WO2000056848A1

WO2000056848A1 - Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers

Info

Publication number: WO2000056848A1
Application number: PCT/US2000/008030
Authority: WO
Inventors: Shulin Zhang; Janet Sue Littig; Neil James Gordon
Original assignee: The Procter & Gamble Company
Priority date: 1999-03-25
Filing date: 2000-03-24
Publication date: 2000-09-28
Also published as: AR023155A1; CA2365303C; DE60020091T2; DE60020091D1; ATE295405T1; AU3923500A; JP4601829B2; JP2002540250A; MXPA01009728A; AU3923400A; WO2000056849A1; EP1163319A1; CA2365282A1; BR0009279A; EP1163320A1; CA2365303A1; CA2365282C; CN1351644A; ES2242612T3; EP1163319B1

Abstract

A) from about 0.1% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer comprising one or more monomers having a cationic group and which is capable of attenuating and/or abating the loss of fabric dye; and B) the balance carriers and adjunct ingredients.

Description

FABRIC MAINTENANCE COMPOSITIONS COMPRISING CERTAIN CATIONICALLY CHARGED FABRIC MAINTENANCE POLYMERS

FIELD OF THE INVENTION The present invention relates to fabπc dye maintenance compositions which compπse one or more dye maintenance compounds which can be o gomers, polymers, co-polymers, and the like which compπse one or more monomers which results in the final dye maintenance compound having a net positive charge. Compositions compπsmg the dye maintenance polymers of this invention impart appearance and mtegπty benefits to fabπcs and textiles treated with solutions formed from such compositions.

BACKGROUND OF THE INVENTION

It is, of course, well known that alternating cycles of using and laundeπng fabπcs and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and mtegπty of the fabπc and textile items so used and laundered. Fabπcs and textiles simply wear out over time and with use. Laundeπng of fabπcs and textiles is necessary to remove soils and stains which accumulate therein and thereon duπng ordinary use. However, the laundeπng operation itself, over many cycles, can accentuate and contπbute to the deteπoration of the mtegnty and the appearance of such fabπcs and textiles

Deteπoration of fabπc mtegnty and appearance can manifest itself in several ways Short fibers are dislodged from woven and knit fabπc/textile structures by the mechanical action of laundeπng. These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabπcs and diminish the appearance of newness of the fabπc. Further, repeated laundeπng of fabπcs and textiles, especially with bleach-contammg laundry products, can remove dye from fabπcs and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and in many cases, as a result of changes in hues or shades of color

Given the foregoing, there is clearly an ongoing need to identify mateπals which could be added to fabπc treatment products, specifically to πnse added fabπc conditioners, pre-wash spray on compositions, pre-soak compositions as well as after wash or between wash malodor control or fabπc re-freshenmg compositions, mateπals which would associate themselves with the fibers of the fabπcs and textiles thereby reducing, abating, or minimizing the tendency of the fabπc/textiles to deteπorate in appearance. Any such fabric treatment/fabric maintenance composition additive mateπal should, of course, be able to benefit fabπc appearance and mtegπty without unduly interfeπng with the ability of the balance of laundry products to perform their intended function The present invention is directed to the use of dye maintenance polymers in fabπc treatment and fabπc enhancement compositions which perform in this desired manner

SUMMARY OF THE INVENTION The present invention meets the aforementioned need in that it has been surpnsmgly discovered that fabπc which is treated, and subsequently re-treated with the compositions of the present invention, will resist normal fading and color loss without regard to the circumstances, inter aha, due to mechanical wear and abrasion. In addition, fabπc which has not been treated can have the loss of fabric dye attenuated by adding the compositions of the present invention to the laundry cycle as an adjunct via pre-soak, πnse additive, etc. The compositions of the present invention can be added is any manner, inter aha, as part of a formulation or as a separate composition

The first aspect of the present invention relates to compositions providing dye protection benefits to fabric comprising

A) from about 0.05%, preferably for about 0 1%, more preferably from about 0 5%, most preferably from about 1% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer comprising one or more units selected from the group consisting of I) linear polymer units having the formula

wherein each R¹ is independently a) hydrogen, b) C,-C₄ alkyl, c) substituted or unsubstituted phenyl, d) substituted or unsubstituted benzyl; e) carbocyclic; f) heterocyclic; g) and mixtures thereof; each R² is independently a) hydrogen; b) halogen c) C,-C₄ alkyl; d) C,-C₄ alkoxy; e) substituted or unsubstituted phenyl; f) substituted or unsubstituted benzyl; g) carbocyclic; h) heterocyclic; i) and mixtures thereof; each Z ^', is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH₂)_mR; wherein R is: i) hydrogen; ii) hydroxyl iii) halogen; iv) nitrilo; v) -OR³; vi) -0(CH₂)_nN(R³)₂; vii) -0(CH₂)_nN⁺(R³)₃X^"; viii) -OCO(CH₂)„N(R³),; ix) -OCO(CH₂)_nN⁺(R³)₃X^"; x) -NHCO(CH₂)_nN(R³)₂; xi) -NHCO(CH₂)_nN⁺(R³)₃X^"; xii) -(CH₂)_nN(R³)₂; xiii) JCH₂)_nN⁺(R³)₃X-; xiv) carbocyclic; xv) heterocyclic; xvi) nitrogen heterocycle quaternary ammonium; xvn) nitrogen heterocycle N-oxide; xvin) aromatic N-heterocychc quaternary ammonium; xix) aromatic N-heterocychc N-oxide; xx) -NHCHO; xxi) or mixtures thereof; each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is i) -OR³; ii) -0(CH₂)_nN(R³)₂; in) -0(CH₂)_nN⁺(R³)₃X^"; iv) -NR³(CH₂)_nN(R³)₂, v) -NR³(CH₂)_nN⁺(R³)₃X-; vi) JCH₂)_πN(R³)₂; vii) JCH₂)_nN⁺(R³)₃X-; vm) or mixtures thereof, each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6, f) and mixtures thereof; the index m is from 0 to 6;

II) cyclic units derived from cyclically polymeπzmg monomers having the formula:

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble amon; and III) mixtures thereof; provided said polymer or co-polymer has a net cationic charge; and B) the balance earners and other adjunct ingredients.

Another aspect of the present invention is the combination a dye protection composition and a fabπc appearance composition to form a system form providing enhanced color and fabπc fiber benefits to fabπc compnsmg clothing and apparel, said dye protection system compπsmg:

A) from about 1% by weight, of a polymer or co-polymer compnsmg dye protection composition as descnbed herein above; and

B) from about 1% by weight, of a fabnc enhancement composition, said composition providing one or more fabric enhancement benefits (fabπc enhancement component); and

C) the balance earners and adjunct ingredients.

The present invention also relates to methods for preventing fading an loss of color to fabπc comprising the step of contacting fabπc with a composition according to the present invention or with a composition which compnses the components of the present invention as a color-care system.

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 attenuation and/or abatement of fabπc appearance loss. The compositions of the present invention comprise a cationic polymer or co-polymer which acts together with a low molecular weight fabric enhancement polyamme, fabric softness agent (crystal growth inhibitor) and dye fixing agent to provide protection to fabπc from appearance loss which is pπmarily due to mechanical loss. Another aspect of the present invention relates to a composition which comprises a cationic polymer or co-polymer which acts together with a low molecular weight fabric enhancement polyamme, fabric softness agent (quaternary ammonium fabnc softener active), dye fixing agent, and one further enhancement agent, inter aha, a stabilizer, co-solvent. Yet another aspect of the present invention relates to a composition which comprises a cationic polymer or co-polymer which acts together with a low molecular weight fabπc enhancement polyamme, fabric softness agent (crystal growth inhibitor) and quaternary ammonium fabπc softness agent, and dye fixing agent. The normal abrasive destruction of the fabπc surface removes the surface layers of fabπc which are dyed. Especially in the case of cotton fabnc, below this layer of dyed fabnc is the less dyed, then non-dyed fabπc. As wears a "washed looked" develops which is due to the abrasive destruction of fabric and the subsequent loss of the weakened fabnc fiber m the laundry cycle.

It has been surpnsmgly discovered that the combination of elements which compπse the compositions of the present invention modify the surface of fabric, especially cellulosic fabπc and ameliorate many of the conditions which enhance fabric fiber surface wear and subsequent loss. The compositions of the present invention also soften the fabnc surface making the fibers less abrasive and thereby reducing the level of friction between the fabnc and surfaces in which the garment comes into contact. This change in surface condition can nullify many of the conditions which contnbute to fabric damage and hence attenuate, and in some cases, abate fabnc damage and therefore the concomitant loss of color.

The compositions of the present invention can be used for a stand alone treatment of fabnc wherein the compositions are added as ingredients to a compatible fully formulated πnsed additive, laundry additive or pre-soak all of which are used together with fabπc softeners, laundry detergent compositions and the like. The compositions of the present invention, either as a stand alone treatment or as a system, are suitable for providing a method for treating fabric and subsequently attenuating or abating the loss of color due to mechanical abrasion and removal of the top layer of dyed fabnc.

Alternatively, the compositions comprise a fabric color integrity system. The systems of the present invention are used as an initial treatment of fabric by the manufacturer of either the fabπc from which apparel is made or the fully formed article of manufacture (apparel). However, if the fabric is not pre-treated by the manufacturer, suitable protection is afforded to the fabric wherein the consumer applies the system to fabπc during laundenng. The systems of the present invention can be used at any point during the lifetime of apparel to abate the loss of color from fabric.

The following is a detailed descπption of the essential elements of the present invention Cationic Polymer or Co-polvmer

Compositions and systems of the present invention comprise from about 0.05%, preferably for about 0.1%, more preferably from about 0.5%, most preferably from about 1% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer, copolymer, or mixture thereof, wherein said polymer or co-polymer comprises at least one catiomcally charged unit, inter aha, quaternary ammonium moiety or unit which can form a cationic charge in situ, inter aha, pπmary amme moiety

I) Linear Polymer Units

The polymers or co-polymers of the present invention can comprise one or more linear polymer units having the formula:

wherein R¹, R², and Z are defined herein below. Preferably, the linear polymer units are formed from linearly polymeπzmg monomers. Linearly polymeπzmg monomers are defined herein as monomers which under standard polymeπzmg conditions result in a linear polymer chain or alternatively which linearly propagate polymenzation. The linearly polymeπzmg monomers of the present invention have the formula:

Rl R²

C—C R¹ Z ■ however, those of skill m the art recognize that many useful linear monomer units are introduced indirectly, inter aha, vinyl amme units, vinyl alcohol units, and not by way of linearly polymerizing monomers. For example, vinyl acetate monomers once incorporated into the backbone are hydrolyzed to form vmyl alcohol units. For the purposes of the present invention, linear polymer units may be directly introduced, i.e. via linearly polymerizing units, or indirectly, i.e. via a precursor as in the case of vmyl alcohol cited herein above.

Each R¹ is independently hydrogen, C_rC₄ alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof. Preferably R¹ is hydrogen, C,-C₄ alkyl, phenyl, and mixtures thereof, more preferably hydrogen and methyl

Each R² is independently hydrogen, halogen, C,-C₄ alkyl, C,-C₄ alkoxy, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, carbocyclic, heterocyclic, and mixtures thereof Preferred R² is hydrogen, C,-C₄ alkyl, and mixtures thereof. Each Z is independently hydrogen; hydroxyl; halogen, -(CH₂)_mR, wherein R is hydrogen, hydroxyl, halogen, mtrilo, -OR³, -0(CH₂)_nN(R³)₂, -0(CH₂)_nN⁺(R³)₃X \ -OCO(CH₂)_nN(R³)₂, -

OCO(CH₂)_nN⁺(R³)₃X^", -NHCO(CH₂)_nN(R³)₂, -NHCO(CH₂)_nN⁺(R³)₃X\ -(CH₂)_nN(R³)₂, -

(CH₂)_nN⁺(R³)₃X ^", a non-aromatic nitrogen heterocycle comprising a quaternary ammonium ion, a non-aromatic nitrogen heterocycle comprising an N-oxide moiety, an aromatic nitrogen containing heterocyclic wherein one or more or the nitrogen atoms is quatermzed; an aromatic nitrogen containing heterocycle wherein at least one nitrogen is an N-oxide; -NHCHO (formamide), or mixtures thereof; wherein each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6; carbocyclic, heterocyclic, or mixtures thereof; -(CH₂)_mCOR' wherein R' is -OR³, -

0(CH₂)_nN(R^J)₂,

-NR³(CH₂)„N(R³)₂,

-(CH₂)_nN(R³)₂₎ -

(CH₂)_nN (R³)₃X^", or mixtures thereof, wherein R³, X, and n are the same as defined herein above

A preferred Z is -0(CH₂)_nN (R³)₃X\ wherein the index n is 2 to 4. The index m is from 0 to 6, preferably 0 to 2, more preferably 0.

Non-hmitmg examples of linearly polymerizing monomers compnsmg a heterocyclic Z unit includes l-vmyl-2-pyrrolιdιnone, 1-vιnylιmιdazole, 2-vιnyl-l,3-dιoxolane, 4-vmyl-l- cyclohexenel,2-epoxιde, and 2-vmylpyndme.

The polymers and co-polymers of the present invention compπse Z units which have a cationic charge or which result in a unit which forms a cationic charge in situ. When the co- polymers of the present invention compnse more than one Z unit, for example, Z¹, Z²,...Zⁿ units, at least about 1% of the monomers which compnse the co-polymers will comprise a cationic unit. Preferred cationic units include -0(CH₂)_nN⁺(R³)₃X ^" and -(CH₂)_nN⁺(R³)₃X ^". When the co- polymers of the present invention are formed from two monomers, Z¹ and Z², the ratio of Z¹ to Z² is preferably from about 9:1 to about 1:9

A non-hmitmg example of an indirect Z unit which can be made to form a cationic charge in situ is the -NHCHO unit, formamide The formulator can prepare a polymer or copolymer comprising formamide units some of which are subsequently hydrolyzed to form vmyl amine equivalents For example the formulator may prepare a co-polymer having the general formula-

which comprises a formamide unit and then subsequently treat the co-polymer such that some of the formamide units are hydrolyzed to form a co-polymer comprising vmyl amme units, said polymer having the formula

wherein Z may be a cationic unit compnsmg or non-cationic unit compnsmg moiety and x' + x" = x.

Another class of preferred linearly polymenzable monomers compπse catio cally charged heteroaromatic Z units having the formula:

an non-hmitmg example of which is 4- vmyl (N-alkyl)pyπdme wherein R¹ and R² are each hydrogen and R⁶ is methyl.

Another class of preferred linearly polymenzable monomers which compnses a heterocyclic πng includes Z units compnsmg an N-oxide, for example, the N-oxide having the formula:

a non-hmitmg example of which is 4-vmyl pyndine N-oxide.

N-alkyl vmylpyπdine monomers and N-oxide vinylpyπdme monomers can be suitably combined with other non aromatic monomers, inter aha, vmyl amme. However, preferred polymers of the present invention include co-polymers derived from a combination of quatemized, N-oxide, and nitrogen containing heteroaromatic monomers, non-hmitmg examples of which includes a copolymer of N-methyl vmyl pyridme and vmyl pyridme m a ratio of 4: 1; a copolymer of N-methyl vinyl pyridme and vmyl pyridme m a ratio of 4:6; a co-polymer of poly(N-methyl v yl pyndine) and vmyl pyridme N-oxide m a ratio of polymer to monomer of 4: 1; poly(N-methyl vinyl pyridme) and vmyl pyridme N-oxide in a ratio of polymer to monomer of 4:6; and mixtures thereof.

A preferred linear co-polymer according to the present has the formula:

wherein Z¹ has the formula:

Z² has the formula:

wherein X is chlonne; x has the value of from about 10 to about 100,000; y has the value of from about 10 to about 100,000; the ratio of x to y is from 9: 1 to 1:9. Co-polymers of this type are available as, e.g., Sedipur^® CF104 ex BASF.

As described herein above, some preferred polymer residues may be formed by treatment of the resulting polymer. For example, vmyl amme residues are preferably introduced via formamide monomers which are subsequently hydrolyzed to the free ammo unit. Also v yl alcohol units are obtained by hydrolysis of residues formed form vmyl acetate monomers. Likewise, acrylic acid residues may be estenfied after polymerization, for example, units having the formula:

may be more conveniently formed after the backbone has been formed by polymerization with acrylic acid or acrylic acid precursor monomers.

II) Cyclic Units Derived from Cyclically Polymerizing Monomers

The polymers or co-polymers of the present invention can compπse one or more cyclic polymer units which are derived from cyclically polymerizing monomers. Cyclically polymenzmg monomers are defined herein as monomers which under standard polymerizing conditions result in a cyclic polymer residue as well as serving to linearly propagate polymerization. Preferred cyclically polymerizing monomers of the present invention have the formula:

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion.

Non-limiting examples of R⁴ units include allyl and alkyl substituted allyl units. Preferably the resulting cyclic residue is a six-member ring comprising a quaternary nitrogen atom.

R⁵ is preferably C C₄ alkyl, preferably methyl.

An example of a cyclically polymerizing monomer which results in a cyclic polymer unit is dimethyl diallyl ammonium having the formula:

which results in a polymer or co-polymer having units with the formula:

wherein preferably the index z is from about 10 to about 50,000. Ill) Mixtures thereof.

The polymers or co-polymers of the present invention must retain a net cationic charge, whether the charged is developed in situ, or whether the polymer or co-polymer itself has a formal positive charge. Preferably the polymer or co-polymer has at least 10%, more preferably at least about 25%, more preferably at least about 35%, most preferably at least about 50% of the residues comprise a cationic charge. The polymers or co-polymers of the present invention can compπse mixtures of linearly and cyclically polymenzmg monomers, for example the poly(dιmethyldιallyl-ammonιum chloπde/acrylamide) co-polymer having the formula:

wherein Z¹, Z², x, y, and z are the same as defined herein above and X is chlonde ion.

A particularly preferred embodiment of this invention is the composition comprising a polymer based on dimethyldiallylammonium chlonde and a copolymer which is based upon acrylamide with a co-monomer selected from the group consisting of N, N dialkylammoalkyl(meth)acrylate, N, N dialkylammoalkylacrylate, N,N dialkylammoalkylacrylamide, N,N dιalkylamιnoalkyl(meth)acrylamιde, their quatemized denvatives and mixtures thereof.

Non-hmitmg examples of preferred polymers according to the present invention include dye maintenance copolymers comprising:

1) a first monomer selected from the group consisting of N, N dιalkylamιnoalkyl(meth)acrylate, N, N dialkylammoalkylacrylate, N,N dialkylammoalkylacrylamide, N,N dιalkylammoalkyl(meth)acrylamιde, their quatemized derivatives and mixtures thereof; and n) a second monomer selected from the group consisting of acrylic acid, methacrylic acid, C,-C₆ alkylmethacrylate, C,-C₆ alkyl acrylate, C,-C₈ hydroxyalkylacrylate, C,-C₈ hydroxyalkylmethacrylate, acrylamide, C,-C₁₆ alkyl acrylamide, C,-C₁₆ dialkylacrylamide, 2-acrylamιdo-2-methylpropane sulfomc acid or its alkali salt, methacrylamide, C,-C₁₆ alkylmethacrylamide, C_rC,₆ dialkylmethacrylamide, vmyl formamide, vmylacetamide, vmyl alcohol, C,-C₈ vmylalkylether, vmyl pyridme, ltacomc acid, vmyl acetate, vmyl propionate, vmyl butyrate and mixtures thereof; wherein the copolymer comprises at least 25 mole % of the first monomer Non-hmitmg examples of co-polymers which are highly effective in the embodiments of the present invention include co-polymer of acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 24:1, K- value 85); co-polymer of polyacrylamides- acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 9: 1, K- value 70); co- polymer of acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 9:1, K- value 60), co-polymer of acrylamide/dimethylammo ethylacrylate methochlonde (molar ratio 49:1, K- value 60); and co-polymer of acrylamide/dimethylammo ethylacrylate methochlonde (molar ratio 24/1, K-value 85).

CARE SYSTEMS The present invention also relates to systems for providing enhanced care to fabric. The care systems according to the present invention comprise a composition providing dye protection benefits to fabnc in combination with a separately added composition which provides a fabπc enhancement benefit, said system compnsmg: a) from about 0.05%, preferably for about 0.1 %, more preferably from about 0.5%, most preferably from about 1% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer or co-polymer compnsmg dye protection composition as descπbed herein; b) from about 0.01%, preferably from about 0.1% to about 20%, preferably to about 10% by weight, of a fabπc abrasion reducing polymer, said fabnc abrasion polymer compnsmg: l) at least one monomeπc unit compnsmg an amide moiety, n) at least one monomenc unit comprising an N-oxide moiety, in) and mixtures thereof, c) 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 quaternary ammonium fabric softening active, an amme derived therefrom, and mixtures thereof, d) 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; e) optionally from about 0.001% to about 90% by weight, of one or more dye fixing agents; f) optionally from about 0.01% to about 50% by weight, of one or more cellulose reactive dye fixing agents; g) optionally from about 0.01% to about 15% by weight, of a chlonne scavenger, h) about 0.005% to about 1% by weight, of one or more crystal growth inhibitors, I) optionally from about 1% to about 12% by weight, of one or more liquid carriers, 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 cationic surfactant; n) from about 0.01% by weight, of one or more linear or cyclic polyammes which provide bleach protection; and o) the balance earner and adjunct ingredients.

A non-hmitmg example of a preferred system according to the present invention compnses: a) from about 0.05%, preferably from about 0.1%, more preferably from about 0.5%), most preferably from about 1% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer or co-polymer compnsmg dye protection composition as described herein; b) from about 0.01% to about 50% by weight, of a polyamme, said polyamme is selected from the group consisting of N,N'-bιs(amιnopropyl)-l,3- propylenediamme; 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)ammopropyl]-l,3- propylenedιamme; N,N'-bιs(2-hydroxybutyl)-N,N'-bιs[3-N,N-bιs(2- hydroxybutyl)ammopropyl] -1,3 -propylenediamme; 5 -N-methyl dipropylenetπamine, 1 , 1 -N-dιmethyl-5 -N' -methyl-9,9-N' ' -dimethyl dipropylenetnamme; l,l-N-dιmethyl-9,9-N" -dimethyl dipropylenetnamme; and mixtures thereof; c) from about 0.005% to about 1 % by weight, of one or more crystal growth inhibitors; d) from about 0.001% to about 90% by weight, of one or more dye fixing agents, and e) the balance carriers and adjunct ingredients.

Another preferred system according to the present invention comprises' a) from about 0.05%, preferably from about 0.1%>, more preferably from about

0.5%, most preferably from about 1% to about 5%, preferably to about 3% by weight, of a polymer or co-polymer comprising dye protection composition as descπbed herein; b) 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 quaternary ammonium fabπc softening active, an amme denved therefrom, and mixtures thereof; c) from about 0.01% to about 50% by weight, of a low molecular polyamme, said polyamme is selected from the group consisting of N,N'-bιs(ammopropyl)-l,3- propylenediamme; 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)ammopropyl]-l,3- propylenedιamιne; N,N'-bιs(2-hydroxybutyl)-N,N'-bιs[3-N,N-bιs(2- hydroxybutyl)amιnopropyl]-l,3-propylenedιamme; 5-N-methyl dipropylenetnamme; 1 , 1 -N-dιmethyl-5 -N' -methyl-9,9-N' ' -dimethyl dipropylenetnamme; l,l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamme; and mixtures thereof; d) from about 0.005% to about 1% by weight, of one or more crystal growth inhibitors; and e) the balance carriers and adjunct ingredients. Low Molecular Weight Polyammes

The compositions of the present invention compπse 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 the herein descπbed low molecular weight polyammes. In general, the polyammes are either linear polyammes or cyclic polyammes.

Linear Polyammes

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

The polyammes of the present invention have 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; 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 compπses only 1,3-propylene units.

R¹ is hydrogen; C,-C₁₂ alkyl, preferably C,-C₈ alkyl, more preferably C C₄ alkyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ wherein R³ is C₂-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. R⁴ιs 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 vanes over the value of m. Also, the dye fixation properties of the substantially linear polyammes are maximized when the alkyleneoxy unit is absent, i.e., R¹ and R² are hydrogen. R¹ is also 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; preferably R⁵ is a hydrocarbyl moiety which sufficiently provides increased fabπc lubricity, more preferably C₆-C₁₂ 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-hmitmg examples of hydroxy alkyl units include 2-hydroxy alkyl, for example, -CH₂CHOHCH₃, -CH₂CHOHCH₂CH₂CH₂CH₃. Two R¹ units can be taken together to form a 5-7 member nng, i.e., pipeπdme, morpholme. An example of a backbone wherein two R¹ units are taken together to form a ring has the formula:

The present invention also includes mixtures of the herein described R¹ units.

R² is hydrogen, R¹, -RN(R')₂, 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-propylenedιamme (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-hmitmg example, when R¹ and R² are each equal to hydrogen, dye fixative properties, in certain liquid fabπc care embodiments, even m the presence of bleach, are maximal. Also when R¹ and R² 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 polypropyleneamme backbones, varying amounts of both the linear and branched mateπals will be present in the final product admixture. The preferred backbones of the linear polyammes 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" polyammes have one or more alkyleneoxy units as descπbed herein above. Preferred substiruents are methyl, 2- hydroxyethyl, 2-hydroxypropyl, 1,2-propyleneoxy, 2-hydroxybutyl, and mixtures thereof, more preferably methyl and 2-hydroxypropyl.

For certain formulations, polyammes which comprise alkylated polyammes are preferred, for example, tetramethyl dipropylenetnamme (l,l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamme) having the formula:

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

CH₃

I

(H₃C)₂N^^^^N^/\^N(CH₃)₂ and the mono-methylated dipropylenetnamme (5-N'-methyl dipropylenetnamme) having the formula-

Cyclic Amines

The enhanced fabπc appearance compositions of the present invention may compnse one or more cyclic polyalkyleneammes wherein at least one of the nng nitrogens is substituted with at least one C₃-C₆ alkyleneimine unit.

The low molecular weight cyclic polyammes of the present invention compπse 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-pιperazme. R is hydrogen, -(CH₂)_kN(R¹)₂, and mixtures thereof, wherein at least one cyclic polyamme R unit is a -(CH₂)_kN(R')₂ unit; preferably both R units are -(CH₂)_kN(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 nng is 1,4-pιperazme.

R¹ is hydrogen; C,-C,₂ alkyl, preferably C_rC₈ alkyl, more preferably C,-C₄ alkyl, most preferably methyl; alkyleneoxy having the formula:

-(R³0)_m-R⁴ wherein R³ is C₂-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. R⁴ιs 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 fabric 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 R⁵ is C_t-C₂₂ 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-C₁₂ 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-hmitmg examples of hydroxy alkyl units include 2-hydroxy alkyl, for example, -CH₂CHOHCH₃, -CH₂CHOHCH₂CH₂CH₂CH₃. Two R¹ units can be taken together to form a 5-7 member nng, i.e., pipendme, morpholme.

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

wherein each R⁷ is independently hydrogen, C_rC₄ alkyl, C_rC₄ hydroxyalkyl, C,-C₄ ammoalkyl, 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 nng atom, and mixture thereof. Examples of carbonyl containing nngs which compπse L units are 1,4-dιketopιpeπzιnes.

Preferably the backbones of the polyammes of the present invention, pnor to modification, have the formula:

H₂N-(CH₂)₃— N N— (CH₂)₃-NH₂

wherein each R unit is -(CH₂)₃NH₂.

However, the cyclic units may be substituted on only one ring nitrogen as in the case wherein one R unit is hydrogen, and the other R unit is -(CH₂)_kNH₂, for example, the piperazine having the formula:

H-N /^~ N— (CH₂)₃-NH₂

The backbones of the cyclic polyammes 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" polyammes have one or more substituent units as descπbed 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. 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 mateπal for use as a crystal growth inhibitor.

Crystal Growth Inhibition Test (CGIT)

The suitability of a mateπal 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., descnbed m "Calcium Phosphate Nucleation and Growth m Solution", Prog. Crystal Growth Charact, 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) in 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, 2.1M 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 10⁶ M. The solution is titrated to pH 7.4 with 0.05M KOH. 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 HC1 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 πnsmg procedure is repeated six more time after which the pH of the solution is adjusted to neutrality using 2N HC1. 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 lO^M. Crystal growth inhibitors are differentiated form chelating 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-hmitmg examples of carboxylic compounds which serve as crystal growth inhibitors include glyco c acid, phytic acid, polycarboxyhc acids, polymers and co-polymers of carboxylic acids and polycarboxyhc acids, and mixtures thereof. The inhibitors may be in the acid or salt form. Preferably the polycarboxyhc 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 m 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 anhydride and the ethylene ether or vmyl methyl ethers of acrylic acid Copolymers of 1,3,5-tπhydroxybenzene, 2, 4, 6-tπsulphonιc acid, and carboxymethyloxysuccimc acid are also useful. Alkali metal salts of polyacetic acids, for example, ethylenediamme tetraacetic acid and nitnlotπacetic acid, and the alkali metal salts of polycarboxylates, for example, melhtic acid, succmic acid, oxydisuccimc acid, polymaleic acid, benzene 1,3,5-tπcarboxylιc acid, carboxymethyloxysuccmic acid, are suitable for use m 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 materials for use as crystal growth inhibitors include, polyacrylate polymers Good-Rite® ex BF Goodrich, Acrysol® ex Rohm & Haas, Sokalan® ex BASF, and Norasol® ex Norso Haas. Preferred are the Norasol® polyacrylate polymers, more preferred are Norasol® 410N (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., citnc 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 succmic acid and salts thereof, of which dodecenyl succmate, lauryl succmate, myπstyl succmate, palmityl succmate, 2-dodecenylsuccmate, 2-pentadecenyl succmate, are non- hmiting 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- diphosphomc acid or salt which does not comprise a nitrogen atom". Preferred organic diphosphonic acids include C_rC₄ 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, vmyhdene- 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). Dye Fixing Agents

The compositions of the present invention optionally compπse 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 mateπals which are designed to improve the appearance of dyed fabrics by minimizing the loss of dye from fabncs due to washing. Not included withm this definition are components which can in some embodiments serve as fabric softener actives.

Many dye fixing agents are cationic, and are based on quatemized 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 vaπous 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; polyethyleneamme-based) ex Sandoz; SANDOFIX TPS, ex Sandoz, is a preferred dye fixative for use herein. Additional non-hmitmg examples include SANDOFD SWE (a cationic resinous compound) ex Sandoz, REWIN SRF, REWIN SRF-0 and REWIN DWR ex CHT-Beitlich GMBH; Tmofix® ECO, Tmofix® FRD and Solfin® ex Ciba-Geigy. A preferred dye fixing agent for use in the compositions of the present invention is CARTAFIX CB® ex Clanant.

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-diamme condensates inter aha the hydrochloπde, acetate, metosulphate and benzyl hydrochloπde salts of diamme esters. Non-limiting examples include oleyldiethyl ammoethylamide, oleylmethyl diethylenediamme methosulphate, monostearylethylene diammotπmethylammonium methosulphate. In addition, the N-oxides of tertiary amines; derivatives of polymeric alkyldiamines, polyamme-cyanuπc chlonde condensates, and animated glycerol dichlorohydrms are suitable for use as dye fixatives in the compositions of the present invention. Cellulose Reactive Dye 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 m order to comprise 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 in the present invention can be defined by the following test procedure.

Cellulose Reactivity Test (CRT .

Four pieces of fabric 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 in 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 "lmen 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 m Launder-O-Meter pots under typical conditions with a commercial detergent used at the recommended dosage for ^lΛ hour at 60°C, followed by a thorough nnsmg of 4 times 200 ml of cold water and subsequently line dned.

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 m 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 the CIE 1976 CIELAB opponent-color space, the Hunter opponent-color space, the Fπele-Mac Adam-Chickermg 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-tπazmes, vmyl sulphones, epichlorhydrme derivatives, 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 denved from formaldehyde and a group selected from an amino-group, an imino-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 tefracarboxilic acid denvatives, citnc 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 Clanant. Still other most preferred cellulosic reactive dye fixing agents are commercialized under the tradename Rewin DWR and Rewm WBS ex CHT R. Beit ch

ADJUNCT INGREDIENTS

The compositions of the present invention may also optionally compnse one or more adjunct ingredients. Non-hmitmg examples of adjunct ingredients are selected from the group consisting of fabnc softener actives, electrolytes, stabilizers, low molecular weight water soluble solvents including pnncipal solvents, chelating agents, cationic charge boosters, dispersibihty aids, soil release agents, nomonic fabπc softening agents, concentration aid, perfume, preservatives, colorants, optical bπghteners, opacifiers, fabric care agents, anti-shrinkage agents, anti-wnnkle agents, fabπc crisping agents, spotting agents, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof Fabnc Softening Actives

The compositions of the present invention optionally comprise at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60%), most preferably to about 45% by weight, of the composition of one or more fabric softener actives.

The preferred fabric softening actives according to the present invention are amines from which cationic fabnc softener actives are derived having the formula.

quaternary ammonium compounds having the formula +

(RV N- CH^-Q-R¹ X

4-m

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

0 0 R² O O R²

II II I II II I

0— c — . — c— 0 — N— c- - , — C-N— _,

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 amon, preferably the amon of a strong acid, for example, chlonde, bromide, methylsulfate, ethylsulfate, sulfate, nitrate and mixtures thereof, more preferably chloride and methyl sulfate. The amon 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 quatemized 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-ammopropyl)(2-hydroxyethyl)amιne

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

X

wherein the unit having the formula- O — O— C— R¹ is a fatty acyl moiety. Suitable fatty acyl moieties for use in the softener actives of the present invention are denved from sources of tπglycendes 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 formulator, depending upon the desired physical and performance properties of the final fabnc softener active, can choose any of the above mentioned sources of fatty acyl moieties, or alternatively, the formulator can mix sources of tπglycende to form a "customized blend". However, those skilled m 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 vaπety of vegetable oil source to vanety of vegetable oil source. DEQA's which are prepared using fatty acids denved from natural sources are preferred.

A preferred embodiment of the present invention provides softener actives compnsmg 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\ 1-C22 alkenyl, including polyalkenyl (polyunsaturated) units inter aha oleic, hnoleic, lmolenic

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 fabric 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 cisltrans ratio is of from 1:1, preferably at least 3: 1, and more preferably from about 4: 1 to about 50: 1, more preferably about 20.1, however, the minimum being 1:1

The level of unsaturation contained withm 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 categones of compounds being distinguished, having a IV below or above 25 Indeed, for compounds having the formula:

(RV N- -(CH -Q-R¹ X ^'

4-m m

denved from tallow fatty acids, when the Iodme Value is from 5 to 25, preferably 15 to 20, it has been found that a cisltrans 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 Iodme 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 compπses DEQA's wherein the average Iodme Value for R* is approximately 45.

The R! units suitable for use in the lsotropic liquids present invention can be further charactenzed in that the Iodme 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 115. 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 primary 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 occurmg" position, for example, at the third carbon of a C \ η 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 tnglycerides 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 materials or with other natural tπglyceπde 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 chlonde;

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 chlonde ;

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-tn(canolyl-oxy-ethyl)-N-methyl ammonium chlonde;

N-(2-tallowyloxy-2-oxoethyl)-N-(tallowyl)-N,N-dιmethyl ammonium chlonde ;

N-(2-canolyloxy-2-oxoethyl)-N-(canolyl)-N,N-dιmethyl ammonium chlonde; l,2-dιtallowyloxy-3-N,N,N-tnmethylammomopropane chlonde; and

1 ,2-dιcanolyloxy-3-N,N,N-tnmethylammomopropane 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-dι(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 fabric softening agents useful herein are described in U.S. 5,643,865 Mermelstem et al, issued July 1, 1997; U.S. 5,622,925 de Buzzaccaπm et al, issued April 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 Tπnh et al, issued April 28, 1987; U.S. 4,439,335 Bums, 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 Rudkm et al, 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 Bernadmo, 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. METHOD OF USE The present invention further relates to methods for utilizing the systems and compositions of the present invention to abate and/or attenuate the loss of fabric color. One method according to the present invention compnses the step of contacting fabnc which has been manufactured at a point wherein the fabnc has not been worn or used, with a composition comprising:

A) from about 0.05%, preferably for about 0.1%, more preferably from about 0.5%, most preferably from about 1% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer compnsmg one or more units selected from the group consisting of: I) linear polymer units having the formula:

wherein each R¹ is independently a) hydrogen; b) C,-C₄ alkyl; c) substituted or unsubstituted phenyl, d) substituted or unsubstituted benzyl; e) carbocyclic; f» heterocyclic; g) and mixtures thereof; each K } is independently a) hydrogen; b) halogen c) C,-C₄ alkyl; d) C_rC₄ alkoxy, e) substituted or unsubstituted phenyl; f) substituted or unsubstituted benzyl; g) carbocyclic, h) heterocyclic; i) and mixtures thereof; each 2 _ is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH₂ .A wherein R is: i) hydrogen;

«) hydroxyl in) halogen;

IV) mtnlo; v) -OR³; vi) -0(CH₂)„N(R³)₂;

Vll) -0(CH₂)_nN⁺(R³)₃X^";

Vlll) -OCO(CH₂)_nN(R³)₂;

IX) -OCO(CH₂)_nN⁺(R³)₃X-_; x) -NHCO(CH₂)_nN(R³)₂;

XI) -NHCO(CH₂)_nN⁺(R³)₃X

Xll) -(CH₂)_nN(R³)₂;

Xlll) -(CH₂)_nN⁺(R³)₃X^", xiv) carbocyclic; xv) heterocyclic;

XVl) nitrogen heterocycle qu_ xvn) nitrogen heterocycle N-oxide; xvin) aromatic N-heterocychc quaternary ammonium; xix) aromatic N-heterocychc N-oxide; xx) -NHCHO; xxi) or mixtures thereof; each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is i) -OR³; n) -0(CH₂)_nN(R³)₂; in) -0(CH₂)_nN⁺(R³)₃X^'; iv) -NR³(CH₂)_nN(R³)₂; v) -NR³(CH₂)_nN⁺(R³)₃X^";

vn) -(CH₂)_ΠN⁺(R³)₃X -; vin) or mixtures thereof; each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6; f) and mixtures thereof; the index m is from 0 to 6; II) cyclic units denved from cyclically polymenzmg monomers having the formula:

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble amon; and

III) mixtures thereof; provided said polymer or co-polymer has a net cationic charge, from about 50% by weight, of a fabric enhancement component, said composition comprising- a) from about 0.01%, preferably from about 0.1%> to about 20%, preferably to about 10% by weight, of a fabric abrasion reducing polymer, said fabric abrasion polymer comprising: l) at least one monomeπc unit comprising an amide moiety, n) at least one monomeπc unit comprising an N-oxide moiety; in) 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 quaternary ammonium fabric softening active, an amme denved therefrom, and mixtures thereof; c) optionally less than about 15% by weight, of a principal solvent, preferably said pπncipal solvent has a ClogP of from about 0.15 to about l; 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; f) optionally from about 0.01% to about 15 > by weight, of a chlonne scavenger; g) about 0.005% to about 1% by weight, of one or more crystal growth inhibitors; h) optionally from about 1% to about 12% by weight, of one or more liquid carriers; l) optionally from about 0.001% to about 1% by weight, of an enzyme, j) optionally from about 0.01% to about 8% by weight, of a polyolefin emulsion or suspension; k) optionally from about 0.01% to about 0.2%> by weight, of a stabilizer;

1) optionally from about 1 % to about 80% by weight, of a cationic surfactant; m) from about 0.01% by weight, of one or more linear or cyclic polyammes which provide bleach protection; and o) the balance earner and adjunct ingredients

A preferred fabric enhancement component according to the present invention comprises-

B) from about 0.01% to about 50% by weight, of a polyamme, said polyamme is selected from the group consisting of N,N'-bιs(ammopropyl)-l,3- propylenediamme ; N,N' -bιs(hydroxy ethy 1)-N,N ' -bis [3 -N,N- bιs(hydroxyethyl)amιnopropyl]- 1 ,3-propylenedιamme; N,N' -bιs(2- hydroxypropyl)-N,N'-bιs[3-N,N-bιs(2-hydroxypropyl)ammopropyl]-l,3- propylenediamme; N,N'-bιs(2-hydroxybutyl)-N,N'-bιs[3-N,N-bιs(2- hydroxybutyl)amιnopropyl]- 1 ,3-propylenedιamme; 5-N-methyl dipropylenetnamme; l,l-N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamme; l,l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamme; and mixtures thereof;

C) from about 0.005% to about 1% by weight, of one or more crystal growth inhibitors;

D) from about 0.001% to about 90% by weight, of one or more dye fixing agents; and

E) the balance carriers and adjunct ingredients.

A preferred usage regime consists of the pre-treatmg the garment, or the fabπc from which it is denved, with a composition according to the present invention. This pre-treatment can be earned out by the manufacturer of the garment, or by the consumer. The pre-treatment can conveniently be earned out by the consumer dunng the pre-treatment or pnmary wash cycle of the domestic washing machine. In conjunction with the pre-treatment step the consumer may also use a co-composition as descnbed herein which can suitably be added to the πnse cycle of the washing process. The co-composition can be optionally used every time that the garment is laundered. The compositions of the invention can be used to re-apply a pre-treatment to the garment on a periodic basis. The frequency of pre-applymg the compositions of the present invention can be varied depending on the degree of color protection desired by the consumer A typical re-application may commence after every 3 or 4 washing cycles to maintain a good level of color protection.

The following are non-limiting examples of the compositions of the present invention.

Table I

Weight %

1. Dye fixing agent ex Clanant under the tradename Cartafix CB

2. Polydimethyl-diallyl ammonium chlonde

3. N'-(3-(dιmethylamιno)propyl)-N,N-dιmethylpropane- 1 ,3-dιamme

4. Hydroxyethanediphosphonate

5. Bayhibit AM ex Bayer

6. Armosoft 12W ex Akzo-Nobel

7. Polyvmylpyrrolidone K85 available ex BASF as Luviskol K85.

8. Polyvmylpyrrolidone Kl 5 available ex BASF as Luviskol Kl 5

9. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 24/1, K-value 85).

Table II

Weight %

1. Dye fixing agent ex Clanant under the tradename Cartafix CB

2. Lupasol SK ex BASF

3. 1 ,4-bιs(3-ammopropyl)pιpeπzme

4. Imidazole/epichlorohydπn co-polymer

5. Hydroxyethanediphosphonate 6 Armosoft 12W ex Akzo-Nobel 7. Polyvmylpyrrolidone K85 available ex BASF as Luviskol K85.

8. Polyvmylpyrrolidone K15 available ex BASF as Luviskol K15

9. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochlonde (molar ratio 24: 1, K- value 85).

10. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochlonde (molar ratio 9: 1, K- value 70).

Table III

Weight %

1. Dye fixing agent ex Clanant under the tradename Cartafix CB

2. Permethylated dipropylenetnamme

3. N'-(3-(dιmethylammo)propyl)-N,N-dιmethylpropane- 1 ,3-dιamιne.

4. Hydroxyethanediphosphonate 5 Bayhibit AM ex Bayer.

6. Armosoft 12W ex Akzo-Nobel.

7. Polyvmylpyrrolidone K85 available ex BASF as Luviskol K85.

8. Polyvmylpyrrolidone K15 available ex BASF as Luviskol K15

9. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochlonde (molar ratio 9:1, K- value 60)

10. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 49:1, K- value 60) The following are non-limiting examples of clear, colorless lsotropic liquid embodiments of the present invention.

Table IV

Weight %

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

2. Ethanol is present from the manufacturing process of the quaternary fabric softener active.

3. Hexylene glycol is present from the manufacturing process of the quaternary fabric softener active.

4. Added hexylene glycol.

5. 2,2,4-Tnmethyl-l,3-pentanedιol (TMPD).

6. C₉-C„ alkyl E8 alcohol available as Neodol^® 91-8 ex Shell.

7. C_n-C₁₅ alkyl E9 alcohol available as Tergitol^® 15S9 ex Union Carbide.

8. Polyvmylpyrrolidone Kl 5 available ex BASF as Luviskol Kl 5

9. Catiomcally modified polyacrylamides: acrylamide/dimethylammo ethylacrylate methochloπde (molar ratio 9: 1, K- value 60) 10. Cationically modified polyacrylamides: acrylamide/dimethylamino ethylacrylate methochloride (molar ratio 49:1, K- value 60).

11. Diethylene triamine pentaacetate.

12. Tetrakis-(2-hydroxypropyl)ethylenediamine.

Table V

Weight %

1. N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium methyl sulfate available ex Witco.

2. N,N-di(canolyl-oxy-ethyl)-N,N-dimethyl ammonium chloride. 3. N,N-di(canoyloxyethyl)-N-2-hydroxyethyl-N-methyl ammonium chloride.

4. Ethanol is present from the manufacturing process of the quaternary fabric softener active.

5. Hexylene glycol is present from the manufacturing process of the quaternary fabric softener active.

6. Added hexylene glycol.

7. 2,2,4-Trimethyl-l,3-pentanediol (TMPD).

8. C₉-C_π alkyl E8 alcohol available as Neodol^® 91-8 ex Shell.

9. C_u-C₁₅ alkyl E9 alcohol available as Tergitol^® 15S9 ex Union Carbide.

10. l,l-N-dimethyl-5-N'-methyl-9,9-N"-dimethyl dipropylenetriamine.

11. 1,1 -N-dimethyl-9,9-N"-dimethyl dipropylenetriamine.

12. 1,1 -N-dihydroxyethyl-7-N'-hydroxyethyl-l 3 , 13-N"-dihydroxyethyl dihexylenetriamine (penta-N-hydroxyethyl dihexylenetriamine) .

13. Sedipur^® CF803 ex BASF.

14. Sedipur^® CF104 ex BASF.

15. Cationically modified polyacrylamides: acrylamide/dimethylamino ethylacrylate methochloride (molar ratio 49:1, K-value 60).

16. Diethylene triamine pentaacetate.

17. Tetrakis-(2-hydroxypropyl)ethylenediamine

Claims

What is claimed is:

1. A composition providmg dye protection benefits to fabnc compnsmg:

A) from 0.05% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer compnsmg one or more units selected from the group consisting of:

I) linear polymer units having the formula:

wherein each R¹ is independently a) hydrogen; b) C,-C₄ alkyl; c) substttuted or unsubstituted phenyl; d) substituted or unsubstituted benzyl; e) carbocyclic; f) heterocyclic; g) and mixtures thereof; each R² is independently a) hydrogen; b) halogen c) C,-C₄ alkyl; d) C,-C₄ alkoxy; e) substituted or unsubstituted phenyl; f) substituted or unsubstituted benzyl; g) carbocyclic; h) heterocyclic,

I) and mixtures thereof; each Z is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH₂)_mR; wherein R is: 1) hydrogen; u) hydroxyl in) halogen; iv) mtnlo; v) -OR³;

vn) -0(CH₂)_nN⁺(R³)₃X-; vm) -OCO(CH₂)_nN(R³)₂; ix) -OCO(CH₂)_nN⁺(R³)₃X-; x) -NHCO(CH₂)„N(R³)₂; xi) -NHCO(CH₂)_nN⁺(R³)₃X ; xn) -(CH₂)_nN(R³)₂; xm) -(CH₂)_nN⁺(R³)₃X-; xiv) carbocyclic; xv) heterocyclic; xvi) nitrogen heterocycle quaternary ammonium; xvn) nitrogen heterocycle N-oxide; xvui) aromatic N-heterocychc quaternary ammonium; xix) aromatic N-heterocychc N-oxide; xx) -NHCHO, xxi) or mixtures thereof; each R³ is independently hydrogen, C C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon, the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is

1) -OR³, u) -0(CH₂)_πN(R³)₂;

111) -0(CH₂)_nN⁺(R³)₃X , iv) -NR³(CH₂)_nN(R³)₂; v) -NR³(CH₂)_nN⁺(R³)₃X ;

VI) -(CH₂)_nN(R³)_:; vii) -(CH₂)_nN⁺(R³)₃X ; vni) or mixtures thereof; each R³ is independently hydrogen, C_rC₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6; f) and mixtures thereof; the index m is from 0 to 6;

II) cyclic units denved from cyclically polymerizing monomers having the formula:

wherein each R⁴ is independently an olefin compnsmg unit which is capable of propagating polymenzation in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble amon; and

III) mixtures thereof; provided said polymer or co-polymer has a net cationic charge; and B) the balance carriers and adjunct ingredients.

2. A composition according to Claim 1 comprising a co-polymer wherein each R¹ is hydrogen, C,-C₄ alkyl, phenyl and mixtures thereof and R² is hydrogen, C,-C₄ alkyl, and mixtures thereof.

3. A composition according to either Claim 1 or 2 compnsmg a co-polymer wherein Z has the formula:

-(CH₂)_mCOR wherein each R is independently -0(CH₂)_nN(R³)₂; -0(CH₂)_nN⁺(R³)₃X ; -(CH₂)_nN(R³)₂, - (CH₂)_nN⁺(R³)₃X ; and mixtures thereof, m is 0, n is from 2 to 4.

4. A composition according to any of Claims 1-3 wherein Z units having the formula - CONH₂, -C0₂(CH₂)₂N⁺(CH₃)₃C1 , and mixtures thereof said ratio of -CONH₂ units to - C0₂(CH₂)₂NJCH₃)₃C1 units is from 9:1 to 1 :9 A system according to Claim 1-4 wherein said composition further comprises a polyamine selected from the group consisting of N,N'-bis(aminopropyl)-l,3- propylenediamine, N,N'-bis(hydroxyethyl)-N,N'-bis[3-N,N- bis(hydroxyethyl)aminopropyl] - 1 ,3-propylenediamine, N,N ' -bis(2-hydroxypropyl)-N,N ' - bis[3-N,N-bis(2-hydroxypropyl)aminopropyl]-l,3-propylenediamine, N,N'-bis(2- hydroxybutyl)-N,N'-bis[3-N,N-bis(2-hydroxybutyl)aminopropyl]-l,3-propylenediamine, 5-N-methyl dipropylenetriamine, 1 , 1 -N-dimethyl-5-N'-methyl-9,9-N' '-dimethyl dipropylenetriamine, l,l-N-dimethyl-9,9-N"-dimethyl dipropylenetriamine, and mixtures thereof.

A composition according to any of Claims 1-5 wherein said composition further comprises from 1 % to 80% by weight, of a fabric softening active, said fabric softener active comprises a quaternary ammonium compound having the formula:

+

(R)- -N- (CH^-Q-R¹ X

4-m

an amine having the formula:

and mixtures thereof; wherein each R is independently C,-C₆ alkyl, C,-C₆ hydroxyalkyl, benzyl, and mixtures thereof; R¹ is C,-C₂₂ alkyl, C₃-C₂₂ alkenyl, and mixtures thereof; Q is a carbonyl moiety having the formula:

O o R² O O R²

II II -o— c — -c— o- — N— C , C— N—

O o R^J O O— C ^{1 1}— R i¹ O

— O— C— O — -CH-O— C — — CH-CH₂-0— C- wherein R² is hydrogen, C,-C₄ alkyl, C,-C₄ hydroxyalkyl, and mixtures thereof; R³ is hydrogen, C_rC₄ alkyl, and mixtures thereof; X is a softener compatible amon; m is from

7. A system according to any of Claims 1-6 compnsmg a crystal growth inhibitor 2- phosphonobutane-l,2,4-tncarboxyhc acid and a dye fixing agent dodecyl tnmethylammomum chlonde.

8. A compositon for providing enhanced fabric protection to fabnc, said composition compnsmg: a) from 0.05% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer compnsmg one or more units selected from the group consisting of: I) linear polymer units having the formula:

wherein each R¹ is independently a) hydrogen; b) C,-C₄ alkyl; c) substituted or unsubstituted phenyl; d) substituted or unsubstituted benzyl; e) carbocyclic, f) heterocyclic; g) and mixtures thereof, each R² is independently a) hydrogen, b) halogen c) C,-C₄ alkyl, d) C_rC₄ alkoxy; e) substituted or unsubstituted phenyl, f) substituted or unsubstituted benzyl, g) carbocyclic, h) heterocyclic; ) and mixtures thereof; each Z is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH₂)_mR, wherein R is- l) hydrogen, n) hydroxyl in) halogen; iv) mtnlo; v) -OR³; vi) -0(CH₂)_nN(R³)₂; vn) -0(CH₂) (R³)₃X ; vm) -OCO(CH₂)_nN(R³)₂, ix) -OCO(CH₂)_nN⁺(R³)₃X , x) -NHCO(CH₂)_nN(R³)₂, xi) -NHCO(CH₂)_nN⁺(R³)₃X ,

x ) -(CH₂)_nN⁺(R³)₃X , xiv) carbocyclic, xv) heterocyclic, xvi) nitrogen heterocycle quaternary ammonium, xvn) nitrogen heterocycle N-oxide, xvui) aromatic N-heterocychc quaternary ammonium, xix) aromatic N-heterocychc N-oxide, xx) -NHCHO, xxi) or mixtures thereof, each R³ is independently hydrogen, C_rC₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof, X is a water soluble amon, the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is i) -OR³;

11) -0(CH₂)_nN(R³)₂;

111) -0(CH₂)_nN⁺(R³)₃X^";

IV) -NR³(CH₂)_nN(R³)₂; v) -NR³(CH₂)_nN⁺(R³)₃X^"; vi) -(CH₂)_nN(R³)₂;

Vll) -(CH₂)„N⁺(R³)₃X-;

Vlll) or mixtures thereof; each R³ is independently hydrogen, C_rC₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6; f) and mixtures thereof; the index m is from 0 to 6;

II) cyclic units denved from cyclically polymenzmg monomers havmg the formula:

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymeπzation in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C_rC₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble a on; and

III) mixtures thereof, provided said polymer or co-polymer has a net cationic charge; b) from 0.01% to 50% by weight, of a polyamme, said polyam e is selected from the group consisting of N,N'-bιs(ammopropyl)-l,3-propylenedιamιne; N,N'- bιs(hy droxyethyl)-N,N ' -bis [3 -N,N-bιs(hydroxyethyl)amιnopropyl] -1,3- propylenediamme; N,N' -bιs(2-hydroxypropyl)-N,N' -bιs[3-N,N-bιs(2- hydroxypropyl)amιnopropyl]- 1 ,3-propylenedιamme; N,N'-bιs(2-hydroxybutyl)- N,N'-bιs[3-N,N-bιs(2-hydroxybutyl)amιnopropyl]- 1 ,3-propylenedιamme, 5-N- methyl dipropylenetriamine; l,l-N-dιmethyl-5-N'-methyl-9,9-N"-dιmethyl dipropylenetnamme; l,l-N-dιmethyl-9,9-N"-dιmethyl dipropylenetnamme; and mixtures thereof, c) from 0.005% to 1% by weight, of one or more crystal growth inhibitors; d) from 0.001% to 90% by weight, of one or more dye fixing agents; and e) the balance carriers b and adjunct ingredients.

9. A composition providing dye protection benefits to fabric comprising: a) from 0.05% by weight, of a copolymer having the formula:

wherein Z' has the formula:

Z² has the formula:

x has the value of from 10 to 100,000; y has the value of from 10 to 100,000; the ratio of x to y is from 9: 1 to 1 :9; b) the balance carriers and adjunct ingredients.

10. A composition providing dye protection benefits to fabric comprising:

A) from 0.05% by weight, of a polymer, copolymer, or mixtures thereof, said polymer or copolymer comprising one or more units selected from the group consisting of: I) linear polymer units having the formula:

wherein each R¹ is independently a) hydrogen; b) C,-C₄ alkyl; c) substituted or unsubstituted phenyl; d) substituted or unsubstituted benzyl; e) carbocyclic; f) heterocyclic; g) and mixtures thereof; each F I² is independently a) hydrogen; b) halogen c) C,-C₄ alkyl; d) C_rC₄ alkoxy; e) substituted or unsubstituted phenyl; f) substituted or unsubstituted benzyl; g) carbocyclic; h) heterocyclic; i) and mixtures thereof; each Z ^', is independently a) hydrogen; b) hydroxyl; c) halogen; d) -(CH₂)_mR; wherein R is: i) hydrogen; ii) hydroxyl iii) halogen; iv) nitrilo; v) -OR³; vi) -0(CH₂)_nN(R³)₂; vii) -0(CH₂)_nN⁺(R³)₃X-; viii) -OCO(CH₂)_nN(R³)₂; ix) -OCO(CH₂)_nN⁺(R³)₃X^"; x) -NHCO(CH₂)_nN(R³)₂; xi) -NHCO(CH₂)_nN⁺(R³)₃X^"; xn) -(CH₂)_nN(R³)₂; xin) -(CH₂)_nN⁺(R³)₃X-; xiv) carbocyclic; xv) heterocyclic; xvi) nitrogen heterocycle quaternary ammonium; xvn) nitrogen heterocycle N-oxide; xviii) aromatic N-heterocychc quaternary ammonium; xix) aromatic N-heterocychc N-oxide; xx) -NHCHO; xxi) or mixtures thereof; each R³ is independently hydrogen, C_rC₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is i) -OR³; n) -0(CH₂)_nN(R³)₂; in) -0(CH₂)_nN⁺(R³)₃X-;

v) -NR³(CH₂)_nN⁺(R³)₃X-; vi) -(CH₂)_nN(R³)₂; vn) -(CH₂)_nN⁺(R³)₃X ; vin) or mixtures thereof; each R³ is independently hydrogen, C C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble amon, the index n is from 0 to 6; f) and mixtures thereof, the index m is from 0 to 6,

II) cyclic units derived from cyclically polymerizing monomers having the formula

wherein each R⁴ is independently an olefin comprising unit which is capable of propagating polymerization in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ linear or branched alkyl, benzyl, substituted benzyl, and mixtures thereof; X is a water soluble anion; and

III) mixtures thereof; provided said polymer or co-polymer has a net cationic charge;

B) from 0.01 % by weight, of a fabric abrasion reducing polymer, said fabric abrasion polymer comprising: i) at least one monomeric unit comprising an amide moiety; ii) at least one monomeric unit comprising an N-oxide moiety; iii) and mixtures thereof;

C) optionally from 1% by weight, of a fabric softening active;

D) optionally less than 15% by weight, of a principal solvent, said principal solvent has a ClogP of from 0.15 to 1;

E) optionally from 0.001% to 90% by weight, of one or more dye fixing agents;

F) optionally from 0.01% to 50% by weight, of one or more cellulose reactive dye fixing agents;

G) optionally from 0.01 % to 15% by weight, of a chlorine scavenger; H) 0.005% to 1% by weight, of one or more crystal growth inhibitors;

I) optionally from 1% to 12% by weight, of one or more liquid carriers;

J) optionally from 0.001% to 1% by weight, of an enzyme;

K) optionally from 0.01% to 8% by weight, of a polyolefin emulsion or suspension;

L) optionally from 0.01% to 0.2%> by weight, of a stabilizer;

M) optionally from 1% to 80% by weight, of a cationic surfactant;

N) from 0.01% by weight, of one or more linear or cyclic polyamines which provide bleach protection; and

O) the balance carrier and adjunct ingredients.