WO2000015745A1 - Rinse-added fabric care compositions comprising low molecular weight linear and cyclic polyamines - Google Patents

Abstract

The present invention relates to fabric care compositions which comprises low molecular weight linear or cyclic polyamines which provide the compositions with addition fabric enhancement benefits inter alia fabric softness, fabric integrity, fabric appearance, fabric lubricity. Preferred polyamines are N,N'-bis(3-aminopropyl)-1,3-propyldiamine (TPTA) and N,N'-bis(3-aminopropyl)-1,4-piperazine (BNPP).

Description

RINSE-ADDED FABRIC CARE COMPOSITIONS

COMPRISING LOW MOLECULAR WEIGHT

LINEAR AND CYCLIC POLYAMINES

FIELD OF THE INVENTION The present application relates to πnse-added fabric care compositions which compnse one or more low molecular weight polyamines which provide enhanced fabπc appearance benefits. The low molecular weight polyamines of the present invention which mitigate fabπc damage and improve fabπc appearance are preferably modified polypropyleneimines having four backbone amino units.

BACKGROUND OF THE INVENTION Formulators of rinse-added fabric care compositions include various ingredients, inter alia cationic softening actives, anti-static agents, dye transfer inhibitors, and bleach-damage mitigating agents, for the purpose of improving fabric appearance, fabπc feel, fabric color and to extend the duration of fabπc life. Ingredients which are added to these compositions must not only provide a benefit, but must be compatible with a variety of product forms, i.e. liquid dispersions, isotropic liquids including clear, colorless/translucent liquids which may include principal solvents inter alia 1,2-hexanedιol, 2,2,4-tπmethyl-l,3-pentanedιol (TMPD).

Many adjunct ingredients which provide fabπc enhancement benefits are highly fabπc substantive and. therefore, once deposited on the fabπc surface remain with the fabπc thereby providing the intended benefit until chemically altered or until displaced by a more fabric substantive mateπal. High molecular weight modified polyalkyleneimines have been used m πnse-added fabπc care compositions to mitigate fabπc damage. These highly fabπc substantive ingredients are deposited onto fabπc duπng the near neutral pH environment of the laundry πnse cycle. Once deposited they serve a vaπety of purposes depending upon the absolute structure of the polyalkyleneamine or polyalkyleneimine and whether the polymeπc amme is modified (for example, ethoxylated).

Color integrity is an important aspect of fabric enhancement. When certain polyamines are deposited onto fabπc they enhance color fidelity via various mechanisms. Other polyamines intercept peroxygen bleaching agents at the fabric surface. Consumers use bleach-containing compositions when washing colored fabric as well as white fabπc because the use of a bleaching material satisfies the consumers need to feel that the fabric has been "thoroughly cleaned". Therefore, there is a long felt need to provide colored fabric with protection against the pejorative effects of laundry-added bleaching materials. In addition, there is a need for materials which will be highly water soluble or water dispersible, hile exhibiting a high degree of fabπc substantivity. And there is also a need for a mateπal which will provide a high level of fabric protection on an efficient per unit weight basis.

SUMMARY OF THE INVENTION The present invention meets the aforementioned needs in that it has been surpnsingly discovered that polyamines, preferably linear propyleneimines and 1 ,4-pιperazmes having at least one N-substituted 3-amιnopropylene unit, and which have a backbone molecular weight, pπor to any subsequent modification, of approximately 250 daltons, and which remain unmodified, or which are partially or fully modified, are suitable for use in rinse-added fabric care compositions to provide a wide array of fabric appearance benefits depending upon the type of substitution selected by the formulator inter alia mitigation of fabric damage via bleaching agents. A first aspect of the present invention which relates to the issue of fabric color fidelity, are πnsed-added fabric enhancement compositions comprising: a) from about 0.01%, preferably from about 0.75%, more preferably from 2%, to about 50%, preferably to about 35%, more preferably to about 20%, most preferably to about 15% by weight, of one or more modified polyamines, said polyamines selected from: l) linear polyamines having the formula: R²

(R')₂N— R— [N- R]— N(R')₂ n wherein each R is independently C_-C₆ linear alkylene, C₃-C₆ branched alkylene, and mixtures thereof; R¹ is hydrogen, Cj-C,: alkyl, alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C -C₆ linear alkylene, C₃-C₆ branched alkylene. or mixtures thereof, R⁴ is hydrogen, C,-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O — C— R⁵ wherein R⁵ is Cj-C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6: two R' units can be taken together to form a 5-7 member nng; and mixtures thereof; R² is hydrogen. R¹, -RN(R') , and mixtures thereof;

11) cyclic polyamines having the formula:

R— L— R wherein L is a linking unit, said linking unit compnsing a nng having at least 2 nitrogen atoms; R is hydrogen, -(CH_:\N(R')₂, and mixtures thereof, wherein each R¹ is hydrogen; Cj-C₁ alkyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C -C_b linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cj-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula: O C ^{1 1}— R 5⁵ wherein R⁵ is C|-C₂₂ linear or branched alkyl, C3-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R¹ units can be taken together to form a 5-7 member nng; k is from 3 to 12; and mixtures thereof: 111) and mixtures thereof; b) optionally from about 1%. preferably from about 10%, more preferably from about 20% to about 80%, preferably to about 60%, more preferably to about 45% by weight, of a fabric softening active; c) optionally less than about 15% by weight, of a principal solvent, preferably said principal solvent has a ClogP of from about 0.15 to about 1 ; d) optionally from about 0.001% to about 90% by weight, of one or more dye fixing agents: e) optionally from about 0.01 % to about 50% by weight, of one or more cellulose reactive dye fixing agents; 0 optionally from about 0.01% to about 15% by weight, of a chlorine scavenger; g) optionally about 0.005% to about 1% by weight, of one or more crystal growth inhibitors; h) optionally from about 0.01% to about 20% by weight, of a fabπc abrasion reducing polymer; 1) optionally from about 1% to about 12% by weight, of one or more liquid earners; j) optionally from about 0.001% to about 1% by weight, of an enzyme; k) optionally from about 0.01% to about 8% by weight, of a polyolefin emulsion or suspension; 1) optionally from about 0.01% to about 0.2% by weight, of a stabilizer; m) optionally from about 1% to about 80% by weight, of a fabric softening active; n) optionally from about 0.5% to about 10% by weight, of a cationic nitrogen compound; and o) the balance carπer and adjunct ingredients.

Another aspect of the present invention relates to clear, colorless or translucent isotropic liquids which are nnse-added fabπc color fidelity enhanced compositions. These isotropic liquid embodiments typically comprise less than about 95%, preferably less than about 50%, more preferably less than about 25%, most preferably less than about 15% by weight of a pnncipal solvent as defined herein below

The present invention also relates to fabric enhancement compositions which compnse a fabric care composition which comprises both a linear polyamme and a cyclic polyamme.

A further aspect of the present invention relates to liquid dispersion forms of the nnse- added compositions which may comprise polyamines which provide, in addition to color fidelity benefits, metal chelation and chlorine scavenging properties which provide enhanced fabπc softness, integrity, and appearance These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims All percentages, ratios and proportions 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 The present invention relates to πnse-added fabnc care compositions. The compositions of the present invention provide increased color fidelity benefits to fabnc in addition to other desirable benefits, inter alia fabric softness, fabric integrity, fabric appearance, fabric lubπcity. The nnse-added fabπc care compositions may take any form, for example, solids (i.e., powders, granules, extrudates), gels, thixotropic liquids, liquids (i.e., dispersions, isotropic solutions), preferably the rinse added fabric care compositions take the form of liquid dispersions or isotropic liquids.

It has now been surpnsingly discovered that low molecular weight propyleneimines, preferably polypropyleneimines (backbones having a MW < 250 daltons) or cyclic amines, preferably compnsing a N,N'-bιs-l,4-substιtuted piperazine ring, are highly fabπc substantive and, in addition, are capable of intercepting bleaching agents which may approach the fabnc surface. It has also been surprisingly discovered that a 3-carbon propylene spacing between nitrogen atoms of linear portions of the polyamme molecules provides for improved discrimination in the chelation of unwanted copper ions m solution over desirable copper which is included in the dye systems of fabric The compositions of the present invention comprise from about 0.01%o, preferably from about 0.75%), more preferably from 2%, to about 50%, preferably to about 35%, more preferably to about 20%), most preferably to about 15% by weight, of the herein descπbed polyamines.

The following descnbe in detail the essential elements of the present invention. Linear Polvammes

The enhanced fabric appearance compositions of the present invention may compnse one or more polyalkyleneimines which have backbones compnsing C₂-C₆ alkylene units, however, the backbones must comprise at least one C₃-C₆ alkylene unit, preferably the linear polyamines have each backbone unit comprising a C₃-C₆ alkylene unit. The polyamines of the present invention have the formula:

R² (R')₂N— R— [N— R1— N(R')₂ wherein each R is independently C₂-C_b linear alkylene, C₃-C₆ branched alkylene, and mixtures thereof; preferably the backbone is a mixture of ethylene, 1,3-propylene, 1.3 -propylene, 1,4- butylene, 1 ,6-hexylene, more preferably a mixture of ethylene and 1 ,3-propylene, most preferably the backbone comprises only 1 ,3-propylene units.

R' is hydrogen; C Ci alkyl. preferably C,-C₈ alkyl, more preferably CpC, alkyl; alkyleneoxy having the formula'

-(R 0)_m- R⁴ wherein R³ is C_:-C₆ linear alkylene. C₃-C₆ branched alkylene, or mixtures thereof: preferably ethylene, mixtures of ethylene and 1 ,2-propylene, 1,2-butylene, preferably ethylene, 1,2- propylene. R⁴ is hydrogen, C]-C_b alkyl, or mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen. The index m is from 1 to 4, however, the value of m is predicated on the desired fabric enhancement benefit sought by the formulator. For example, the level of bleach protection vanes over the value of m Also, the dye fixation properties of the substantially linear polyamines are maximized when the alkyleneoxy unit is absent, i.e., R¹ and R² are hydrogen. R¹ IS also acyl having the formula:

O

II

— C— R wherein R is C_:-C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; preferably R⁵ is a hydrocarbyl moiety which sufficiently provides increased fabnc lubncity, more preferably C₆-Cj₂ alkyl: hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein the index y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6 and the -(CHOH)- unit is not directly attached to a nitrogen atom. Non-limiting examples of hydroxy alkyl units include 2-hydroxy alkyl, for example, -CH₂CHOHCH₃, -CH₂CHOHCH₂CH₂CH₂CH₃. Two R units can be taken together to form a 5-7 member nng, i.e., pipendme, morphohne. An example of a backbone wherein two R¹ units are taken together to form a nng has the formula:

The present invention also includes mixtures of the herein described R¹ units. R^: is hydrogen, R¹, -RN(R') , and mixtures thereof. The integer n has the value from 1 or

6. preferably from 1 to 4, more preferably 1 or 3.

Most prefered linear polyamme has a backbone wherein R is 1 ,3-propylene and n is equal to 2, N.N^'-bιs(3-amιnopropyl)-l ,3-propylenedιamιne (TPTA). This preferred backbone can then be substituted or left unsubstituted in a manner which affords the formulator the maximal fabπc benefit and compatibility of the low molecular weight amine with the particular embodiment. As a non-limiting example, when R¹ and R^" are each equal to hydrogen, dye fixative properties, in certain liquid fabric care embodiments, even in the presence of bleach, are maximal. Also when R and R^" are not equal to hydrogen, bleach scavenging benefits are enhanced.

Those of ordinary skill in the art will recognize that depending upon the synthetic procedure used to prepare the polypropyleneamine backbones, varying amounts of both the linear and branched materials will be present in the final product admixture. The preferred backbones of the linear polyamines of the present invention comprise at least one 1,3-propylene unit, preferably at least two 1 ,3-propylene units.

For the purposes of the present invention, when a backbone nitrogen is referred to as "unmodified" the nitrogen contains only hydrogen atoms. "Modified" polyamines have one or more alkyleneoxy units as described herein above. Preferred substituents are methyl, 2- hydroxyethyl, 2-hydroxypropyl, 1,2-propyleneoxy, 2-hydroxybutyl, and mixtures thereof, more preferably methyl and 2-hydroxypropyl.

For certain formulations, polyamines which compnse alkylated polyamines are preferred, for example, tetramethyl dipropylenetπamine (5-N-methyl dipropylenetnamine) having the formula:

H

I

(H₃C)₂N^^^N.^^^N(CH₃)₂ the permethylated dipropylenetnamine (l , l -N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamine) having the formula:

CH₃ I (H,C)₂N_N^^N^_/- _/N(CH₃)2 and the mono-methylated dipropylenetnamine (5-N-methyl dipropylenetnamine) having the formula.

Cyclic Amines

The enhanced fabnc appearance compositions of the present invention may compnse one or more cyclic polyalkyleneamines wherein at least one of the ring nitrogens is substituted with at least one O-C alkyleneimine unit. The low molecular weight cyclic polyamines of the present invention compnse polyamme backbones having the formula-

R— L— R wherein L is a linking unit, said linking unit comprising a nng having at least 2 nitrogen atoms; for example. 1 ,4-piperazine. R is hydrogen. -(CH₂)_N(R')_:, and mixtures thereof, wherein at least one cyclic polyamme R unit is a -(CH₂)_N(R')₂ unit; preferably both R units are -(CH₂)„N(R')₂; wherein each index k independently has the value from 3 to 12, preferably k is 3. Preferably the backbone of the cyclic amines including R units is 250 daltons or less. Most preferred backbone ring is 1.4-piperazme. R¹ is hydrogen; Cj-C₁₂ alkyl, preferably Cj-C₈ alkyl, more preferably Cj-C₄ alkyl, most preferably methyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ wherein R³ is C₂-C₆ linear alkylene, C^-C_f, branched alkylene, or mixtures thereof; preferably ethylene, mixtures of ethylene and 1.2-propylene. 1,2-butylene, preferably ethylene, 1,2- propylene. R⁴ is hydrogen, C]-C₆ alkyl, or mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen. The index m is from 1 to 4, however, the value of m is predicated on the desired fabnc enhancement benefit sought by the formulator. For example, the level of bleach protection varies over the value of m. R¹ IS also acyl having the formula:

O

— C ^{1 1}— R 5⁵ wherein R³ is Cj-C₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof, preferably R⁵ is a hydrocarbyl moiety which sufficiently provides increased fabπc lubricity, more preferably C₆-C|₂ alkyl; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)₂H wherein the index y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6 and the -(CHOH)- unit is not directly attached to a nitrogen atom Non-limiting examples of hydroxy alkyl units include 2-hydroxy alkyl. for example, -CH.CHOHCH,, -CH₂CHOHCH₂CH₂CH₂CH₃. Two R' units can be taken together to form a 5-7 member ring, i.e., pipendine, morpho ne.

Preferably the backbone of the cyclic amines of the present invention compnse a N,N'- bis-substituted 1 ,4-pιperazme ring having the formula:

wherein each R⁷ is independently hydrogen, C|-C alkyl, C,-C₄ hydroxyalkyl, C C₄ aminoalkyl, or two R⁷ units of the same carbon atom are bonded to oxygen thus forming a carbonyl group (C=0) wherein the carbon atom is a ring atom, and mixture thereof. Examples of carbonyl containing πngs which compnse L units are 1,4-dιketopιpeπzmes. Preferably the backbones of the polyamines of the present invention, pπor to modification, have the formula:

H₂N-(CH₂)₃— N N— (CH₂)₃-NH₂

wherein each R unit is -(CH₂)₃NH .

However, the cyclic units may be substituted on only one nng nitrogen as m the case wherein one R unit is hydrogen, and the other R unit is -{CH₂)ι_tNH , for example, the piperazme having the formula:

H-N N— (CH₂)₃-NH₂ \ /

The backbones of the cyclic polyamines of the present invention preferably comprise at least one 1,3-propylene unit, more preferably at least two 1,3-propylene units.

For the purposes of the present invention, when a backbone nitrogen is referred to as "unmodified" the nitrogen contains only hydrogen atoms. "Modified" polyamines have one or more substituent units as described herein above. Preferably when the backbone units are modified all of the nitrogens are modified. Preferred alkyleneoxy substituents are ethyleneoxy, 1 ,2-propyleneoxy, and mixtures thereof, more preferably 1 ,2-propyleneoxy.

An example of a preferred polyamme according to the present invention is N,N'- bιs(hydroxyethyl)-N,N'-bιs[3-N,N-bιs(hydroxyethyl)amιnopropyl]-l ,3-propylenedιamιne having the formula:

Effects of Backbone Modifications

The polyamines of the present invention provide a multiplicity of fabnc care and fabnc enhancement benefits. Chlorine scavenging benefits are achieved with all of the polyamines independent of the degree of branching (i.e. the number of primary, secondary, and tertiary nitrogens). It has been surpπsmgly found that bleach protection is enhanced when the backbone nitrogens are substituted with one or more modifications which compnse an alkyleneoxy unit having the general formula:

R

I — CH₂CHO wherein said unit is R³ as defined herein above. However, if the formulator wishes to enhance the dye fixation properties of the presently disclosed polyamines, the backbone nitrogens will not be substituted with an alkyleneoxy unit.

The negative chelation effects, inter alia, extraction of heavy metal ions associated with fabπc dyes, are overcome and optimal dye integrity is achieved when the polyamme backbone comprises C₂-C₃, preferably C₃ (1.3 -propylene) units, and the backbone nitrogens are per- substituted, preferably by steπcally hindered substituents. However, when the polyamme backbone, prior to nitrogen substitution compπses C₂ (ethylene) untis, for dye integrity benefits, the nitrogens must be "per-substituted". The term "per-substituted" is defined as "each hydrogen of the polyamme backbone is substituted". This choice of substituent being affected by the other properties which are desired and to the compatibility of the polyamme within the final formulation

ADJUNCT INGREDIENTS The compositions of the present invention may also optionally compnse one or more adjunct ingredients. Non-limiting examples of adjunct ingredients are selected from the group consisting of electrolytes, stabilizers, low molecular weight water soluble solvents, chelating agents, cationic charge boosters, dispersibility aids, soil release agents, nonionic fabnc softening agents, concentration aid, perfume, preservatives, colorants, optical bπghteners, opacifiers, fabπc care agents, anti-shrinkage agents, anti-wnnkle agents, fabnc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof. Dye Fixing Agents

The compositions of the present invention optionally compnse from about 0.001%, preferably from about 0.5% to about 90%, preferably to about 50%, more preferably to about 10%, most preferably to about 5% by weight, of one or more dye fixing agents. Dye fixing agents, or "fixatives", are well-known, commercially available materials which are designed to improve the appearance of dyed fabncs by minimizing the loss of dye from fabrics due to washing. Not included within this definition are components which can in some embodiments serve as fabric softener actives. Many dye fixing agents are cationic, and are based on quatermzed nitrogen compound or on nitrogen compounds having a strong cationic charge which is formed in situ under the conditions of usage. Cationic fixatives are available under various trade names from several suppliers. Representative examples include: CROSCOLOR PMF (July 1981, Code No. 7894) and CROSCOLOR NOFF (January 1988, Code No. 8544) ex Crosfield; INDOSOL E-50

(February 27, 1984, Ref. No. 6008.35.84; polyethyleneamine-based) ex Sandoz; SANDOFDC TPS, ex Sandoz, is a preferred dye fixative for use herein. Additional non-hmitmg examples include SANDOFIX SWE (a cationic resmous compound) ex Sandoz, REWIN SRF, REWIN SRF-0 and REWIN DWR ex CHT-Beitlich GMBH; Tinofix® ECO, Tmofix® FRD and Solfm® ex Ciba-Geigy.

Other cationic dye fixing agents are descnbed in "Aftertreatments for Improving the Fastness of Dyes on Textile Fibres", Christopher C. Cook. Rev. Prog Coloration. Vol. XII, ( 1982) Dye fixing agents suitable for use in the present invention are ammonium compounds such as fatty acid-diamine condensates inter alia the hydrochlonde, acetate, metosulphate and benzyl hydrochloride salts of diamme esters. Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyl diethylenediamme methosulphate, monostearylethylene diaminotπmethylammonium methosulphate. In addition, the N-oxides of tertiary amines; derivatives of polymeπc alkyldiamines, polyamine-cyanuπc chloride condensates, and aminated glycerol dichlorohydπns are suitable for use as dye fixatives in the compositions of the present invention

Cellulose Reactive Dve Fixing Agents

Another dye fixing agent suitable for use in the present invention are cellulose reactive dye fixing agents. The compositions of the present invention optionally comprise from about 0.01%, preferably from about 0.05%>. more preferably from about 0.5%> to about 50%, preferably to about 25%, more preferably to about 10% by weight, most preferably to about 5% by weight, of one or more cellulose reactive dye fixing agents. The cellulose reactive dye fixatives may be suitably combined with one or more dye fixatives described herein above in order to compnse a "dye fixative system".

The term "cellulose reactive dye fixing agent" is defined herein as "a dye fixative agent which reacts with the cellulose fibers upon application of heat or upon a heat treatment either in situ or by the formulator". The cellulose reactive dye fixing agents suitable for use m the present invention can be defined by the following test procedure.

Cellulose Reactivity Test (CRT) Four pieces of fabnc which are capable of bleeding their dye (e.g. 10 x 10 cm of knitted cotton dyed with Direct Red 80) are selected. Two swatches are used as a first control and a second control, respectively. The two remaining swatches are soaked for 20 minutes m an aqueous solution containing 1% (w/w) of the cellulose reactive dye fixing agent to be tested. The swatches are removed and thoroughly dned. One of the treated swatches which has been thoroughly dned, is passed ten times through an ironing calender which is adjusted to a "linen fabπc" temperature setting. The first control swatch is also passed ten times through an ironing calender on the same temperature setting.

All four swatches ( the two control swatches and the two treated swatches, one of each which has been treated by the ironing calender) are washed separately in Launder-O-Meter pots under typical conditions with a commercial detergent used at the recommended dosage for Vi hour at 60°C. followed by a thorough πnsing of 4 times 200 ml of cold water and subsequently line dried.

Color fastness is then measured by comparing the DE values of a new untreated swatch with the four swatches which have undergone the testing. DE values, the computed color difference, is defined in ASTM D2244. In general, DE values relate to the magnitude and direction of the difference between two psychophysical color stimuli defined by tnstimulus values, or by chromaticity coordinates and luminance factor, as computed by means of a specified set of color-difference equations defined in the CIE 1976 CIELAB opponent-color space, the Hunter opponent-color space, the Fπele-Mac Adam-Chickeπng color space or any equivalent color space. For the purposes of the present invention, the lower the DE value for a sample, the closer the sample is to the un-tested sample and the greater the color fastness benefit.

As the test relates to selection or a cellulose reactive dye fixing agent, if the DE value for the swatch treated in the ironing step has a value which is better than the two control swatches, the candidate is a cellulose reactive dye fixing agent for the purposes of the invention.

Typically cellulose reactive dye fixing agents are compounds which contain a cellulose reactive moiety, non limiting examples of these compounds include halogeno-tπazines, vmyl sulphones, epichlorhydπne denvatives, hydroxyethylene urea derivatives, formaldehyde condensation products, polycarboxylates, glyoxal and glutaraldehyde derivatives, and mixtures thereof. Further examples can be found in "Textile Processing and Properties", Tyrone L. Vigo, at page 120 to 121, Elsevier (1997), which discloses specific electrophihc groups and their corresponding cellulose affinity.

Preferred hydroxyethylene urea denvatives include dimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal. Preferred formaldehyde condensation products include the condensation products deπved from formaldehyde and a group selected from an ammo-group, an immo-group, a phenol group, an urea group, a cyanamide group and an aromatic group. Commercially available compounds among this class are Sandofix WE 56 ex Clanant, Zetex E ex Zeneca and Levogen BF ex Bayer. Preferred polycarboxylates denvatives include butane tetracarboxilic acid derivatives, citric acid denvatives, polyacrylates and denvatives thereof. A most preferred cellulosic reactive dye fixing agents is one of the hydroxyethylene urea denvatives class commercialized under the tradename of Indosol CR ex Claπant. Still other most preferred cellulosic reactive dye fixing agents are commercialized under the tradename Rewin DWR and Rewin WBS ex CHT R. Beithch. Chlorine Scavengers

The compositions of the present invention optionally compnse from about 0.01%, preferably from about 0.02%, more preferably from about 0.25% to about 15%, preferably to about 10%. more preferably to about 5%o by weight, of a chlonne scavenger. In cases wherein the cation portion and the anion portion of the non-polymeric scavenger each react with chlonne, the amount of scavenger can be adjusted to fit the needs of the formulator.

Suitable chlorine scavengers include ammonium salts having the formula:

[(R)₃R'N] ⁺ X ^' w herein each R is independently hydrogen, Cj-C₄ alkyl. C,-C₄ substituted alkyl, and mixtures thereof, preferably R is hydrogen or methyl, more preferably hydrogen. R¹ is hydrogen Cj-C₉ alkyl, C Cq substituted alkyl, and mixtures thereof, preferably R is hydrogen. X is a compatible anion. non-limiting examples include chloπde, bromide, citrate, sulfate; preferably X is chlonde.

Non-limiting examples of preferred chlorine scavengers include ammonium chloπde, ammonium sulfate, and mixtures thereof; preferably ammonium chloride. Crystal Growth Inhibitor

The compositions of the present invention optionally comprise from about 0.005%, preferably from about 0.5%, more preferably from about 0.1% to about 1%, preferably to about 0.5%, more preferably to about 0.25%, most preferably to about 0.2% by weight, of one or more crystal growth inhibitors. The following "Crystal Growth Inhibition Test" is used to determine the suitability of a matenal for use as a crystal growth inhibitor.

Crystal Growth Inhibition Test (CGIT) The suitability of a material to serve as a crystal growth inhibitor according to the present invention can be determined by evaluating in vitro the growth rate of certain inorganic micro- crystals. The procedure of Nancollas et al., descπbed in "Calcium Phosphate Nucleation and Growth m Solution", Prog Crystal Growth Char act., Vol 3, 77-102, (1980), incorporated herein by reference, is a method which is suitable for evaluating compounds for their crystal growth inhibition. The graph below serves as an example of a plot indicating the time delay (t-lag) m crystal formation afforded by a hypothetical crystal growth inhibitor.

The observed t-lag provides a measure of the compound's efficiency with respect to delaying the growth of calcium phosphate crystal. The greater the t-lag, the more efficient the crystal growth inhibitor. Exemplary Procedure

Combine in a suitable vessel. 2.1 M KC1 (35 mL), 0.0175M CaCl₂ (50mL), 0 01M KH₂P0₄ (50mL), and de-ionized water (350mL). A standard pH electrode equipped with a Standard Calomel Reference electrode is inserted and the temperature adjusted to 37° C while purging of the solution of oxygen. Once the temperature and pH are stabilized, a solution of the crystal growth inhibitor to be test is then added. A typical inhibitor test concentration is 1 x 10^'6 M. The solution is titrated to pH 7.4 with 0.05M K.OH. The mixture is then treated with 5 mL's of a hydroxyapatite slurry. The hydroxyapatite slurry can be prepared by digesting Bio-Gel^® HTP hydroxyapatite powder (100 g) in 1 L of distilled water the pH of which is adjusted to 2.5 by the addition of sufficient 6N HCI and subsequently heating the solution until all of the hydroxyapatite is dissolved (heating for several days may be necessary). The temperature of the solution is then maintained at about 22° C while the pH is adjusted to 12 by the addition of a solution of 50%) aqueous KOH. Once again the solution is heated and the resulting slurry is allowed to settle for two days before the supernatant is removed. 1.5 L of distilled water is added, the solution stirred, then after settling again for 2 days the supernatant is removed. This πnsing procedure is repeated six more time after which the pH of the solution is adjusted to neutrality using 2N HCI. The resulting slurry can be stored at 37°C for eleven months.

Crystal growth inhibitors which are suitable for use in the present invention have a t-lag of at least 10 minutes, preferably at least 20 minutes, more preferably at least 50 minutes, at a concentration of 1 x 10^*6M. Crystal growth inhibitors are differentiated form chelatmg agents by the fact that crystal growth inhibitors have a low binding affinity of heavy metal ions, i.e., copper. For example, crystal growth inhibitors have an affinity for copper ions m a solution of 0.1 ionic strength when measured at 25° C, of less than 15, preferably less than 12. The preferred crystal growth inhibitors of the present invention are selected from the group consisting of carboxylic compounds, organic diphosphonic acids, and mixtures thereof. The following are non-limiting examples of preferred crystal growth inhibitors. Carboxylic Compounds

Non-limiting examples of carboxylic compounds which serve as crystal growth inhibitors include glycolic acid, phytic acid, polycarboxylic acids, polymers and co-polymers of carboxylic acids and polycarboxylic acids, and mixtures thereof. The inhibitors may be in the acid or salt form Preferably the polycarboxylic acids comprise materials having at least two carboxylic acid radicals which are separated by not more than two carbon atoms (e.g.. methylene units). The preferred salt forms include alkali metals; lithium, sodium, and potassium; and alkanolammonium. The polycarboxylates suitable for use in the present invention are further disclosed in U.S. 3.128.287. U.S. 3,635,830. U.S. 4,663,071, U.S. 3,923,679; U.S. 3.835,163; U.S. 4.158.635; U.S. 4, 120,874 and U.S. 4,102,903, each of which is included herein by reference.

Further suitable polycarboxylates include ether hydroxypolycarboxylates, polyacrylate polymers, copolymers of maleic anhydπde and the ethylene ether or vinyl methyl ethers of acrylic acid. Copolymers of 1,3,5-tnhydroxybenzene, 2, 4, 6-tnsulphonιc acid, and carboxymethyloxysuccinic acid are also useful. Alkali metal salts of polyacetic acids, for example, ethylenediamme tetraacetic acid and nitrilotnacetic acid, and the alkali metal salts of polycarboxylates, for example, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tncarboxylic acid, carboxymethyloxysuccinic acid, are suitable for use in the present invention as crystal growth inhibitors

The polymers and copolymers which are useful as crystal growth inhibitors have a molecular weight which is preferably greater than about 500 daltons to about 100,000 daltons, more preferably to about 50,000 daltons. Examples of commercially available matenals for use as crystal growth inhibitors include, polyacrylate polymers Good-Rite® ex BF Goodπch, Acrysol® ex Rohm & Haas, Sokalan® ex BASF, and Norasol® ex Norso Haas. Preferred are the Norasol® polyacrylate polymers, more preferred are Norasol® 4 ION (MW 10,000) and Norasol® 440N (MW 4000) which is an ammo phosphonic acid modified polyacrylate polymer, and also more preferred is the acid form of this modified polymer sold as Norasol® QR 784 (MW 4000) ex Norso-Haas.

Polycarboxylate crystal growth inhibitors include citrates, e.g., citric acid and soluble salts thereof (particularly sodium salt), 3,3-dιcarboxy-4-oxa-l,6-hexanedιoates and related compounds further disclosed in U.S. 4,566,984 incorporated herein by reference, C5-C20 alkyl, C5-C20 alkenyl succinic acid and salts thereof, of which dodecenyl succmate, lauryl succmate, myπstyl succmate, palmityl succmate. 2-dodecenylsuccιnate, 2-pentadecenyl succmate, are non- limiting examples. Other suitable polycarboxylates are disclosed m U.S. 4,144,226, U.S. 3,308,067 and U.S. 3,723,322, all of which are incorporated herein by reference. Organic Diphosphonic Acids Organic diphosphonic acid are also suitable for use as crystal growth inhibitors. For the purposes of the present invention the term "organic diphosphonic acid" is defined as "an organo- diphosphonic acid or salt which does not compnse a nitrogen atom". Preferred organic diphosphonic acids include C_j-C₄ diphosphonic acid, preferably C₂ diphosphonic acid selected from the group consisting of ethylene diphosphonic acid, α-hydroxy-2 phenyl ethyl diphosphonic acid, methylene diphosphonic acid, v ylidene- 1 ,1 -diphosphonic acid , l,2-dιhydroxyethane-l ,l- diphosphomc acid, hydroxy-ethane 1 , 1 diphosphonic acid, the salts thereof, and mixtures thereof. More preferred is hydroxyethane- 1, 1 -diphosphonic acid (HEDP) Fabric Abrasion Reducing Polymers

The herein disclosed polymers provide for decreased fabric abrasion as well as providing a secondary benefit related to dye transfer inhibition. The compositions of the present invention comprise from about 0.01%, preferably from about 0.1%o to about 20%, preferably to about 10% by weight, of a fabnc abrasion reducing polymer.

The prefered reduced abrasion polymers of the present invention are water-soluble polymers. For the purposes of the present invention the term "water-soluble" is defined as "a polymer which when dissolved in water at a level of 0.2% by weight, or less, at 25° C, forms a clear, isotropic liquid"

The fabric abrasion reducing polymers useful in the present invention have the formula.

[-P(D)_m-]„ wherein the unit P is a polymer backbone which compnses units which are homopolymeπc or copolymenc. D units are defined herein below. For the purposes of the present invention the term "homopolymeπc" is defined as "a polymer backbone which is compnsed of units having the same unit composition, i.e., formed from polymeπzation of the same monomer. For the purposes of the present invention the term "copolymenc" is defined as "a polymer backbone which is comprised of units having a different unit composition, i.e., formed from the polymeπzation of two or more monomers".

P backbones preferably comprise units having the formula:

[CR₂-CR₂] or [(CR₂) - L]— wherein each R unit is independently hydrogen, Cj-C₁₂ alkyl, C₆-C_!2 aryl, and D units as described herein below; preferably C,-C₄ alkyl.

Each L unit is independently selected from heteroatom-containing moieties, non-limiting examples of which are selected from the group consisting of:

R' 0 0 0 0

I II II II II

^■N — — O — — O— C — — C— O — — O— C— O — — C-

0 0 O 0 0

II II II II II — 0— s — — s— o — — o— s— 0

II II II II 0 O 0 0 polysiloxane having the formula:

units which have dye transfer inhibition activity:

R⁴ O O

I II II

^■ N — — N— C- C— N-

J R^J and mixtures thereof; wherein R' IS hydrogen, Cj-Cj₂ alkyl, C₆-Cj aryl, and mixtures thereof. R² is Cj-C₁₂ alkyl, Cι-C,₂ alkoxy, C₆-Cj₂ aryloxy, and mixtures thereof; preferably methyl and methoxy. R³ is hydrogen CrCj₂ alkyl, C₆-C_]2 aryl, and mixtures thereof; preferably hydrogen or C,-C₄ alkyl, more preferably hydrogen. R⁴ is C Cι₂ alkyl, C₆-Cj₂ aryl, and mixtures thereof. The backbones of the fabric abrasion reducing polymers of the present invention compnse one or more D units which are units which compnse one or more units which provide a dye transfer inhibiting benefit. The D unit can be part of the backbone itself as represented m the general formula:

[-P(D)_m-]„ or the D unit may be incorporated into the backbone as a pendant group to a backbone unit having, for example, the formula.

[CR-CR₂] or [(CR) -L]—

D D However, the number of D units depends upon the formulation. For example, the number of D units will be adjusted to provide water solubility of the polymer as well as efficacy of dye transfer inhibition while providing a polymer which has fabnc abrasion reducing properties. The molecular weight of the fabric abrasion reducing polymers of the present invention are from about 500. preferably from about 1.000. more preferably from about 100,000 most preferably from 160.000 to about 6.000,000, preferably to about 2,000,000, more preferably to about 1 ,000,000, yet more preferably to about 500,000, most preferably to about 360,000 daltons. Therefore the value of the index n is selected to provide the indicated molecular weight, and providing for a water solubility of least 100 ppm, preferably at least about 300 ppm, and more preferably at least about 1,000 ppm in water at ambient temperature which is defined herein as 25°C.

Polymers Comprising Amide Units

Non-limiting examples of preferred D units are D units which compnse an amide moiety. Examples of polymers wherein an amide unit is introduced into the polymer via a pendant group includes polyvinylpyrrohdone having the formula. [CH-CH₂]_n

polyvinyloxazohdone having the formula:

polyvmylmethyloxazolidone having the formula:

polyacrylamides and N-substituted polyacrylamides having the formula:

[CH-CH₂]_n c=o I . N(R )_ wherein each R' is independently hydrogen. Q_\-Q_b alkyl. or both R' units can be taken together to form a nng comprising 4-6 carbon atoms: polymethacrylamides and N-substituted polymethacrylamides having the general formula:

l "^J [C-CH₂]_n

C=0

I . N(R )₂ wherein each R' is independently hydrogen, Cj-C₆ alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms: poly(N-acrylylglycιnamιde) having the formula: [CH-CH₂]_n

C=0 o

I II

NH— CH₂-C— N(R')₂ wherein each R' is independently hydrogen, Cj-C₆ alkyl, or both R' units can be taken together to form a nng compnsing 4-6 carbon atoms; poly(N-methacrylylglycmamιde) having the formula:

CH₃ [C-CH₂]_n c=o o

I II NH— CH₂-C— N(R')₂ wherein each R' is independently hydrogen, C,-C₆ alkyl. or both R' units can be taken together to form a ring comprising 4-6 carbon atoms: polyvinylurethanes having the formula.

[CH-CH₂]_n

O

I C=0

I

N(R')2 wherein each R' is independently hydrogen, C C₆ alkyl, or both R' units can be taken together to form a ring comprising 4-6 carbon atoms.

An example of a D unit wherein the nitrogen of the dye transfer inhibiting moiety is incorporated into the polymer backbone is a poly(2-ethyl-2-oxazohne) having the formula:

[CH₂-CH₂-N]_n —

C=0 CH₂CH₃ wherein the index n indicates the number of monomer residues present.

The fabric abrasion reducing polymers of the present invention can comprise any mixture of dye transfer inhibition units which provides the product with suitable properties. The preferred polymers which comprise D units which are amide moieties are those which have the nitrogen atoms of the amide unit highly substituted so the nitrogen atoms are in effect shielded to a varying degree by the surrounding non-polar groups. This provides the polymers with an amphiphilic character. Non-limiting examples include polyvinyl-pyrrolidones, polyvinyloxazohdones, N,N-dιsubstιtuted polyacrylamides, and N,N-dιsubstιtuted polymethacrylamides. A detailed descnption of physico-chemical properties of some of these polymers are given m "Water-Soluble Synthetic Polymers: Properties and Behavior", Philip Molyneux, Vol. I, CRC Press, (1983) included herein by reference.

The amide containing polymers may be present partially hydrolyzed and/or crosslmked forms. A preferred polymeric compound for the present invention is polyvinylpyrrolidone (PVP). This polymer has an amphiphihc character with a highly polar amide group confemng hydrophilic and polar-attracting properties, and also has non-polar methylene and methine groups, in the backbone and or the ring, conferring hydrophobic properties. The πngs may also provide planar alignment with the aromatic rings in the dye molecules. PVP is readily soluble m aqueous and organic solvent systems. PVP is available ex ISP, Wayne, New Jersey, and BASF Corp.. Parsippany. New Jersey, as a powder or aqueous solutions m several viscosity grades, designated as, e.g., K-12, K-15, K-25, and K-30. These K-values indicate the viscosity average molecular weight, as shown below:

PVP K-12, K-15, and K-30 are also available ex Polysciences, Inc. Wamngton, Pennsylvania, PVP K-15. K-25. and K-30 and poly(2-ethyl-2-oxazolιne) are available ex Aldπch Chemical Co., Inc.. Milwaukee. Wisconsin. PVP K30 (40,000) through to K90 (360,000) are also commercially available ex BASF under the tradename Luviskol or commercially available ex ISP. Still higher molecular PVP like PVP 1.3MM, commercially available ex Aldπch is also suitable for use herein. Yet further PVP-type of material suitable for use in the present invention are polyvinylpyrro done-co-dimethylaminoethylmethacrylate, commercially available commercially ex ISP in a quatemised form under the tradename Gafquat® or commercially available ex Aldπch Chemical Co. having a molecular weight of approximately 1.0MM; polyvinylpyrrolidone-co-vinyl acetate, available ex BASF under the tradename Luviskol®, available in vιnylpyrrolιdone:vιnylacetate ratios of from 3.7 to 7:3

Polymers Compnsing N-oxide Units

Another D unit which provides dye transfer inhibition enhancement to the fabnc abrasion reducing polymers described herein, are N-oxide units having the formula:

wherein R¹, R^:, and R³ can be any hydrocarbyl unit (for the purposes of the present invention the term "hydrocarbyl" does not include hydrogen atom alone). The N-oxide unit may be part of a polymer, such as a polyamme, i.e., polyalkyleneamine backbone, or the N-oxide may be part of a pendant group attached to the polymer backbone. An example of a polymer which compnses an the N-oxide unit as a part of the polymer backbone is polye hyleneimine N-oxide. Non-limiting examples of groups which can comprise an N-oxide moiety include the N-oxides of certain heterocycles inter alia pyridine, pyrrole, imidazole, pyrazole, pyrazme, pyπmidine, pyndazine, piperidine, pyrrolidine. pyrrolidone, azo dine, morpholine. A preferred polymer is poly(4- vinylpyπdine N-oxide, PVNO) In addition, the N-oxide unit may be pendant to the ring, for ^" example, aniline oxide.

N-oxide compnsing polymers of the present invention will preferably have a ration of N- oxidized amme nitrogen to non-oxidized amme nitrogen of from about 1 :0 to about 1.2. preferably to about 1 : 1 , more preferably to about 3: 1. The amount of N-oxide units can be adjusted by the formulator. For example, the formulator may co-polymenze N-oxide compnsing monomers w ith non N-oxide compnsing monomers to arπve at the desired ratio of N-oxide to non N-oxide amino units, or the formulator may control the oxidation level of the polymer dunng preparation The amine oxide unit of the polyamme N-oxides of the present invention have a Pk_a less than or equal to 10, preferably less than or equal to 7, more preferably less than or equal to 6 The average molecular weight of the N-oxide compnsing polymers which provide a dye transfer inhibitor benefit to reduced fabπc abrasion polymers is from about 500 daltons, preferably from about 100.000 daltons, more preferably from about 160.000 daltons to about 6,000,000 daltons, preferably to about 2.000,000 daltons, more preferably to about 360,000 daltons. Polymers Compnsing Amide Units and N-oxide Units A further example of polymers which are fabnc abrasion reducing polymers which have dye transfer inhibition benefits are polymers which compnse both amide units and N-oxide units as descπbed herein above. Non-limiting examples include co-polymers of two monomers wherein the first monomer compnses an amide unit and the second monomer compnses an N- oxide unit. In addition, o gomers or block polymers compnsing these units can be taken together to form the mixed amide/N-oxide polymers. However, the resulting polymers must retain the water solubihtv requirements descnbed herein above Molecular weight

For all the above polymer of the invention, it most preferred that they have a molecular weight in the range as descπbed herein above. This range is typically higher than the range for polymers which render only dye transfer inhibition benefits alone. Indeed, the high molecular weight enables the abrasion occurring subsequent to treatment with the polymer to be reduced, especially in a later washing procedure. Not to be bound by theory, it is believed that that this benefit is partly due to the high molecular weight, thereby enabling the deposition of the polymer on the fabric surface and providing sufficient substantivity that the polymer is able to remain adhered to the fabnc during the subsequent use and washing of the fabnc. Further, it is believed that for a given charge density, increasing the molecular weight will increase the substantivity of the polymer to the fabric surface Ideally the balance of charge density and molecular weight will provide both a sufficient rate of deposition onto the fabnc surface and a sufficient adherence to the fabric during a subsequent wash cycle. Increasing molecular weight is considered preferable to increasing charge density as it allows a greater choice in the range of materials which are able to provide the benefit and avoids the negative impact that increasing charge density can have such as the attraction of soil and residue onto treated fabrics. It should be noted however that a similar benefit may be predicted from the approach of increasing charge density while retaining a lower molecular weight material. Solvents or Liquid Carriers The compositions of the present invention may optionally comprise from about 10%>, preferably from about 12%, more preferably from about 14% to about 40%, preferably to about 35%, more preferably to about 25%, most preferably to about 20% by weight of one or more solvents (liquid earners). These solvents are further disclosed in WO 97/03169 incorporated herein by reference. The use of solvents is especially critical when formulating clear, isotropic liquid fabric care compositions comprising cationic fabπc softening actives. The solvent is selected to minimize solvent odor impact m the composition and to provide a low viscosity to the final composition. For example, isopropyl alcohol is not very effective and has a strong odor, n- Propyl alcohol is more effective, but also has a distinct odor. Several butyl alcohols also have odors but can be used for effective clarity/stability, especially when used as part of a ease of formulation solvent system to minimize their odor. The alcohols are also selected for optimum low temperature stability, that is they are able to form compositions that are liquid with acceptable low viscosities and translucent, preferably clear, down to about 40°F (about 4.4°C) and are able to recover after storage down to about 20°F (about 6.7°C). The suitability of any solvent for the formulation of embodiments which are clear isotropic liquids, is surpnsingly selective. Suitable solvents can be selected based upon their octanol/water partition coefficient (P) as defined in WO 97/03169. The solvents suitable for use herein are selected from those having a ClogP of from about 0.15 to about 0.64, preferably from about 0.25 to about 0.62, and more preferably from about 0.40 to about 0.60, said ease of formulation solvent preferably being at least somewhat asymmetric, and preferably having a melting, or solidification, point that allows it to be liquid at, or near room temperature. Solvents that have a low molecular weight and are biodegradable are also desirable for some purposes. The more asymmetric solvents appear to be very desirable, whereas the highly symmetncal solvents such as 1 ,7-heptanediol, or 1 ,4-bιs(hydroxymethyl) cyclohexane, which have a center of symmetry, appear to be unable to provide the essential clear compositions when used alone, even though their ClogP values fall in the preferred range.

Non-limiting examples of solvents include mono-ols, C6 diols, C7 diols, octanediol isomers, butanedio! derivatives, tnmethylpentanediol isomers, ethylmethylpentanediol isomers, propyl pentanediol isomers, dimethylhexanediol isomers, ethylhexanediol isomers, methylheptanediol isomers. octanediol isomers, nonanediol isomers, alkyl glyceryl ethers, dι(hydroxy alkyl) ethers, and aryl glyceryl ethers, aromatic glyceryl ethers, alicyc c diols and denvatives, C₃-C₇ diol alkoxylated derivatives, aromatic diols, and unsaturated diols. Preferred solvents include 1,2- hexanediol, 2-Ethyl-l ,3-hexanedιol, and 2,2,4-Tπmethyl-l ,3-pentanedιol Enzymes

The compositions and processes herein can optionally employ one or more enzymes inter alia lipases. proteases, cellulase, amylases and peroxidases. A preferred enzyme for use herein is cellulase enzyme Cellulases usable for use in the fabric enhancement compositions of the present invention include both bacteπal and fungal types which preferably exhibit an optimal performance at a pH of from 5 to 9.5. U.S. 4,435,307 Barbesgaard et al., issued March 6, 1984, included herein by reference, discloses suitable fungal cellulases ex Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producιng fungus belonging to the genus Aeromonas. and cellulase enzymes extracted from the hepatopancreas of a manne mollusk, Dolabella Auricula Solander Suitable cellulases are also disclosed in GB-A-2.075 028; GB-A- 2.095.275 and DE-OS-2.247.832 each of which is included herein by reference. CAREZYME® and CELLUZYME® (Novo) are especially useful. Other suitable cellulases are also disclosed m WO 91/17243 to Novo, WO 96/34092, WO 96/34945 and EP-A-0,739,982. Compositions may comprise up to 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the composition Stated otherwise, the compositions herein will typically comprise from 0.001%, preferably from 0.01% to 5%, preferably to 1% by weight, of a commercial enzyme preparation. In the particular cases where activity of the enzyme preparation can be defined otherwise such as with cellulases, corresponding activity units are preferred (e.g. CEVU or cellulase Equivalent Viscosity Units). For instance, the compositions of the present invention can contain cellulase enzymes at a level equivalent to an activity from 0.5 to 1000 CEVU/gram of composition. Cellulase enzyme preparations used for the purpose of formulating the compositions of this invention typically have an activity compnsed between 1,000 and 10,000 CEVU/gram in liquid form, around 1,000 CEVU/gram in solid form. Polvolefm dispersion The compositions of the present invention optionally compnse from about 0.01%, preferably from about 0.1% to about 8%, preferably to about 5%, more preferably to about 3% by weight, of a poly olefin emulsion or suspension in order to provide anti-wrinkle and improved water absorbency benefits to the fabncs treated by the fabπc care compositions of the present invention. Preferably, the polyolefin is a polyethylene, polypropylene or mixtures thereof. The polyolefin may be at least partially modified to contain vaπous functional groups, such as carboxyl, carbonyl, ester, ether, alkylamide, sulfonic acid or amide groups. More preferably, the polyolefin employed m the present invention is at least partially carboxyl modified or, in other words, oxidized. In particular, oxidized or carboxyl modified polyethylene is preferred in the compositions of the present invention. When considenng ease of formulation, the polyolefin is preferably introduced as a suspension or an emulsion of polyolefin dispersed by use of an emulsifying agent. The polyolefin suspension or emulsion preferably has from 1 , preferably from 10%. more preferably from 15% to 50%, more preferably to 35% more preferably to 30% by weight, of polyolefin in the emulsion. The polyolefin preferably has a molecular weight of from 1,000, preferably from 4,000 to 15,000, preferably to 10,000. When an emulsion is employed, the emulsifier may be any suitable emulsification or suspending agent. Preferably, the emulsifier is a cationic, no onic, zwitteπomc or anionic surfactant or mixtures thereof. Most preferably, any suitable cationic, nomonic or anionic surfactant may be employed as the emulsifier. Preferred emulsifiers are cationic surfactants such as the fatty amme surfactants and in particular the ethoxylated fatty amme surfactants. In particular, the cationic surfactants are preferred as emulsifiers m the present invention. The polyolefin is dispersed with the emulsifier or suspending agent in a ratio of emulsifier to polyolefin of from 1: 10 to 3.1. Preferably, the emulsion includes from 0.1, preferably from 1%, more preferably from 2.5% to 50%, preferably to 20%>, more preferably to 10%) by weight, of emulsifier in the polyolefin emulsion. Polyethylene emulsions and suspensions suitable for use in the present invention are available under the tradename VELUSTROL exHOECHST Aktiengesellschaft of Frankfurt am Main, Germany. In particular, the polyethylene emulsions sold under the tradename VELUSTROL PKS, VELUSTROL KPA, or VELUSTROL P-40 may be employed m the compositions of the present invention. Stabilizers

The compositions of the present invention can optionally compnse from about 0.01%, preferably from about 0.035% to about 0.2%>, more preferably to about 0.1%> for antioxidants, preferably to about 0.2%o for reductive agents, of a stabilizer. The term "stabilizer," as used herein, includes antioxidants and reductive agents. These agents assure good odor stability under long term storage conditions for the compositions and compounds stored m molten form. The use of antioxidants and reductive agent stabilizers is especially cntical for low scent products (low perfume).

Non-limiting examples of antioxidants that can be added to the compositions of this invention include a mixture of ascorbic acid, ascorbic palmitate, propyl gallate, ex Eastman Chemical Products. Inc.. under the trade names Tenox® PG and Tenox S-l ; a mixture of BHT (butylated hydroxytoluene), BHA (butylated hydroxya sole), propyl gallate, and citπc acid, ex Eastman Chemical Products, Inc., under the trade name Tenox-6; butylated hydroxytoluene, available from UOP Process Division under the trade name Sustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products. Inc., as Tenox TBHQ; natural tocopherols, Eastman Chemical Products. Inc., as Tenox GT-l/GT-2; and butylated hydroxyamsole. Eastman Chemical Products, Inc.. as BHA. long chain esters (C8-C22) of gallic acid, e.g., dodecyl gallate: Irganox® 1010; Irganox® 1035, Irganox® B 1 171; Irganox® 1425; Irganox® 3114; Irganox® 3125; and mixtures thereof: preferably Irganox® 3125, Irganox® 1425, Irganox® 31 14, and mixtures thereof: more preferably Irganox® 3125 alone or mixed with citnc acid and/or other chelators such as isopropyl citrate, Dequest® 2010, ex Monsanto with a chemical name of 1- hydroxyethylιdene-1, 1 -diphosphonic acid (etidronic acid), and Tiron®, ex Kodak with a chemical name of 4,5-dιhydroxy-m-benzene-sulfonιc acid/sodium salt, EDDS, and DTP A®, ex Aldπch with a chemical name of diethylenetπammepentaacetic acid. Fabric Softening Actives The compositions of the present invention compnse at least about 1%>, preferably from about 10%. more preferably from about 20% to about 80%, more preferably to about 60% by weight, of the composition of one or more fabric softener actives.

The preferred fabric softening actives according to the present invention are amines having the formula:

quaternary ammonium compounds having the formula:

and mixtures thereof wherein each R is independently C i -Cg alkyl, Ci -Cg hydroxyalkyl, benzyl, and mixtures thereof; R^ is preferably C \ j -C22 lmear alkyl, C\ 1 -C22 branched alkyl, Ci 1-C22 linear alkenyl, C_j 1-C22 branched alkenyl, and mixtures thereof; Q is a carbonyl moiety independently selected from the units having the formula:

O o R- O O R^z

II II I II II I -o— c- — c- -o- ^•N— C- — C— N — o o R^J o O— C— R O

II II

— O— C— O — _t — CH-O— C _, — CH-CH₂-0— C wherein R^ is hydrogen, C1-C4 alkyl, preferably hydrogen; R^ is C1-C4 alkyl, preferably hydrogen or methyl; preferably Q has the formula:

O O

II II — O— C or — NH-C .

X is a softener compatible anion, preferably the anion of a strong acid, for example, chlonde, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chlonde and methyl sulfate. The anion can also, but less preferably, carry a double charge, in which case x'^") represents half a group. The index m has a value of from 1 to 3; the index n has a value of from 1 to 4, preferably 2 or 3, more preferably 2.

One embodiment of the present invention provides for amines and quaternized amines having two or more different values for the index n per molecule, for example, a softener active prepared from the starting amme methyl(3-amιnopropyl)(2-hydroxyethyl)amme.

More preferred softener actives according to the present invention have the formula:

wherein the unit having the formula:

O — O— C— R¹ is a fatty acyl moiety. Suitable fatty acyl moieties for use m the softener actives of the present invention are deπved from sources of triglycerides including tallow, vegetable oils and/or partially hydrogenated vegetable oils including inter aha canola oil. safflower oil, peanut oil, sunflower oil. com oil. soybean oil. tall oil, rice bran oil. Yet more preferred are the Diester Quaternary Ammonium Compounds (DEQA's) wherein the index m is equal to 2.

The R ' units are typically mixtures of linear and branched chains of both saturated and unsaturated aliphatic fatty acids, an example of which (canola oil), is descnbed in Table I herein below

Table I

The formulator, depending upon the desired physical and performance properties of the final fabπc softener active, can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of tnglyceπde to form a "customized blend". However, those skilled in the art of fats and oils recognize that the fatty acyl composition may vary, as in the case of vegetable oil, from crop to crop, or from variety of vegetable oil source to vaπety of vegetable oil source. DEQA's which are prepared using fatty acids deπved from natural sources are preferred.

A preferred embodiment of the present invention provides softener actives compnsing R' units which have at least about 3%. preferably at least about 5%. more preferably at least about 10%, most preferably at least about 15% C \ _j -C22 alkenyl, including polyalkenyl (polyunsaturated) units inter alia oleic, linoleic, linolenic.

For the purposes of the present invention the term "mixed chain fatty acyl units" is defined as "a mixture of fatty acyl units comprising alkyl and alkenyl chains having from 10 carbons to 22 carbon atoms including the carbonyl carbon atom, and in the case of alkenyl chains, from one to three double bonds, preferably all double bonds in the cis configuration". With regard to the R ' units of the present invention, it is preferred that at least a substantial percentage of the fatty acyl groups are unsaturated, e.g., from about 25%, preferably from about 50% to about 70%. preferably to about 65% The total level of fabπc softening active containing polyunsaturated fatty acyl groups can be from about 3%, preferably from about 5%, more preferably from about 10% to about 30%. preferably to about 25%, more preferably to about

18%. As stated herein above cis and trans isomers can be used, preferably with a cisl trans ratio is of from 1 .1 , preferably at least 3: 1. and more preferably from about 4: 1 to about 50: 1 , more preferablv about 20' 1. however, the minimum being 1 : 1

The level of unsaturation contained ithin the tallow, canola, or other fatty acyl unit chain can be measured by the Iodine Value (IV) of the corresponding fatty acid, which in the present case should preferably be in the range of from 5 to 100 with two categories of compounds being distinguished, having a IV below or above 25. Indeed, for compounds having the formula

(R)- ^■ N-t .CItø_n-Q— R I

4-m -Tn

deπved from tallow fatty acids, when the Iodine Value is from 5 to 25, preferably 15 to 20, it has been found that a ctsltrans isomer weight ratio greater than about 30/70, preferably greater than about 50 50 and more preferably greater than about 70/30 provides optimal concentrability.

For compounds of this type made from tallow fatty acids having a Iodine Value of above 25, the ratio of cis to trans isomers has been found to be less cntical unless very high concentrations are needed. A further preferred embodiment of the present invention compnses DEQA's w herein the average Iodine Value for R^ IS approximately 45. The R! units suitable for use in the isotropic liquids present invention can be further charactenzed in that the Iodine Value (IV) of the parent fatty acid, said IV is preferably from about 10, more preferably from about 50, most preferably from about 70, to a value of about 140, preferably to about 130, more preferably to about 1 15. However, formulators, depending upon which embodiment of the present invention they choose to execute, may wish to add an amount of fatty acyl units which have Iodme Values outside the range listed herein above. For example, "hardened stock" (IV less than or equal to about 10) may be combined with the source of fatty acid admixture to adjust the properties of the final softener active.

A prefered source of fatty acyl units, especially fatty acyl units having branching, for example, "Guerbet branching", methyl, ethyl, etc. units substituted along the pnmary alkyl chain, synthetic sources of fatty acyl units are also suitable. For example, the formulator may with to add one or more fatty acyl units having a methyl branch at a "non-naturally occunng" position, for example, at the third carbon of a Ci 7 chain. What is meant herein by the term "non-naturally occunng" is "acyl units whihc are not found in significant (greater than about 0.1%) quantities is common fats and oils which serve as feedstocks for the source of triglycerides described herein." If the desired branched chain fatty acyl unit is unavailable from readily available natural feedstocks, therefore, synthetic fatty acid can be suitably admixed with other synthetic mateπals or with other natural triglyceride derived sources of acyl units.

The following are examples of preferred softener actives according to the present invention.

N.N-dι(tallowyl-oxy-ethyl)-N,N-dιmethyl ammonium chloπde; N,N-dι(canolyl-oxy-ethyl)-N,N-dιmethyl ammonium chloride; N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(tallowylamιdoethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate;

N,N-dι(2-tallowyloxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde; N,N-dι(2-canolyloxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde; N,N-dι(2-tallowyloxyethylcarbonyloxyethyl)-N,N-dιmethyl ammonium chlonde; N,N-dι(2-canolyloxyethylcarbonyloxyethyl)-N,N-dιmethyl ammonium chloπde; N-(2-tallowoyloxy-2-ethyl)-N-(2-tallowyloxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde; N-(2-canolyloxy-2-ethyl)-N-(2-canolyloxy-2-oxo-ethyl)-N,N-dιmethyl ammonium chlonde; N,N,N-tn(tallowyl-oxy-ethyl)-N-methyl ammonium chlonde; N,N,N-tπ(canolyl-oxy-ethyl)-N-methyl ammonium chlonde; N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dιmethyl ammonium chloπde; N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dιmethyl ammonium chloπde; l,2-dιtallowyloxy-3-N,N,N-tnmethylammonιopropane chlonde; and l,2-dιcanolyloxy-3-N,N,N-tπmethylammonιopropane chlonde; and mixtures of the above actives. Particularly preferred is N,N-dι(tallowoyl-oxy-ethyl)-N,N-dιmethyl ammonium chlonde, where the tallow chains are at least partially unsaturated and N,N-di(canoloyl-oxy-ethyl)-N,N- dimethyl ammonium chlonde, N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.

Additional fabnc softening agents useful herein are described m U.S. 5,643,865 Mermelstein et al., issued July 1 , 1997; U.S. 5,622,925 de Buzzaccanni et al., issued Apnl 22, 1997; U.S. 5,545,350 Baker et al., issued August 13, 1996; U.S. 5,474,690 Wahl et al., issued December 12, 1995; U.S. 5,417,868 Turner et al., issued January 27, 1994; U.S. 4,661.269 Tnnh el al., issued April 28, 1987; U.S. 4,439,335 Burns, issued March 27, 1984; U.S. 4,401,578 Verbruggen. issued August 30, 1983; U.S. 4,308,151 Cambre, issued December 29, 1981; U.S. 4,237,016 Rudkin e/ α/., issued October 27, 1978; U.S. 4,233,164 Davis, issued November 11, 1980, U.S. 4,045,361 Watt et al, issued August 30, 1977; U.S. 3,974,076 Wiersema et al., issued August 10. 1976; U.S. 3.886,075 Bernadino, issued May 6, 1975; U.S. 3,861,870 Edwards et al., issued January 21 1975; and European Patent Application publication No. 472,178, by Yamamura et al., all of said documents being incorporated herein by reference.

Principal solvent

The compositions of the present invention, preferably the isotropic liquid embodiments thereof, may also optionally comprise a pnncipal solvent. The level of pnncipal solvent present in the compositions of the present invention is typically less than about 95%, preferably less than about 50%, more preferably less than about 25%, most preferably less than about 15% by weight. Some embodiments of isotropic liquid embodiments of the present invention may compnse no pnncipal solvent but may substitute instead a suitable nomonic surfactant. The principal solvents of the present invention are pπmaπly used to obtain liquid compositions having sufficient clarity and viscosity. Principal solvents must also be selected to minmize solvent odor impact in the composition. For example, isopropyl alcohol is not an effective principal solvent in that it does not serve to produce a composition having suitable viscosity. Isopropanol also fails as a suitable pnncipal solvent because it has a relatively strong odor.

Pnncipal solvents are also selected for their ability to provide stable compositions at low temperatures, preferably compositions compnsing suitable pnncipal solvents are clear down to about 4° C and have the ability to fully recover their clanty if stored as low as about 7° C.

The principal solvents according to the present invention are selected base upon their octanol/water partition coefficient (P). The octanol/water partition coefficient is a measure of the ratio of the concentrations of a particular pnncipal solvent m octanol and water at equihbπum. The partition coefficients are conveniently expressed and reported as their loganthm to the base 10; logP.

The logP of many principal solvent species has been reported; for example, the Ponmona92 database, available from Daylight Chemical Information Systems, Inc. (Daylight CIS), contains many, along with citations to the original literature.

However, the logP values are most conveniently calculated by the "CLOGP" program, also available from Daylight CIS. This program also lists expenmental logP values when they are available in the Pomona92 database. The "calculated logP" (ClogP) is determined by the fragment approach of Hansch and Leo ( cfi, A. Leo, in Comprehensive Medicinal Chemistry, Vol 4, C. Hansch, P. G Sammens, J. B. Taylor and C A. Ransden, Eds., p. 295, Pergamon Press, 1990, incorporated herein by reference) The fragment approach is based on the chemical structure of each HR species, and takes into account the numbers and types of atoms, the atom connectivity, and chemical bonding ClogP values are the most reliable and widely used estimates for octanol water partitioning. It will be understood by those skilled in the art that experimental log P values could also be used. Expenmental log P values represent a less preferred embodiment of the invention. Where expenmental log P values are used, the one hour log P values are preferred. Other methods that can be used to compute ClogP include, e.g., Cπppen's fragmentation method as disclosed in J Chem. Inf Comput. Sci., 27a,21 (1987); Viswanadhan's fragmentation method as disclosed m J. Chem Inf Comput. Sci., 29, 163 (1989); and Broto's method as disclosed in Eur J Med Chem - Chun. TJieor., 19, 71 (1984).

The pnncipal solvents suitable for use m the present invention are selected from those having a ClogP of from about 0.15 to about 1 , preferably from about 0.15 to about 0.64, more preferably from about 0.25 to about 0.62, most preferably form about 0.4 to about 0.6. Preferably the principal solvent is at least to some degree an asymmetric molecule, preferably having a melting, or solidification point which allows the pnncipal solvent to be liquid at or near room temperature. Low molecular weight pnncipal solvents may be desirable for some embodiments. More preferred molecules are highly asymmetncal.

A further descπption of pnncipal solvents suitable for use in the isotropic liquid compositions of the present invention are thoroughly descnbed in WO 97/03169 "Concentrated, Stable Fabπc Softening Composition", published January 30, 1997 and assigned to the Procter & Gamble Co.; WO 97/03170 "Concentrated, Water Dispersible, Stable, Fabnc Softening Composition", published January 30, 1997 and assigned to the Procter & Gamble Co.; and WO 97/34972 "Fabric Softening Compound/Composition", published September 25, 1997 and assigned to the Procter & Gamble Co. all included herein by reference. Hydrophobic Dispersant

A preferred composition of the present invention compnses from about 0.1 %>, preferably from about 5%, more preferably form about 10%) to about 80%, preferably to about 50%>, more preferably to about 25% by weight, of a hydrophobic polyamme dispersant having the formula:

R¹ B

[(R')₂N- R]_W [N- R]_X [N- R]_y N(R^,)₂ wherein R. R' and B are suitably descnbed in U.S. 5,565,145 Watson et al., issued October 15, 1996 incorporated herein by reference, and w, x, and y have values which provide for a backbone prior to substitution of preferably at least about 1200 daltons, more preferably 1800 daltons. R' units are preferably alkyleneoxy units having the formula:

-(CH₂CHRO)_m(CH2CH₂0)_nH wherein R' is methyl or ethyl, m and n are preferably from about 0 to about 50, provided the average value of alkoxylation provided by m + n is at least about 0.5.

A further descnption of polyamme dispersants suitable for use in the present invention is found in U.S. 4,891,160 Vander Meer, issued January 2, 1990; U.S.4,597,898, Vander Meer, issued July 1. 1986; European Patent Application 1 1 1,965, Oh and Gosselink, published June 27, 1984, European Patent Application 1 1 1,984, Gosselink, published June 27, 1984; European Patent Application 1 12,592, Gosselink, published July 4, 1984; U.S. 4,548,744, Connor, issued October 22, 1985; and U.S. 5,565,145 Watson et al., issued October 15, 1996; all of which are included herein by reference. However, any suitable clay/soil dispersent or anti-redepostion agent can be used in the laundry compositions of the present invention. Electrolyte

The fabπc softening embodiments of the compositions of the present invention, especially clear, isotropic liquid fabric softening compositions, may also optionally, but preferably compnse, one or more electrolytes for control of phase stability, viscosity, and/or clanty. For example, the presence of certain electrolytes inter aha calcium chlonde, magnesium chloπde may be key to msunng initial product clanty and low viscosity, or may affect the dilution viscosity of liquid embodiments, especially isotropic liquid embodiments. Not wishing to be limited by theory, but only wishing to provide an example of a circumstance wherein the formulator must insure proper dilution viscosity, includes the following example. Isotropic or non-isotropic liquid fabnc softener compositions can be introduced into the πnse phase of laundry operations via an article of manufacture designed to dispense a measured amount of said composition. Typically the article of manufacture is a dispenser which delivers the softener active only dunng the nnse cycle. These dispensers are typically designed to allow an amount of water equal to the volume of softener composition to enter into the dispenser to insure complete delivery of the softener composition An electrolyte may be added to the compositions of the present invention to insure phase stability and prevent the diluted softener composition from "gelling out" or from undergoing an undesirable or unacceptable viscosity increase. Prevention of gelling or formation of a "swelled", high viscosity solution insures thorough delivery of the softener composition

However, those skilled in the art of fabπc softener compositions will recognize that the level of electrolyte is also influenced by other factors inter aha the type of fabπc softener active, the amount of principal solvent, and the level and type of no onic surfactant For example, tπethanol amme derived ester quaternary amines suitable for use as softener actives according to the present invention are typically manufactured in such a way as to yield a distribution of mono-, di-. and tπ- esteπfied quaternary ammonium compounds and amme precursors. Therefore, as in this example, the vanability in the distnbution of mono-, di-, and tπ- esters and amines may predicate a different level of electrolyte. Therefore, the formulator must consider all of the ingredients, namely, softener active, nomonic surfactant, and in the case of isotropic liquids, the pnncipal solvent type and level, as well as level and identity of adjunct ingredients before selecting the type and/or level of electrolyte

A wide variety of lonizable salts can be used. Examples of suitable salts are the halides of the Group IA and IIA metals of the Periodic Table of the elements, e.g., calcium chlonde, sodium chloπde, potassium bromide, and lithium chlonde. The lonizable salts are particularly useful dunng the process of mixing the ingredients to make the compositions herein, and later to obtain the desired viscosity. The amount of lonizable salts used depends on the amount of active ingredients used m the compositions and can be adjusted according to the desires of the formulator. Typical levels of salts used to control the composition viscosity are from about 20 to about 10,000 parts per million (ppm), preferably from about 20 to about 5,000 ppm, of the composition.

Alkylene polyammonium salts can be incorporated into the composition to give viscosity control in addition to or m place of the water-soluble, lonizable salts above, In addition, these agents can act as scavengers, forming ion pairs with anionic detergent earned over from the mam wash, in the rinse, and on the fabncs, and can improve softness performance. These agents can stabilized the viscosity over a broader range of temperature, especially at low temperatures, compared to the inorganic electrolytes. Specific examples of alkylene polyammonium salts include L-lysine, monohydrochloπde and l ,5-dιammonιum 2-methyl pentane dihydrochlonde. Cationic Charge Booster System

The compositions of the present invention may optionally compnse from about 0.2%_>, preferably from about 5% to about 10%, preferably to about 7% by weight, of a charge booster system. Typically, ethanol is used to prepare many of the below listed ingredients and is therefore a source of solvent into the final product formulation. The formulator is not limited to ethanol, but instead can add other solvents inter aha hexyleneglycol to aid in formulation of the final composition. This is especially true m clear, translucent, isotropic compositions. Cationic Charge Booster Admixtures

One type of preferred cationic charge booster system of the present invention is an admixture of two or more di-amino compounds wherein at least one of said di-amino compounds is a di-quaternary ammonium compound.

Preferably said charge booster system is the admixture of di-amino compounds which results from a process compnsing the steps of:

I) reacting one equivalent of a diamine having the formula:

R¹— N— R— N— R¹ R R wherein R is C₂-Cj₂ alkylene; each R' IS independently hydrogen, C C alkyl, a unit having the formula:

^■ R -Z wherein R² is C₂-C_b linear or branched alkylene, C₂-C₆ linear or branched hydroxy substituted alkylene, C₂-C₆ linear or branched amino substituted alkylene, and mixtures thereof; Z is hydrogen, -OH, -NH₂, and mixtures thereof; with from about 0.1 equivalent to about 8 equivalents of an acylatmg unit to form an acylated di-ammo admixture; and ii) reacting said acylated di-ammo admixture with from 0.1 equivalents to 2 equivalents of a quatemizing agent to form said cationic charge booster system. Step (i) of the present cationic charge booster producing process, is an acylation step. The acylation of the ammo compound may be conducted under any conditions which allow the formulator to prepare the desired final cationic admixture or an admixture which has the desired final charge boosting properties.

Step (n) of the present cationic charge booster producing process, is the quatemization step. The formulator may use any quatemizing agent which provides an admixture having the desired charge boosting properties. The choice of from 0.1 equivalents to 2 equivalents of quatemizing agent will provide the formulator with a wide array of cationically charged di- ammes in the final admixture.

Non-hmitmg examples of acylating agents suitable for use in the present invention include, acylating agents selected from the group consisting of: a) acyl halides having the formula:

O

R⁴— C— Hal b) an ester having the formula:

O

R⁴— C— O— R⁶ c) anhydrides having the formula:

O O

, II II

R⁴— c— o— c— Y d) carboxy lie/carbonic anhydrides having the formula:

O O

. II II R — C— O— C— O— R⁶ e) acyl azides having the formula:

O

R⁴— C— N₃ 0 and mixtures thereof; wherein R⁴ is C₆-C₂₂ linear or branched, substituted or unsubstituted alkyl, C₆-C₂₂ linear or branched, substituted or unsubstituted alkenyl, or mixtures thereof; Hal is a halogen selected from chlonne, bromine, or iodine; R⁶ is R⁴, C C₅ linear or branched alkyl; Y is R⁴, -CF₃, -CC1₃, and mixtures thereof.

An example of a preferred process compnses the reaction of an amme having the formula:

HOCH^CH_2\ H₂CH₂OH

^N— R— N^ HOCH₂CH₂ ^/ CH₂CH₂OH wherein R is hexamethylene, with about two equivalents of an acylating agent to form a partially acylated diamine admixture, followed by reaction of said admixture with from about 1.25 to about 1 75 equivalents of a quatemizing unit, preferably dimethyl sulfate.

Non-limiting examples of preferred di-amines which compnse the cationic charge booster systems of the present invention include:

0 one or more diammes having the formula:

R³— N— R— N— R³

R³ R^J

H) one or more quaternary ammonium compounds having the formula:

in) one or more di-quaternary ammonium compounds having the formula:

Q Q

, + 1 1 + ₃

R— N— R— N— R³ n X -2/n

R^J R^J wherein R is C₂-Cj₂ alkylene, preferably C_:-C₈ alkylene, more preferably hexamethylene; each R³ is independently R' , an acyl compnsing unit having the formula: R⁵ O (CH)— W— C— R⁴ wherein R⁴ is C₆-C₂₂ linear or branched, substituted or unsubstituted alkyl, C₆-C₂₂ linear or branched, substituted or unsubstituted alkenyl, or mixtures thereof; and mixtures thereof; each R³ is independently hydrogen, -OH, -NH₂, -(CH₂)_zWC(0)R⁴, and mixtures thereof; Q is a quatemizing unit selected from the group consisting of Cj-C|₂ alkyl, benzyl, and mixtures thereof; W is -0-, -NH-, and mixtures thereof; X is a water soluble cation; the index n is 1 or 2; y is from 2 to 6; z is from 0 to 4; y + z is less than 7.

Suitable sources of acyl units which compnse the cationic charge booster systems include acyl units which are denved from sources of triglycerides selected from the group consisting of tallow, hard tallow, lard, coconut oil, partially hydrogenated coconut oil, canola oil, partially hydrogenated canola oil, safflower oil, partially hydrogenated safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated sunflower oil, com oil, partially hydrogenated com oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated nee bran oil, synthetic tπglycende feedstocks and mixtures thereof

Preferably at least two R³ units are units having the formula:

O (CH₂)₂-0— C ^{1 1}— R 4⁴ wherein R⁴ comprises an acyl which is denved from a triglyceride source selected from the group consisting of hard tallow, soft tallow, canola, oleoyl, and mixtures thereof, Q is methyl; X is a water soluble cation; the index n is 2.

The following is an example of a di-ammo admixture suitable for use as a cationic charge boosting system according to the present invention. 0 diammes having the formula:

(HOCH₂CH₂)₂N(CH₂)₆N(CH₂CH₂OH)₂

(HOCH₂CH₂)₂N(CH₂)₆N(CH₂CH₂OH)(CH₂CH₂OCR⁴)

(R COCH₂CH₂)(HOCH₂CH₂)N(CH₂)₆N(CH₂CH₂OH)(CH₂CH₂OCR⁴)

(R COCH₂CH₂)(HOCH₂CH₂)N(CH₂)₆N(CH₂CH₂OCR⁴)₂ (R⁴COCH₂CH₂)(HOCH₂CH₂)N(CH₂)₆N(CH₂CH₂OH)₂

(R⁴COCH₂CH₂)₂N(CH₂)₆N(CH,CH₂OCR⁴)

ii) quaternary ammonium compounds having the formula:

(HOCH_:CH_:)₂N^'(CH₃)(CH₂)₆N(CH₂CH₂θH)₂

(HOCH₂CH₂)₂N^'(CH₃)(CH₂)₆N(CH₂CH₂OH)(CH₂CH₂OCR⁴)

(R⁴COCH₂CH₂)(HOCH₂CH₂)N^~(CH₃)(CH₂)₆N(CH₂CH₂OH)₂

(R⁴COCH₂CH₂)(HOCH₂CH₂)N^'(CH₃)(CH₂)₆N(CH₂CH₂OH)(CH₂CH₂OCR⁴)

(HOCH₂CH₂)₂N^'(CH,)(CH₂)6N(CH₂CH₂OCR⁴)₂

(R COCH₂CH₂)₂N^'(CH₃)(CH₂)₍,N(CH₂CH₂OH)₂

(R⁴COCH_:CH:):N^'(CH₃)(CH_:)₍,N(CH₂CH_:OH)(CH₂CH₂OCR⁴)

(R COCH:CH:)(HOCH_:CH:)N^'(CH₃)(CH_:)₍,N(CH_:CH:OCR⁴);

(R COCH₂CH₂);N^'(CH. )(CH₂).N(CH₂CH₂OCR⁴)₂

in) di-quatemary ammonium compounds having the formula:

(HOCH₂CH₂) N (CH. KCH ).N^'(CH,)(CH₂CH₂OH)j

(R COCH CH:)(HOCH;CH_; )N (CH,)(CH₂)₍,N (CH₃)(CH_:CH₂OH)₂

(R⁴COCH₂CH₂)(HOCH₂CH₂)N^'(CH,)(CH₂)_ΛN^'(CH₃)(CH₂CH₂OH)(CH₂CH₂OCR⁴)

(R⁴COCH CH:)₂N^'(CH,)(CH )_>,N"(CH₃KCH₂CH_:OH)(CH₂CH₂OCR⁴)

(R COCH₂CH₂),N^"(CH₃)(CH₂)₆N (CH₃)(CH₂CH₂OCR⁴)₂ wherein the acyl unit -C(0)R⁴ is deπved from canola. Non-admixture Cationic Charge Boosters

When formulating non-admixture cationic charge booster systems into the fabπc enhancement or fabric care compositions of the present invention, the following are non-limiting preferred examples. 1) Quaternary Ammonium Compounds

A preferred composition of the present invention compnses at least about 0.2%, preferably from about 0.2% to about 10%>, more preferably from about 0.2% to about 5% by weight, of a cationic charge booster having the formula:

R2

Rl— N-R3 X

wherein R' , R^, R3, and R^ are each independently Ci -C22 alkyl, C3-C22 alkenyl, R^-Q-

(CH2)_m-, wherein R^ is C1-C22 alkyl, and mixtures thereof, m is from 1 to about 6; X is an anion. Preferably R is Cg-C22 alkyl, Cg-C22 alkenyl, and mixtures thereof, more preferably

C_] 1 -C 1 g alkyl. C\ 1 -C_j g alkenyl, and mixtures thereof; R^, R3, and R^ are each preferably Ci -

C4 alkyl. more preferably each R^, R3, and R^ are methyl.

The formulator may similarly choose R^ to be a R5-Q-(CH2)_m- moiety wherein R^ is an alkyl or alkenyl moiety having from 1 to 22 carbon atoms, preferably the alkyl or alkenyl moiety when taken together with the Q unit is an acyl unit denved preferably denved from a source of triglyceride selected from the group consisting of tallow, partially hydrogenated tallow, lard, partially hydrogenated lard, vegetable oils and/or partially hydrogenated vegetable oils, such as, canola oil. safflower oil, peanut oil, sunflower oil, com oil, soybean oil, tall oil, rice bran oil, etc. and mixtures thereof An example of a fabric softener cationic booster comprising a R->-Q-(CH2)_m- moiety has the formula.

wherein R->-Q- is an oleoyl units and m is equal to 2. X is a softener compatible anion, preferably the anion of a strong acid, for example, chloride, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate. 11) Polwinyl Ammes A preferred embodiment of the present invention contains at least about 0.2%., preferably from about 0.2% to about 5%, more preferably from about 0.2% to about 2% by weight, of one or more polyvmyl amines having the formula

wherein y is from about 3 to about 10,000, preferably from about 10 to about 5,000, more preferably from about 20 to about 500. Polyvmyl amines suitable for use in the present invention are available from BASF.

Optionally, one or more of the polyvmyl amme backbone -NH2 unit hydrogens can be substituted by an alkyleneoxy unit having the formula:

(RlO)_xR2 wherein R^ IS C2-C4 alkylene, R- is hydrogen, CJ-C4 alkyl, and mixtures thereof; x is from 1 to 50. In one embodiment or the present invention the polyvmyl amme is reacted first with a substrate which places a 2-propyleneoxy unit directly on the nitrogen followed by reaction of one or more moles of ethylene oxide to form a unit having the general formula:

CH₃ I (CH₂CHO) — (CH₂CH₂O)_xH wherein x has the value of from 1 to about 50. Substitutions such as the above are represented by the abbreviated formula PO-EO_x-. However, more than one propyleneoxy unit can be incorporated into the alkyleneoxy substituent.

Polyvmyl amines are especially preferred for use as cationic charge booster m liquid fabnc softening compositions since the greater number of amme moieties per unit weight provides substantial charge density. In addition, the cationic charge is generated in situ and the level of cationic charge can be adjusted by the formulator. 111) Poly-Quaternary Ammonium Compounds

A preferred composition of the present invention compnses at least about 0.2%>, preferably from about 0.2%> to about 10%, more preferably from about 0.2% to about 5%> by weight, of a cationic charge booster having the formula:

wherein R is C₂-Cι₂ alkylene, preferably C₂-C₈ alkylene, more preferably hexamethylene; each R³ is independently R' , an acyl compnsing unit having the formula:

wherein R⁴ is C₆-C₂₂ linear or branched, substituted or unsubstituted alkyl, C₆-C₂₂ linear or branched, substituted or unsubstituted alkenyl, or mixtures thereof; and mixtures thereof; each R³ is independently hydrogen, -OH, -NH₂, -(CH₂)_zWC(0)R⁴, and mixtures thereof; Q is a quatemizing unit selected from the group consisting of C|-Cj₂ alkyl, benzyl, and mixtures thereof; W is -0-. -NH-. and mixtures thereof; X is a water soluble cation; the index n is 1 or 2; y is from 2 to 6: z is from 0 to 4; y + z is less than 7.

An example of a fabric softener cationic booster comprising a -(CH₂)_zWC(0)R moiety has the formula.

wherein R³ is methyl or -(CH₂)_zWC(0)R⁴, Q is methyl, W is oxygen, the index z is equal to 2, such that -WC(0)R⁴ is an oleoyl unit.

Cationic Nitrogen Compounds

The fabnc enhancement compositions of the present invention may optionally compnse from about 0 5%, preferably from about 1% to about 10%, preferably to about 5% by weight, of one or more cationic nitrogen containing compound, preferably a cationic compound having the formula.

R— N(R'), X wherein R is C|₀-Cj₈ alkyl, each R' is independently C,-C₄ alkyl, X is a water soluble anion; preferably R is C_I2-C,₄, preferably R' is methyl. Preferred X is halogen, more preferably chlonne. Examples of cationic nitrogen compounds suitable for use the fabric care compositions of the present invention are Non-limiting examples of preferred cationic nitrogen compounds are N,N-dιmethyl-(2- hydroxyethyl)-N-dodecyl ammonium bromide, N,N-dιmethyl-(2-hydroxyethyl)-N-tetradecyl ammonium bromide. Suitable cationic nitrogen compounds are available ex Akzo under the tradenames Ethomeen T/15^®, Secomme TA15^®, and Ethoduomeen T/20^®. Dispersibility Aids Relatively concentrated compositions containing both saturated and unsaturated diester quaternary ammonium compounds can be prepared that are stable without the addition of concentration aids. However, the compositions of the present invention may require organic and/or inorganic concentration aids to go to even higher concentrations and/or to meet higher stability standards depending on the other ingredients. These concentration aids which typically can be viscosity modifiers may be needed, or preferred, for ensuring stability under extreme conditions when particular softener active levels are used. The surfactant concentration aids are typically selected from the group consisting of (1 ) single long chain alkyl cationic surfactants; (2) nomonic surfactants; (3) amme oxides; (4) fatty acids; and (5) mixtures thereof. These aids are described in P&G Copending Application Serial No. 08/461.207, filed June 5, 1995, Wahl et al., specifically on page 14, line 12 to page 20, line 12, which is herein incorporated by reference. When said dispersibility aids are present . the total level is from 2% to 25%. preferably from 3% to 17%, more preferably from 4% to 15%. and even more preferably from 5% to 13% by weight of the composition. These mateπals can either be added as part of the active softener raw matenal, e.g., the mono-long chain alkyl cationic surfactant and/or the fatty acid which are reactants used to form the fabric softener active as discussed hereinbefore, or added as a separate component. The total level of dispersibility aid includes any amount that may be present as part of the softener active. Soil Release Agents

Particular to the embodiments of the nnse-added fabnc softeners according to the present invention, certain soil release agents provide not only the below descnbed soil release properties but are added for their suitability in maintaining proper viscosity, especially in the dispersed phase, non-isotropic compositions.

Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention. Polymeπc soil release agents are characteπzed by having both hydrophilic segments, to hydrophi ze the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of the nns g cycle and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurπng subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.

If utilized, soil release agents will generally compnse from about 0.01%o to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1 %> to about 5%, preferably from about 0.2% to about 3.0%>.

The following, all included herein by reference, descπbe soil release polymers suitable for us m the present invention. U.S. 5,728,671 Rohrbaugh et al., issued March 17, 1998; U.S.

5,691,298 Gosselink et al . issued November 25, 1997; U.S. 5,599,782 Pan et al., issued February 4. 1997: U.S. 5.415.807 Gosselink et al., issued May 16, 1995; U.S. 5,182,043 Morrall et al., issued January 26, 1993, U.S 4,956,447 Gosselink et al., issued September 11, 1990; U.S. 4,976,879 Maldonado et al. issued December 1 1, 1990; U.S. 4,968,451 Scheibel et al.. issued November 6. 1990; U.S. 4,925,577 Borcher, Sr. et al , issued May 15, 1990; U.S. 4,861,512 Gosselink. issued August 29, 1989; U.S. 4,877,896 Maldonado et al, issued October 31, 1989; U.S. 4,721,580 Gosselink issued January 26, 1988; U.S. Patent 4,702,857 Gosselink, issued October 27, 1987, U.S. 4,71 1 ,730 Gosselink et al., issued December 8, 1987; U.S. 4,000,093 Nicol et al. issued December 28, 1976; U.S. 3.959.230 Hayes, issued May 25. 1976; U.S. 3,893.929 Basadur, issued July 8, 1975; and European Patent Application 0 219 048, published April 22, 1987 by Kud et al.

Further suitable soil release agents are described in U.S. 4,201 ,824 Voilland et al.; U.S. 4,240,918 Lagasse et al ; U.S. 4,525,524 Tung et al ; U.S. 4,579,681 Ruppert et al.; U.S. 4,220,918; U.S. 4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF ( 1991 ): and DE 2,335,044 to Unilever N. V., 1974; all incorporated herein by reference.

Cationic Nitrogen Compounds

The fabπc enhancement compositions of the present invention may optionally compnse from about 0.5%>, preferably from about 1% to about 10%, preferably to about 5%> by weight, of one or more cationic nitrogen containing compound, preferably a cationic compound having the formula:

+ _ ,,

R— N(R')₃ X wherein R is Cι₀-Cj₈ alkyl, each R¹ is independently Cj-C₄ alkyl, X is a water soluble anion; preferably R is Cι₂-Cj₄, preferably R' is methyl. Preferred X is halogen, more preferably chlorine. Examples of cationic nitrogen compounds suitable for use in the fabπc care compositions of the present invention are

Non-hmitmg examples of preferred cationic nitrogen compounds are N,N-dιmethyl-(2- hydroxyethyl)-N-dodecyl ammonium bromide, N,N-dιmethyl-(2-hydroxyethyl)-N-terradecyl ammonium bromide. Suitable cationic nitrogen compounds are available ex Akzo under the tradenames Ethomeen T/15^®, Secomine TA15^®, and Ethoduomeen T/20^®.

The following compositions illustrate the present invention.

TABLE I

Weight %

Ingredients 2 3

1. N,N-dι(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium methyl sulfate available from Witco.

2. Monocanolyl tnmethyl ammonium chloride, available as Adogen 417® from Witco.

3. N,N^,-(3-amιnopropyl)ethylenedιamιne. 4 N,N'-(3-amιnopropyl)butylenedιamme.

5. Tnpropylenetetraamme.

6. Tnmethyl pentanediol available from Eastman Chemical.

7 1 ,4-cyclohexane dimethanol available from Eastman Chemical. Minors can include perfume, dye, acid, preservatives, etc.

TABLE π weight %

1 N.N-dι-(canolyl-oxy-ethyl)-N-methy -N-(2-hydroxyethyl) ammonium methyl sulfate.

2 Tπpropylenetetraamine.

3 PEG-6 cocamide, (Rewopal C6 ex Witco Chemical).

4 PEG-5 lauramide (Amidox L-5, ex Stepan Chemical).

TABLE III weight %

2. N,N'-bιs(3-ammopropyl)-l,4-pιperazιne.

3. PEG-6 cocamide, (Rewopal C6 ex Witco Chemical).

4. PEG-7 oleamide (Ethomid 0/17, ex Akzo Chemical). 5 Adogen 417, ex Witco Chemical.

TABLE IV weight %>

Miscellaneous 1.4 1.0 0.7 0.4 1.0 1.3

Water balance balance balance balance balance balance

1. N,N-dι(tallowyl-oxy-ethyl)-N,N-dιmethyl ammonium chlonde (tallowyl having an LV. of 50).

2. N,N-dι(tallowyl-oxy-ethyl)-N,N-dιmethyl ammonium chlonde (tallowyl having an LV. of 18).

3. l,2-Dιtallowyloxy-3-N,N,N-tnmethylammonιopropane chlonde.

4. Ditallow dimethyl ammonium chloπde.

5. Methyl bιs(tallow amιdoethyl)-2-hydroxyethyl ammonium methyl sulfate.

6. 1 -Tallowamιdoethyl-2-ιmιdazolme.

7 N.N,N^',N^,-terakιs(2-hydroxypropyl)ethylenedιamιne.

8 Dimethyl terephthalate, 1 ,2-propylene glycol, methyl capped PEG polymer. 9. N,N^,-bιs(3-amιnopropyl)-l,3-propylenedιamιne.

10 N.N'-bιs(3-amιnopropyl)-l ,3-propylenedιamιne wherein each N-H unit is replaced by a 1 ,2- propyleneoxy unit

1 1 Pentrol* available ex BASF.

12. Bιs(hexamethylene)tπamιne wherein each N-H unit is replaced by a methyl unit. 13 N.N^'-bιs(2-hydroxybutyl)-N,N^,-bιs[3-N,N-bιs(2-hydroxybutyl)amιnopropyl]-l ,3- propylenediamine. which is N,N^,-bιs(3-ammopropyl)-l ,3-propylenedιamιne wherein each hydrogen of the backbone is replaced by a 2-hydroxybutyl moiety.

The following are examples of compositions which prevent the fading of dye from fabπc, especially cotton fabric.

TABLE V weight %

1. N,N-dι-(canolyl-oxy-ethyl)-N-methyl-N-(2-hydroxyethyl) ammonium methyl sulfate.

2. Selected from REWIN SRF, REWIN SRF-0 and REWIN DWR ex CHT-Beitlich GMBH.

3. Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 4.

4. Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 1

5. Polyalkyleneimine having a molecular weight of 1800 and an average ethoxylation per backbone nitrogen of approximately 7.

6. Hydroxyethanediphosphonate (HEDP). 7 BAYHBIT AM ex Baeyer.

8. Suitable enzymes include cellulase, hpase, protease, peroxidase, and mixtures thereof.

9. N,N'-bιs(propyleneamιno)-l ,4-pιperazme.

10. 5-N-methyl dipropylenetnamine.

1 1. N,N'-bιs(propyleneamιno)-l,4-pιperazιne PI .

The following examples descnbe fabπc enhancement compositions of the present invention which can be applied to fabnc to achieve color fidelity and other fabnc benefits.

Table VI

Weight %

1. N,N^,-bιs(3-amιnopropyl)-l ,3-propylamme.

2. Hexapropyleneoxy N,N'-bιs(3-amιnopropyl)-l ,3-propylamine (TPTA having each nitrogen fully substituted with a propyleneoxy unit). 3. N,N'-bιs(3-amιnopropyl)-l,4-pιperazme.

4. Tetraethvleneoxy N,N'-bιs(3-ammopropyl)-l ,4-pιperazme (BNPP having each terminal nitrogen fully substituted with an ethyleneoxy unit).

The following are non-limiting examples of fabnc care compositions according to the present invention.

Table VII

Weight %

Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85. Dye fixing agent ex Claπant under the tradename Cartafix CB^X. 1 , 1 -N-dιmethyl-9,9-N' '-dimethyl dipropylenetnamine. l , l-N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamine. 2-Phosphonobutane-1.2.4-trιcarboxyhc acid ex Bayer.

Table VIII

Weight %

1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol* K85.

2. Dye fixing agent ex Claπant under the tradename Cartafix CB^l.

3. N,N ' -bi s( 3-amιnopropyl )- 1 ,4-piperazine. 4. Di (tallowyloxyethyl)dιmethyl ammonium chlonde.

5. 2-Phosphonobutane- 1 ,2.4-tncarboxylιc acid ex Bayer.

Table IX

Weight %

1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol K85.

2. Dye fixing agent ex Claπant under the tradename Cartafix CB .

3. l, l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamine.

4. l ,l-N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamine.

5. N,N^,-bιs(3-amιnopropyl)-l ,4-pιperazme.

6. 2-Phosphonobutane-1.2.4-tπcarboxyhc acid ex Bayer.

Table X

Weight %

1. Polyvinylpyrrolidone K85 available ex BASF as Luviskol^* K85.

2. Dye fixing agent ex Claπant under the tradename Cartafix CB*.

3. N,N'-bιs(3-amιnopropyl)-l ,4-pιperazme.

4. 1,1 -N-dιmethyl-5-N ' -methyl-9.9-N' ' -dimethyl dipropylenetnamine. 5. 2-Phosphonobutane-1.2.4-tπcarboxyhc acid ex Bayer.

TABLE XI

Weight %

Ingredients 46 47 48 49

1. N,N-dι(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium methyl sulfate available from Witco.

Monocanolyl tnmethyl ammonium chloride, available as Adogen 417® from Witco. 5-N-methyl dipropylenetnamine. l ,l-N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamine. Tπpropy lenetetraamine .

Tnmethyl pentanediol available from Eastman Chemical. 1 ,4-cyclohexane dimethanol available from Eastman Chemical. Minors can include perfume, dye, acid, preservatives, etc.

Claims

WHAT IS CLAIMED IS :

1 A πnse-added fabric care composition comprising: a) from 0.01% to 50% by weight, of a polyamme, said polyamme selected from: l) linear polyamines having the formula:

R²

(R')₂N- R— [N— R1— N(R')₂ wherein each R is independently C₂-C₆ linear alkylene, C₃-C₆ branched alkylene. and mixtures thereof; R¹ is hydrogen, Cι-Cj₂ alkyl, alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, C,-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O C I'— R 5⁵ wherein R³ is -C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R¹ units can be taken together to form a 5-7 member ring; and mixtures thereof; R² is hydrogen, R¹, -RN(R')₂, and mixtures thereof;

11) cyclic polyamines having the formula:

R— L— R wherein L is a linking unit, said linking unit compnsing a ring having at least 2 nitrogen atoms; R is hydrogen, -(CH₂)_kN(R')₂, and mixtures thereof wherein at least one cyclic polyamme R unit is a -(CH₂)κN(R')_: unit; R¹ is hydrogen; C|-C_]2 alkyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cι-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O

— C 'I— R 5⁵ wherein R⁵ is C]-C₂_ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R' units can be taken together to form a 5-7 member nng; k is from 3 to 12; and mixtures thereof; in) and mixtures thereof; b) optionally less than 15% by weight, of a principal solvent; and c) the balance earner and adjunct ingredients.

2. A composition according to Claim 1 wherein said polyamme is a linear polyamme wherein at least one R unit is 1,3-propylene.

3. A composition according to either Claim 1 or 2 wherein R¹ is hydrogen, Cj-Cj₂ alkyl, alkyleneoxy unit having the formula:

-(R³0)_m-R⁴ wherein R³ is C₂-C₆ linear alkylene, C₃-C₆ linear alkylene, or mixtures thereof, R⁴ is hydrogen; and mixtures thereof; m is 1. A composition according to any of Claims 1-3 wherein each R¹ is independently hydrogen, hydroxyethyl, 2-hydroxypropyl, and mixtures thereof.

A composition according to any of Claims 1-4 wherein said polyamme is N,N'- bιs(ammopropyl)-l,3-propylenedιamme, N,N'-bιs(hydroxyethyl)-N,N'-bιs[3-N,N- bιs(hydroxyethyl)amιnopropyl]-l,3-propylenedιamme, N,N'-bιs(2-hydroxypropyl)-N,N'- bιs[3-N.N-bιs(2-hydroxypropyl)amιnopropyl]-l,3-propylenedιamιne, N,N'-bιs(2- hydroxybutyl)-N,N'-bιs[3-N,N-bιs(2-hydroxybutyl)amιnopropyl]-l,3-propylenedιamme, and mixtures thereof.

A composition according to any of Claims 1-5 wherein said polyamme is a linear polyamme wherein at least on R unit is hexylene.

A composition according to any of Claims 1 -6 wherein R¹ is hydrogen, alkyleneoxy having the formula:

-(R³0)_m-R⁴ wherein R³ is C₂-C₆ linear alkylene, C₃-C₆ linear alkylene. or mixtures thereof; R⁴ is hydrogen, Cι-C₄ alkyl, or mixtures thereof; and mixtures thereof; m is 1 to 4.

A composition according to any of Claims 6 or 7wherem said linear polyamme comprises at least on R unit which is ethylene and R¹ is not hydrogen.

A composition according to Claim 1 wherein said polyamme is a cyclic polyamme wherein L is piperazme.

A composition according to Claim 9 wherein R is -(CH₂)_kN(R')₂, k is from 3 to 6; R¹ is hydrogen, alkyleneoxy having the formula:

-(R³0)_m- R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cj-C₆ alkyl, or mixtures thereof, m is from 1 to 4; and mixtures thereof.

1 1. A composition according to Claim 1 wherein said polyamme is N,N^,-bιs(ammopropyl)- 1,3-propylenedιamιne. N,N'-bιs(hydroxyethyl)-N,N'-bιs[3-N,N- bιs(hydroxyethyl)ammopropyl]-l,3-propylenedιamme, N,N'-bιs(2-hydroxypropyl)-N,N'- bιs[3-N.N-bιs(2-hydroxypropyl)amιnopropyl]-l,3-propylenedιamιne, N.N'-bιs(2- hydroxybutyl)-N,N'-bιs[3-N,N-bιs(2-hydroxybutyl)amιnopropyl]-l,3-propylenedιamιne, 5-N-methyl dipropylenetnamine, 1 , 1 -N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamine, l ,l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamine, and mixtures thereof.

12. A composition according to any of Claims 1-1 1 wherein said composition further compnses from 1% to 80% by weight, of a fabnc softening active, said fabric softener active comprises a quaternary ammonium compound having the formula:

an amme having the formula:

(R) — N (CH₂)„-Q-R'

3-m and mixtures thereof; wherein each R is independently Cj-C₆ alkyl, Cι-C₆ hydroxyalkyl, benzyl, and mixtures thereof; R' IS Cj-C₂₂ alkyl, C₃-C₂₂ alkenyl, and mixtures thereof; Q is a carbonyl moiety having the formula:

O O R² O O R²

II II I II II I

— o— c — , — c— o — , — N— c — , — c— N — o

O R 3³ O O— C "— R .¹ O

II I II I II

— o— c— o — — CH-O— c — — CH-CH₂-o— c — wherein R² is hydrogen, C,-C alkyl, Cj-C hydroxyalkyl, and mixtures thereof: R³ is hydrogen, C_rC_A alkyl, and mixtures thereof; X is a softener compatible anion; m is from 1 to 3; n is from 1 to 4.

13. A composition according to any of Claims 1-12 wherein said fabπc softening active comprises an acyl moiety which is derived from a source of triglyceride selected from the group consisting of tallow, hard tallow, lard, canola oil, partially hydrogenated canola oil. safflower oil, partially hydrogenated safflower oil, peanut oil, partially hydrogenated peanut oil, sunflower oil, partially hydrogenated sunflower oil, com oil, partially hydrogenated com oil, soybean oil, partially hydrogenated soybean oil, tall oil, partially hydrogenated tall oil, rice bran oil, partially hydrogenated πce bran oil, synthetic triglyceride feedstocks, and mixtures thereof.

14. A composition according to Claim 1 further compnsing a pnncipal solvent wherein said pnncipal solvent has a ClogP of from 0.15 to 1.

15 A composition according to Claim 14 wherein said principal solvent is selected from the group consisting of mono- alcohols, C diols, C diols, the isomers of octanediol, denvatives of butanediol, the isomers of tπmethylpentanediol, the isomers of ethylmethylpentanediol, the isomers of propylpentanediol, the isomers of dimethylhexanediol, the isomers of ethylhexanediol, the isomers of methylheptanediol, the isomers of octanediol, the isomers of nonanediol, alkyl glyceryl ethers, dι(hydroxy alkyl) ethers, aryl glyceryl ethers, the denvatives of ahcyclic diols, denvatives of alkoxylated C3-C7 diols, aryl diols, and mixtures thereof.

16. A composition according to Claim 15 comprising 2,2,4-tnmethyl-l,3-pentandιol, 1,2- hexandiol, 2-ethyl-l,3-hexanedιol, phenoxyethanol, butyl carbitol, and mixtures thereof.

17. A composition according to any of Claims 1-16 further compnsing adjunct ingredients selected from the group consisting of electrolytes, stabilizers, low molecular weight water soluble solvents, chelatmg agents, cationic charge boosters, dispersibility aids, soil release agents, nomonic fabπc softening agents, concentration aid, perfume, preservatives, colorants, optical bnghteners, opacifiers, fabnc care agents, anti-shnnkage agents, anti-wπnkle agents, fabπc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.

8 A nnse-added fabnc softener composition compnsing: a) from 0.01 % to 50%> by weight, of a linear polyamme having the formula:

R²

(R')₂N— R— [N— R]— N(R')₂ wherein each R is independently C₂-C₆ linear alkylene, C -C₆ branched alkylene, and mixtures thereof; R' is hydrogen, Cι-C_]2 alkyl, alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cj-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O

— C I I — R 5⁵ wherein R⁵ is Cj-C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5. z is from 1 to 3, provided y + z is less than or equal to 6; two R' units can be taken together to form a 5-7 member ring; and mixtures thereof; R² is hydrogen, R¹, -RN(R') , and mixtures thereof; n is from 1 to 6; b) from 1%) to 80%> by weight, of a fabπc softener active, said fabric softener active is selected from the group consisting of N,N-dι(tallowyl-oxy-ethyl)-N,N- dimethyl ammonium chloride; N,N-dι(canolyl-oxy-ethyl)-N,N-dιmethyl ammonium chloride; N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(canolyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; and mixtures thereof; and c) the balance carriers and adjunct ingredients, said adjunct ingredients selected from the group consisting of electrolytes, stabilizers, low molecular weight water soluble solvents, chelatmg agents, cationic charge boosters, dispersibility aids, soil release agents, nomonic fabric softening agents, concentration aid, perfume, preservatives, colorants, optical bnghteners, opacifiers, fabnc care agents, anti- shπnkage agents, anti-wrmkle agents, fabnc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.

A composition according to Claim 18 wherein said polyamme is N,N'-bιs(amιnopropyl)- 1 ,3-propylenedιamme, N,N'-bιs(hydroxyethyl)-N,N'-bιs[3-N,N- bιs(hydroxyethyl)arnιnopropyl]-l,3-propylenedιamιne, N,N'-bιs(2-hydroxypropyl)-N,N'- bis[3-N,N-bis(2-hydroxypropyl)ammopropyl]-l,3-propylenediamme, N,N'-bιs(2- hydroxybutyl)-N,N'-bis[3-N,N-bis(2-hydroxybutyl)ammopropyl]-l,3-propylenediamme, and mixtures thereof.

A nnse-added fabric softener composition compnsing: a) from 0.01% to 50% by weight, of a cyclic polyamme having the formula:

R— L— R wherein L is a linking unit, said linking unit comprising a ring having at least 2 nitrogen atoms; R is hydrogen, -(CH₂)ι₍N(R¹)₂, and mixtures thereof, wherein at least one cyclic polyamme R unit is a -(CH₂)_kN(R')₂ unit; R¹ is hydrogen; Cj-Cj₂ alkyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cj-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O C i i— R 5⁵ wherein R⁵ is C C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R¹ units can be taken together to form a 5-7 member nng; k is from 3 to 12; and mixtures thereof; b) from 1% to 80%> by weight, of a fabnc softener active, said fabπc softener active is selected from the group consisting of N,N-dι(tallowyl-oxy-ethyl)-N,N- dimethyl ammonium chloπde: N,N-dι(canolyl-oxy-ethyl)-N,N-dιmethyl ammonium chloride; N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(canolyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; and mixtures thereof; and c) the balance earners and adjunct ingredients, said adjunct ingredients selected from the group consisting of electrolytes, stabilizers, low molecular weight water soluble solvents, chelat g agents, cationic charge boosters, dispersibility aids, soil release agents, no onic fabric softening agents, concentration aid, perfume, preservatives, colorants, optical bnghteners, opacifiers, fabnc care agents, anti- shπnkage agents, anti-wrinkle agents, fabnc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.

21. A composition according to Claim 20 wherein said cyclic polyamme is N,N'- bιs(amιnopropyl)-l,4-pιperazme, N,N'-bιs(hydroxyethyl)-N,N'-bιs[3-N,N- bιs(hydroxyethyl)amιnopropyl]- 1 ,4-pιperazme, N,N'-bιs(2-hydroxypropyl)-N,N'-bιs[3- N,N-bιs(2-hydroxypropyl)amιnopropyl]- 1 ,4-piperazine, and mixtures thereof.

22 A clear and/or translucent nnse-added fabπc softening composition compnsing: a) at least an effective amount of a modified polyamme having the formula:

R²

(R')₂N— R— [N— R1— N(R')₂ wherein R is 1,3-propylene; R¹ is an alkyleneoxy having the formula:

-(R³0)-R⁴ wherein R³ is 1,2-propylene; R ιs hydrogen; R² is hydrogen, -RN(R')₂, and mixtures thereof; n is 1 or 2, provided at least 50% of said modified polyamines have n equal to 2 and one R² equal to hydrogen; b) at least an effective amount of a fabnc softener active, said fabnc softener active is selected from the group consisting of N,N-dι(tallowyl-oxy-ethyl)-N,N- dimethyl ammonium chlonde, N,N-dι(canolyl-oxy-ethyl)-N,N-dιmethyl ammonium chloπde; N,N-dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N-dι(canolyl-oxy-ethyl)-N-methyl, N-(2- hydroxyethyl) ammonium methyl sulfate; and mixtures thereof; c) less than 15% by weight, of a pnncipal solvent, said pnncipal solvent having a ClogP of from 0.15 to 1; and d) the balance earners and adjunct ingredients.

23. A composition according to Claim 22 further compnsing from 0.5% to 10%> by weight, of a polyoxyalkylene alkylamide surface active agent having the formula:

wherein R is C7-C21 linear alkyl, C7-C21 branched alkyl, C7-C21 linear alkenyl, C7- C21 branched alkenyl, and mixtures thereof; R is ethylene; R^ is C3-C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; R3 IS hydrogen, Ci -C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; R^ is hydrogen, C1-C4 linear alkyl, C3-C4 branched alkyl, and mixtures thereof; m is 1 or 2, n is 0 or 1, provided that when m is 1 n is 1 and when m is 2 n is 0; x is from 0 to 50; y is from 0 to 10.

24. A nnse-added fabric care composition compnsing: a) from 0.01% to 20% by weight, a cyclic polyamme having the formula:

H₂N-(CH₂)_k— L— (CH₂)_k-NH₂ wherein L is a linking unit, said linking unit compπsmg a ring having at least 2 nitrogen atoms; each k is independently from 3 to 12; b) from 1%) to 80% by weight, of a fabric softening active; c) from 0.1% to 10% by weight, of a dye fixative; and d) the balance camer and adjunct ingredients.

25. A composition according to Claim 24 wherein said polyamme has the formula: / \

H₂N-(CH₂)_k— N N— (CH₂)_k-NH₂

wherein each R¹ unit is hydrogen; each k is equal to 3.

26. A composition according to either of Claims 24 or 25 wherein said fabric softener active is selected from the group consisting of N,N-dι(tallowyl-oxy-ethyl)-N,N-dιmethyl ammonium chloride; N,N-dι(canolyl-oxy-ethyl)-N,N-dιmethyl ammonium chloride; N,N- dι(tallowyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; N,N- dι(canolyl-oxy-ethyl)-N-methyl, N-(2-hydroxyethyl) ammonium methyl sulfate; and mixtures thereof.

27 A composition according to any of Claims 24-26 wherein said adjunct ingredients are selected from the group consisting of nomonic fabnc softening agents, concentration aid, soil release agent, perfume, preservatives, stabilizers, colorants, optical bnghteners, opacifiers, fabnc care agents, anti-shnnkage agents, anti-wrinkle agents, fabπc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.

28. A fabric care composition comprising: a) from 0.01% to 20% by weight, of a fabric enhancement system compnsing- l) a linear polyamme having the formula:

R^z

(R')₂N-R— [N- R]— N(R')₂ wherein R is 1,3-propylene; R' is an alkyleneoxy having the formula:

-(R³0)-R⁴ wherein R³ is 1,2-propylene; R⁴ is hydrogen; R² is hydrogen, R¹, - RN(R')₂, and mixtures thereof; n is 1 or 2; provided at least 50% of said modified polyamines have n equal to 2 and one R~ equal to hydrogen; and n) a cyclic polyamme having the formula: H₂N-(CH₂)_k— L— (CH₂)_k-NH₂ wherein L is a linking unit, said linking unit compnsing a ring having at least 2 nitrogen atoms; each k is independently from 3 to 12: and b) the balance camer and adjunct ingredients.

A nnse-added fabπc care composition compnsing: a) from 0.01% to 50%> by weight, of a polyamme, said polyamme selected from:

I) linear polyamines having the formula:

R²

(R')₂N— R— [N— R]— N(R')₂ n wherein each R is independently C₂-C₆ linear alkylene, C^-^ branched alkylene, and mixtures thereof; R¹ is hydrogen, C_J-C_J2 alkyl, alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, C C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O — C— R⁵ wherein R⁵ is C,-C₂₂ linear or branched alkyl, C₃-C₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R¹ units can be taken together to form a 5-7 member nng; and mixtures thereof; R² is hydrogen, R¹, -RN(R')₂, and mixtures thereof;

n) cyclic polyamines having the formula: R— L— R wherein L is a linking unit, said linking unit compnsing a ring having at least 2 nitrogen atoms; R is hydrogen, -(CH₂)_kN(R')₂, and mixtures thereof, wherein at least one cyclic polyamme R unit is a -(CH₂)_kN(R') unit; R¹ is hydrogen; Cj-Cι₂ alkyl: alkyleneoxy having the formula:

-(R³0)_m-R⁴ R³ is C₂-C₆ linear alkylene, C₃-C₆ branched alkylene, or mixtures thereof, R⁴ is hydrogen, Cj-C₆ alkyl, or mixtures thereof, m is from 1 to 4; acyl having the formula:

O C— R⁵ wherein R⁵ is Cj-C₂₂ linear or branched alkyl, C₃-C₂₂ linear or branched alkenyl, or mixtures thereof; hydroxy alkyl having the formula:

(CH₂)_y(CHOH)_zH wherein y is from 1 to 5, z is from 1 to 3, provided y + z is less than or equal to 6; two R' units can be taken together to form a 5-7 member nng; k is from 3 to 12; and mixtures thereof; in) and mixtures thereof; b) optionally from 0.001 ) to 90%o by weight, of one or more dye fixing agents; c) optionally from 0.01% to 50%> by weight, of one or more cellulose reactive dye fixing agents; d) optionally from 0.01%) to 15%> by weight, of a chlonne scavenger; e) optionally 0.005%) to 1%> by weight, of one or more crystal growth inhibitors; f) optionally from 0.01%) to 20%> by weight, of a fabnc abrasion reducing polymer; g) optionally from 1% to 12%> by weight, of one or more liquid earners; h) optionally from 0.001 %> to 1 % by weight, of an enzyme;

1) optionally from 0.01% to 8% by weight, of a polyolefin emulsion or suspension; j) optionally from 0.01%) to 0.2% by weight, of a stabilizer; k) optionally from 1 % to 80% by weight, of a fabπc softening active;

1) optionally less than 15%> by weight, of a principal solvent; and m) the balance earner and adjunct ingredients.