof;
b) at least about 0.05% by weight, of a water-soluble or dispersible, modified polyamine agent, said agent comprising a polyamine backbone corresponding to theformula:

[ ~R2 ) 2 -N] w~ [Rl-N] x~ [Rl-N] y~ [Rl-N] z B R2 (R2) 2 wherein each Rl is independently C2-Cs alkylene, alkenylene or arylene; each R2 is independently H, or a moiety of formula OH[(CH2)XO]n, wherein x is from about I to about 8 and n is from about 10 to about 50; w is 0 or l; x+y+z is from about 5 to about 30; and B represents a continn~tion of this structure by br~n~hing; and wherein said polyamine before alkylation has an average molecular weight of from about 300 to about 1,200; and c) one or more additional detersive additives selected from the group consisting of amylase, detersive amine, cationic surf~rt~nt~, antiredeposition agents, ~ntif~f~in~ agent, dye fixative agents, prill/fuzzing red~lçing agents, and mixtures thereof.
The detergent compositions herein can comprise additional adjunct ingredients selected from the group con~i~ting of builders, optical brightenPrs, soil release polymers, dye transfer inhibitors, polymeric dispersing agents, non-amylase enzymes, suds suppressers, dyes, pclrul"cs, colorants, filler salts, hydrotropes, and mixtures thereof.
In pref~ d embodimentc, Rl is C2-C4 alkylene, more preferably ethylene; R2 is OH[CH2CH2O3n, wherein n is from about 15 to about 30, more preferably n is about 20.
The average Molecular Weight of the polyamine before alkylation is from about 300 to about 1200, more preferably from about 500 to about 900, still more preferably from about 600 to about 700, even more preferably from about 600 to about 650.
The present invention further relates to a method of providing dye transfer inhibiting and other fabric appearance benefits to fabric by contacting said fabric with a laundry composition comprising:
a) at least about 0.05% by weight, of a water-soluble or dispersible, modified polyamine agent as disclose above; and b) one or more additional detersive additives selected from the group consisting of selected amylases, selected detersive amines, selected cationic surf~t~nt~, CA 022~28~2 1998-10-29 antiredeposition agents, 7~ntif~-iin~ agent, dye fixative agents, prill/fuzzing reducing agents, and mixtures thereof.
The detergent compositions of this invention may be in liquid, gel or structuredliquid form.
All percentages, ratios and pro~ullions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (~ C) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
Preferred laundry detergent compositions of this invention comprise:
a) from about 0.1% to about 95% by weight, of an anionic detersive surfactant, preferably selected from alkyl sl.lf~tç~, alkyl alkoxy (preferably ethoxy) sl.lf~tes, and mixtures thereof;
b) at least about 0.1% to about 95% by weight, of a nonionic detersive surfactant, preferably selected from polyhydroxy fatty acid amides and alky ethoxylates;
c) from about 0.05% to about 15% by weight, p~efelably from about 0.1% to about 10%, of a water-soluble or dispersible modified polyamine fabric a~pe~1ce agent of this invention;
d) one or more additional detersive additives selected from the group consisting of amylase, detersive amine, cationic sllrfact~nt.~, antiredeposition agents, ~ntifaAing agent, dye fixative agents, prill/fuzzing reducing agents, and mixtures thereof; and e) the balance carrier and adjunct ingredients.
The compositions of this invention preferably have a pH of about 6 to about 12, more preferably from about 7.0 to about 10.5, when measured as a 10% solution inwater.
Modified Polyamines -The present invention employs an "effective amount" of the polyamine fabric appe~ud,lce agent herein to improve the pclro~lllance of cleaning compositions which contain other adjunct ingredients. By an "effective arnount" herein is meant an amount which is sufficient to improve, either directionally or significantly at the 90% confidence level, the l,~.ro~ al-ce of the cleaning composition against at least some of the target soils and stains. Thus, in a composition whose targets include certain food stains, the formulator will use sufficient polyamine fabric a~pealance agent to at least directionally improve cleaning performance against such stains. Inll)ol tm1tly, in a fully-formulated laundry detergent the fabric ~,ea-~lce agents can be used at levels which provide at least a directional improvement in cleaning performance over a wide variety of soils and stains, as will be seen from the data presented hereinafter.

s As noted, the fabric appearance agents are used herein in detergent compositions in combination with detersive surfactants at levels which are effective for achieving at least a directional improvement in cleaning performance. In the context of a fabric laundry composition, such "usage levels" can vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water and the type of washing m~rhine.
As can be seen from the foregoing, the amount of fabric appearance agent used in a rn~çhin~-wash laundering context can vary, depending on the habits and practices of the user, the type of washing m~rhin~, and the like. In this context, however, one heretofore unappreciated advantage of the fabric appearance agents is their ability to provide at least directional improvements in performance over a spectrum of soils and stains.
The modified polyamine agents of the present invention are water-soluble or dispersible, modified polyamines. These polyamines comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine br~nrhing chains to a greater or lesser degree. In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substitute~l qu~le. ";~P~l, or combinations thereof.
For the purposes of the present invention the term "modification" is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution) or by quaternizing a backbone nitrogen (quaternized). The terms "modification" and "substitution" are used interçh~ng~bly when referring to the process of replacing a hydrogen atom ~tt~rhP~l to a backbone nitrogen with an E unit. Q~ e ..i~ ion may take place in some circnm~t~nces ~,vithout substitution.
P~rell~d polymers of the present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially qll~t~rni7Pd ~minps~ nitrogens totally, and mixtures thereof. However, not all backbone arnine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the formulator. The degree of ethoxylation is also detP.rniner~ by the specific requirements of the formulator.
The preferred polyamines that comprise the backbone of the compounds of the present invention are generally polyalkylPne~minPs (PAA's), polyalkyleneimines (PAI's), preferably polyethylene~minP, (PEA's), polyethyle~ ines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's. A common polyalkylene~mine (PAA) is tetrabutylenepent~mine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional (li.~till~tion. The common PEA's obtained are triethylenetetramine (TETA) and teraethylen~ line (TEPA). Above the pent~min~c, i.e., the he~min~, hept~minçs, octamines and possibly nonamines, the cogenerically derived mixture does not appear to separate by (lictill~tion and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the p-e~ lion of PEA's.
Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethyle~ c (PEI's). Preferred PEI's have at least moderate br~n~hin~, that is the ratio of m to n is less than 4: 1, however PEI's having a ratio of m to n of about 2: 1 are most preferred.
These polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. Specific methods for plc~ g these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference.
The following formula depicts a plcf~ d modified polyamine agent coll-p.;sing a PEI backbone wherein all substitutable nitrogens are modified by repl~-~ement ofhydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)20H, having the formula:
[H(ocH2cH2kokN~ N[(CH2CH20)20H]2 ~N~ H(OCH2CH2)20 ~N~ (CH2CH20)20H

(CH2CH20)20H ~ ~ (CH2CH20koH
[H(ocH2cH2)2o]2N~N--N~N--N~N--N~N--N[(CH2CH20)20Hk (cH2cH2okoH
N[(CH~cH.0)2oHl2 Nl(CH2CH~0)20H]2 Cationic Surfactants - The alkoxylated ql~tern~ry ~mmonium (AQA) surfactants useful in the present invention are of the general forrnula:

R~ /ApR
N~ X
R2/ \R3' I

-- . . .

CA 022S28s2 1998-10-29 R~ /A~R
N X
R2/ AqR II

wherein Rl is an alkyl or alkenyl moiety Con~ining from about 8 to about 18 carbon atoms, preferably 10 to about 16 carbon atoms, most preferably from about 10 to about 14 carbon atoms; R2 and R3 are each independently alkyl groups cont~ining from one to about three carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from hydrogen (preferred), methyl and ethyl, X~ is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is selected from C I -C4 alkoxy, especially ethoxy (i.e., -CH2CH2O-), propoxy, butoxy and mixtures thereof;and for formula I, p is from 2 to about 30, preferably 2 to about 15, most preferably 2 to about 8; and for formula II, p is from 1 to about 30, preferably I to about 4 and q is from } to about 30, preferably 1 to about 4, and most preferably both p and q are 1.
The levels of the AQA surfArt~ntc used to prepare fini.chPcl laundry d~ gelll compositions can range from about 0.1% to about 5%, typically from about 0.45% to about 2.5%, by weight.
Amylase - Complete removal of the very hydrophobic "everyday" or "body" soils isdifficu1t and low levels of residual soils often remain on the fabric after washing. These residues build up and act like an amorphous glue between the fibers, enLl~ping particulate dirt and leading to fabric yellowing. It has now further been discovered that detergent compositions co~ g a combination of the water-soluble polyamine agentsherein and amylase enzymes delivers superior cleaning and whiteness perforrnance vs.
compositions cont~inin~ either technology alone.
Such amylase enzymes include those described in W095/26397 and in co-pending application by Novo Nordisk PCT/DK96/00056. These enzymes are incorporated into detergent compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of total weight composition.
Specific amylase enzymes for use in the detergent compositions of the present invention therefore include:
(a) a-amylases characterised 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 .

CA 022~28~2 1998-10-29 in the range of 8 to 10, measured by the Phadebas~) a-amylase activity assay. Such Phadebas(g) a-arnylase activity assay is described at pages 9-lO, W095/26397.
(b) a-amylases according (a) comprising the amino sequence shown in the SEQ ID
listings in the above cited reference. or an a-amylase being at least 80% homologous with the amino acid sequence shown in the SEQ ID listing.
(c) a-amylases according (a) comprising the following amino sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-~eu-Pro-Asn-Asp.
A polypeptide is considered to be X% homologous to the parent amylase if a comparison of the respective amino acid sequences, performed via algorithms, such as the one described by Lipman and Pearson in Science 227, 1985, p. 1435, reveals an identity of X%
(d) a-amylases according (a-c) wherein the a-amylase is obtainable from an alkalophilic Bacillus species; and in particular, from any ofthe strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.
In the context of the present invention, the term "obtainable from" is inter~ d not only to indicate an amylase produced by a Bacillus strain byt also an amylase encoded by a DNA
sequence isolated from such a Bacillus strain and produced in an host organism transformed with said DNA sequence.
(e)a-amylase showing positive immunological cross-reactivity with antibodies raised against an a-amylase having an amino acid sequence corresponding respectively to those a-amylases in (a-d).
(f) Variants of the following parent a-amylases which (i) have one of the amino acid sequences shown in co.l~s~onding respectively to those a-amylases in (a-e), or (ii) displays at least 80% homology with one or more of said amino acid sequences, and/or displays immunological cross-reactivity with an antibody raised against an a-arnylase having one of said amino acid sequences, and/or is encoded by a DNA sequence wich hybridizes with the same probe as a DNA sequence encoding an a-amylase having one of said amino acid sequence; in which variants:
1. at least one arnino acid residue of said parent a-amylase has been deleted; and/or 2.at least one arnino acid residue of said parent a-amylase has been replaced by a different amino acid residue; and/or 3. at least one amino acid residue has been inserted relative to said parent a-amylase;
said variant having an a-amylase activity and exhibiting at least one of the following properties relative to said parent a-amylase: increased thermostability, increased stability towards oxidation, reduced Ca ion dependency, increased stability and/or a-amylolytic activity at neutral to relatively high pH values, increased a-amylolytic activity at relatively high temperature and increase or decrease of the isoelectric point (pI) so as to better match the pI value for a-amylase variant to the pH of the medium.
The preferred arnylayses of this invention are those described by the following:(a) a-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl(~) at a te~ .dL~re range of 25~C to 55~C and at a pH value in the range of 8 to 10, measured by the Ph~leb~c(~) a-arnylase activity assay;
(b) a-arnylase showing positive immunological cross-reactivity with antibodies raised against an a-amylase having an amino acid sequence corresponding respectively to those a-arnylases in (a); and (c) mixtures thereof.
Said variants are described in the patent application PCT/DK96/00056.
Other arnylases suitable herein include, for example, a-amylases described in GB1,296,839 to Novo; RAPIDASE(~), IntPrn~tional Bio-Synthetics, Inc. and TERMAMYL(~', Novo. FUNGAMYL~) from Novo is especially useful.
F,ngineçring 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 embo~ of the present compositions can make use of amylaseshaving improved stability in d~elg~ s, especially improved oxidative stability as measured against a reference-point of TERMAMYL~) in commercial use in 1993. These pl~;..ed amylases herein share the characteristic of being "stability-enh~nred" amylases, characterized, at a minim~lm, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylen.o~i~mine in buffered solution at pH
9-10; thermal stability, e.g., at common wash telllpeldl~lres such as about 60~C; or ~lk~linP stability, e.g., at a pH from about 8 to about 11, measured versus the above-identified reference-point amylase. Stability can be measured using any of the art-disclosed technical tests. See, for example, referc.1ccs disclosed in WO 9402597.
Stability-enhanced amylases can be obtained from Novo or from Genencor Inttorn~tional. One class of highly plerell~d amylases herein have the commonality 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 or multiple amylase strains are the irnmediate precursors. Such pl~r~,.led 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.
Iicheniformis alpha-amylase, known as TERMAMYL(~), or the homologous position CA 022~28~2 1998-10-29 variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B.
stearo~hermophilus; (b) stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively P~esict~nt alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17 1994, by C.
Mitchinson. Therein it was noted that bleaches in det~ nt~ inactivate alpha-amylases but that improved oxidative stability amylases have been made by Genencor from B.
Iicheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 leading to specific mutants, particularly important being M197L and M197T
with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE(~) and SUNLIGHT~; (c) particularly ~olcr~ d amylases herein include amylase variants having additional modification in the imme~ t~ parent as described in WO 9510603 A and are available from the ~ccign~e~ Novo, as DURAMYL(~). Other particularly p~ef~l,ed oxidative stability enh~nce~ amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidativestability-enh~n~e-l amylase can be used, for example as derived by site-directedmutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications are accessible. See WO 9509909 A to Novo.
Other Enzymes - enzymes can be included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from surfaces such as textiles or dishes, for the prevention of refugee dye transfer, for example in ~ n-i~r~ng, and for fabric le~lo.~lion. Suitable other enzymes include proteases, lipases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active dt:le,ge,lls, builders and the like. In this respect bacterial or fungal enzymes are plcr~ d, such as bacterial amylases and proteases.
"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.
Enzymes are normally incorporated into d~ ent or dc~ ent 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 frechn~ss improving effect on substrates such as fabrics, dishware and the like. In practical terrns for current CA 022~28~2 1998-10-29 commercial prcp~dlions, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme plc~ dlion Protease enzymesare usually present in such commercial p.~,~,alalions at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per grarn of composition. Higher active levels may be desirable in highly concentrated detergent formulations.
Peroxidase enzymes may be used in combination with oxygen sources, e.g., ~e.c~l)onate, perborate, hydrogen peroxide, etc., for "solution blea~hin~" or prevention of transfer of dyes or pigmPntc removed from substrates during the wash to othersubstrates present in the wash solution. Known peroxidases include horseradish peroxidase, li~nin~ce, and haloperoxi~l~ces such as chloro- or bromo-peroxidase.PerDxidase-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 Tntlorn~tional, 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 usefill 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 detergents can be stabilized by various techniques. Enzyme stabilization 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 stabilization 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.
Ploteases - Suitable exarnples 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 Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE~) by Novo Industries A/S of Denm~rk, hereinafter "Novo". The ~ ualion 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 Tnterll~tional 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 p~I protease from Bacillus sp. NCIMB 40338 described in WO

CA 022~28~2 1998-10-29 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased 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 arnino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by subsLilulhlg a dir~,e..l amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residuepositions 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-Co~ init-g Cleaning Compositions"
having US Serial No. 08/322,676, and C. Ghosh, et al, "Ble~hing Compositions Comprising Protease Enzymes" having US Serial No. 08/322,677, both filed October 13, 1994.
Preferred proteolytic enzymes are also modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303,761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme which is called "Protease A"
herein, 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.
Also preferred proteases are subtilisin enzymes, in particular BPN', that have been modified by mutating the various nucleotide sequences that code for the enzyme, thereby modifying the amino acid sequence of the enzyme. These modified subtilisin enzymes have decreased adsorption to and increased hydrolysis of an insoluble substrate as co.llpa,ed to the wild-type subtilisin. Also suitable are mutant genes encoding for such BPN' variants.
Preferred BPN' variants comprise wild-type amino acid sequence wherein the wild-type amino acid sequence at one or more of positions 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 218, 219 or 220 is substituted;
wherein the BPN' variant has decreased adsorption to, and increased hydrolysis of, an CA 022~28~2 1998-10-29 WO 97/42287 PCTrUS97/06989 insoluble substrate as compared to the wild-type subtilisin BPN'. Preferably, the positions having a substituted arnino acid are 199, 200, 201, 202,205, 207,208,209, 210,211,212, or 215; more preferably, 200,201,202,205 or 207.
Preferred protease enzymes for use according to the present invention also include the subtilisin 309 variants. These protease enzymes include several classes of subtilisin 309 variants.
A. Loop Re~ion 6 Substitution Variants - These subtilisin 309 variants have a modified amino acid sequence of subtilisin 309 wild-type arnino acid sequence, wherein the modified amino acid se~uence comprises a substitution at one or more of positions 193,194,19S,196,197,199,200,201,202,203,204,205, 206, 207,208,209,210,211, 212,213 or 214; whereby the subtilisin 309 variant has decreased adsorption to, and increased hydrolysis of, an insoluble substrate as compared to the wild-type subtilisin 309. Preferably these proteases have amino acids substituted at 193,194,195,196,199, 201,202,203,204,205,206 or 209; more preferably 194,195,196,199 or 200.
B. Multi-Loop Regions Substitution Variants - These subtilisin 309 variants may also be a modified amino acid sequence of subtilisin 309 wild-type amino acid sequence, wherein the modified amino acid sequence comprises a substitution at one or morepositions in one or more of the first, second, third, fourth, or fifth loop regions; whereby the subtilisin 309 variant has decreased adsorption to, and increased hydrolysis of, an insoluble substrate as colllp~ed to the wild-type subtilisin 309.
C. Substitutions at Positions other than the loop re~ions - In addition, one or more s~lbstihltion of wild-type subtilisin 309 may be made at positions other than positions in the loop regions, for example, at position 74. If the additional substitution to the subtilisin 309 is mad at position 74 alone, the substitution is preferably with Asn, Asp, Glu, Gly, His, Lys, Phe or Pro, pl~,f~ldbly His or Asp. However modifications can be made to one or more loop positions as well as position 74, for example residues 97,99, 01,102,105 and 121.
Subtilisin BPN' variants and subtilisin 309 variants are further described in WO95/29979, WO 95/30010 and WO 95/30011, all of which were published November 9, 1995, all of which are incorporated herein by reference.
Li~ases - Suitable lipase enzymes for detergent usage include those produced by ~ microor~ni.cm~ of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in J~p~n~e Patent Application 53,20487, laid open Feb. 24,1978. Other suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is available from , CA 022~28~2 l998-l0-29 Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade narne Lipase P
"Amano," hereinafter referTed to as "Amano-P". Further suitable lipases are lipases such as M I LipaseR and LipomaxR (Gist-Brocades). Other suitable commercial lipases include Arnano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacrer viscosumvar. 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(~ enzyme derived fromHumicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
Highly preferred lipases are the D96L lipolytic enzyme variant of the native lipase derived from ~umicola l~nllginos~ as described in US Serial No. 08/341,826. (See also patent application WO 92/05249 viz. wherein the native lipase ex Hurnicola lanuginosa aspartic acid (D) residue at position 96 is changed to Leucine (L). According to this nomenclature said substitution of aspartic acid to Leucine in position 96 is shown as:
D96L.) Preferably the Humicola lanuginosa strain DSM 4106 is used.
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 tradPn~m~ LipolaseTM, as noted above. In order to optimize the stain removal perforrnance of Lipolase, Novo Nordisk have made a number of variants. As described in WO 92/05249, the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes co~ ared in an arnount 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 col.es~onding to 0.001 - 100- mg (5-500,000 LU/liter) lipase variant per liter of wash llquor.
Lipase enzyme is incorporated into the composition in accordance with the invention at a level of from 50 LU to 8500 LU per liter wash solution. Preferably the variant D96L is present at a level of from 100 LU to 7500 LU per liter of wash solution.
More preferably at a level of from 150 LU to 5000 LU per liter of wash solution.The lipases and/or clltin~ses are normally inco.~G~al~d in the detelge.ll composition at levels from 0.0001% to 2% of active enzyme by weight of the detergent composition.
Also suitable are c~ltin~ces [EC 3.1.1.50] which can be considered as a special kind o mipase, namely lipases which do not require interfacial activation. Addition of CA 022~28~2 1998-10-29 cl.tin~ces to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor).
Cellulase Enzvmes - The laundry detergent compositions according to the present invention may further comprise at least 0.001% by weight, preferably at least about 0.01 %, of a cellulase enzyme. However, an effective arnount of cellulase enzyme is sufficient for use in the laundry detergent compositions described herein. The terrn "an effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like. The compositions herein will typically comprise from about 0.05% to about 2%, preferably from about 0.1 % to about 1.5% by weight of a cornmercial enzyme pl~l,a alion. The cellulase enzymes of the present invention are usually present in such cornmercial l,iel,~dlions at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Preferably, the optimurn pH of the enzyme-co~ t~g composition is between about 7 and about 9.5.
U. S. Patent No. 4,435,307, Barbesgaard et al, issued March 6, 1984, discloses cellulase produced from Humicola insolens. Exarnples of other suitable cellulases include those produced by a strain of Humicola insolens, Humicola gr isea var.
thermoidea, and cellulases produced by a species of Bacillus sp. or Aeromonas sp. Other useful cellulases are those extracted from the hepatopancreas of the marine mollusc Dolabella Auricula Solander. Suitable cellulases are also disclosed in the following:
GB 2,075,028 A (Novo ~nAllstri A/S); GB 2,095,275 A (Kao Soap Co., Ltd.); and Horikoshi et al, U.S. Patent No. 3,844,890 (P~ik~ga'-ll Kenkyusho). In addition, suitable cellulases and metho ls for their prcp&~lion are described in PCT Tntem~tional Publication Number WO 91/17243, published November 14, 1991, by Novo Nordisk A/S.
Cell~ c~s are known in the art and can be obtained from suppliers under the tra~r..~.nf s. Celluzyme~g), Endol~e~, and Carezyme~.
For industrial production of the cellulases herein it is pler~.lcd that recombinant DNA techniques be employed. However other techniques involving adjustments of ferment~tions or mutation of the microorg~ni.cm~ involved can be employed to ensure overproduction of the desired enzymatic activities. Such methods and techniques are known in the art and may readily be carried out by persons skilled in the art.
PolYamide-Polyamine Materials - Another optional but plcr~ ,d component of the detergent compositions herein comprises one or more polyamide-polyamine materials fabric treatment agents. Such materials, especially when combined with the modified polyamine fabric apl,e~dl1ce agents of this invention, have been found to impart a CA 022~28~2 1998-10-29 number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions forrned from detergent compositions which contain such combinations. These fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, etc. The polyamine-polyamide polymers used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such materials are incorporated.
The polyamide-polyamines useful herein will generally comprise from about 0.1%
to 8% by the weight of the composition. More preferably, such polyamide-polyamine materials will comprise from about 0.5% to 4% by weight of the compositions herein.
Most preferably, these polyamide-polyamines will comprise from about 1% to 3% byweight of the composition.
The polyarnide-polyamine materials used in this invention are those which have el)e~lhlg, substituted arnido-amine units which col~ ond to the general Structural Formula No. I as follows:

~C - Rl - C - NH - R2 - Nl - R5 - N H

Structural Formula N o.l In Structural Formula No. I, Rl, R2 and R5 are each indepen-lçntly C 1-4 alkylene, Cl 4 alkarylene or arylene. It is also possible to elimin~t~. Rl entirely so that the polyarnide-polyamine is derived from oxalic acid.
Also in Structural Formula No. I, R3 is H, epichlorohydrin, an azetidinium group, an epoxypropyl group or a dimethylaminohydroxypropyl group, and R4 can be H, Cl 4 alkyl, C 1-4 alkaryl, or aryl. R4 may also be any of the foregoing groups con~en~ed with Cl 4 alkylene oxide.
R1 is preferably butylene, and R2 and Rs are preferably ethylene. R3 is preferably epichlorohydrin. R4 is preferably H.
The polyamide-polyamine materials useful herein can be prepared by reacting polyamines such as diethylenetriamine, triethylenetetr~mine, tetraethylenepçnt~minP or dipropylenetriamine with C2-C 12 dicarboxylic acids such as oxalic, succinic, glutaric, adipic and diglycolic acids. Such materials may then be further derivatized by reaction with, for exarnple, epichlorohydrin. Pl~,paralion of such materials is described in greater CA 022~28~2 1998-10-29 WO 97/42287 PCT~US97/06989 detail in Keim, U.S. Patent 2,296,116, Issued February 23,1960; Keim, U.S. Patent 2.296,154, Issued February 23,1960 and Keim, U.S. Patent 3,332,901, Issued July 25, 1967. The disclosures of all three of these patents are incorporated herein by reference.
The polyamide-polyamine-epichlorohydrin fabric treatment agents preferred for use herein are commercially marketed by Hercules, Inc. under the tr~dçn~n~e Kymene(3 .
Especially useful are Kymene 557H(g~ and Kymene 557LX~ which are epichlorohydrinadducts of polyamide-polyamines which are the reaction products of diethylenetriamine and adipic acid. Other suitable materials are those marketed by Hercules under the tra(len~m~c Reten~) and Delsette~ and by Sandoz under the tr~d~n~me C~L~Clh~@ .,These polyamide-polyamine materials are marketed in the form of aqueous suspensions of the polymeric material cont~ining for example, about 12.5% by weight of solids.
Dye Fixative Materials - optionally but plef~lled for use herein are selected dye fixative materials which do not form precipitates with anionic surfactant. Such non-plc~ aLing dye fixative materials, particularly in combination with the modifiedpolyamine fabric appedl~lce agents of this invention, have been found to dye fixative benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such dye fixatives. Additional benefits from the combination of these dye fixative materials and the modified polyamine fabric appea~ce agents of this invention can include, for example, improved overall appe~lce of the laundered fabrics and protection against color fading. The selected dye fixatives used in the compositions and methods herein can provide such fabric appearance benefits with acceptably little or no loss in cleaning pclrollllal1ce provided by the laundry del~.gent compositions into which such materials are incol~oldled.
The selected dye fixatives useful herein may be in the form of unpolymerized materials, oligomers or polymers. Moreover, the p~efcll~,d dye fixatives useful herein are cationic. The dye fixative colllponent of the compositions herein will generally comprise from about 0.1% to 5% by the weight ofthe composition. More plefeldbly,such dye fixative m~tt~ will comprise from about 0.5% to 4% by weight of the compositions, most p~efcl~bly from about 1% to 3%. Such concentrations should besufficient to provide from about 10 to 100 ppm of the dye fixative in the aqueous washing solutions formed from the laundry d~l~,rgellt compositions herein. More prefearably from about 20 to 60 ppm of the dye fixative will be delivered to the aqueous washing solution, most preferably about 50 ppm.
The non-precipitating dye fixatives useful herein include a number that are commercially marketed by CLARIANT Corporation under the Sandofix~', Sandolec and Polymer VRN(~ tr~den~mes. These include, for example, Sandofix SWE(~, Sandofix WA(~, Sandolec CT(3~, Sandolec CS(~), Sandolec Cl~, Sandolec CF~, Sandolec WA(g) and Polymer VRN(~;). Other suitable dye fixatives are marketed byCiba-Geigy Corporation under the tradename Cassofix FRN-300(~ and by Hoechst Celanese Corporation under the tr~ n~me Tinofix EW g).
A preferred non-precipitating dye fixative is the Sandofix SWE(~ material which has the structure:

H2--ICH2 Cl H2--ICH2 N ~C,NH~C,N ~ H2S~4 N NH HN N
Another ~refell~d non-precipitating dye fixative is the Sandofix WA(E~) materialwhich is polymer having the following structure:
C) ~HO--CH2NH--C--N--I--N~H HCl Another l,~er~-~ed non-plecipildling dye fixative is the Cassofix FRN-300 material which is also a polymer l.lep~ed from the following monomers:
NH
o NC--N--C--NH2 + H2NCH2CH2NH2 + H-C-H

The dye fixative materials used in this invention are generally all water-soluble materials. They can therefore be utilized for detergent composition plt;p~dlion in the form of aqueous solutions of such dye fixatives if desired.
Alkvl alkoxYlated sulfates and/or alkyl sulfates - The alkyl alkoxylated sulfatesurf~ct~nt~ hereof are water soluble salts or acids of the formula RO(A)mSO3M wherein R is an unsubsliluled Clo-C24 alkyl or hydroxyalkyl group having a C1o-C24 alkylcomponent, preferably a C12-C1 8 alkyl or hydroxyalkyl, more preferably C12-Cls alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, m~3gn.ocium, etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.

.. .. ..

CA 022~28~2 1998-10-29 Specific examples of substituted ammonium cations include ethanol-, triethanol-, methyl-, dimethyl, trimethyl-amrnonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-Cls alkyl polyethoxylate (1.0~ sulfate (C12-C 1 sE( 1 .0)M), C 1 2-C 15 alkyl polyethoxylate (2.25) sulfate (C 1 2-C I sE(2.25)M), C 12-C 15 alkyl polyethoxylate (3 .0) sulfate (C 1 2-C 1 sE(3 .0)M), and C 1 2-C 15 alkyl polyethoxylate (4.0) sulfate (C12-C1sE(4.0)M), wherein M is conveniently selected from sodium and potassium.
The alkyl sulfate surf~ct~nt~ hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a Cg-C 18 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 1 o-C 18 alkyl component, more preferably a C 1 2-C 15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted amrnonium (e.g. methyl-, dimethyl-, and trimethyl arnmonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperidinium cations and qu~tern~ry ammonium cations derived from alkyl~ntinP~ such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like).
Commerical alkyl alkoxylate sulfates comprise a mixture of compounds with varying degrees of alkoxylation. For example, C 12-15 polyoxyethylene (3) sulfate from Shell Chemical Company, Houston, TX, will contain molecules with from zero ethoxylates to five or more, for an average degree of ethoxylation = 3. The lower the average degree of ethoxylation of a given sample, the higher the level of alkyl sulfate (EO=0) which may be present in the mixture.
For purposes of this invention, the total amount of alkyl sulfate present in thedetergent compositions herein include not only the alkyl sulfate added to the composition but also any alkyl sulfate which may be present in the alkyl alkoxyate sulfate surfactant mixture.
The amine - Suitable amine surfact~nt~ for use herein include amines according to the formula:

Rl -X - ( CH2 ) n~N

wherein R1 is a C6-Cl2 alkyl group; n is from about 2 to about 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are CA 022~28~2 1998-10-29 individually selected from H, C l -C4 alkyl, or (CH2-CH2-O(Rs)) wherein Rs is H or methyl.
Preferred amines include the following:
Rl -(cH2)2-NH2 Rl-O-(CH2)3-NH2 R1 -c(o)-NH-(cH2)3-N(cH3)2 CH2-CH (OH) -R5 Rl -N
CH2-CH (OH) -R5 wherein R1 is a C6-C12 alkyl group and Rs is H or CH3.
In a highly pr~ ,d embodiment, the amine is described by the formula:
R1 -C(O)-NH-(CH2)3 -N(CH3)2 wherein Rl is Cg-C12 alkyl.
Particularly preferred amines include those selected from the group con~icting of octyl arnine, hexyl amine, decyl amine, dodecyl amine, Cg-Cl2 bis(hydroxyethyl)amine, Cg-C12 bis(hydroxyisopropyl)arnine, and Cg-C12 amido-propyl dimethyl asnine, andmixtures.
Detersive Surfactants - Nonlimiting examples of anionic surf~rt~ntc useful herein typically at levels of at least about 0.1%, preferably from about 0.1% to about 95%, more preferably from about 1% to about 55%, by weight, include the conventional Cl l-C1g alkyl benzene sulfonates ("LAS"), primary, branched-chain and random C1o-C20 alkyl sulfates ("AS"), the C1o-C1g secondary (2,3) alkyl sulfates ofthe formula CH3(CH2)x(CHOSO3-M+) CH3 and CH3 (CH2)y(CHOSO3~M+) CH2CH3 where x and (y + 1 ) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodiurn, ullsdluldled sulfates such as oleyl sulfate, the Clo-C1 8 alpha-sulfonated fatty acid esters, the C1o-C1g sulfated alkyl polyglycosides, the C1o-C18 alkyl alkoxy sulfates (''AEXS''; especially EO 1-7 ethoxy sulfates), and C1o-C 18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates). The C 1 2-C 1 8 betaines and sulfobetaines ("sultaines"), C l o-C 1 8 amine oxides, and the like, can also be included in the overal} compositions. C l o-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C1o-C16 soaps may be used. Other conventional useful surfactants are listed in standard texts.

CA 022~28~2 1998-10-29 Nonionic Surfact~nt.c - Nonlimiting examples of nonionic surfactants useful herein typically at levels of at least about 0.1%, preferably from about 0.1% to about 95%, more preferably from about 1% to about 55%, by weight, include the alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), Clo-Clg glycerol ethers, and the like.
More specifically, the con~lenc~tion products of primary and secondary aliphaticalcohols with from about I to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Pl~r~.,ed are the con.lenc~tion products of alcohols having an alkyl group cont~ining from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about I to about 10 moles, preferably 2 to 7, most preferably 2 to 5, of ethylene oxide per mole of alcohol.
Examples of commercially available nonionic surf~rt~ntc of this type include: TergitolTM
1 5-S-9 (the con~enC~tion product of C I I -C 15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the con-ienc~tion 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 con.lenc~tion product of C14-Cls linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the con-lenc~tion product of C 1 2-C 13 linear alcohol with 3 moles of ethylene oxide), Neodol TM 45 7 (the confi~nc~tion product of C 1 4-C 1 5 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the conflen.c~tion product of C 14-C 15 linear alcohol with 5 moles of ethylene oxide) m~rkete~ by Shell Chemical Company; KyroTM EOB (the con~iPncation product of C 1 3-C 1 5 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Genapol LA 030 or 050 (the con~lenc~tion product of C12-Cl4 alcohol with 3 or 5 moles of ethylene oxide) marketed by Hoechst.
The l~lef~ ,d range of HLB in these AE nonionic surf~ct~nt~ is from 8-11 and most preferred from 8-10. Con-lerlc~te~c with propylene oxide and butylene oxides may also be used.
Another class of prer. ll~d nonionic surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula.
R2 C--N--Z, Il 11 O R
wherein Rl is H, or C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an .

CA 022~28~2 1998-10-29 WO 97/42287 PCT~US97/06989 alkoxylated derivative thereof. Typical exarnples include the C 1 2-C 18 and C 1 2-C 14 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid arnides 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 about 6 to about 30 carbon atoms. The preferred alkylpolyglycosides have the forrnula R20(CnH2nO)t(glYC~sYl)x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3,preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
Polyethylene, polypropylene, and polybutylene oxide con~len~tes of alkyl phenolsare also suitable for use ~ the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide conrlen~tes being plefe,led. Co,lllllc.cially available nonionic surf~t~nt~ of this type include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-45, X- 1 14, X- 100 and X- 102, all marketed by the Rohrn & Haas Company. These surf~.~t~nt~ are cornmonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
The con~lPn~tion products of ethylene oxide with a hydrophobic b~e for ned by the con~n~tion of propylene oxide ~,vith propylene glycol are also suitable for use as the additional nonionic surfactant in the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. Examples of compounds of this type include certain of the commPrcially-available PluronicTM surf~t~ntc, marketed by BASF.
Also suitable for use ~ the nonionic surfactant of the nonionic surfactant system of the present invention, are the con~Pn~tion products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylPnP~ minP,. Examples of this type of nonionic surfactant include certain of the co.lll.l~,cially available TetronicTM
compounds, marketed by BASF.
Builders - De~ gent builders can optionally but preferably be included in the compositions herein, for example to assist in controlling mineral, especially Ca andlor Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
Builder level can vary widely depending upon end use and physical forrn of the composition. Built detergents typically comprise at least about 1% builder. Liquid CA 022~28~2 1998-10-29 forrnulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder. Lower or higher levels of builders are not excluded. For example, certain detergent additive or high-surfactant formulations can be unbuilt.
A preferred builder for use herein are citrates, e.g., citric acid and soluble salts thereof. It is believed that the combination of polyamine fabric appearance agents of this invention in combination with citrate builder provides increase levels of cleaning. Thus, in one embodiment of the present invention, the detergent composition comprises from about 1 % to about 10%, more preferably from about 2% to about 8%, still more preferably from about 4% to about 7%, by weight of citrate builder.
Suitable builders herein can be selected from the group con~i~ting of phosphatesand 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 arnorphous-solid or non-structured-liquid types; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate or sesquicarbonate; aluminosilicates; organic mono-, di-, tri-, and tetracarboxylates especially water-soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
These may be complçmPnt~(l by borates, e.g., for pH-b--rrc,.;l g purposes, or by sulfates, especially sodium sulfate and any other fillers or carriers which may be important to the enginPPring of stable surfactant and/or builder-cont~ining de~ .l compositions.
Builder mixtures, sometimÇs termed "builder systems" can be used and typically comprise two or more conventional builders, optionally complPmPnted by chelants, pH-buffers or fillers, though these latter materials are generally accounted for separately when describing quantities of materials herein.
P-con~ g d~ g~nt builders often p,~fel~ed where permitted by legislation include, but are not limited to, the alkali metal, arnmonium and alkanolammonium salts of polyphosph~tes exemplified by the tripolyphosph~tes, pyrophosphates, glassy polymeric meta-phosph~tes; and phosphonates.
Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a SiO2:Na20 ratio in the range 1.6: I to 3.2: 1, including, particularly for automatic dishwashing purposes, solid hydrous 2-ratio silicates marketed by PQ Corp.
under the tr~den~me BRITESIL~, e.g., BRITESIL H20; and layered silicates, e.g., those described in U.S. 4,664,839, May 12, 1987, H. P. Rieck. See plepalalive methods in Gerrnan DE-A-3,417,649 and DE-A-3,742,043.

CA 022~28~2 1998-10-29 Also suitable for use herein are synthesized crystalline ion exchange materials or hydrates thereof as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995.
Suitable carbonate builders include ~Ik~linP earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids. Suitable for the present purposes are those having empirical formula: [MZ(Alo2)z(sio2)v] xH2O wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
Aluminosilicates can be crystalline or amorphous, naturally-occurring or synthetically derived. An aluminosilicate production method is in U.S. 3,985,669, Krummel, et al, October 12, 1976. Pl~fe.lcd synthetic crystalline all.minosilicate 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.
Suitable organic detelge,ll builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, andlithium, or alkanolammonium salts aré ~lcfell~,d. Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S. 3,635,830, January 18, 1972; "TMS/TDS" builders of U.S.4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163;

4,158,635; 4,120,874 and 4,102,903.
Other suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid; carboxymethyloxysuccinic acid; the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylene.li~minP 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 thereo~
Oxydisuccinates are also especially useful in such compositions and combinations.
Certain detersive surf~ct~nt~ or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are sl.mmed up as detersive surfact~nt~ Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the CA 022~28~2 1998-10-29 WO 97/42287 PCTrUS97/06989 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 (plef~ d), 2-p~nt~ecenylsuccinate, and the like. Lauryl-succinates are described in European Patent Application 86200690.5/0,200,263, published November 5,1986. Fatty acids, e.g., C 12-cl 8 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 ~ l 5(x; multiplied by the valence of Mi) + 2y = 2z is satisfied such that the formula has a neutral or "b~l~nced" charge. These builders are referred to herein as "Mineral Builders".
Enzyme Stabilizing System - The enzyme-co~ g compositions herein may optionally also comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added sepa.alely, e.g., by the formulator or by a m~nllfachlrer of del~lgelll-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 de~igned to address different stabilization problems depending on the type and physical form of the detergent composition.
Another stabilizing approach is by use of borate species. See Severson, U.S.
4,537,706.
Stabilizing systems of certain cleaning compositions may further comprise from 0to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine scavengers, added to prevent chlorine bleach species present in many water supplies from a~ king and inactivating the enzymes, especially under alkaline conditions.Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylen~Ai~minetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine CA 022~28~2 1998-10-29 (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 andsodium pelca~l,onate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired.
Polvmeric Soil Release A~ent - Known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be employed in the present detergent compositions. If ili7.l fl SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the composition.
S~A's can include a variety of charged, e.g., anionic or even cationic (see U.S.4,956,447), as well as noncharged monomer units and structures may be linear, branched or even star-shaped. They may include capping moieties which are especially effective in controlling molecular weight or altering the physical or surface-active properties.
Structures and charge distributions may be tailored for application to different fiber or textile types and for varied detergent or detergent additive products.
Suitable SRA's include a sulfonated product of a subst~nti~lly linear ester oligomer comprised of an oligomeric ester backbone of telep}llhaloyl and oxyalkyleneoxy repeat units, for example as described in U.S. 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink. See U.S. 4,711,730, December 8, 1987 to Gosselink et al, for examples of those produced by tr~neesterification/ oligomerization of poly(ethyleneglycol) methyl ether, DMT, PG and poly(ethyleneglycol) ("PEG"). Partly- and fully- anionic-end-capped oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers from ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoct~n~s~llfonate; 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 terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al.
SRA's also include simple copolymeric blocks of ethylene terephth~l~te or propylene terephth~l~te with polyethylene oxide or polypropylene oxide terephth~l~t~, 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 asMETHOCEL from Dow; and the C 1 -C4 alkylcelluloses and C4 hydroxyalkyl celluloses;

CA 022~28~2 1998-10-29 WO 97/42287 PCT~US97/06989 see U.S. 4,000,093, December 28,1976 to Nicol, et al. Suitable SRA's characterised by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g.. C I -C6 vinyl esters, preferably poly(vinyl acetate), grafted onto polyalkylene oxide backbones. See European Patent Application 0 219 048, published April 22,1987 byKud, 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. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.
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)-eth~nes.llfonate, DMT,Na- dimethyl 5-sulfoisophth~l~t~ EG and PG.
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 I.~g~ce et al; (II) SRA's with carboxylate tennin~l 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 flormin~lc 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 hydroxyltennin~l groups which may be esterified. See U.S. 4,525,524 Tung et al.; (III) anionic terephth~l~te-based SRA's of the urethane-linked variety, see U.S. 4,201,824, Violland et al; (IV) poly(vinyl caprolactam) and related co-polymers with monomers such as vinyl pyrrolidone and/or dimethyl~minoethyl methacrylate, including both nonionic and cationic polymers, see U.S. 4,579,681, Ruppert et al.; (V) graft copolymers, in addition to the SOKALAN types from BASF made, by grafting acrylic monomers on to sulfonated polyesters; these SRA's assertedly have soil release and anti-redeposition activity similarto known cellulose ethers: see EP 279,134 A, 1988, to Rhone-Poulenc Chemie; (VI) grafts of vinyl monomers such ~ acrylic acid and vinyl acetate on to proteins such as caseins, see EP 457,205 A to BASF (1991); (VII) polyester-polyamide SRA's l~repaled by condensing adipic acid, caprolactam, and polyethylene glycol,especially for treating polyamide fabrics, see Bevan et al, DE 2,335,044 to Unilever N.
V.,1974. Other useful SRA's are described in U.S. Patents 4,240,918,4,787,989, 4,525,524 and 4,877,896.

CA 022~28~2 1998-10-29 ClaY Soil Removal/Anti-redeposition A~ents - The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal arld antiredeposition plo~c~lies. Liquid detergent compositions which contain these compounds typically contain from about 0.01% to about 5% by weight of the water-soluble ethoxylates ~min-os, The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene-pPnt~mine. 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 EuropeanPatent 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. Patent4,548,744, Connor, issued October 22,1985. Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein. See U.S. Patent 4,891,160, VanderMeer, issued January 2,1990 and WO 95/32272, published November 30,1995. Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
Optionally, but preferred antiredeposition agents useful for this invention are alkoxylated qn~l....,.. ~ ~li~mines of the general formula:
A A
Rl--N--R--I--Rl 2X
A A
where R is selected from linear or branched C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, [(CH2CH20)qCH2CH2]- and -CH2CH(OH)CH20~(CH2CH20)qCH2CH(OH)CH2]~ where q is from about I to about 100. ~ach Rl is in~3~p~n~1~ntly selected from Cl-C4 alkyl, C7-C12 alkylaryl, or A. A is of the formula:
(CH-CH2-0) nB
I

where R3 is selected from H or Cl-C3 alkyl, n is from about 5 to about 100, and B is selected from H, Cl-C4 alkyl, acetyl, or benzoyl; X is a water soluble anion.

CA 022~28~2 1998-10-29 In preferred embo~ime~t~, R is selected from C4 to Cg alkylene, Rl is selected from C1-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-O) nH

where R3 is selected from H or methyl, and n is from about 10 to about S0.
In another p~ ,.ed embodiment R is linear or branched C6, Rl is methyl, R3 is H,and n is from about 20 to about S0.
Another optional but preferred antideposition agent is alkoxylated qll~t~ ry polyamines of the general formula:
A A A
Rl--N~ R N--R N--Rl (m + 2) X
A Rl m A

where R is selected from linear or branched C2-C 12 alkylene, C3-C 12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-C12 dialkylarylene, [(CH2CH2O)qCH2CH2]- and -CH2CH(OH)CH2O~(CH2CH2O)qCH2CH(OH)CH2]~ where q is from about I to about 100. If present, Each Rl is independently selected from Cl-C4 alkyl, C7-C12 alkyla~yl, or A. Rl may be absent on some nitrogens; however, at least three nitrogens must be qu~telni7~l A is of the formula:
(CH-CH2-0) nB
I

where R3 is selected from H or C1-C3 alkyl, n is from about 5 to about 100, and B is selected from H, C 1 -C4 alkyl, acetyl, or benzoyl; m is from about 1 to about 4, and X is a water soluble anion.
In ~refell~,d embodiments, R is selected from C4 to C8 alkylene, Rl is selected from Cl-C2 alkyl or C2-C3 hydroxyalkyl, and A is:
(CH-CH2-0) nH
I

where R3 is selected from H or methyl, and n is from about 10 to about 50; and m is 1.
In another preferred embodiment R is linear or branched C6, Rl is methyl, R3 is H, and n is from about 20 to about 50, and m is 1.

CA 022~28~2 1998-10-29 These antiredeposition agents can be synth~si7ed following the methods outline in US. Patent No. 4,664,848, or other ways known to those skilled in the art.
The levels of the redeposition agents used to prepare fiini~he-l laundry detergent compositions can range from about 0.1% to about 10%, typically from about 0.4% to about 5%, by weight.
Polvmeric Dispersin~ A,eents - Polymeric dispersing agents can advantageously beutilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not int~n~lec~ 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~Li;Gdlion, and anti-redeposition.
Polymeric polycarboxylate materials can be p~e~ d by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
The presence in the polymeric polycarboxylates herein or monomeric segmentc, CO-~inillg no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form prer~:,dbly ranges from about 2,000 to 10,000, more ~l~,fclably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued march 7, 1967.
Acrylic/maleic-based copolymers may also be used as a plerell~d component of thedispersing/anti-redeposition agent. Such m~teri~l~ 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 about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The CA 022~28~2 1998-10-29 WO 97142287 PCTtUS97106989 ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 toabout l:l,morepreferablyfromabout 10:1 to2:1. Water-solublesaltsofsuch acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No.
66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comprising hydroxypropylacrylate. Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193,360, including, for example, the 45/45/10terpolymer of acrylic/maleic/vinyl alcohol.
Another polymeric material which can be included is polyethylene glycol (PEG).
PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
Polya~ and polyglut~ln~te dispersing agents may also be used, especially in conjunction with zeolite builders. Dispersing agents such as poly~ e preferably have a molecular weight (avg.) of about 10,000.
Bri~htener - Any optical brightf ~ or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.01% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical bright~n~rs which may be useful in the present invention can be cl~sifie~ into subgroups, which include, but are not neces~rily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, m~thinPcyallincs, dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such bright.?nf~rs are ~lisclosed in "The Production and Application of Fluolesct;lll Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Specific examples of optical bright~ors which are useful in the present compositions are those identified in IJ.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighten~rs include the PHORWHITE series of bri~hl~nf.
from Verona. Other brightf n~rs disclosed in this ~e~rellce include: Tinopal U~PA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and ArticWhite 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 arninocournarins. See also U.S. Patent 3,646,015, issued February 29, 1972 to Harnilton.

CA 022~28~2 1998-10-29 Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective for inhibiting the transfer of dyes from one fabric to another during the cleaning process. Generally, such dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, m~ng~n~se phthalocyanine,peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
More specifically, the polyamine N-oxide polymers p,efell~d 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 ~ ched or the N-O group can form part of the polymerizable unit or the N-O group can be ~tt~he~l to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be ~ ch~d or the N-O group is part of these groups. ~l~f~"~d polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imi-l~7O1e, pyrrolidine, piperidine and derivatives thereof.
The N-O group can be ~eplesel~ted by the following general structures:
The most plefel,ed polyarnine N-oxide useful in the delelgent compositions herein is poly(4-vinylpyridine-N-oxide) which ~ an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
Copolymers of N-vinylpyrrolidone and N-vinylimida_ole polymers (referred to as aclass as "PVPVI") are also p,efe.l~;d for use herein. Preferably the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is deterrnin~ by light sc~lt~,l;ng as described in Barth, et al., Chemical Analvsis, Vol 113.
"Modern Methods of Polymer Characterization", the disclosures of which are incorporated herein by reference.) The PVPVI copolymers typically have a molar ratio of N-vinylimid~ole to N-vi~,yl~yllolidone 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 poly-vinyl-pyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000,preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000. PVP's are known to persons skilled in the detergent field; see, for example, CA 022~28~2 1998-10-29 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 about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2:1 to about 50:1, and more preferably from about 3:1 to about 10:1.
The detergent compositions herein may also optionally contain from about 0.005%
to 5% by weight of certain types of hydrophilic optical brighteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01% to 1% by weight of such optical bri~hteners.
When in the above formula, Rl is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightçnto,r is 4,4',-bis[(4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazine-2-yl)arnino]-2,2'-stilbene~lieulfonic acid and disodium salt. This particular brightçnPr species is commercially m~rk~tçd under the tr~den~me Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightPnP,r useful in the del~lgent compositions herein.
When in the above formula, Rl is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightenPr is 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'-stilben~odieulfonic acid di-sodium salt. This particular brightenPr species is colllnle..;ially marketed under the tr~clPn~me Tinopal 5BM-GX by Ciba-Geigy Corporation.
When in the above formula, Rl is anilino, R2 is morphilino and M is a cation such as sodium, the bri~htPnrr is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2-yl)amino]2,2'-stilbenedisulfonic acid, sodium salt. This particular bright~nPr species is commercially marketed under the tr~dPn~me Tinopal AMS-GX by Ciba Geigy Corporation.
Chelatin~e Agents - The dctergent co",posilions herein may also optionally contain one or more iron and/or m~ng~n~se rhPl~tin~ agents. Such che!~tin~ agents can beselected from the group con~isting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without int~n-ling 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~n~pnPse ions from washing solutions by formation of soluble rh~l~t~s.
Amino carboxylates useful as optional chelating agents include ethylPne~ minPtetr~cet~tes, N-hydroxyethylethylenedi~minetn~cet~tes, nitrilotri-acetates, ethyl~nedi~minP t~lla~rop,;onates, triethylenetetr~minrhex~cetates, diethylenetriaminepçnt~cet~tes, and ethanoldiglycines, alkali metal, amrnonium, and substituted ammonium salts therein and mixtures therein.

CA 022~28~2 1998-10-29 Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenPdi~minetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al.
Preferred compounds of this type in acid form are dihydroxydisulfobPn7.on~s such as 1,2-dihydroxy-3,5-disulfobenzene.
A pl~f~ d biodegradable chelator for use herein is ethylene.li~mine disuccinate ("EDDS"), especially the ~S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
The compositions herein may also contain water-soluble methyl glycine diacetic acid (MGDA) salts (or acid form) as a chelant or co-builder useful with, for example, insoluble builders such as zeolites, layered silicates and the like.
If Utili7f~ these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if utili7e~1, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
Suds Suppressors - Compounds for reducing or sul,~lcssing 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 conce~ lion cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
A wide variety- of materials may be used as suds ~u~plessors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of ChPmic~l Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category of suds suppressor of particular interest enc~.".~csesmonocarboxylic fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolamrnonium salts.
The d~telgen~ compositions herein may also contain non-surfactant suds ~p~ ssors. These include, for example: high molecular weight hydrocarbons such as CA 022~28~2 1998-10-29 paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C I g-C40 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated arnino tri~ines such as tri- to hexa-alkylmel~minPs or di- to tetra-alkyl~ mine chlortriazines forrned as products of cyanuric chloride with two or three moles of a primary or secondary amine cont~ining 1 to 24 carbon atoms, propyleneoxide, 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.
Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
Another preferred category of non-surfactant suds su~plessor~ conll,.ises 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 cl-~mi.~orbed or fused onto the silica. Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
Other silicone suds ~u~iessols 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 ~ n~ted silica are described, for in.ct~nce, in German Patent Application DOS 2,124,526. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, R~in~l-i et al, issued March 24, 1987.
Other suds ~ul~p~ssors 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 Cl-C16 chain. A plef~ d alcohol is 2-butyl octanol, which is available from Condea under the tr~dPm~rk ISOFOL 12. Mixtures of seco~ ry alcohols are available under the tr~d~m~rk ISALC~IEM 123 from Enichem. Mixed suds SU~ eSSO~:~ typically comprise mixtures of alcohol + silicone at a weight ratio of 1 :5 to 5:1.
Alkoxylated PolYcarboxvlates - 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 CA 022~28~2 1998-10-29 se~., incorporated herein by reference. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% toabout 10%, by weight, of the compositions herein.
Fabric Softeners - Various through-the-wash fabric softeners, especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits con-;ullenlly with fabric cl~nine Clay softeners can be used in combination with amine and cationic softeners as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
Perfurnes - Perfumes and perfiunery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and ess~nces which can comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedar, and the like. Finished perfi~mes can comprise extremely complex mixtures of such ingredients. Finished perfumes typically comprise from about 0.01% to about 2%, by weight, of the de~el~e.ll compositionsherein, and individual l~.,.ru~ ,.y ingredients can comprise from about 0.0001% to about 90% of a fini~h~tl perfume composition.
Non-limit;np examples of perfume ingredients useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl ~pk~ n~; ionone methyl; ionone gamma methyl; methyl cedrylone; methyl dihydrojasmonate; methyl 1,6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyl tetralin; 4-acetyl-6-tert-butyl-1,1-dimethyl indane; para-hydroxy-phenyl-b-lt~nor~; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1,1,2,3,3,5-hexamethyl indane; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indane; 1-dodec~n~l, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carboxaldehyde; 7-hydroxy-3,7-dimethyl ocatanal; 10-lln~çcPn-1-al; iso-hexenylcyclohexyl carboxaldehyde; formyl tricyclodecane; con-lçn~tion products of hydroxycitronellal and methyl ~llhldi~ilate~ conde~tion products of hydroxycitronellal and indol, condensation products of phenyl acetaldehyde and indol; 2-methyl-3-(para-CA 022~28~2 1998-10-29 tert-butylphenyl)-propionaldehyde; ethyl vanillin; heliotropin; hexyl cinnamic aldehyde;
arnyl cinnamic aldehyde; 2-methyl-2-(para-iso-propylphenyl)-propionaldehyde;
coumarin; ~.~c~l~ctone gamm~, cyclopel-t~dec~nolide; 16-hydroxy-9-hexadecenoic acid lactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzo-pyrane; beta-naphthol methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethyl-naphtho[2,1b]furan; cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten- 1 -yl)-2-buten- 1 -ol; caryophyllene alcohol;
tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; cedryl acetate; and para-(tert-butyl) cyclohexyl acetate.
Particularly preferred perfume materials are those that provide the largest odorimprovements in fini~hed product compositions cont~ining cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3-(para-tert-butylphenyl)-propi~ n~ hyde; 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-h~ t~,yl 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-hP~mPthyl-cyclopenta-gamma-2-benzopyrane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan; ~nie~l-leltyde; coumarin; cedrol; vanillin;
cyclopçnt~dec~nolide; tricyclodecenyl acetate; and tricyclodecenyl propionate.
Other perfume materials include e~sçnti~l oils, resinoids, and resins from a variety of sources including, but not limited to: Peru balsam, Olib~nl~nn resinoid, styrax, labdanum resin, nlltmeg cassia oil, benzoin resin, coriander and lavandin. Still other perfume chemicals include phenyl ethyl alcohol, terpineol, linalool. Iinalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexanol acetate, benzyl acetate, and eugenol.
Carriers such as diethylphth~l~te can be used in the fini~hPd perfume compositions.
Other In~eredients - A wide variety of other ingredients useful in detergent conlposilions can be included in the compositions herein, including other activeingre~lient~, carriers, hydlotr~pes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high sudsing is desired, suds boosters such as the C1o-C16 alkanol~mi~es can be incorporated into the compositions, typically at 1%-10% levels. The Clo-C14 monoethanol and diethanol arnides illustrate a typical class of such suds boosters. Use of such suds boosters ~vith high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is alsoadvantageous. If desired, water-soluble magnesiurn and/or calcium salts such as MgC12, MgS04, CaC12, CaS04 and the like, can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enh~nce grease removal performance.

CA 022~28~2 1998-10-29 A porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution cont~ining 3%-5% of C 13- 15 ethoxylated alcohol (EO 7) nonionic surfactant. Typically, the enzyme/surfactant solution is 2.5 X the weight of silica. The resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final dete.gclll matrix. By this means, ingredients such as the aforementioned enzymes, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergent compositions.
Liquid detergent compositions can contain water and other solvents as carriers.
Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those co.~ g from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-plopanediol, 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~ ted such that, duringuse in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably bclw~:el~ about 7.5 and 10.5. Liquid dishwashing product forrnulations preferably have a pH between about 6.8 and about 9Ø Laundry products are typically at pH 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Liquid Deter~ents The m~nllf~ture of heavy duty liquid detergent compositions, especially those ignç-l for fabric laundering, which comprise a non-aqueous carrier m~ lm can be prepared accoldi~g to the disclosures of U.S. Patents 4,753,570; 4,767,558; 4,772,413;
4,889,652; 4,892,673; GB-A-2,158,838; GB-A-2,195,125; GB-A-2,195,649; U.S.
4,988,462; U.S. 5,266,233; EP-A-225,654 (6116/87); EP-A-510,762 (10t28/92); EP-A-540,089 (5/5/93); EP-A-540,090 (515193); U.S. 4,615,820; EP-A-565,017 (10/13/93);
EP-A-030,096 (6/10/81), incorporated herein by reference. Such compositions can contain various particulate detersive ingredients stably suspended therein. Such non-aqueous compositions thus comprise a LIQUID PHASE and, optionally but preferably, a SOLID PHASE, all as described in more detail hereinafter and in the cited references.
The modified polyamine fabric apped~ ce agents are incorporated in the compositions at CA 022~28~2 1998-10-29 the levels and in the manner described hereinabove for the m~nllfActure of other laundry detergent compositions.
The compositions of this invention can be used to form aqueous washing solutionsfor use in the laundering of fabrics. Cienerally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing ,n~çhine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith.
An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous solution. More preferably, from about 800 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.
The following exarnples are illustrative of the present invention, but are not meant to limit or otherwise define its scope. All parts, pel~entages 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.
EXAMPLE I
~le~ dtion of PEI 600 E~o The ethoxylation is con.l~lcte~ in a 2 gallon stirred stain}ess steel autoclave equipped for tw.lp~ measurement and control, plei.;,u,e measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid. A ~20 Ib.
net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change of the cylinder could be monitored.
A 250 g portion of polyethyleneimine (PEI) (Nippon Shokubai, having a listed average molecular weight of 600 equating to about 0.4 17 moles of polymer and 6.25 moles of nitrogen functions) is added to the autoclave. The autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure). The autoclave contents are heated to 130 ~C while applying vacuum. After about one hour, the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 ~C. Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate. The ethylene oxide pump is turr ed off and cooling is applied to limit any t~ p~,lal~lre increase resulting from any CA 022~28~2 1998-10-29 reaction exotherm. The temperature is m:~int~ine~l between 100 and 110 ~C while the total pressure is allowed to gradually increase during the course of the reaction. After a total of 275 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to 110 ~C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
Next, vacuum is continuously applied while the autoclave is cooled to about 50 ~C
while introducing 135 g of a 25% sodium methoxide in methanol solution (0.625 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions). The methoxide solution is sucked into the autoclave under vacuum and then the autoclave ttlllp~ldtule controller setpoint is increased to 130 ~C. A device is used to monitor the power consumed by the agitator. The agitator power is monitored along with the tel~lpeldlule and pressure. Agitator power and telllpel~lule values gradually increase as methanol is removed from the autoclave and the viscosity of the lni~lule increases and stabilizes in about 1 hour indicating that most of the methanol has been removed. The mixture is further heated and agitated under vacuum for an additional 30 min~tes, Vacuum is removed and the autoclave is cooled to 105 ~C while it is being charged with nitrogen to 250 psia and then vented to ambient ~Jies~ule. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrernent~lly as before while closely monitoring the autoclave ples~ule, telllpcldlllre~ and ethylene oxide flow rate while m;.i~ ini~g the telll~ dlule between 100 and 110 ~C and limiting any temperature increases due to reaction exotherm. After the addition of approximately 5225 g of ethylene oxide (resulting in a total of 20 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the tellll,~.dl lre is increased to 110 ~C and the mixture stirred for an additional hour.
The reaction ~ is then collected in nitrogen purged co~llainel~ and eventually ll~lsr~ d into a 22 L three neck round bottomed flask equipped with heating and agitation. The strong alkali catalyst is neutralized by adding 60 g meth~n~culfonic acid (0.625 moles). The reaction lllixlule is then deodori~d by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 ~C.
The final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
In other plepaldlions the neutralization and deodorization is accomplished in the reactor before discharging the product.
EXAMPLE II

CA 022~28~2 1998-10-29 The following describe liquid detergent compositions according to the present invention: ' Wei rht %
Ingredients A B C D
~ Polyhydroxy coco-fatty acid 3.5 3.5 3.5 3.5 arnlde N~-ODOL 23-9 1 2.0 2.0 2.0 2.0 C2s Alkyl ethoxylate sulphate19.0 19.0 19.0 19.0 C2s Alkyl sulfate -- 3 5 2.0 C l o-Aminopropylamide -- 0.5 1.5 0.5 Citric acid 3.0 5.0 3.0 5.0 Tallow fatty acid 2.0 -- 2.0 --Ethanol 3 5 3 5 3 5 3 5 Propanediol 6.0 6.0 6.0 6.0 Monomethanol amine 0.5 0.5 0.5 0.5 Sodium hydroxide 3.0 2.5 3.5 2.5 Sodium p-toluene sulfonate 2.5 2.5 2.5 2.5 Borax 2.5 2.5 2.5 2.5 Protease 2 0.8 0.8 0.8 0.8 Lipolase 3 0.1 0.1 0.1 0.1 Duramyl 4 0.1 0.1 -- --a-arnylase S -- -- 0.1 0.1 CAREZYME 0.05 0.05 0.05 0.05 Optical Bri~l~tf .. l ,6 0.1 0.1 0.1 0.1 Modified Polyaminc7 1.2 1.2 1.2 1.2 Soil release agent 8 0.2 0.2 0.2 0.2 Furned silica 0.1 0.1 0.1 0.1 Minors, aestetics, water Balance to 100%
1. C12-C13 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillus amyloliguefaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor International.
3. Derived from Humicola lanuginosa and commercially available from Novo.
4. Disclosed in WO 9510603 A and available from Novo.
5. a-amylase disclosed herein, including TERMAMYL(~)~ RAPIDASE~, FUNGAMYL(g, DURAMYL~.

CA 022~28~2 1998-10-29 6. Bright~ner is selected from Brigh~çn~or 49 (Tinopal CBS), inopal UNPA~ Tinopal CBS, Tinopal SBM, Artic White CC, Artic White CWD, 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 amino-coumarins.

7. PEI 600 E20 as described above.

8. Terephth~l~te co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et al., issuedNovember6, 1990.

EXAMPLE III
The following describe liquid d~lel~ellt compositions according to the present invention:
Weight %
Ingredients A B C
Polyhydroxy coco-fatty acid 3.5 3.5 --amide NEODOL 23 91 2.0 2.0 2.0 C2s Alkyl ethoxylate sulphate15.0 15. 0 15.0 C2s Alkyl sulfate 2.0 2.0 --C 1 o-Aminopropylamide -- -- 0.5 Linear alkylbenzene sulfonate 4.0 4.0 4.0 Citric acid 3.0 5.0 5.0 Tallow fatty acid 2.0 2.0 2.0 Ethanol 3.4 3.4 3.4 Plo~al1ediol 6.0 6.0 6.0 Monomethanol arnine 0.5 0.5 0.5 Sodium hydroxide 3.0 2.5 2.5 Sodium p-toluene sulfonate 2.5 2.5 2.5 Borax 2.5 2.5 2.5 Protease2 0.8 0.8 0.8 Lipolase3 0.1 0.1 0.1 a-amylaseS 0.1 0.1 0.1 CAREZYME 0.05 0.05 0.05 Optical Brightçner 0.1 0.1 0.1 Modified Polyamine6 1.2 1.2 1.2 CA 022~28~2 1998-10-29 Ethoxylated tetraethylene- 3.0 3.0 3.0 pent~mine Soil releaseagent7 0.2 0.2 0.2 Fumed silica 0.1 0.1 0.1 Acrylic acid/maleic acid -- -- 0.05 co-polymer Ethylene.li~mine disuccinate -- 1.0 --chelant Fabric Integrity agents8 2.0 3.5 0.75 Minors, aestetics, water Balance to 100%
1. C 1 2-C 1 3 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillus amyloliq2~efaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor International.
3. Derived from Humicola lanuginosa and cornmercially available from Novo.
5. a-amylase disclosed herein, including TERMAMYL~)~ RAPIDASE(E~), FUNGAMYL(~), DURAMYL(Z~.
6. PEI 600 E20 as described above.
7. Terephth~l~te co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et al., issued November 6, 1990.
8. Fabric inle~ ~;ly agents selected from prill/fuzz reduction agents, antiredeposition agents, ~ntif~Aing agents, dye fixatives, and mixtures thereof.

Weight %
Ingredients D E F
Polyhydroxycoco-fatty acid 4.0 5.0 5.0 amide NEODOL 23-91 4.0 4.0 2.0 C2s Alkyl ethoxylate sulphate 4.0 17.0 25.0 C2s Alkyl sulfate 14.0 7.0 C 1 o-Aminopropylamide 1.0 2.0 1.0 Linear alkylbenzene sulfonate -- -- 4.0 Citric acid 5.0 5.0 5.0 Tallow fatty acid 7.0 5.0 5.0 Ethanol 2.0 5.5 10.0 Propanediol 9.0 8.0 8.0 Monomethanol amine 5.0 9.0 7.0 Sodium hydroxide 2.0 1.5 0.5 Sodium p-toluene sulfonate 0.1 2.0 2.0 Borax 2.0 3.5 3.5 Protease2 0.2 1.5 1.5 Lipolase3 0.06 0.2 --a-arnylase5 0.2 0.1 0.1 CAREZYME -- 0.1 0.1 Optical Brightener 0.15 0.1 0.1 Modified Polyamine6 1.2 1.2 1.2 Ethoxylated tetraethylene- 1.0 3.0 3.0 pentamine Soil release agent7 0.2 0.5 0.5 Fumed silica 0.2 0.1 --Acrylic acid/maleic acid 0.05 - --co-polymer Ethylenedi~3min~ disuccinate 1.0 0.5 --chelant Fabric Integrity agents8 1.0 1.5 --Minors, aestetics, water Balance to 100%
1. C 12-C 13 alkyl E9 ethoxylate as sold by Shell Oil Co.
2. Bacillus amyloliquefaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor Tntçrn~tional.
3. Derived from Humicola lanuginosa and col"lllel~iially available from Novo.
5. a-amylase disclosed, including TERMAMYL(~), RAPIDASE(~), FUNGAMYL(g), DURAMYL~).
6. PEI 600 E20 as described above.
7. Terephth~l~te co-polymer as disclosed in U.S. Patent 4,96~,451, Scheibel et al., issued November 6, 1990.
8. Fabric integrity agents selected from prill/fuzz reduction agents, antiredeposition agents, ~ntif~ing agents, dye fixatives, and mixtures thereof.

EXAMPLE IV
The following describe structured liquid detergent compositions according to thepresent invention:
Weight %

Ingredients A B
NEODOL 45 71 2.0 2.0 C2s Alkyl ethoxylate sulphate 16.0 16.0 C2s Alkyl sulfate Cationic surfactant2 5.0 4.0 C 12-16 alkyl dimethyl aminoxide -- 1.0 Citric acid 5.0 5.0 Ethanol Propanediol 6.4 2.0 Monomethanol amine -- 0.5 Sodium hydroxide to pH 8.0to pH 6.7 Borax 2.0 1.0 Protease3 0.5 E0 Lipolase4 0.06 0.2 a-amylaseS 1.2 0.5 CAREZYME -- 0.5 Optical Brighten~r 0.2 0.1 Modified Polyamine6 1.0 1.5 Fabric IntegrityAgent7 1.0 3.0 Soil release agent8 0.2 0.5 Fumed silica 0.2 0.1 Acrylic acid/maleic acid 0.05 co-polymer Ethyl~n~ mine ~iic~lccin~te 1.0 0.5 chelant Minors, aestetics, water Balance to 100%
1. C 14-C 15 alkyl E7 ethoxylate as sold by Shell Oil Co.
2. Lauryl trimethyl ammonium chloride 3. Bacillus amyloliqueSaciens subtilisin as described in WO 95/10615 published April 20, 1995 by Genencor Tnt~rn~tional.
3. Derived from Humicola lanuginosa and co~ c.cially available firom Novo.
5. a-amylase disclosed herein, including TERMAMYL(3), RAPIDASE(~), FUNGAMYL(~), DURAMYL~.
6. PEI 600 E20 as described above.

, I

7. Fabric integrity agents selected from prill/fuzz reduction agents, antiredeposition agents, ~ntifa-lin~ agents, dye fixatives, and mixtures thereof.
8. Terephthalate co-polymer as disclosed in U.S. Patent 4,968,451, Scheibel et al., issued November 6, 1990.

. . .

Claims (9)

WHAT IS CLAIMED IS:

l. A liquid laundry detergent composition comprising:
a) at least 0.1% by weight, of detersive anionic and nonionic surfactants selected from one or more of the following alkyl sulfates, alkyl alkoxy sulfates, linear alkylbenzene sulfonates, polyhydroxy fatty acid amides, and mixtures thereof;
b) at least 0.05% by weight, of a water-soluble or dispersible, modified polyamine fabric appearance agent, said agent comprising a polyamine backbone corresponding to the formula:

[ (R2) 2-N] w- [R1-N] x- [R1-N] y- [R1-N] z B R2 (R2) 2 wherein each R1 is independently C2-C5 alkylene, alkenylene or arylene; each R2 is independently H, or a moiety of formula OH[(CH2)xO]n, wherein x is from

1 to 8 and n is from 10 to 50; w is 0 or 1; x+y+z is from 5 to 30; and B represents a continuation of this structure by branching; and wherein said polyamine beforealkylation has an average molecular weight of from 300 to 1,200; and c) one or more additional detersive additives selected from the group consisting of .alpha.
-amylase, detersive amine, cationic surfactants, antiredeposition agents, antifading agent, dye fixative agents, prill/fuzzing reducing agents, and mixtures thereof; and wherein said detersive amine is of the formula:

R1 -X- (CH2) n-N

wherein R1 is a C6-C12 alkyl group; n is from 2 to 4, X is a bridging group which is selected from NH, CONH, COO, or O or X can be absent; and R3 and R4 are individually selected from H, C1-C4 alkyl, or (CH2-CH2-O(R5)) wherein R5 is H
or methyl.

2. A composition according to Claim 1 wherein the detergent composition additional comprises adjunct ingredients selected from the group consisting of builders, optical brighteners, soil release polymers, dye transfer inhibitors, polymeric dispersing agents, non-amylase enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, and mixtures thereof.

3. A composition according to Claim 2 wherein said adjunct ingredient is a citrate builder; wherein said composition comprises from 2% to 8%, by weight, of said citrate.

4. A composition according to Claim 1 wherein the additional detersive additive is amylase enzyme; wherein said amylase enzyme is selected from the group consisting of:
(a) .alpha.-amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl R 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 R .alpha.-amylase activity assay;
(b) .alpha.-amylase showing positive immunological cross-reactivity with antibodies raised against an .alpha.-amylase having an amino acid sequence corresponding respectively to those .alpha.-amylases in (a); and (c) mixtures thereof.

5. A composition according to Claim 1 wherein said amine is selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl amine, C8-C12 bis(hydroxyethyl)amine, C8-C12 bis(hydroxyisopropyl)amine, C8-C12 amido-propyl dimethyl amine, and mixtures.

6. A composition according to Claim 1 wherein the additional detersive additive is a cationic surfactant of the formula:

wherein R1 is an alkyl or alkenyl moiety containing from 8 to 18 carbon atoms;
R2 and R3 are each independently alkyl groups containing from one to about three carbon atoms; R3 and R4 can vary independently and are selected from hydrogen, methyl and ethyl; X- is an anion such as chloride, bromide, methylsulfate, sulfate, or the like, to provide electrical neutrality; A is selected from C1-C4 alkoxy;and for formula I, p is from 2 to 30; and for formula II, p isfrom 1 to 30 and q is from 1 to 30.

7. A composition according to Claim 1 wherein the additional detersive additive is an antiredeposition agent, said antiredeposition agent is selected from the following formulae:

where R is selected from linear or branched C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, [(CH2CH2O)q CH2CH2]-and-CH2CH(OH)CH2O-(CH2CH2O)q CH2CH(OH)CH2]- where q is from 1 to 100; each R1 is independently selected from C1-C4 alkyl, C7-C12 alkylaryl, or A, wherein A is of the formula:

where R3 is selected from H or C1-C3 alkyl, n is from 5 to 100, and B is selected from H, C1-C4 alkyl, acetyl, or benzoyl; X is a water soluble anion; and where R is selected from linear or branched C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, [(CH2CH2O)q CH2CH2]- and-CH2CH(OH)CH2O-(CH2CH2O)q CH2CH(OH)CH2]-, where q is from 1 to 100; if present, each R1 is independently selected from C1-C4 alkyl, C7-C12 alkylaryl, or A; R1 may be absent on some nitrogens; however, at least three nitrogens must be quaternized,A is of the formula:

where R3 is selected from H or C1-C3 alkyl, n is from 5 to 100, and B is selected from H, C1-C4 alkyl, acetyl, or benzoyl; m is from 1 to 4, and X is a water soluble anion.

8. A composition according to Claim 1 wherein the additional detersive additive is an antifading agent comprising from 0.1% to 5% by weight of a dye fixative selected from the group consisting of Cassofix FRN-300R, Sandofix SWE R, Sandofix WA R, Tinofix EW R, Polymer VRN R, Sandolec CF R, Sandolec WA
R, Sandolec CT R, Sandolec CS R and Sandolec Cl R; wherein said Sandofix SWE R has the formula:

; and wherein said Cassofix FRN-300R polymer is prepared from monomers having the following structures:

; and wherein said Sandofix WA R polymer has the following structure:

.

9. A composition according to Claim 1 wherein the additional detersive additive is a pill/fuzz reduction agent comprising from 0.1% to 8% by weight of a polyamide-polyamine fabric treatment agent formed from repeating units of the structural formula:

wherein R1, R2, and R5 are each independently C1-4 alkylene, C1-4 alkarylene or arylene, or wherein R1 can be eliminated; R3 is H, epichlorohydrin, an azetidinium group, an epoxypropyl group, or a dimethylaminohydroxypropyl group; and, R4 is H, C1-4 alkyl, C1-4 alkaryl, or aryl; and said R4 groups may optionally be condensed with C1-4 alkylene oxide.