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101520253035W0 98Il2296CA 02265740 l999-03- 10PCT/US97/165461COLOR CARE COMPOSITIONSField gf the inventionThe present invention relates to compositions which provide care to thecolors of fabrics in laundry treatment.Bagkground of the inventionThe appearance of colored fabrics, e.g., clothing, bedding, householdfabrics like table linens is one of the areas of concern to consumers.Indeed, upon typical consumer's uses of the fabrics such as wearing,washing, rinsing and/or tumble-drying of fabrics, a loss in the fabricappearance, which is at least partly due to loss of color fidelity andcolor definition, is observed. Such a problem of color loss is even moreacute in laundry treatment after multiwash cycles.It is therefore an object of the invention to provide a composition whichprovides improved color appearance of the laundered fabrics, especiallyafter multiwash cycles.The Applicant has now surprisingly found that the combination of a dyefixing agent and an amino-functional polymer overcomes the problem.Summary of the inventionThe present invention is a composition comprising a dye fixing agentand an amino-functional polymer comprising a polyamine backbonecorresponding to the formula:*3â llR'2N-R1n+iâ[N-R1mâiN-R1nâNRa10152025W0 98/ 12296CA 02265740 l999-03- 10PCTIU S97/ 165462âhaving a polyamine formula V(n+1)WmYnZ or a polyamine backbonecorresponding to the formula:IRâ | RrR'2N-Rim»H141-R1mâiN-R1nâtriI-R1kâNRahaving a polyamine formula V(n_k+1)WmYnY'kZ, wherein k is less thanor equal to n, said polyamine backbone has a molecular weight greaterthan 200 daltons, whereini) V units are terminal units having the formula:1:â Xâ âiâRâ-I71-âRâ 0, RââI;I+âRââ or 111-111-11-R' Râ Râ ;iil W units are backbone units having the formula:âFâ Xâ âiââ"IfâR" or ""TTI+-R" or '_TTI"'R"âRâ Râ Râ ;iii)Y units are branching units having the formula:Râ Xâl+ TâNâR-â or âNâR-â or -âNâR-âI ; andiv)Y' units are branch point for a backbone or branch ring having theformula: 'Râ X ' +â'IâlIâR" or ""1TI:'Râ_ or "Iâ|I"RâR R Rv) Z units are terminal units having the formula:101520253035CA 02265740 l999-03- 10W0 98/12296 PCT/US97/ 165463Râ X ' C;âI\|IâR' or âr\|1*âR' 0, â-âI\|J âR'Râ Râ Râwherein backbone linking R units are selected from the group consistingof C2-C12 alkylene, C4âC12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C3-C12 dialkylarylene, -(R1O)xR1â, â(R1OlxFl5lOR1)x- , -(CH2CHlOR2)CH2O)z(R1O)yR1(OCH2CH(OR2)CH2lw- , -c(o)(R4),c(ol-, -CH2CH(OR2)CH2-, and mixtures thereof; wherein R1 is selectedfrom the group consisting of C2-C5 alkylene and mixtures thereof; R2 isselected from the group consisting of hydrogen, -(Fl1O)xB, and mixturesthereof; R4 is selected from the group consisting of C1-C12 alkylene,C4-C12 alkenylene, C3-C12 arylalkylene, C5-C10 arylene, and mixturesthereof; R5 is selected from the group consisting of C1-C12 alkylene,C3-C12 hydroxyalkylene, C4âC12 dihydroxy-alkylene, C3-C12dialkylarylene, -ClO)â , -C(OlNHR5NHCl0)- , âR1(0Fl1)-. âC(O)lR4),ClO)â,âCH2CH(OH)CH2â, -CH2CH(0HlCH2O(R1O)y R1OCH2CH(0H)CH2-, andmixtures thereof; R6 is selected from the group consisting of C2âC12alkylene or C5-C12 arylene; Râ units are selected from the groupconsisting of hydrogen, C1-C22 alkyl, C3âC22 alkenyl, C7âC22 arylalkyl, C2-C22 hydroxyalkyl , -lCH2)pCO2M , -(CH2)qS03M ,-CH(CH2CO2M)C02M, -(CH2)pPO3M, -(R1O)XB, -ClO)R3, and mixturesthereof; oxide; B is selected from the group consisting of hydrogen, C1-C5 alkyl, -(CH2lqSO3M, -(CH2lpC02M, -(CH2)q(CHSO3M)CH2SO3M, -(CH2)qâ(CHSO2M)CH2SO3M, â(CH_9_)pPO3M, -PO3M, and mixturesthereof; R3 is selected from the group consisting of C1-C13 alkyl, C7-C12 arylalkyl, C7-C12 alkyl substituted aryl, C5-C12 aryl, and mixturesthereof; M "is hydrogen or a water-soluble cation in sufficient amount tosatisfy charge balance; X is a waterâsolubIe anion; m has the value from2 to 700; n has the value from 0 to 350; p has the value from 1 to 6, qhas the value from 0 to 6; r has the value of 0 or 1; w has the value 0 or1; x has the value from 1 to 100; y has the value from 0 to 100; 2 hasthe value 0 or 1.In a preferred embodiment of the invention, the composition furthercomprises a fabric softener component.10CA 02265740 l999-03- 10W0 98/12296 PCTIUS97/16546In another aspect of the invention, there is provided a method forproviding color care to fabrics upon domestic laundering treatmentswhich comprise the step of contacting the fabrics with an aqueousmedium comprising said composition.in a further aspect, there is provided a method for providing color careon treated fabrics upon domestic treatment which comprises the step ofcontacting the fabrics with said composition, wherein said compositionis applied on a substrate, preferably a dryer-sheet.101520253035WO 98112296CA 02265740 l999-03- 105Detailed description of the inventionDye fixing agentAn essential component of the invention is a dye fixing agent. Dye fixingagents, or "fixatives", are well-known, commercially available materialswhich are designed to improve the appearance of dyed fabrics byminimizing the loss of dye from fabrics due to washing. Not includedwithin this definition are components which are fabric softeners or thosedescribed hereinafter as aminoâfunctional polymers.Many dye fixing agents are cationic,quaternized orand are based on variouscationically charged organic nitrogencompounds. Cationic fixatives are available under various trade namesfrom several suppliers. Representative examples include: CROSCOLDRPMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January1988, Code No. 8544) from Crosfield; INDOSOL E-50 (February 27,1984, Ref. No. 6008.35.84; polyethyleneamineâbased) from Sandoz;SANDOFIX TPS, which is also available from Sandoz and is a preferredpolycationic fixative for use herein and SANDOFIX SWE (cationicresinous compound), REWIN SRF, REWIN SRF-O and REWIN DWR fromCHT-Beitlich GMBH, Tinofix® ECO, Tinofix®FRD and So|fin® availablefrom Ciba-Geigy.otherwiseOther cationic dye fixing agents are described in "Aftertreatments forimproving the fastness of dyes on textile fibres" by Christopher C. Cook(REV. PROG. COLORATION Vol. 12, 1982).for use in the present invention are ammonium compounds such as fattyacid - diamine condensates e.g. the hydrochloride, acetate, metosulphateand benzyl hydrochloride of oleyldiethyl aminoethylamide, oley|methyl-diethylenediaminemethosulphate, monostearyl-ethylenediaminotrimethylammonium methosulphate and oxidized products oftertiary amines; derivatives of polymeric alkyldiamines, polyamine-cyanuric chloride condensates and aminated glycerol dichlorohydrins.A typical amount of the dye fixing agent to be employed in thecomposition of the invention is preferably up to 90% by weight,PCT/US97/16546Dye fixing agents suitable .101520253035WO 98112296CA 02265740 l999-03- 106* preferably up to 50% by weight, more preferably from 0.001% to 10%by weight, most preferably from 0.5% to 5% active by weight of thecomposition.Amino-functional polymerThe other essential component of the invention is an aminoâfunctionalpolymer The amino-functionalpolymers of the present invention are water-soluble or dispersible,polyamines. Typically, the amino-functional polymers for use herein havea molecular weight between 200 and 105, preferably between 600 and20,000, most preferably between 1000 and 10,000. These polyaminescomprise backbones that can be either linear or cyclic. The polyaminecomprising a polyamine backbone.backbones can also comprise polyamine branching chains to a greater orlesser degree. Preferably, the polyamine backbones described herein aremodified in such a manner that at least each nitrogen of the polyaminechain is thereafter described in terms of a unit that is substituted,quaternized, oxidized, or combinations thereof.For the purposes of the present invention the term "modification" as itrelates to the chemical structure of the polyamines is defined asreplacing a backbone -NH hydrogen atom by an Râ unit (substitution),quaternizing a backbone nitrogen (quaternized) or oxidizing a backboneThe terms and"substitution" are used interchangably when referring to the process ofnitrogen to the Nâoxide (oxidized). "modification"replacing a hydrogen atom attached to a backbone nitrogen with an Râunit. Quaternization or oxidation may take place in some circumstanceswithout substitution, but substitution is preferablyoxidation or quaternization of at least one backbone nitrogen.accompanied byThe linear or non-cyclic polyamine backbones that comprise the amino-functional polymer have the general formula:13' IrR'2N-R1n+1 -[N-R1mâ[N-Rin-NR'2PCT/US97/ 16546101520253035W0 98/12296CA 02265740 l999-03- 107â âThe cyclic polyamine backbones that comprise the amino-functionalpolymer have the general formula:lRâ I RiRaN-Rim-k+1âiI'«-R1mâiN-Rin-{$1-RikâNRaThe above backbones prior to optional but preferred subsequentmodification, comprise primary, secondary and tertiary amine nitrogensconnected by Fl "linking" units.For the purpose of the present invention, primary amine nitrogenscomprising the backbone or branching chain once modified are defined asV or 2 ââterminal'' units. For example, when a primary amine moiety,located at the end of the main polyamine backbone or branching chainhaving the structureH2N-R]-is modified according to the present invention, it is thereafter defined asa V. "terminal" unit, or simply a V unit. However, for the purposes of thepresent invention, some or all of the primary amine moieties can remainunmodified subject to the restrictions further described herein below.These unmodified primary amine moieties by virtue of their position inthe backbone chain remain "terminal" units. Likewise, when a primaryamine moiety, located at the end of the main polyamine backbone havingthe structureâNH2is modified according to the present invention, it-is thereafter defined asa 2 "terminal" unit, or simply a 2 unit. This unit can remain unmodifiedsubject to the restrictions further described hereinbelow.In a similar manner, secondary amine nitrogens comprising the backboneor branching chain once modified are defined as W "backbone" units.For example, when a secondary amine moiety, the major constituent ofthe backbones and branching chains of the present invention, having thestructurePCT/US97/16546CA 02265740 l999-03- 10WO 98/12296 PCT/US97/16546101520253035*3___[N_R]_is modified according to the present invention, it is thereafter defined asa W "backbone" unit, or simply a W unit. However, for the purposes ofthe present invention, some or all of the secondary amine moieties canremain unmodified. These unmodified secondary amine moieties byvirtue of their position in the backbone chain remain "backbone" units.In a further similar manner, tertiary amine nitrogens comprising thebackbone or branching chain once modified are further referred to as Y"branching" units. For example, when a tertiary amine moiety, which isa chain branch point of either the polyamine backbone or other branchingchains or rings, having the structure_[,l_R]_is modified according to the present invention, it is thereafter defined asa Y. "branching" unit, or simply a Y unit. However, for the purposes ofthe present invention, some or all of the tertiary amine moieties canremain unmodified. These unmodified tertiary amine moieties by virtueof their position in the backbone chain remain "branching" units. The Runits associated with the V, W and Y unit nitrogens which serve toconnect the polyamine nitrogens, are described hereinbelow.The final modified structure of the polyamines of the present inventioncan therefore be represented by the general formulaV(n + 1)WmYnZfor linear amino-functional polymer and by the general formulaV(n-k +1)WmYnY'kzfor cyclic amino-functional polymer. For the case of polyaminescomprising rings, a Yâ unit of the formula1015202530W0 98/ 12296CA 02265740 l999-03- 10IR_D{;-R]__serves as a branch point for a backbone or branch ring. For every Yâ unitthere is a Y unit having the formulaI_[N .. R]...that will form the connection point of the ring to the main polymer chainor branch. in the unique case where the backbone is a complete ring, thepolyamine backbone has the formulaRâ l[R'zNâR1nârb'I-R1mârN-Rin-therefore comprising no 2 terminal unit and having the formulaVn-kWmYnY'kwherein k is the number of ring forming branching units. Preferably thepolyamine backbones of the present invention comprise no rings.In the case of nonâcyclic polyamines, the ratio of the index n to the indexm relates to the relative degree of branching. A fully non-branched linearmodified polyamine according to the present invention has the formulavwmzthat is, n is equal to O. The greater the value of n (the lower the ratio ofm to n), the greater the degree of branching in the molecule. Typically,the value for m ranges from a minimum value of 2 to 700, preferably 4to 400, however, larger values of m are also preferred, especially whenthe value of the index n is very low or nearly 0.Each polyamine nitrogen whether primary, secondary or tertiary, oncemodified according to the present invention, is further defined as being amember of one of three general classes; simple substituted, quaternizedPCT/U S97/ 165461015202530CA 02265740 l999-03- 10W0 98/12296 PCT/US97/ 1654610or oxidized. Those polyamine nitrogen units not modified are classed intoV, W, Y, Yâ or Z units depending on whether they are primary,secondary or tertiary nitrogens. That is unmodified primary aminenitrogens are V or 2 units, unmodified secondary amine nitrogens are Wunits or Yâ units and unmodified tertiary amine nitrogens are Y units forthe purposes of the present invention.Modified primary amine moieties are defined as V "terminal" units havingone of three forms:a) simple substituted units having the structure:R!b) quaternized units having the structure:R! X .|+R'â-N-Râ-IR!wherein X is a suitable counter ion providing charge balance; andc) oxidized units having the structure:0RIModified secondary amine moieties are defined as W "backbone" unitshaving one of three forms:a) simple substituted units having the structure:._}'I-R:RII10152025CA 02265740 l999-03- 10W0 98l12296 PCT/US97I165461 1b) quaternized units having the structure:RI X -|+wherein X is a suitable counter ion providing charge balance; andc) oxidized units having the structure:0R.Other modified secondary amine moieties are defined as Yâ units havingone of three forms:a) simple substituted units having the structure:_N-R_RIb) quaternized units having the structure:wherein X is a suitable counter ion providing charge balance; andc) oxidized units having the structure:0_...1\|1_R.__RW0 98/12296CA 02265740 l999-03- 10PCT/US97ll 65461 2-Modified tertiary amine moieties are defined as Y "branching" unitshaving one of three forms:unmodified units having the structure:__1II_R_..quaternized units having the structure:wherein X is a suitable counter ion providing charge balance; andoxidized units having the structure:Certain modified primary amine moieties are defined as 2 "terminal" unitshaving one of three forms:a)5bl10c)1520a)25 b)simple substituted units having the structure:__Iâq_R'RVquaternized units having the structure:wherein X is a suitable counter ion providing charge balance; and101520253035CA 02265740 l999-03- 10WO 98112296 PCTIUS97l 1654613c) oxidized units having the structure:âlââNâR'When any position on a nitrogen is unsubstituted of unmodified, it isunderstood that hydrogen will substitute for Râ. For example, a primaryamine unit comprising one Râ unit in the form of a hydroxyethyl moiety isa V terminal unit having the formula (HOCH2CH2)HNâ.For the purposes of the present invention there are two types of chainterminating units, the V and 2 units. The 2 "terminal" unit derives froma terminal primary amino moiety of the structure -NH2. Non-cyclicpolyamine backbones according to the present invention comprise onlyone Z unit whereas cyclic polyamines can comprise no 2 units. The 2"terminal" unit can be substituted with any of the Râ units describedfurther herein below, except when the Z unit is modified to form an N-oxide. In the case where the 2 unit nitrogen is oxidized to an Nâoxide,the nitrogen must be modified and therefore Râ cannot be a hydrogen.The polyamines of the present invention comprise backbone R "linking"units that serve to connect the nitrogen atoms of the backbone. R unitscomprise units that for the purposes of the present invention are referredto as "hydrocarbyl R" units and "oxy R" units. The "hydrocarbyI" Runits are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylenewherein the hydroxyl moiety may, take any position on the R unit chainexcept the carbon atoms directly connected to the polyamine backbonenitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties mayoccupy any two of the carbon atoms of the R unit chain except thosecarbon atoms directly connected to the polyamine backbone nitrogens;Cg-C12 dialkylarylene which for the purpose of the present invention arearylene moieties having two alkyl substituent groups as part of thelinking chain. For example, a dialkylarylene unit has the formula101520253035WO 98/12296CA 02265740 l999-03- 1014-<cH2)2â©âCH2â01'although the unit need not be 1,4-substituted, but Can also be 1,2 or 1,3substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, andmixtures thereof, more preferably ethylene. The "oxy" R units comprise-(R1o),,R5(oRl)x-. _CH2CH(OR2)CH2O)z(R1O)yR1(OCH2CHlOR2)CH2lw-, -CH2CH(OR2)CH2-, â(R1O)xR1â, and mixtures thereof. Preferred R unitsare selected from the group consisting of C2-C12 alkylene, C3-C12hydroxyalkylene, C4-C12 dihydroxyalkylene, C3-C12 dialkylarylene, -lR1OlxR1-, âCH2CHlOR2)CH2-, -(CH2CH(OHlCH2O)zlR1OlyR1(OCH2CH-(OH)CH2lw-. -(R1o)xR5<oR1)x-, more preferred Fl units are C2.-C12 alkylene, C3-C12 hydroxy-alkylene ,C4-C12 dihydroxyalkylene , -(R1O)xR1- , â(R1o),,R5(oR1),,-,-(CH2CH(oHiCH2o)z(R1oiynl<oCH2CH-<oH)CH2)w-, and mixturesthereof, even more preferred R units are C2-C1; alkylene, C3hydroxyalkylene, and mixtures thereof, most preferred are C2-C5alkylene.â<cH2>4â©â<CH2»âIThe most preferred backbones of the present invention comprise at least50% R units that are ethylene.R1 units are C2-C5 alkylene, and mixtures thereof, preferably ethylene.R2 is hydrogen, and â(R1OlxB, preferably hydrogen.R3 is C1-C13 alkyl, C7-C12 arylalkylene, C7âC12 alkyl substituted aryl,C5-C12 aryl, and.mixtures thereof , preferably C1-C12 alkyl, C7-C12arylalkylene, more preferably C1~C12 alkyl, most preferably methyl. R3units serve as part of Râ units described herein below.R4 is C1-C12 alkylene, C4-C12 alkenylene, C3-C12 arylalkylene, C5-C10 arylene, preferably C1âC10 alkylene, Cg-C12 arylalkylene, morepreferably C2-Cg alkylene, most preferably ethylene or butylene.PCT/U S97! 16546âI01520253035CA 02265740 l999-03- 10WO 98/12296 PCTIUS97/1654615âR5 is C1âC12 alkylene, C3-C12 hydroxyalkylene, C4âC12dihydroxyalkylene, C3-C12 dialkylarylene, -C(Ol-, âC(O)NHR5NHClO)-. -clollR4l,clol- , -R1l0R1)-, -CH2CHlOH)CH2OlR1OlyR10CH2CHlOH)CH2-, -clolll=i4>,clol-. -CH2CH(OH)CH2- , R5 is preferably ethylene , âc(ol- , -CiO)NHR5NHClO)- , -Rilonil-, -CH2CHlOHlCH2-, -CH_9_CHlOH)CH2O(R1O)yR1OCH2CH-(0H)CH2-, more preferably -CH2CH(0H)CH2-.R5 is C2-C12 alkylene or C5-C12 arylene.The preferred "oxy" R units are further defined in terms of the R1, R2,and R5 units.and R5 units. The preferred cotton soil release agents of the presentinvention comprise at least 50% R1 units that are ethylene. PreferredR1, R2, and R5 units are combined with the "oxy" R units to yield thepreferred "oxy" R units in the following manner.Preferred "oxy" R units comprise the preferred R1, R2,i) . Substituting more preferred R5 into â(CH2CH2O)xR5(OCH2CH2)x-yields -(CH2CH2O)xCH2CHOHCH2(OCH2CH2lx-.ii) Substituting preferred R1 and R2 into -(CH2CH(OR2)CH2O)Z-(R1olyR1olcH2cHloa2lcH2lw- yields âlCH2CH(OH)CH2O)Z-(CH2CH2O)yCH2CH2O(CH2CH(OHlCH2)w-.iii) Substituting preferred R2 into-CH2CH(0H)CH2-.-CH2CHlOR2lCH2â yieldsRâ units are selected from the group consisting of hydrogen, C1-C22alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -lCH2)pCO2M, -(CH2lqSO3M, -CH(CH2CO2M)CO2M, -(CH2)pPO3M, -(R1O)mB, -C(O)R3, preferably hydrogen, C2-C22 hydroxyalkylene,benzyl, C1-C22 alkylene, -lrliolms, âClO)R3, -(CH2)pCO2M, â(CH2)qSO3M, -CH(CH2CO2M)CO2M, more preferably C1-C22 alkylene,-(R1O)xB, -clolR3, -(CH2)pQ02M, âlCH2lqSO3M, -CH(CH2CO2M)CO2M, most preferably C1-C22 alkylene, -lR1O)xB, andCA 02265740 l999-03- 10W0 98/12296 PCT/US97l 16546l0152025A3016â-C(OlR3. When no modification or substitution is made on a nitrogenthen the hydrogen atom will remain as the moiety representing Râ.Râ units do not comprise a hydrogen atom when the V, W or 2 units areoxidized, that is the nitrogens are N-oxides. For example, the backbonechain or branching chains do not comprise units of the followingstructure:0 Ol T 1â-1â|\IâR or H"']l\IâR or â'I'\IâHH H HAdditionally, Râ units do not comprise carbonyl moieties directly bondedto a nitrogen atom when the V, W or Z units are oxidized, that is, thenitrogens are N-oxides. According to the present invention, the Râ unit -C(O)R3 moiety is not bonded to an N-oxide modified nitrogen, that is,there are no N-oxide amides having the structureâ-âNââR or R3âCâNâR orl I Ic=o Râ RâlR3or combinations thereof.B is hydrogen, C1-C5 alkyl, -(CH2)qSO3M, -(CH2)pCO2M, -lCH2lq-(CHSO3M)CH2SO3M, -(CH2)q(CHSO2M)CH2SO3M, -(CH2lpPO3M, âP03M, preferably hydrogen, â(CH2)qSO3M, -(CH2lq(CHSO3M)CH2SO3M, -(CH2)q-(CHSO2M)CH2SO3M,preferably hydrogen or -(CH2)qSO3M.moreM is hydrogen or a water-soluble cation in sufficient amount to satisfyFor example, a sodium cation equally satisfies --lCH2)qSO3M, thereby resulting in -charge balance.(CH2)pCO2M, and101520253035WO 98112296CA 02265740 l999-03- 1017-(CH2)pCO2Na, and -(CH2)qSO3Na moieties. More than one monovalentcation, (sodium, potassium, etc.) can be combined to satisfy the requiredchemical charge balance. However, more than one anionic group may becharge-balanced by a divalent cation, or more than one mono-valentcation may be necessary to satisfy the charge requirements of a poly-anionic radical. For example, a â(CH2)pPO3M moiety substituted withsodium atoms has the formula â(CH2)pP03Na3. Divalent cations suchas calcium (Ca2+) or magnesium (Mg2+) may be substituted for orcombined with other suitable mono-valent water-soluble cations.Preferred cations are sodium and potassium, more preferred is sodium.X is a water-soluble anion such as chlorine (Cl'), bromine (Brâ) and iodinellâ) or X can be any negatively-charged radical such as sulfate (S0421and methosulfate (CH3SO3â).The formula indices have the following values: p has the value from 1 to I6, q has the value from O to 6; r has the value 0 or 1; w has the value 0or 1, x has the value from 1 to 100; y has the value from O to 100; 2has the value 0 or 1; m has the value from 2 to 700, preferably from 4to 400, n has the value from O to 350, preferably from O to 200; m + nhas the value of at least 5.Preferably, x has a value lying in the range of from 1 to 20, preferablyfrom 1 to 10.polymers of the present inventioncomprise polyamine backbones wherein less than 50% of the R groupsThe preferred amino-functionalcomprise "oxy" R units, preferably less than 20% , more preferably lessthan 5%, most preferably the R units comprise no "oxy" R units.The most preferred amino-functional polymers which comprise no "oxy"R units comprise polyamine backbones wherein less than 50% of the Rgroups comprise more than 3 carbon atoms. For example, ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and arethe preferred "hydrocarbyl" Fl units. That is when backbone R units areC2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.PCT/US97l 16546101520253035CA 02265740 l999-03- 10W0 98/122961 8.The amino-functional polymers of the present invention comprisemodified homogeneous and non-homogeneous polyamine backbones,wherein 100% or less of the âNH units are modified. For the purpose ofthe present invention the term "homogeneous polyamine backbone" isdefined as a polyamine backbone having R units that are the same li.e.,all ethylene). However, this sameness definition does not excludepolyamines that comprise other extraneous units comprising the polymerbackbone which are present due to an artifact of the chosen method ofchemical synthesis. For example, it is known to those skilled in the artthat ethanolamine may be used as an "initiator" in the synthesis ofpolyethyleneimines, therefore a sample of polyethyleneimine thatcomprises one hydroxyethyl moiety resulting from the polymerization"initiator" would be considered to comprise a homogeneous polyaminebackbone for the purposes of the present invention. A polyaminebackbone comprising all ethylene R units wherein no branching Y unitsare present is a homogeneous backbone. A polyamine backbonecomprising all ethylene R units is a homogeneous backbone regardless ofthe degree of branching or the number of cyclic branches present.For the purposes of the present invention the term "nonâhomogeneouspolymer backbone" refers to polyamine backbones that are a compositeof various R unit lengths and R unit types. For example, a non-homogeneous backbone comprises R units that are a mixture of ethyleneand 1,2-propylene units. For the purposes of the present invention amixture of "hydrocarbyl" and "oxy" R units is not necessary to provide anon-homogeneous backbone.Preferred amino-functional polymers of the present invention compriseare totally orsubstituted by polyethyleneoxy moieties, totally or partially quaternizedhomogeneous polyamine backbones that partiallyamines, nitrogens totally or partially oxidized to N-oxides, and mixturesthereof. However, not all backbone amine nitrogens must be modified inthe same manner, the choice of modification being left to the specificneeds of the formulator. The degree of ethoxylation is also determinedby the specific requirements of the formulator.PCT/US97/16546101520253035W0 98ll2296CA 02265740 l999-03- 10PCT/US97/165461 9~ The preferred polyamines that comprise the backbone of the compoundsof the present invention are generally polyalkyleneimines (PAl's),preferably polyethyleneimines (PEl's), or PEl's connected by moietieshaving longer R units than the parent PA|'s or PEl's.Preferred amine polymer backbones comprise R units that are C2alkylene (ethylene) units, also known as polyethylenimines (PEl's).Preferred PEl's have at least moderate branching, that is the ratio of m ton is less than 4:1, however PEl's having a ratio of m to n of 2:1 aremost preferred. Preferred backbones, prior to modification have thegeneral formula:7 I[R'2NCH2CH2 I n â I 'NCH2CH2 1 m â I NCH2CH2 ] n _ NR'2wherein Râ, m and n are the same as defined hereinabove. PreferredPEl's will have a molecular weight greater than 200 daltons.The relative proportions of primary, secondary and tertiary amine units inthe polyamine backbone, especially in the case of PEl's, will vary,depending on the manner of preparation. Each hydrogen atom attachedto each nitrogen atom of the polyamine backbone chain represents apotential site for subsequent substitution, quaternization or oxidation.These polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide.sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issuedDecember 5, 1939; U.S. Patent 3,033,746, Mayle et aI., 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 incorporatedby reference.101520WO 98/12296CA 02265740 l999-03- 10PCT/US97/1654620a Examples of amino-functional polymers comprising PEl's, are illustratedin Formulas l â IV:Formula I depicts an amino-functional polymer comprising a PEIbackbone wherein all substitutable nitrogens are modified by replacementof hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2Ol7H, having theformulaNr(cH2cH20>7H12H(0CH2CH2}7\N/\,N[(CH2CH20)7Hl2lCH2CHï¬)7H R H gCH2CH20)vH N\/\ N/\/ N\/\ N-/\/ N\/\ -N/\/ N\/\-N/\/N[(CH2CH2O)7H]2icH2cH2o>7H lCH2CH20>7H lCH2CH2o>7H[H(0CH2CH.â»97l2N\LN1 N[(CH2CH20K,Nr(cH2cH2o)7Hl2Formula IThis is an example of an amino-functional polymer that is fully modifiedby one type of moiety.Formula II depicts an amino-functional polymer comprising a PE!backbone wherein all substitutable primary amine nitrogens are modifiedby replacement of hydrogen with a polyoxyalkyleneoxy unit, ~lCH2CH2O)7H, the molecule is then modified by subsequent oxidation ofall oxidizable primary and secondary nitrogens to N-oxides, said polymer âhaving the formulaCA 02265740 l999-03- 10WO 98/12296 PCTlUS97l1654621âl âlâiH<ocH2cH»71zN Ni<cH2cH2or7H12 '/i°âC"2(+§"2°â6âINI Ox Nl(CH2CH20>7H]2H(0CH(2)CH âO 0(CH2CH20)6H 0(CH2CH20)gi0 l S ï¬ K 0 l ï¬ +[H(OG,2CH2)7]2,l,/\/N\/\N/\/E\/\N/\/âiâ\/\IIJ/\/Nx/\N/\/Nl(CH2CH$3)7Hl2râ 3 5 0 5 1 30(CH2CH20)6H N 0(CH2Cl320)5Hâ3 ll I I Nl(CH2CH hm[H(0CH2CH2)7l2N 0/Nâ\â 20 2K,T;ll(CH2CH20)7Hl20Formula ll5 Formula lll depicts an amino-functional polymer comprising a PEIbackbone wherein all backbone hydrogen atoms are substituted andsome backbone amine units are quaternized. The substituents arepolyoxyalkyleneoxy units, -(CH2CH2O)7H, or methyl groups. Themodified PEI has the formula1 O$H3[H(0CH2CH2)7]2N N(CH2CH20)7H1 * - âFâ3Câ Câ3~N/\,N(cH2cH2o>7HCH3\ /CH3 Kâ /2 CH3\ ;CH3[H(0CH2CH?)7]2N/\/1:"\/\N/\/N\/\N/\/Nx/\N/\/âEx/\N/\/N(Câ3l2' 'cH3 éng \ C1â 'cH3Cl'+ _CH3fl lH(0CH2CH2>7l2N Nâ\âNâC"â)3K,N<cH3>2Formula Ill1 5Formula IV depicts an aminoâfu_nctional polymer comprising a PE!backbone wherein the backbone nitrogens are modified by substitutionli.e. by -(CH2CH2O)7H or methyl), quaternized, oxidized to Nâoxides orcombinations thereof. The resulting polymer has the formula10152025CA 02265740 l999-03- 10wo 98/12296 PCT/US97I1654622(ITH3lH(0CH2CH2)7]2N\L O (EH3N Câ Câ3~§/\,rg<gg2cH2onHCH3â ,CH3 0 5 CH3â [CH3 E). CH3C1 CH3 0 âO S Cl CH3C I" + __CH3ZN/1/âKL +crlH(0CH2CH2)7] Nâ\/Nâ°â3â3K,N<cH3>2Formula IVIn the above examples, not all nitrogens of a unit class comprise theâsame modification. The present invention allows the formulator to have aportion of the secondary amine nitrogens ethoxylated while having othersec_ondary amine nitrogens oxidized to Nâoxides. This also applies to theprimary amine nitrogens, in that the formulator may choose to modify allor a portion of the primary amine nitrogens with one or moresubstituents prior to oxidation or quaternization. Any possiblecombination of Râ groups can be substituted on the primary andsecondary amine nitrogens, restrictions describedhereinabove.except for theCommercially available amino-functional polymer suitable for use hereinare polylethyleneiminel with a MW1200, hydroxyethylatedpolylethyleneiminel from Polysciences, with a. MW2000, and 80%hydroxyethylated polylethyleneiminel from Aldrich.A typical amount of aminoâfunctional polymer to be employed in thecomposition of the invention is preferably up to 90% by weight,preferably from 0.01% to 50°/o active by weight, more preferably from0.1% to 20% by weight and most preferably from 0.5% to 5% byweight of the composition.101520253035W0 98I12296CA 02265740 l999-03- 1023t -The composition may also contain optional components which may besuitable for further improving the aesthetic appearance of the fabricstreated therewith. Suitable optional components include a polyolefindispersion, a fabric softener component, additional components andmixtures thereof.For optimum performance of the compositions, the compositions of theinvention comprise the dye fixing agent and the amino-functionalpolymer in a weight ratio of dye fixing agent to amino-functional polymerof from 100:1 to 0.01:1, preferably of from 10:1 to 0.1 :1, morepreferably of from 2:1 to 0.5:1.Polyolefin dispersionA polyolefin dispersion may optionally be used in the composition of theinvention in order to provide anti-wrinkles and improved waterabsorbency benefits to the fabrics. Preferably, the polyolefin i-s apolyethylene, polypropylene or mixtures thereof. The polyolefin may beat l_east partially modified to contain various functional groups, such ascarboxyl, carbonyl, ester, ether, alkylamide, sulfonic acid or amidegroups. More preferably, the polyolefin employed in the present inventionis at least partially carboxyl modified or, in other words, oxidized. Inparticular, oxidized or carboxyl modified polyethylene is preferred in thecompositions of the present invention.For ease of formulation, the polyolefin is preferably introduced as asuspension or an emulsion of polyolefin dispersed by use of anemulsifing agent. The polyolefin suspension or emulsion preferably hasfrom 1% to 50%, more preferably from 10% to 35% by weight, andmost preferably from 15% to 30% by weight of polyolefin in theemulsion. Theâ polyolefin preferably has a molecular weight of from1,000 to 15,000 and more preferably from 4,000 to 10,000.When an emulsion is employed, the emulsifier may be any suitableemulsification or suspending agent. Preferably, the emulsifier is acationic, nonionic, zwitterionic or anionic surfactant or mixtures thereof.Most preferably, any suitable cationic, nonionic or anionic surfactant maybe employed as the emulsifier. Preferred emulsifiers are cationicPCT/U S97/ 16546101520253035W0 98/12296CA 02265740 l999-03- 1024' surfactants such as the fatty amine surfactants and in particular theethoxylated fatty amine surfactants. in particular, the cationicsurfactants are preferred as emulsifiers in the present invention. Thepolyolefin is dispersed with the emulsifier or suspending agent in a ratioof emulsifier to polyolefin of from 1:10 to 3:1. Preferably, the emulsionincludes from 0.1 % to 50%, more preferably from 1% to 20% and mostpreferably from 2.5% to 10% by weight of emulsifier in the polyolefinemulsion. Polyethylene emulsions and suspensions suitable for use inthe present invention are available under the tradename VELUSTROLfrom HOECHST Aktiengesellschaft of Frankfurt am Main, Germany. Inparticular, the polyethylene emulsions sold under the tradenameVELUSTROL PKS, VELUSTROL KPA, or VELUSTROL P-40 may beemployed in the compositions of the present invention.The compositions of the present invention contain from 0.01% to 8% byweight of the dispersible polyolefin. More preferably, the compositionsinclude from 0.1% to 5% by weight and most preferably from 0.1% to3% by weight of the polyolefin. When the polyolefin is added to thecompositions of the present invention as an emulsion or suspension, theemulsion or suspension is added at sufficient enough quantities toprovide the above noted levels of dispersible polyolefin in thecompositions.Fabric softener componentA fabric softener component may also suitably be used in thecomposition of the invention so as to provide softness and antistasticWhen used, the fabric softenercomponent will typically be present at a level sufficient to provideand antistatic thoseconventionally used in fabric softening compositions, i.e from 1% toproperties to the treated fabrics.softening properties. Typical levels are99% by weight of the composition. Depending on the compositionexecution, i.e liquid or solid, the composition will preferably comprise alevel of fabric softening components for liquid compositions of from 1%to 5% by weight for the diluted compositions or from 5% to 80%, morepreferably 10% to 50%, most preferably 15% to 35% by weight forconcentrated compositions. Where nonionic fabric softener componentsPCT/U S97/ 16546101520253035CA 02265740 l999-03- 10W0 98l12296 PCT/US97/ 1654625â âare present, the level of nonionic softener component in the compositionwill typically be from 0.1% to 10%, preferably from 1% to 5% byweight.Where the composition comprising the softener component is applied ona substrate such as a dryer-sheet, the preferred level of fabric softenercomponent will preferably be from 20% to 99%, more preferably from30% to 90% by weight, and even more preferably from 35% to 85% byweight.Said fabric softening component may be selected from cationic,nonionic, amphoteric or anionic fabric softening component.The preferred, typical cationic fabric softening components include thewater-insoluble quaternaryâammonium fabric softening actives, the mostcommonly used having been diâlong alkyl chain ammonium chloride ormethyl sulfate.Preferred cationic softeners among these include the following:1) ditallow dimethylammonium chloride (DTDMAC);2) dihydrogenated tallow dimethylammonium chloride;3) dihydrogenated tallow dimethylammonium methylsulfate;4) distearyl dimethylammonium chloride;5) dioleyl dimethylammonium chloride;6) dipalmityl hydroxyethyl methylammonium chloride;7) stearyl benzyl dimethylammonium chloride;8) tallow trimethylammonium chloride;9) hydrogenated tallow trimethylammonium chloride;10) C12-14 alkyl hydroxyethyl dimethylammonium chloride;1 1) C-12-13 alkyl dihydroxyethyl methylammonium chloride;12) dilstearoyloxyethyl) dimethylammonium chloride(DSOEDMACl;13) diltallowoyloxyethyl) dimethylammonium chloride;14) ditallow imidazolinium methylsulfate;15) 1-(2-tallowylamidoethyl)â2âtallowyl imidazoliniummethylsulfate.10152025CAW0 98l1229602265740 1999-03-10PCT/US97/ 1654626However, in recent years, the need has arisen for more environmental-friendly materials, and rapidly biodegradable quaternary ammoniumcompounds have been presented as alternatives to the traditionally useddi-long alkyl chain ammonium chlorides and methyl sulfates. Saidmaterials and fabric softeningcompositions containing them aredisclosed in numerous publications such as EP-A-0,040,562, and EP-A-0,239,910.The quaternary ammonium compounds and amine precursors herein havethe formula (I) or (II), below :R3\ /R2ââ Igâ<cH2n~QâT 1 x-lâ (I) wor __R3\ R3/ -+ 1TJâ(CH2)n-CIH -CH2 XR3llTIT?(ll)wherein a is selected from âO-C(O)â, -C(O)-O-, -O-C(O)-O-, âNR4-C(Ol-, âC(O)-NR4-;R1 is (CH2)n-0-T2 or T3;R2 is (CH2),-n-Q-T4 or T5 or R3;R3 is C1-C4 alkyl or C1-C4 hydroxyalkyl or H;R4 is H or C1-C4 alkyl or C1-C4 hydroxyalkyl;T1, T2, T3, T4, T5 are independently C11-C22 alkyl or alkenyl;n and m are integers from 1 to 4; andXâ is a softenerâcompatible anion.101520253035W0 98/12296CA 02265740 l999-03- 1027' Non-limiting examples of softener-compatible anions include chloride ormethyl sulfate.The alkyl, or alkenyl, chain T1, T2, T3, T4, T5 must contain at least 11carbon atoms, preferably at least 16 carbon atoms.straight or branched.The chain may beTallow is a convenient and inexpensive source of long chain alkyl andalkenyl material. The compounds wherein T1, T2, T3, T4, T5 representthe mixture of long chain materials typical for tallow are particularlypreferred.Specific examples of quaternary ammonium compounds suitable for usein the aqueous fabric softening compositions herein include :1) N,N-di(tallowyl-oxy-ethyl)âN,N-dimethyl ammonium chloride;2) N,N-di(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl)methyl sulfate;3) N,N-di(2-ta||owyl-oxy-2-oxo-ethyl)âN,N-dimethyl ammonium chloride;4) _N,N-dil2-talIowyl-oxy-ethylcarbonyl-oxy-ethyl)-N,N-dimethylammonium chloride;5) N-(2-tallowyl-oxy-2âethy|)-N-(2-talIowyl-oxy-2-oxo-ethyl)-N,N-dimethyl ammonium chloride;6) N,N,N-tri(tallowyl-oxy-ethyl)-N-methyl ammonium chloride;7) N-(2-taIlowy|-oxy-2âoxo-ethyl)-N-(tallowyl-N,N-dimethyl-ammoniumchloride; and8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride;and mixtures of any of the above materials.Of these, compounds 1-7 are examples of compounds of Formula (I);compound 8 is a compound of Formula (II).Particularly preferred is N,N-diltallowyl-oxy-ethyl)-N,N-dimethylammonium chloride, where the tallow chains are at least partiallyunsaturated.The level of unsaturation of the tallow chain can be measured by theIodine Value (IV) of the corresponding fatty acid, which in the presentPCT/US97/16546ammonium '101520253035CA 02265740 l999-03- 10WO 98/122962 8âcase should preferably be in the range of from 5 to 100 with twocategories of compounds being distinguished, having a lV below or above25.indeed, for compounds of Formula (I) made from tallow fatty acidshaving a IV of from 5 to 25, preferably 15 to 20, it has been found thata cis/trans isomer weight ratio greater than 30/70, preferably greaterthan 50/50 and more preferably greater than 70/30 provides optimalconcentrability.For compounds of Formula ll) made from tallow fatty acids having a IVof above 25, the ratio of cis to trans isomers has been found to be lesscritical unless very high concentrations are needed.Other examples of suitable quaternary ammoniums of Formula (I) and (II)are obtained by, e.g. :- replacing "tallow" in the above compounds with, for example, coco,palm, lauryl, oleyl, ricinoleyl, stearyl, palmityl, or the like, said fattyacyl chains being either fully saturated, or preferably at least partlyunsaturated;- replacing "methyl" in the above compounds with ethyl, ethoxy, propyl,propoxy, isopropyl, butyl, isobutyl or t-butyl;- replacing "chloride" in themethylsulfate, formate, sulfate, nitrate, and the like.above compounds with bromide,in fact, the anion is merely present as a counterion of the positivelycharged quaternary ammonium compounds. The nature of the counterionis not critical at all to the practice of the present invention. The scope ofthis invention is not considered limited to any particular anion.By "amine precursors thereof" is meant the secondary or tertiary aminescorresponding to the above quaternary ammonium compounds, saidamines being substantially protonated in the present compositions due tothe pH values.Additional fabric softening materials may be used in addition oralternatively to the cationic fabric softener. These may be selected fromPCT/US97/16546101520253035WO 98/12296CA 02265740 l999-03- 1029ânonionic, amphoteric or anionic fabric softening material, Disclosure ofsuch materials may be found in US 4,327,133; US 4,421,792; US4,426,299; US 4,460,485; US 3,644,203; US 4,661,269; U.S4,439,335; U.S 3,861,870; US 4,308,151; US 3,886,075; US4,233,164; US 4,401,578; US 3,974,076; US 4,237,016 and EP472,178.Typically, such nonionic fabric softener materials have an HLB of from 2to 9, more typically from 3 to 7. Such nonionic fabric softener materialstend to be readily dispersed either by themselves, or when combinedwith other materials such as single-long-chain alkyl cationic surfactantdescribed in detail hereinafter. Dispersibility can be improved by usingmore single-long-chain alkyl cationic surfactant, mixture with othermaterials as set forth hereinafter, use of hotter water, and/or moreagitation. in general, the materials selected should be relativelycrystalline, higher melting, (e.g. >40°Cl and relatively water-insoluble.Preferred nonionic softeners are fatty acid partial esters of polyhydricalcohols, or anhydrides thereof, wherein the alcohol, or anhydride,contains from 2 to 18, preferably from 2 to 8, carbon atoms, and eachfatty acid moiety contains from 12 to 30, preferably from 16 to 20,carbon atoms. Typically, such softeners contain from one to 3,preferably 2 fatty acid groups per molecule.The polyhydric alcohol portion of the ester can be ethylene glycol,glycerol, poly (e.g., di-, tri-, tetra, penta-, and/or hexa-) glycerol, xylitol,sucrose, erythritol, pentaerythritol, sorbitol or sorbitan. Sorbitan estersand polyglycerol monostearate are particularly preferred.The fatty acid portion of the ester is normally derived from fatty acidshaving from 12 to 30, preferably from 16 to 20, carbon atoms, typicalexamples of said fatty acids being lauric acid, myristic acid, palmitic acid,stearic acid and behenic acid.Highly preferred optional nonionic softening agents for use in the presentinvention are the sorbitan esters, which are esterified dehydrationproducts of sorbitol, and the glycerol esters.PCT /US97/ 16546101520253035CA 02265740 l999-03- 10W0 98/1229630Commercial sorbitan monostearate is a suitable material. Mixtures ofsorbitan stearate and sorbitan palmitate having stearate/palmitate weightratios varying between 10:1 and 1:10, and 1,5-sorbitan esters are alsouseful.Glycerol and polyglycerol esters, especially glycerol, diglycerol,triglycerol, and polyglycerol monoâ and/or di-esters, preferably monoâ, arepreferred herein (e.g. polyglycerol monostearate with a trade name ofRadiasurf 7248).Useful glycerol and polyglycerol esters include monoâesters with stearic,oleic, palmitic, lauric, isostearic, myristic, and/or behenic acids and thediesters of stearic, oleic, palmitic, Iauric, isostearic, behenic, and/ormyristio acids. It is understood that the typical mono-ester contains somedi- and tri-ester, etc.The "glycerol esters" also include the polyglycerol, e.g., diglycerolthrough octaglycerol esters. The polyglycerol polyols are formed bycondensing glycerin or epichlorohydrin together to link the glycerolmoieties via ether linkages. The monoâ and/or diesters of the polyglycerolpolyols are preferred, the fatty acyl groups typically being thosedescribed hereinbefore for the sorbitan and glycerol esters.Further fabric softening components suitable for use herein are thesoftening clays, such as the low ion-exchange~capacity ones described inEP-A-0,150,531.For the preceding fabric softening agents, especially with biodegradablefabric softening agents, the pH of the liquid compositions herein is anessential parameter of the present invention. Indeed, it influences thestability of the quaternary ammonium or amine precursors compounds,especially in prolonged storage conditions. The pH, as defined in thepresent context, is measured in the neat compositions at 20°C. Foroptimum hydrolytic stability of these compositions, the neat pH,measured in the above-mentioned conditions, must be in the range offrom 2.0 to 4.5. liquid fabric softeningPreferably. where thePCT/US97ll6546101520253035W0 98/ 12296CA 02265740 l999-03- 10PCTIUS97l165463 1' compositions of the invention are in a concentrated form, the pH of theneat composition is in the range of 2.0 to 3.5, while if it is in a dilutedform, the pH of the neat composition is in the range of 2.0 to 3Ø ThepH of these compositions herein can be regulated by the addition of aBronsted acid.Examples of suitable acids include the inorganic mineral acids, carboxylicacids, in particular the low molecular weight (C1-C5) carboxylic acids,and alkylsulfonic acids. Suitable inorganic acids include HCI, H2804,HNO3 and H3PO4. Suitable organic acids include formic, acetic, citric,methylsulfonic and ethylsulfonic acid. Preferred acids are citric,hydrochloric, phosphoric, formic, methylsulfonic acid, and benzoic acids.Additional componentsThe composition may also optionally contain additional components suchas enzymes, surfactant concentration aids, electrolyte concentration aids,stabilisers, such as well-known antioxidants and reductive agents, soilrelease polymers, emulsifiers, bacteriocides, colorants, perfumes,preservatives, optical brighteners, anti-ionisation agents, and antifoamagents and mixtures thereof. These ingredients, especially the minoringredients, and especially perfume, can be usefully added with, andpreferably protected by, "carrier materials" such as zeolites, starch,cyclodextrin, wax, etc.EnzymesThe composition herein can optionally employ one or more enzymes suchas lipases, proteases, cellulase, amylases and peroxidases. A preferredenzyme for use herein is a cellulase enzyme. Indeed, this type of enzymewill further provide a color care benefit to the treated fabric. Cellulasesusable herein include both bacterial and fungal types, preferably having apH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al,March 6, 1984, discloses suitable fungal cellulases from Humicolainso/ens or Humicola strain DSM180O or a cellulase 212-producingfungus belonging to the genus Aeromonas, and cellulase extracted fromthe hepatopancreas of a marine mollusk, Dolabella Aur/âcu/a So/ander.101520253035WO 98/12296CA 02265740 l999-03- 10PCT/U S97/ 1654632âSuitable cellulases are also disclosed in GB-A-2.075.028; GB~A-2.095.275 and DE-OSâ2.247.832. CAREZYME® and CELLUZYME®(Novol are especially useful. Other suitable cellulases are also disclosedin WO 91/17243 to Nova, WO 96/34092, WO 96/34945 and EP-A-0,739,982.In practical terms for current commercial preparations, typical amountsare up to about 5 mg by weight, more typically 0.01 mg to 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from 0.001% to 5%,preferably 0.01%-1% by weight of a commercial enzyme preparation. Inthe particular cases where activity of the enzyme preparation can bedefined otherwise such as with cellulases, corresponding activity unitsare preferred (e.g. CEVU or cellulase Equivalent Viscosity Units). Forinstance, the compositions of the present invention can contain cellulaseenzymes at a level equivalent to an activity from about 0.5 to 1000CEVU/gram of composition. Cellulase enzyme preparations used for thepurpose of formulating the compositions of this invention typically havean activity comprised between 1,000 and 10,000 CEVU/gram in liquidform, around 1,000 CEVU/gram in solid form.Surfactant concentration aidsSurfactant concentration aids may also optionally be used. When used,said surfactant concentration aid will help achieving the desired finishedproduct viscosity as well as stabilising the finished product upon storage.Surfactant concentration aids are typically selected from single longchain alkyl cationic surfactants, nonionic alkoxylated surfactants, amineoxides, fatty acids, and mixtures thereof, typically- used at a level of from0 to 15% by weight of the composition.Single long chain alkyl cationic surfactantsSuch monoâlong-chain-alkyl cationic surfactants useful in the presentinvention are, preferably, quaternary ammonium salts of the generalformula :1015202530WO 98/12296CA 02265740 l999-03- 10PCT/US97/1654633[R2N + H3] Xâwherein the R2 group is C10-C22 hydrocarbon group, preferably C12-C13 alkyl group of the corresponding ester linkage interrupted group witha short alkylene (C1-C4) group between the ester linkage and the N, andhaving a similar hydrocarbon group, e.g., a fatty acid ester of choline,preferably C12-C14 (coco) choline ester and/or C15-C13 tallow cholineester at from 0.1% to 20% by weight of the softener active. Each R is aC1-C4 alkyl or substituted (e.g., hydroxy) alkyl, or hydrogen, preferablymethyl, and the counterion Xâ is a softener compatible anion, forexample, chloride, bromide, methyl sulfate, etc.Other cationic materials with ring structures such as alkyl imidazoline,imidazolinium, pyridine, and pyridinium salts having a single C12-C30alkyl chain can also be used. Very low pH is required to stabilize, e.g.,imidazoline ring structures.Some alkyl imidazolinium salts and their imidazoline precursors useful inthe.present invention have the general formula :CII-I2é(|IH2+N Nâ-C H -Y-R Xl RR8wherein Y2 is -ClOl-O-, -oâ(o)c-, -C(Ol-N(R5)-, or -N(R5l-C(O)- in whichR5 is hydrogen or a C1-C4 alkyl radical; R6 is a C1-C4 alkyl radical or H(for imidazoline precursors); R7 and R3 are each independently selectedfrom R and R2 as defined hereinbefore for the sing|eâlong-chain cationicsurfactant with only one being R2,Some alkyl pyridinium salts useful in the present invention have thegeneral formula :5101520253035W0 98/ 12296CA 02265740 l999-03- 10PCT/U S97/ 1654634wherein R2 and X- are as defined above. A typical material of this typeis cetyl pyridinium chloride.Nonionic Alkoxylated SurfactantSuitable nonionic alkoxylated surfactants for use herein include additionproducts of ethylene oxide and, optionally, propylene oxide, with fattyalcohols, fatty acids and fatty amines.Suitable compounds are substantially water-soluble surfactants of thegeneral formula :R2 - Y - lC2H40lz - C2H4O'Hwherein R2 is selected from primary, secondary and branched chain alkyland/or acyl hydrocarbyl groups; primary, secondary and branched chainalkenyl hydrocarbyl groups; and primary, secondary and branched chainalkyl- alkenyl-substituted phenolic groups; saidhydrocarbyl groups having a hydrocarbyl chain length of up to 20,preferably from 10 to 18 carbon atoms.and hydrocarbylY is typically -0-, -ClO)O-, -C(O)N(Fl)-, or -C(O)N(R)R-, in which R2 andR, when present, have the meanings given hereinbefore, and/or R can behydrogen, and z is of from 5 to 50, preferably of from 1- to 30.The nonionic surfactants herein are characterized by an HLB (hydrophilic-lipophilic balance) of from 7 to 20, preferably from 8 to 15.Examples of particularly suitable nonionic surfactants include- Straight-Chain, Primary Alcohol Alkoxylates such as tallow alcohol-EO(11), tallow alcohol-EO(18l, and tallow alcohol-EO(25);- Straight-Chain, Secondary Alcohol Alkoxylates such as 2-C15EO(11);2âC20EOl11): and 2-C13EO(14l;101520253035WO 98112296CA 02265740 l999-03- 1035'- Alkyl Phenol Alkoxylates, such as p-tridecylphenol EO(11) and p-pentadecylphenol EO(18), as well as- Olefinic Alkoxylates, and Branched Chain Alkoxylates such asbranched chain primary and secondary alcohols which are availablefrom the well-known "0XO" process.Amine OxidesSuitable amine oxides include those with one alkyl or hydroxyalkyl moietyof 8 to 28 carbon atoms, preferably from 8 to 16 carbon atoms, and twoalkyl moieties selected from alkyl groups and hydroxyalkyl groups with 1to 3 carbon atoms.Examples include dimethyloctylamine oxide, diethyldecylamine oxide, bis-(2-hydroxyethylldodecylamine oxide, dimethyldodecyl-amine oxide,dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,dimethyl-2-hydroxyoctadecylamine oxide, and coconut fatty alkyldimethylamine oxide.Fatty AcidsSuitable fatty acids include those containing from 12 to 25, preferablyfrom 16 to 20 total carbon atoms, with the fatty moiety containing from10 to 22, preferably from 15 to 17 (mid cut), carbon atoms.A preferred surfactant concentration aid for use herein is a nonionicalkoxylated surfactant. When used, such nonionic alkoxylated surfactantwill be present in an amount of 0.01% to 10% by weight, preferablyfrom 0.05% to 2% by weight of the composition. Most preferably, foroptimum stabilisation of the composition, the composition of theinvention has a weight ratio of amino-functional polymer to nonionicalkoxylated surfactant of from 500:1 to O.5:1, preferably of from 30:1to 1:1.PCT/US97/16546101520253035W0 98/ 12296CA 02265740 l999-03- 10PCT/U S97/ 1654636â Electrolyte Concentration Aidslnorganic viscosity control agents which can also act like or augment theeffect of the surfactant concentration aids, include water-soluble,ionizable salts which can also optionally be incorporated into thecompositions of the invention.present Incorporation of thesecomponents to the composition must be processed at a very slow rate.A wide variety of ionizable salts can be used. Examples of suitable saltsare the halides of the Group IA and l|A metals of the Periodic Table ofthe Elements, e.g., magnesium chloride, sodiumchloride, potassium bromide, and lithium chloride. The ionizable salts arecalcium chloride,particularly useful during the process of mixing the ingredients to makethe compositions herein, and later to obtain the desired viscosity. Theamount of ionizable salts used depends on the amount of activeingredients used in the compositions and can be adjusted according tothe desires of the formulator. Typical levels of salts used to control thecomposition viscosity are from 20 to 20,000 parts per million (ppm),preferably from 20 to 1 1,000 ppm, by weight of the composition.Alkylene polyammonium salts can be incorporated into the compositionto give viscosity control in addition to or in place of the water-soluble,ionizable salts above. In addition, these agents can act as scavengers,forming ion pairs with anionic detergent carried over from the mainwash, in the rinse, and on the fabrics, and may improve softnessperformance. These agents may stabilise the viscosity over a broaderrange of temperature, especially at low temperatures, compared to theinorganic electrolytes.Specific examples of alkylene polyammonium salts include I-lysinemonohydrochloride 2-methyldihydrochloride.and 1 ,5-diammonium pentaneAnother optional ingredient is a liquid carrier. Suitable liquid carriers areselected from water, organic solvents and mixtures thereof. The liquidcarrier employed in the instant compositions is preferably at leastprimarily water due to its low cost relative availability, safety, and101520253035WO 98/12296CA 02265740 l999-03- 1037environmental compatibility. The level of water in the liquid carrier ispreferably at least 50%, most preferably at least 60%, by weight of theMixtures of water and low molecular weight, e.g., <200,e.g., such as ethanol, propanol,isopropanol or butanol are useful as the carrier liquid. Low molecularweight alcohols include monohydric, dihydric (glycol, etc.) trihydric(glycerol, etc.), and higher polyhydric (polyols) alcohols.carrier.organic solvent, lower alcoholMethodIn another aspect of the invention, there is provided a method forproviding color care to fabrics upon domestic laundering treatment whichcomprises the step of contacting the fabrics with an aqueous mediumcomprising a composition as defined hereinbefore. Preferably, saidaqueous medium is at a temperature between 2°C to 40°C, morepreferably between 5°C to 25°C.In a further aspect of the invention, the composition of the inventionmay be applied on a substrate, such as a dryerâsheet. Accordingly, thereis also provided a method for providing color care on treated» fabrics upondomestic treatment which comprises the step of contacting the fabricswith a composition as defined hereinbefore, wherein said composition isapplied on a substrate, preferably a dryerâsheet. Preferably, where thecomposition of theinvention is applied on a dryerâsheet. thecompositions are used in tumble-drying processes.By "color care" is meant that fabrics which have been in contact with anaqueous solution of a composition comprising a combination of a dyefixing agent and an aminoâfunctional polymer, as defined hereinbefore,and after, and/or prior and/or simultaneously washed with a detergentcomposition exhibit a better fabric color appearance compared to fabricswhich have not been contacted with said composition.ApplicationsThe compositions of the invention are suitable for use in differentapplications such as a pre-treatment composition prior to the launderingPCT/US97/16546101520253035W0 98/12296CA 02265740 l999-03- 1038* of the fabrics, as a wash additive, as a composition suitable for use inthe rinse-cycle of the laundry cycle or applied on a dryerâsheet. Thecompositions of the invention may also be in a spray, foam, or aerosolform which for example can be suitable for use while ironing, or appliedon the surfaces of the tumble dryer.The color care benefit may either be assessed visually or bydetermination of the so-called delta-E values.When the visual assessment is used, a panel of expert graders visuallycompare, according to the established panel score unit (PSU) scales,fabrics treated with and without the composition according to thepresent invention. A positive PSU value indicates a better performance(PSU scale: 0 = no difference, 1 = I think there is a difference, 2 = Iknow there is a difference, 3 = I know there is a lot of difference, 4 = iknow there is a whole lot of difference).Another method for the assessment of the color care benefit to fabrics isthe_ determination of the so-called delta-E values. Delta E's are defined,for instance, in ASTM D2244. Delta E is the computed color differenceas defined in ASTM D2244, i.e the magnitude and direction of thedefined bytristimulus values, or by chromaticity coordinates and luminance factor,difference between two psychophysical color stimulias computed by means of a specified set of color-difference equationsdefined in the CIE 1976 CIELAB opponent-color space, the Hunteropponent-color space, the Friele-Mac AdamâChickering color space orany equivalent color space.The invention is illustrated in the following non-limiting examples, inwhich all percentages are on an active weight basis unless otherwisestated.In the examples, the abbreviated component identifications have thefollowing meanings:DEQADOEQAPCT/US97/16546Di-(tallowyl-oxy-ethyl) dimethyl ammonium chlorideDi-(oleyloxyethyl) dimethyl ammonium methylsulfateW0 98/12296A ' DTDMACDHEQAFatty acidElectrolyteDTDMAMSSDASAGlycosperse S-20ClayNeodol 45-13TAE25PEGPEIPEI 1800 E1PEI 1200 E1Dye Fix 1Dye Fix 2CarezymeCA 02265740 l999-03- 10PCT/US97l1654639Ditallow dimethylammonium chlorideDi-(soft-tallowylâoxy-ethyl) hydroxyethyl methylammonium methylsulfateStearic acid of lV=OCalcium chlorideDitallow dimethyl ammonium methylsulfate1:2 Ratio of stearyldimethyl amineztriple-pressedstearic acidPolyethoxylated sorbitan monostearate available fromLonzaCalcium Bentonite Clay, Bentonite L, sold bySouthern Clay ProductsC14-C15 linear primary alcohol ethoxylate, sold byShell Chemical Co 'Tallow alcohol ethoxylated with 25 moles of ethyleneoxide per mole of alcoholPolyethylene Glycol 4000Solution of polyethylene imine (MW 2000, at 50%active) available under the tradename Lupasol G35from BASFEthoxylated polyethylene imine (MW 1800, at 50%active) as synthesised in Synthesis example 1Ethoxylated polyethylene imine (MW 1200, at 50%active in water) as synthesised in Synthesis example5Cationic dye fixing agent (50% active) available underthe tradename Tinofix Eco from Ciba-GeigyEmulsified cationic dye fixative (30% active) availableunder the tradename Rewin SRF-O from CHT-Beitlichcellulytic enzyme sold by NOV0 Industries A/SSynthesis Example 1 -Pregaration of PEI 1800 E1Step A}The ethoxylation is conducted in a 2 gallon stirred stainless steelautoclave equipped for temperature measurement and control, pressure101520253035W0 98/ 12296âmeasurement, vacuum and inert gas purging. sampling,CA 02265740 l999-03- 1040and forintroduction of ethylene oxide as a liquid. A ~20 lb. net cylinder ofethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by apump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, EpominSP-018 having a listed average molecular weight of 1800 equating to0.417 moles of polymer and 17.4 moles of nitrogen functions) is addedto the autoclave. The autoclave is then sealed and purged of air (byapplying vacuum to minus 28'' H9 followed by pressurization withTheautoclave contents are heated to 130 °C while applying vacuum. Afterabout one hour, the autoclave is charged with nitrogen to about 250 psiawhile cooling the autoclave to about 105 °C. Ethylene oxide is thenadded to the autoclave incrementally over time while closely monitoringnitrogen to 250 psia, then venting to atmospheric pressure).the autoclave pressure, temperature, and ethylene oxide flow rate. Theethylene oxide pump is turned off and cooling is applied to limit anytemperature increase resulting from any reaction exotherm. Thetemperature is maintained between 100°C and 110°C while the totalpressure is allowed to gradually increase during the course of thereaction. After a total of 750 grams of ethylene oxide has been chargedto the autoclave (roughly equivalent to one mole ethylene oxide per PEInitrogen function), the temperature is increased to 110°C and theautoclave is allowed to stir for an additional hour. At this point, vacuumis applied to remove any residual unreacted ethylene oxide.Step 8)The reaction mixture is then deodorized by passing about 100 cu. ft. ofinert gas (argon or nitrogen) through a gas dispersion frit and through thereaction mixture while agitating and heating the mixture to 130°C.The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen.PC'IâIUS97ll6546101520253035WO 98/12296CA 02265740 l999-03- 10PCT/US97/ 1654641- In other preparations the neutralization and deodorization is accomplishedin the reactor before discharging the product.if a PEI 1800 E7 is desired, the following step of catalyst addition will beincluded between Step A and B.Vacuum is continuously applied while the autoclave is cooled to about50°C while introducing 376g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PEInitrogen functions). The methoxide solution is sucked into the autoclaveunder vacuum and then the autoclave temperature controller setpoint isincreased to 130°C. A device is used to monitor the power consumedby the agitator. The agitator power is monitored along with thetemperature and pressure. Agitator power and temperature valuesgradually increase as methanol is removed from the autoclave and theviscosity of the mixture increases and stabilizes in about 1 hourindicating that most of the methanol has been removed. The mixture isfurther heated and agitated under vacuum for an additional 30 minutes.Vacuum is removed and the autoclave is cooled to 105°C while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100°C and110°C and limiting any temperature increases due to reaction exotherm.After the addition of 4,500g of ethylene oxide (resulting in a total of 7moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110°C and themixture stirred for an additional hour.The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles).101520253035WO 98/12296CA 02265740 l999-03- 1042â âSvnthesis Example 2 -4.7% Quaternization of PEI 1800 E7To a 500m) erlenmeyer flask equipped with a magnetic stirring bar isadded polylethyleneimine), MW 1800 ethoxylated to a degree of 7(2249, 0.637 mol nitrogen, prepared as in Synthesis Example 1) andacetonitrile (Baker, 150g, 3.65 mol). Dimethyl sulfate (Aldrich, 3.89,0.030 mol) is added all at once to the rapidly stirring solution, which isthen stoppered and stirred at room temperature overnight. Theacetonitrile is evaporated on the rotary evaporator at ~60°C, followedby a Kugelrohr apparatus (Aldrich) at ~80°C to afford ~220g of thedesired material as a dark brown viscous liquid. A 13C-NMR (D20)spectrum shows the absence of a peak at ~58ppm corresponding todimethyl sulfate. A 1H-NMR (D20) spectrum shows the partial shiftingof the peak at 2.5ppm (methylenes attached to unquaternized nitrogens)to ~3.0ppm.Svnthesis Example 3 -Oxidation of 4.7% Quaternized PE) 1800 E7To-a 500ml erlenmeyer flask equipped with a magnetic stirring bar isadded poly(ethyleneimine), MW 1800 which has been ethoxylated to adegree of 7, and ~4.7% quaternized with dimethyl sulfate (121.79,~0.32 mol oxidizeable nitrogen, prepared as in Synthesis Example 2),hydrogen peroxide (Aldrich, 40g of a 50 wt% solution in water, 0.588mol), and water (109.49). The flask is stoppered, and after an initialexotherm the solution is stirred at room temperature overnight. A âH-NMR (D20) spectrum shows the total shifting of the methylene peaks at2.5â3.0ppm to ~3.5ppm. To the solution is added ~59 of 0.5% Pd onalumina pellets, and the solution is allowed to stand at room temperaturefor ~3 days. Peroxide indicator paper shows that no peroxide is left inthe system. The material is stored as a 46.5% solution in water.Svnthesis Example 4 -Formation of amine oxide of PE) 1800 E2To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar isadded polyethyleneimine having a molecular weight of 1800 andethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI-1800, E7) (209 g, 0.595 mol nitrogen, prepared as in Synthesis ExamplePCT/US97/ 16546101520253035WO 98/12296CA 02265740 l999-03- 1043'l), and hydrogen peroxide (120 g of a 30 wt % solution in water, 1.06mol). The flask is stoppered, and after an initial exotherm the solution is1H-NMR (D20) spectrumobtained on a sample of the reaction mixture indicates completestirred at room temperature overnight.conversion. The resonances ascribed to methylene protons adjacent tounoxidized nitrogens have shifted from the original position at ~2.5 ppmto ~3.5 ppm. To the reaction solution is added approximately 5 g of0.5% Pd on alumina pellets, and the solution is allowed to stand at roomtemperature for approximately 3 days. The solution is tested and foundto be negative for peroxide by indicator paper. The material as obtainedis suitably stored as a 51.1% active solution in water.Svnthesis Example 5 -Preparation of PEI 1200 E 1Step A)The ethoxylation is conducted in a 2 gallon stirred stainless steelautoclave equipped for temperature measurement and control, pressureand forintroduction of ethylene oxide as a liquid. A ~20 lb. net cylinder ofmeasurement, vacuum and inert gas purging, sampling,ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by apump to the autoclave with the cylinder placed on a scale so that theweight change of the cylinder could be monitored.A 750 g portion of polyethyleneimine (PEI) ( having a listed averagemolecular weight of 1200 equating to about 0.625 moles of polymer andTheautoclave is then sealed and purged of air (by applying vacuum to minus28" Hg followed by pressurization with nitrogen to 250 psia, then17.4 moles of nitrogen functions) is added to the autoclave.venting to atmospheric pressure). 'The autoclave contents are heated to130°C while applying vacuum. After about one hour, the autoclave ischarged with nitrogen to about 250 psia while cooling the autoclave toabout 105°C. Ethylene oxide is then added to the autoclaveincrementally over time while closely monitoring the autoclave pressure,temperature, and ethylene oxide flow rate. The ethylene oxide pump isturned off and cooling is applied to limit any temperature increaseresulting from any reaction exotherm. The temperature is maintainedPCT/US97/ 16546CA 02265740 l999-03- 10WO 98/12296 PCTlUS97l 1654610152025303544âbetween 100°C and 110°C while the total pressure is allowed togradually increase during the course of the reaction. After a total of 750grams of ethylene oxide has been charged to the autoclave (roughlyequivalent to one mole ethylene oxide per PEl nitrogen function), thetemperature is increased to 110°C and the autoclave is allowed to stirfor an additional hour. At this point, vacuum is applied to remove anyresidual unreacted ethylene oxide.Step B)The reaction mixture is then deodorized by passing about 100 cu. ft. ofinert gas (argon or nitrogen) through a gas dispersion frit and through thereaction mixture while agitating and heating the mixture to 130°C.The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen-.in other preparations the neutralization and deodorization is accomplishedin the reactor before discharging the product.If a PEI 1200 E7 is desired, the following step of catalyst addition will beincluded between Step A and B.Vacuum is continuously applied while the autoclave is cooled to about50°C while introducing 376g of a 25% sodium methoxide in methanolsolution (1.74 moles, to achieve a 10% catalyst loading based upon PElnitrogen functions).The methoxide solution is sucked into the autoclave under vacuum andthen the autoclave temperature controller setpoint is increased to 130°C.A device is used to monitor the power consumed by the agitator. Theagitator power is monitored along with the temperature and pressure.Agitator power and temperature values gradually increase as methanol isremoved from the autoclave and the viscosity of the mixture increasesand stabilizes in about 1 hour indicating that most of the methanol hasbeen removed. The mixture is further heated and agitated under vacuumfor an additional 30 minutes.101520253035WO 98112296CA 02265740 l999-03- 1045âVacuum is removed and the autoclave is cooled to 105°C while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100°C and110°C and limiting any temperature increases due to reaction exotherm.After the addition of 4,5009 of ethylene oxide (resulting in a total of 7moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110°C and themixture stirred for an additional hour.The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167g methanesulfonic acid (1.74 moles).Other preferred examples such as PEI 1200 E15 and PEI 1200 E20 canbe prepared by the above method by adjusting the reaction time and therelative amount of ethylene oxide used in the reaction.Synthesis Example 6 -9.7% Quaternization of PEI 1200 E7To a 500ml erlenmeyer flask equipped with a magnetic stirring bar isadded polylethyleneiminel, MW 1200 ethoxylated to a degree of 7(248.49, 0.707 mol nitrogen, prepared as in Synthesis Example 5) andacetonitrile (Baker, 200 mL). Dimethyl sulfate (Aldrich, 8.489, 0.067mall is added all at once to the rapidly stirring solution, which is thenstoppered and stirred at room temperature overnight. The acetonitrile isevaporated on the rotary evaporator at ~60°C, followed by a Kugelrohrapparatus (Aldrich) at ~80°C to afford ~220g of the desired material asa dark brown viscous liquid. A 13C-NMR (D20) spectrum shows theabsence of a peak at ~58ppm corresponding to dimethyl sulfate. A 1H-NMR (D20) spectrum shows the partial shifting of the peak at 2.5ppm(methylenes attached to unquaternized nitrogens) to ~3.0ppm.Svnthesis Example 7-4.7% Oxidation of 9.5% Quaternized PEI 1200 E7PCT/US97Il65461015W0 98/ 12296CA 02265740 l999-03- 1046To a 500ml erlenmeyer flask equipped with a magnetic stirring bar isadded polylethylenelmine), MW 1200 which has been ethoxylated to adegree of 7, and ~9.5% quaternized with dimethyl sulfate (144g,~O.37 mol oxidizeable nitrogen, prepared as in Example 6), hydrogenperoxide (Aldrich, 35.4g of a 50 wt% solution in water, 0.52 mol), andwater (1009). The flask is stoppered, and after an initial exotherm thesolution is stirred at room temperature overnight. A 1H-NMR (D20)spectrum shows the total shifting of the methylene peaks at 2.5-3.0ppmto ~3.5ppm. To the solution is added just enough sodium bisulfite as a40% water solution to bring the residual peroxide level down to 1-5ppm.The sodium sulfate which forms causes an aqueous phase to separatewhich contains salts, but little or no organics. The aqueous salt phase isremoved and the desired oxidized polyethyleneimine derivative isobtained and stored as a 52% solution in water.PCT/US97/ 16546CA 02265740 l999-03- 10W0 98/12296 PCT/US97/1654647Example 1The following compositions are in accordance with the present inventionComponent A B C D E F GDEQA 2.6 2.9 18.0 19.0 19.0 - -TAE25 - 1.0 - - - -Fatty acid 0.3 - 1.0 â - - -Hydrochloride acid 0.02 0.02 0.02 0.02 0.02 - -PEG - - 0.6 0.6 0.6 - -Perfume 1.0 1.0 1.0 1.0 1.0 â -Silicone antifoam 0.01 0.01 0.01 0.01 0.01 - -PEI 3 3 3 3 3 ~ 15 10Dye ï¬x 1 1 1 1 1 1 5 10Dye ï¬x 2 2 2 2 2 - - âElectrolyte (ppm) - - 600 600 1200 - -Dye (ppm) 10 10 50 50 50 - -Water and minors to balance to 100Component H I I K L M N O PDTDMAC â - - - - â - 4.5 15DEQA 2.6 2.9 18.0 19.0 19.0 - - - âTAE25 0.3 - 1.0 - 0.1 - - - -Fatty acid 0.3 - 1.0 - - - - - -Hydrochloride 0.02 0.02 0.02 0.02 0.02 - - 0.02 0.02acidPEG - - 0.6 0.6 0.6 - - - 0.6Perï¬ime ' 1.0 1.0 1.0 1.0 1.0 - - 1.0 1.0Silicone antifoam 0.01 0.01 0.01 0.01 0.01 - - 0.01 0.01PEI 1800 E1 3 - â 3 - 10 - - 3PEI 1200 E1 - 3 3 - 3 - 15 3 -Dye ï¬x 1 1 1 1 1 3 10 5 1 1Dye ï¬x 2 2 2 2 2 - - - 2 2Electrolyte (ppm) - - 600 600 1200 - - â 600Dye (ppm) 10 10 50 50 50 - â 10 50SUBSTITUTE SHEET (RULE 26)W0 98/ 12296CA 02265740 l999-03- 1048PCT/US97/ 16546CarezymeCEVU/ g ofcomposition '50Water and minors to balance to 100Example 2The following compositions for use as dryer-added sheets are in accordance with theinventionQ R S T U VDOEQA 3 9. 16 24.79 -- -- -- --DHEQA -- -- 21.81 -- -- --DTDMAMS -- -- â- 18.64 1 1.94 62.0SDASA 34.41 28.16 21.33 28.04 21.52 --Glycosgerse S-20 -- -â 12.38 -- -- --Glycerol _ -- -- -- 18.87 13.23 --MonostearateClay 4.02 4.02 3.16 3.91 3.90 --Perfume 0.7 1.1 0.7 1.6 2.6 1.4PEI - 5.3 - - - -PEI 1200 E1 - â 4.1 2.2 â -PEI 1800 B1 2.1 - - â 5.2 7.0Dye ï¬x 1 2.1 5.3 4.1 2.2 5.2 3.2Stearic acid to balanceSUBSTITUTE SHEET (RULE 26)
