EP1163320A1 - Laundry detergent compositions with certain cationically charged dye maintenance polymers - Google Patents

Abstract

The present invention relates to laundry detergent compositions providing dye protection benefits to fabric comprising: a) from about 4 % to about 70 % by weight, of a surfactant; b) from about 0.01 % by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more linearly polymerizing monomers, cyclically polymerizing monomers, and mixtures thereof; and c) the balance carriers and adjunct ingredients.

Description

LAUNDRY DETERGENT COMPOSITIONS WITH CERTAIN CATIONICALLY CHARGED

DYE MAINTENANCE POLYMERS

FIELD OF THE INVENTION The present invention relates to compositions, in either liquid or granular form, for use in laundry applications, wherein the compositions compπse certain dye mamtenance polymers that have a net positive charge. Compositions comprising the dye mamtenance polymers of this invention impart appearance and integrity benefits to fabπcs and textiles laundered in washing 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 integrity 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 ordmary use However, the laundeπng operation itself, over many cycles, can accentuate and contπbute to the deteπoration of the mtegπty and the appearance of such fabncs and textiles

Deteπoration of fabπc mtegπty 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 laundenng of fabπcs and textiles, especially with bleach-contaming 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 materials which could be added to laundry products that would associate themselves with the fibers of the fabπcs and textiles laundered using such products and thereby reduce or minimize the tendency of the laundered fabπc/textiles to detenorate m appearance Any such detergent product additive mateπal should, of course, be able to benefit fabπc appearance and mtegπty without unduly interfering with the ability of the laundry product to perform its intended function. The present invention is directed to the use of dye maintenance polymers in laundry applications that perform in this desired manner.

SUMMARY OF THE INVENTION

The present invention meets the aforementioned need in that it has been surpπsmgly 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 alia, due to mechanical wear and abrasion. In addition, fabric which has not been treated can have the loss of fabπc dye attenuated by washing clothing with the laundry detergent compositions of the present invention. The compositions of the present invention can take any form, inter alia, heavy duty liquid (HDL), heavy duty granular (HDG), bars, pastes, thixotropic compositions.

The first aspect of the present invention relates to laundry detergent compositions providing dye protection benefits to fabπc compπsmg: a) from about 4% to about 70% by weight, of a surfactant selected from the group consisting of noniomc, anionic, cationic, amphoteπc, zwitteπonic surfactants and mixtures thereof, preferably at least one of said surfactants is an anionic surfactant; b) from about 0.01 %, preferably from about 0.1 %, more preferably from about 0.5%, most preferably from about 0.8% to about 10%, preferably to about 8%, more preferably to about 6%, most preferably to about 5% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer compπsmg one or more units having the formula

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)„N(R³)₂; vii) -O(CH₂)_nN⁺(R³)₃X-; viii) -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; xvin) aromatic N-heterocychc quaternary ammonium; xix) aromatic N-heterocychc N-oxide; xx) -NHCHO; xxi) or mixtures thereof; each R³ is mdependently 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; ii) -O(CH₂)_nN(R³)₂; in) -O(CH₂)_nN⁺(R³)₃X^"; iv) -NR³(CH₂)_πN(R³)₂; v) -NR³(CH₂)„N⁺(R³)₃X^', v -(CH₂)_πN(R³)₂; vn) -(CH₂)_nN⁺(R³)₃X^", vin) 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 derived from cyclically polymerizing monomers having the formula:

wherein each R⁴ is independently an olefin compπsmg 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 wherein said dye maintenance polymer is not an polyethyleneimme or alkoxylated derivative thereof; and b) the balance earners and other adjunct ingredients.

In addition to the surfactant and the dye maintenance polymer of this invention, the laundry detergent compositions herein compπse from about 0.01% to 80% by weight of an organic or inorganic detergency builder and other conventional laundry detergent products. In its method aspect, the present invention relates to the laundeπng or treating of fabπcs and textiles in aqueous washmg, πnsmg, or treating solutions formed from effective amounts of any of the detergent compositions, fabric softener compositions, or aqueous solution treatments described herein, or formed from the individual components of such compositions. Laundeπng of fabrics and textiles in such washing, πnsmg and/or treatment solutions, followed by drying, imparts fabric appearance benefits to the fabric and textile articles so treated. Such benefits can include improved overall appearance, pill/fuzz reduction, anti-fadmg, improved abrasion resistance, and/or enhanced softness. It has been surpπsmgly determined that the dye maintenance polymers of this invention impart fabric appearance and integrity benefits that are greater than the benefits achieved by a corresponding amount of either component by itself 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 descπption 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 As noted, when fabric or textiles are laundered in solutions which comprise the dye maintenance polymers of the present invention fabric appearance and integrity are enhanced The dye maintenance polymers can be added to wash solutions by incorporating them into a detergent composition, a fabric softener or by adding them separately to the washing solution. The dye maintenance polymers are described herein primarily as liquid or granular detergent additives but the present invention is not meant to be so limited. The dye maintenance polymers, detergent composition components, optional ingredients for such compositions and methods of using such compositions, are descπbed in detail below. All percentages are by weight unless other specified.

Dye Maintenance Polymers

Compositions and systems of the present invention compπse from about 0.1%, preferably for about 1%, more preferably from about 2%, most preferably from about 3% to about 10%, preferably to about 7%, more preferably to about 5% by weight, of a polymer, co-polymer, or mixture thereof, wherein said polymer or co-polymer compπses at least one catiomcally charged unit, ϊMter alia, quaternary ammonium moiety or unit which can form a cationic charge m situ, inter aha, pπmary amine moiety. Stated in another way, the oligomer, polymer, or co-polymer resulting from the herein below descπbed monomer units must have a net cationic charge. The charge can be distπbuted among any of the herein descπbed units.

The dye maintenance polymers of this invention can be used in any fabπc laundeπng process and provide certain appearance benefits to the fabrics laundered m these processes. Such fabπc appearance benefits can include, for example, improved overall appearance of the laundered fabπcs, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The dye maintenance polymers used in the compositions and methods herein can provide such fabric appearance benefits when incorporated in a wash or rinse added products.

As will be apparent to those skilled m the art, an oligomer is a molecule consisting of only a few monomer units while polymers comprise considerably more monomer units. For the present invention, oligomers are defined as molecules having an average molecular weight below about 1 ,000 and polymers are molecules having an average molecular weight of greater than about 1,000. Copolymers are polymers or oligomers wherein two or more dissimilar monomers have been simultaneously or sequentially polymeπzed. Copolymers of the present invention can include, for example, polymers or oligomers copolymeπzing acrylamide with dimethyldiallylammonium chloride, vinyl amine with vinyl alcohol, etc

Cationic polymers in general and their method of manufacture are know. For example, a detailed description of cationic polymers can be found in an article by M. Fred Hoover that was published m the Journal of Macromolecular Science-Chemistry, A4(6), pp 1327-1417, October, 1970. The entire disclosure of the Hoover article is incorporated herein by reference. The dye maintenance polymers of this invention will be better understood when read in light of the Hoover article, the present disclosure and the Examples herein.

I) Linear Polymer Units The polymers or co-polymers of the present invention can compπse 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 polymeπz g monomers are defined herein as monomers which under standard polymerizing conditions result in a linear polymer chain or alternatively which linearly propagate polymeπzation. The linearly polymeπzmg monomers of the present invention have the formula:

Rl R²

\ /

R Z • however, those of skill m the art recognize that many useful lmear monomer units are introduced indirectly, inter a a, vmyl amine units, vmyl alcohol units, and not by way of linearly polymeπzmg monomers. For example, vmyl 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,-C₄ 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_rC₄ alkyl, and mixtures thereof. Each Z is independently hydrogen; hydroxyl; halogen; -(CH₂)_mR, wherein R is hydrogen, hydroxyl, halogen, mtπlo, -OR³, -0(CH₂)_nN(R³)₂, -0(CH₂)_nN⁺(R³)₃X ^", -OCO(CH₂)„N(R³)₂, - OCO(CH₂)_nN⁺(R³)₃X^", -NHCO(CH₂)_nN(R³)₂, -NHCO(CH₂)_nN⁺(R³)₃X^", -(CH₂)„N(R³)₂, -

(CH₂)_nN (R³)₃X^", a non-aromatic nitrogen heterocycle compπsmg 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 quaternized; 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, C,-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, -O(CH₂)_πN(R³)₂,

-O(CH₂)_nN⁺(R³)₃X^", -NR³(CH₂)_πN(R³)₂, -NR³(CH₂)_nN⁺(R³)₃X \ -(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

-O(CH₂)„N (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-limiting examples of linearly polymeπzmg monomers compπsmg a heterocyclic Z unit includes l-vιnyl-2-pyrrolιdmone, 1-vmylιmιdazole, 2-vmyl-l,3-dιoxolane, 4-vmyl-l- cyclohexenel,2-epoxιde, and 2-vmylpyπdme.

The polymers and co-polymers of the present invention compπse Z units which have a cationic charge or which result m a unit which forms a cationic charge in situ. When the copolymers of the present invention compπse more than one Z unit, for example, Z¹, Z²,...Zⁿ units, at least about 1% of the monomers which compπse the co-polymers will compπse a cationic unit.

Preferred cationic units include -O(CH₂)_nN⁺(R³)₃X ^" and -(CH₂)_nN⁺(R³)₃X ^". When the copolymers 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-limiting example of a 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 co-polymer compπs g 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 compπsmg or non-catiomc unit compπsmg moiety and x' + x" ^• x.

Another class of preferred linearly polymeπzable monomers compπse cationically charged heteroaromatic Z units having the formula:

an non-limiting 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 polymeπzable monomers which compπses a heterocyclic πng includes Z units compπsmg an N-oxide, for example, the N-oxide having the formula:

a non-limitmg example of which is 4-vmyl pyridme N-oxide.

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

wherein Z¹ has the formula:

Z² has the formula:

wherein X is chloπne; 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 descπbed 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 vmyl alcohol units are obtained by hydrolysis of residues formed form vmyl acetate monomers. Likewise, acrylic acid residues may be esteπfied 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 comprise one or more cyclic polymer units which are derived from cyclically polymeπzmg monomers. Cyclically polymeπzing 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 polymeπzing monomers of the present invention have the formula: wherein each R⁴ is independently an olefin compπsmg unit which is capable of propagating polymeπzation 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.

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

R⁵ is preferably C C₄ alkyl, preferably methyl.

An example of a cyclically polymeπzing monomer 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 compnse a cationic charge.

The polymers or co-polymers of the present invention can comprise mixtures of linearly and cyclically polymerizing 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 chloπde ion.

A particularly preferred embodiment of this invention is the composition compπsmg a polymer based on dimethyldiallylammomum chloπde and a copolymer which is based upon acrylamide with a co-monomer selected from the group consisting of N, N dιalkylamιnoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N dialkylammoalkylacrylamide, N,N dιalkylammoalkyl(meth)acrylamιde, their quatemized deπvatives and mixtures thereof.

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

1) a first monomer selected from the group consisting of N, N dιalkylammoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, N,N dialkylammoalkylacrylamide, N,N dιalkylamιnoalkyl(meth)acrylamιde, their quatemized deπvatives and mixtures thereof; and n) a second monomer selected from the group consisting of acrylic acid, methacryhc acid, C,-C₆ alkylmethacrylate, C,-C₆ alkyl acrylate, C_rC₈ hydroxyalkylacrylate, C,-C₈ hydroxyalkylmethacrylate, acrylamide, C C₁₆ alkyl acrylamide, C_rC_I6 dialkylacrylamide, 2-acrylamιdo-2-methylpropane sulfomc acid or its alkali salt, methacrylamide, C_rC₁₆ alkylmethacrylamide, C_rC₁₆ dialkylmethacrylamide, vmyl formamide, vmylacetamide, vmyl alcohol, C,-C₈ vmylalkylether, vmyl pyridme, ltaconic acid, vinyl acetate, vinyl propionate, vmyl butyrate and mixtures thereof, wherein the copolymer comprises at least 25 mole % of the first monomer

ADJUNCT INGREDIENTS The compositions of the present invention may also optionally comprise one or more adjunct ingredients. Non-limitmg examples of adjunct ingredients are selected from the group consisting of detersive surfactants, electrolytes, stabilizers, low molecular weight water soluble solvents, chelatmg agents, dispersibility aids, soil release agents, nomonic fabric softening agents, concentration aid, perfume, preservatives, colorants, optical bπghteners, opacifiers, germicides, fungicides, anti-corrosion agents, antofoam agents, and mixtures thereof.

The following are applications which descπbe vaπous detergent additive, methods of making these additives and methods of using them are all included herein by reference. WO 99/07813 Al Randall et al., "Laundry Detergent Compositions with Ammo Acid Based Polymers to Provide Appearance and Integπty Benefits to Fabπcs Laundered Therewith"; WO 99/07814 Al Randall et al., "Laundry Detergent Compositions with Ammo Acid Based Polymers to Provide Appearance and Integrity Benefits to Fabπcs Laundered Therewith"; WO 99/14299 Al Panandiker et al., "Laundry Detergent Compositions with Amonically Modified, Cyclic Amine Based Polymers; WO 99/14300 Al Panandiker et al., "Laundry Detergent Compositions with Cyclic Am e-Based Polymers to Provide Appearance and Integπty Benefits to Fabπcs Laundered Therewith"; WO 99/14301 Al Panandiker et al., "Laundry Detergent Compositions and Fabric Conditioning Compositions with Oxidized Cyclic Amme-Based Polymers"; and US 99/23146 Panandiker et al., "Laundry Detergent Compositions with A Combination of Cyclic Amine Based Polymers and Hydrophobically Modified Carboxy Methyl Cellulose".

SURFACTANT SYSTEM

The laundry detergent compositions of the present invention compπse a surfactant system. The surfactant systems of the present invention may compπse any type of detersive surfactant, non-limiting examples of which include one or more mid-cham branched alkyl sulfate surfactants, one or more mid-chain branched alkyl alkoxy sulfate surfactants, one or more mid- cham branched aryl sulfonate surfactants, one or more non mid-chain branched sulphonates, sulphates, cationic surfactants, zwitteπonic surfactants, ampholytic surfactants, and mixtures thereof

The total amount of surfactant present m the compositions of the present invention is from about 4% by weight, preferably from about 10% more preferably from about 15% to about 60%, preferably to about 30% by weight, of said composition

Nonlimiting examples of surfactants useful herein include. a) C , , -C _{! 8} alkyl benzene sulfonates (LAS) , b) C₆-C₁₈ mid-cham branched aryl sulfonates (BLAS), c) C₁₀-C₂₀ primary, α or ω-branched, and random alkyl sulfates (AS), d) C₁₄-C₂₀ mid-cham branched alkyl sulfates (BAS), e) C₁₀-C₁₈ secondary (2,3) alkyl sulfates as described in U.S. 3,234,258 Morns, issued February 8, 1966, U.S 5,075,041 Lutz, issued December 24, 1991; U.S. 5,349,101 Lutz et al., issued September 20, 1994; and U.S. 5,389,277 Pneto, issued Febmary 14, 1995 each incorporated herein by reference; f) C,₀-C₁₈ alkyl alkoxy sulfates (AE_XS) wherein preferably x is from 1-7; g) C₁₄-C₂₀ mid-cham branched alkyl alkoxy sulfates (BAE_XS); h) C₁₀-C₁₈ alkyl alkoxy carboxylates preferably compnsing 1-5 ethoxy units; l) C₁₂-C₁₈ alkyl ethoxylates, C₆-C₁₂ alkyl phenol alkoxylates wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units, C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenol condensates with ethylene oxide/propylene oxide block polymers inter aha Pluronic^® ex BASF which are disclosed m U.S. 3,929,678 Laughlm et al., issued December 30, 1975, incorporated herein by reference; j) C₁₄-C₂₂ mid-cham branched alkyl alkoxylates, BAE_X; k) Alkylpolysacchaπdes as disclosed in U.S. 4,565,647 Llenado, issued January 26, 1986, incorporated herein by reference;

1) Polyhydroxy fatty acid amides having the formula:

O R⁸

₇ II I

R⁷-C— N— Q wherein R⁷ is C₅-C₃₁ alkyl; R⁸ is selected from the group consisting of hydrogen, C,-C₄ alkyl, C,- C₄ hydroxyalkyl, Q is a polyhydroxyalkyl moiety having a linear alkyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof; preferred alkoxy is ethoxy or propoxy, and mixtures thereof; preferred Q is derived from a reducing sugar m a reductive animation reaction, more preferably Q is a glycityl moiety; Q is more preferably selected from the group consisting of -CH₂(CHOH)_πCH₂OH, -CH(CH₂OH)(CHOH)_n ,CH₂OH, - CH₂(CHOH)₂(CHOR')(CHOH) CH₂ OH, and alkoxylated deπvatives thereof, wherein n is an integer from 3 to 5, inclusive, and R' is hydrogen or a cyclic or aliphatic monosaccharide, which are described m U.S. 5,489,393 Connor et al., issued Febmary 6, 1996; and U.S. 5,45,982 Murch et al., issued October 3, 1995, both incorporated herein by reference.

A non-limiting example of a nomonic surfactant suitable for use in the present invention has the formula.

wherein R is C₇-C₂₁ linear alkyl, C₇-C₂₁ branched alkyl, C₇-C_2I linear alkenyl, C₇-C₂₁ branched alkenyl, and mixtures thereof R¹ is ethylene; R²ιs C₃-C₄ linear alkyl, C₃-C₄ branched alkyl, and mixtures thereof; preferably R² is 1,2-propylene. Nomonic surfactants which comprise a mixture of R¹ and R²unιts preferably compnse from about 4 to about 12 ethylene units in combination with from about 1 to about 4 1,2-propylene units. The units may be alternating, or grouped together in any combmation suitable to the formulator. Preferably the ratio of R¹ units to R² units is from about 4 : 1 to about 8 : 1. Preferably an R² units (i.e. 1,2-propylene) is attached to the nitrogen atom followed by the balance of the chain compπsmg from 4 to 8 ethylene units.

R² is hydrogen, C,-C₄ linear alkyl, C₃-C₄ branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.

R⁴ is hydrogen, C_rC₄ linear alkyl, C₃-C₄ branched alkyl, and mixtures thereof; preferably hydrogen. When the mdex m is equal to 2 the index n must be equal to 0 and the R⁴ unit is absent and is instead replaced by a -[(R'O)_x(R²O)_yR³] unit.

The mdex m is 1 or 2, the index n is 0 or 1, provided that when m is equal to 1, n is equal to 1; and when m is 2 n is 0; preferably m is equal to 1 and n is equal to one, resulting in one - [(R¹O)_x(R²O)_yR³] unit and R⁴ bemg present on the nitrogen. The mdex x is from 0 to about 50, preferably from about 3 to about 25, more preferably from about 3 to about 10. The index y is from 0 to about 10, preferably 0, however when the index y is not equal to 0, y is from 1 to about 4. Preferably all of the alkyleneoxy units are ethyleneoxy units. Those skilled the art of ethoxylated polyoxyalkylene alkyl amide surface active agents will recognized that the values for the indices x and y are average values and the true values may range over several values depending upon the process used to alkoxylate the amides.

The mid-cham branched alkyl sulfate surfactants of the present invention have the formula:

R R¹ R²

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_HOSO₃M_; the alkyl alkoxy sulfates have the formula:

R R¹ R²

I I I 3

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_z(OR³)_mOSO₃M the alkyl alkoxylates have the formula R R¹ R²

I I I

CH₃CH₂(CH₂)_wCH(CH₂)_xCH(CH₂)_yCH(CH₂)_z(OR³)_nOH wherein R, R¹, and R² are each independently hydrogen, C,-C₃ alkyl, and mixtures thereof; provided at least one of R, R¹, and R² is not hydrogen; preferably R, R¹, and R² are methyl; preferably one of R, R¹, and R² is methyl and the other units are hydrogen. The total number of carbon atoms m the mid-cham branched alkyl sulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; the index w is an integer from 0 to 13; x is an integer from 0 to 13; y is an integer from 0 to 13; z is an integer of at least 1; provided w + x + y + z is from 8 to 14 and the total number of carbon atoms in a surfactant is from 14 to 20; R³ is C,-C₄ linear or branched alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1 ,4-butylene, and mixtures thereof. However, a preferred embodiment of the present invention compnses from 1 to 3 units wherein R³ is 1,2-propylene, 1,3-propylene, or mixtures thereof followed by the balance of the R³ units compπsmg ethylene units. Another preferred embodiment compnses R³ units which are randomly ethylene and 1,2-propylene units. The average value of the mdex m is at least about 0.01. When the mdex m has low values, the surfactant system compnses mostly alkyl sulfates with a small amount of alkyl alkoxy sulfate surfactant. Some tertiary carbon atoms may be present in the alkyl chain, however, this embodiment is not desired.

M denotes a cation, preferably hydrogen, a water soluble cation, and mixtures thereof. Non-limiting examples of water soluble cations include sodium, potassium, lithium, ammonium, alkyl ammonium, and mixtures thereof Detersent Builder

The detergent compositions herein may also comprise from about 0.1% to 80% by weight of a detergent builder. Preferably such compositions in liquid form will comprise from about 1% to 10% by weight of the builder component. Preferably such compositions in granular form will comprise from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can comprise, for example, phosphate salts as well as various organic and inorganic nonphosphorus builders.

Water-soluble, nonphosphorus organic builders useful herein include the vanous alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates. Suitable polycarboxylates for use herein are the polyacetal carboxylates descπbed m U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al , both of which are incorporated herein by reference. Particularly preferred polycarboxylate builders are the oxydisuccmates and the ether carboxylate builder compositions compnsmg a combination of tartrate monosuccmate and tartrate disuccinate descπbed in U.S Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.

Examples of suitable nonphosphoms, inorganic builders include the silicates, aluminosilicates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates havmg a weight ratio of S1O2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4. Also preferred are aluminosilicates including zeolites. Such mateπals and their use as detergent builders are more fully discussed in Corkill et al., U. S. Patent No. 4,605,509, the disclosure of which is incorporated herein by reference. Also discussed m U. S. Patent No. 4,605,509 are crystallme layered silicates which are suitable for use m the detergent compositions of this mvention.

Optional Detergent Ingredients

In addition to the surfactants, builders and dye maintenance polymers of the detergent compositions of the present invention can also include any number of additional optional ingredients. These include conventional detergent composition components such as enzymes and enzyme stabilizing agents, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, bleaching agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelatmg agents, organic and inorganic fillers, solvents, hydrotropes, optical bπghteners, dyes and perfumes. pH adjusting agents may be necessary m certain applications where the pH of the wash solution is greater than about 10.0 because the fabric integrity benefits of the defined compositions begin to dimmish at a higher pH. Hence, if the wash solution is greater than about 10.0 after the addition of the dye maintenance polymers of the present mvention a pH adjuster should be used to reduce the pH of the washing solution to below about 10.0, preferably to a pH of below about 9.5 and most preferably below about 7.5. Suitable pH adjusters will be known to those skilled m the art

A preferred optional ingredients for incorporation into the detergent compositions herein comprises a bleaching agent, e g , a peroxygen bleach Such peroxygen bleaching agents may be organic or inorganic in nature Inorganic peroxygen bleaching agents are frequently utilized in combination with a bleach activator

Useful organic peroxygen bleaching agents include percarboxy c acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4- nonylammo-4-oxoperoxybutync acid and dφeroxydodecanedioic acid. Such bleaching agents are disclosed m U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published Febmary 20, 1985; and U.S. Patent 4,412,934, Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6- nonylammo-6-oxoperoxycaproιc acid (NAPAA) as descnbed in U.S. Patent 4,634,551, Issued January 6, 1987 to Bums et al.

Inorganic peroxygen bleaching agents may also be used, generally in particulate form, in the detergent compositions herein. Inorganic bleaching agents are m fact preferred. Such inorganic peroxygen compounds include alkali metal perborate and percarbonate mateπals. For example, sodium perborate (e.g. mono- or tetra-hydrate) can be used. Suitable inorganic bleachmg agents can also mclude sodium or potassium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate particles are available from vanous commercial sources such as FMC, Solvay Interox, Tokai Denka and Degussa.

Inorganic peroxygen bleaching agents, e.g., the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production m aqueous solution (i.e., duπng use of the compositions herein for fabric laundermg/bleachmg) of the peroxy acid corresponding to the bleach activator. Various non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamme (TAED) activators are typical and preferred. Mixtures thereof can also be used. See also the hereinbefore referenced U.S. 4,634,551 for other typical bleaches and activators useful herein

Other useful amido-deπved bleach activators are those of the formulae: R¹N(R⁵)C(O)R²C(0)L or R¹C(O)N(R⁵)R²C(O)L wherein R! IS an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R^ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophi c attack on the bleach activator by the perhydrolysis amon. A preferred leaving group is phenol sulfonate.

Preferred examples of bleach activators of the above formulae include (6- octanamιdo-caproyl)oxybenzenesulfonate, (6-nonanamιdocaproyl) oxybenzene-sul-fonate, (6- decanamιdo-caproyl)oxybenzenesulfonate and mixtures thereof as described the hereinbefore referenced U.S. Patent 4,634,551 Another class of useful bleach activators compnses the benzoxazm-type activators disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated herein by reference. See also U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, mcludmg benzoyl caprolactam, adsorbed into sodium perborate.

If utilized, peroxygen bleachmg agent will generally compnse from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleachmg agent will compπse from about 2% to 20% by weight of the compositions. Most preferably, peroxygen bleaching agent will be present to the extent of from about 3% to 15% by weight of the compositions herein. If utilized, bleach activators can compπse from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleachmg agent to activator ranges from about 1:1 to 10:1, more preferably from about 1.5:1 to 5:1.

Additional suitable bleaching agents and bleach activators are disclosed in one or more of the co-pending PCT Applications listed in Table A and incorporated herein by reference.

Another highly preferred optional ingredient in the detergent compositions herem is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a vaπety of purposes, including removal of protem-based, carbohydrate-based, or tnglyceπde-based stains from substrates, for the prevention of refugee dye transfer in fabric laundeπng, and for fabric restoration Suitable enzymes include proteases, amylases, hpases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast ongm Preferred selections are influenced by factors such as pH- activity and/or stability, optimal thermostabihty, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry detergent composition Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, hpases, amylases and peroxidases.

Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically compπse from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation Protease enzymes are usually present m such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may be desirable m highly concentrated detergent formulations.

Cellulases usable herein include those disclosed m U.S. Patent No. 4,435,307, Barbesgoard et al., March 6, 1984, and GB-A-2.075.028; GB-A-2.095.275 and DE-OS-

2.247.832. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 9117243 to Novo.

The enzyme-containing compositions herein may optionally also compπse from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilizmg system can be any stabilizmg system which is compatible with the detersive enzyme. Such a system may be mherently provided by other formulation actives, or be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizing systems can, for example, compπse calcium ion, bone acid, propylene glycol, short chain carboxy c acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

Detergent Composition Preparation

The detergent compositions according to the present invention can be m liquid, paste or granular form. Such compositions can be prepared by combining the essential and optional components in the requisite concentrations in any suitable order and by any conventional means The forgoing description of uses for the dye maintenance polymers defined herein are intended to be exemplary and other uses will be apparent to those skilled in the art and are intended to be within the scope of the present invention

Granular compositions, for example, are generally made by combining base granule ingredients, e.g., surfactants, builders, water, etc., as a slurry, and spray drying the resulting slurry to a low level of residual moisture (5-12%) The remaining dry ingredients, e g., granules of the essential dye maintenance polymers, can be admixed in granular powder form with the spray dned granules in a rotary mixing dmm The liquid ingredients, e.g., solutions of the essential dye maintenance polymers, enzymes, binders and perfumes, can be sprayed onto the resulting granules to form the finished detergent composition. Granular compositions according to the present invention can also be m "compact form", 1 e they may have a relatively higher density than conventional granular detergents, i.e from 550 to 950 g/1. In such case, the granular detergent compositions according to the present invention will contain a lower amount of "inorganic filler salt", compared to conventional granular detergents; typical filler salts are alkaline earth metal salts of sulphates and chlorides, typically sodium sulphate; "compact" detergents typically comprise not more than 10% filler salt.

Liquid detergent compositions can be prepared by admixing the essential and optional ingredients thereof in any desired order to provide compositions containing components in the requisite concentrations. Liquid compositions according to the present invention can also be in "compact form", in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. Addition of the dye maintenance polymers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired dye maintenance polymers.

Fabric Laundering Method

The present invention also provides a method for laundering fabrics in a manner which imparts fabric appearance benefits provided by the dye maintenance polymers used herein. Such a method employs contacting these fabrics with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore described or formed from the individual components of such compositions. Contacting of fabrics with washing solution will generally occur under conditions of agitation although the compositions of the present invention may also be used to form aqueous unagitated soaking solutions for fabric cleaning and treatment. As discussed above, it is preferred that the washing solution have a pH of less than about 10.0, preferably it has a pH of about 9.5 and most preferably it has a pH of about 7.5.

Agitation is preferably provided in a washing machine for good cleaning. Washing is preferably followed by drying the wet fabric in a conventional clothes dryer. An effective amount of a high density liquid or granular detergent composition in the aqueous wash solution in the washing machine is preferably from about 500 to about 7000 ppm, more preferably from about 1000 to about 3000 ppm.

EXAMPLES The following examples illustrate the compositions and methods of the present invention, but are not necessarily meant to limit or otherwise define the scope of the invention.

EXAMPLE I TABLE I comprises numerous examples according to the present invention along with some comparative examples of material known to the art of laundry detergents. The chemical stmctures shown in the examples below are idealized structures. Side reactions expected to occur during the condensation are not shown.

TABLE II

EXAMPLE II Granular Detergent Test Composition Preparation Several heavy duty granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. These granular detergent compositions all have the following basic formula:

TABLE II

Enzymes 0.59

Dye Maintenance Polymer 3.0

Perfume, Brightener, Suds Suppressor, Other Balance Minors, Moisture, Sulfate

100%

EXAMPLE III Liquid Detergent Test Composition Preparation Several heavy duty liquid detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this invention. These liquid detergent compositions all have the following basic formula:

TABLE III

Component Wt. %

Ci _ι ς alkyl ether (2.5) sulfate 38

Ci ι glucose amide 6.86

Citric Acid 4.75

Ci 7_ι 4 Fatty Acid 2.00

Enzymes 1.02

MEA 1.0

Propanediol 0.36

Borax 6.58

Dispersant 1.48

Na Toluene Sulfonate 6.25

Dye Maintenance Polymer 1.0

Dye, Perfume, Brighteners, Preservatives, Suds Balance Suppressor, Other Minors, Water

100%

EXAMPLE IV Granular Detergent Test Composition Preparation Several granular detergent compositions are prepared containing one or more dye maintenance polymer having a DMP according to this mvention. Such granular detergent compositions all have the following basic formula:

TABLE IV

Example Comparative

Component Wt. % Wt%

Na Cj ?. Linear alkyl benzene sulfonate 9.40 9.40

Na Ci4_tς alkyl sulfonate 11.26 11.26

Zeolite Builder 27.79 27.79 Sodium Carbonate 27.31 27.31

PEG 4000 1.60 1.60

Dispersant, Na polyacrylate 2.26 2.26

Ci .1 -* alkyl ethoxylate (E9) 1.5 1.5

Sodium Perborate 1.03 1.03

Dye Maintenance Polymer 0.8 0

Other Adjunct ingredients Balance Balance

100% 100%

Claims

What is claimed is:

1. A detergent compositions comprising: a) from 4% to 70% by weight, of a surfactant; b) from 0.01% to 5% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more units having the formula:

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; wherein R is: i) hydrogen; ϋ) hydroxyl iϋ) halogen; iv) nitrilo; v) -OR³; vi) -O(CH₂)_nN(R³)₂; vii) -O(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 ^"; xii) -(CH₂)_nN(R³)₂; xiii) -(CH₂)_nN⁺(R³)₃X^"; xiv) carbocyclic; xv) heterocyclic; xvi) nitrogen heterocycle quaternary ammonium; xvii) nitrogen heterocycle N-oxide; xviii) aromatic N-heterocyclic quaternary ammonium; xix) aromatic N-heterocyclic N-oxide; xx) -NHCHO; xxi) or mixtures thereof; each R .³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble anion; the index n is from 0 to 6 e) -(CH₂) _mCOR' wherein R' is i) -OR³; ϋ) -O(CH₂)_nN(R³)₂; iϋ) -O(CH₂)_nN⁺(R³)₃X-; iv) -NR³(CH₂)_nN(R³)₂; v) -NR³(CH₂)_nN⁺(R³)₃X^"; vi) -(CH₂)_nN(R³)₂; vii) -(CH₂)_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 deπved from cyclically polymenzing monomers havmg the formula:

wherem each R⁴ is independently an olefin compπsmg unit which is capable of propagating polymeπzation in addition to forming a cyclic residue with an adjacent R⁴ unit; R⁵ is C,-C₁₂ lmear 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 wherem said dye maintenance polymer is not an polyethyleneimine or alkoxylated derivative thereof; and b) the balance earners and other adjunct ingredients.

2. A detergent composition accordmg to Claim 1, wherem said dye maintenance polymer is a copolymer compnsmg:

I) a first monomer selected from the group consisting of N, N dιalkylammoalkyl(meth)acrylate, N, N dialkylaminoalkylacrylate, 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, methacryhc acid, C,-C₆ alkylmethacrylate, C C₆ alkyl acrylate, C,-C₈ hydroxyalkylacrylate, C,-C₈ hydroxyalkylmethacrylate, acrylamide, C_rC₁₆ alkyl acrylamide, C,-C₁₆ dialkylacrylamide, 2-acrylamιdo-2-methylpropane sulfonic acid or its alkali salt, methacrylamide, C,-C₁₆ alkylmethacrylamide, C_rC₁₆ dialkylmethacrylamide, vmyl formamide, v ylacetamide, vinyl alcohol, C,-C₈ vinylalkylether, vmyl pyndme, itaconic acid, vinyl acetate, vinyl propionate, vinyl butyrate and mixtures thereof; wherein the copolymer compnses at least 25 mole % of the first monomer.

3. A composition accordmg to either Claim 1 or 2 wherein said adjunct ingredients are selected from the group consisting of electrolytes, stabilizers, low molecular weight water soluble solvents, chelating agents, dispersibility aids, soil release agents, nonionic fabric softening agents, concentration aid, perfume, preservatives, colorants, optical brighteners, opacifiers, germicides, fungicides, anti-corrosion agents, antifoam agents, and mixtures thereof.

4. A detergent composition comprising: a) from 4% to 70% of a surfactant; b) from 0.01% to 10% by weight, of a dye maintenance polymer or oligomer, said dye mamtenance polymer is selected from the group consistmg of homopolymers, co-polymers, ter-polymers and mixtures thereof having the formula:

wherem each R¹, R² is hydrogen or methyl; Z has the formula:

-(CH₂)_mR wherein m is equal to 0 or 1 ; R is

-N(R³)₂ or -N⁺(R³)₃X^" R³ is selected from the group consisting of hydrogen, C_rC₄ alkyl, C₂-C₄ hydroxyalkyl, and mixtures thereof; X is a water soluble amon; and c) the balance carriers and adjunct ingredients.

5. A composition accordmg to any of Claims 1-4 compnsmg from 0.1% to 8% by weight of said dye mamtenance polymer.

6. A composition according to any of Claims 1-5 wherein said dye maintenance polymer is a co-polymer comprising a linearly polymerizing monomers and a cyclically polymenzmg monomer, said cyclically polymenzmg monomer havmg the formula:

wherem R⁵ is C C₄ alkyl, and mixtures thereof; X is a water soluble amon.

7. A composition accordmg to any of Claims 1-5 wherem the dye mamtenance polymer is selected from the group consisting of homopolymers, co-polymers, ter- polymers and mixtures thereof, of diallyl dimethylammomum chloπde, bromide or methyl sulfate and a co-monomer selected from the group consisting of acrylic acid, methacryhc acid, C,-C₆ alkylmethacrylate, C C₆ alkyl acrylate, C,-C₈ hydroxyalkylacrylate, C,-C₈ hydroxyalkylmethacrylate, acrylamide, C_rC₁₆ alkyl acrylamide, C_rC₁₆ dialkylacrylamide, 2-acrylamιdo-2-methylpropane sulfonic acid or its alkali salt, methacrylamide, C,-C₁₆ alkylmethacrylamide, C_rC₁₆ dialkylmethacrylamide, vmyl formamide, vmylacetamide, vmyl alcohol, C_rC₈ vmylalkylether, vmyl pyπdme, ltacomc acid, vmyl acetate, vmyl propionate, vinyl butyrate and mixtures thereof.

8. A composition according to any of Claims 1-5 wherem said dye maintenance polymer a co-polymer comprising a linearly polymeπzmg monomers and a cyclically polymerizing monomer, said cyclically polymerizing monomer having the formula:

wherein R⁵ is C,-C₄ alkyl, and mixtures thereof; X is a water soluble amon.

A composition according to any of Claims 1-5 comprising a co-polymer wherem Z has the formula:

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

10. A composition according to Claim 1 wherein said dye maintenance polymer comprises copolymer of N-methyl vinyl pyridme and vinyl pyridine in a ratio of 4:1, a copolymer of N-methyl vinyl pyridine and vinyl pyridine in a ratio of 4:6, a co-polymer of poly(N-methyl vinyl pyridme) and vinyl pyridine N-oxide in a ratio of polymer to monomer of 4:1, a polymer comprising poly(N-methyl vinyl pyridine) and vinyl pyridine N-oxide in a ratio of polymer to monomer of 4:6, and mixtures thereof.

11. A method for reducing the loss of fabric dye comprising the step of contacting dyed fabric with a laundry detergent comprising: a) from 4% to 70% by weight, of a surfactant; b) from 0.01% to 5% by weight, of a dye maintenance polymer or oligomer, said polymer or copolymer comprising one or more units having the formula:

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)_raR; wherein R is: i) hydrogen; ii) hydroxyl iii) halogen; iv) nitrilo; v) -OR³; vi) -O(CH₂)_nN(R³)₂; vii) -O(CH₂)_nN⁺(R³)₃X-; viii) -OCO(CH₂)_nN(R³)₂; ix) -OCO(CH₂)_nN⁺(R³)₃X-; x) -NHCO(CH₂)_πN(R³)₂; xi) -NHCO(CH₂)_nN⁺(R³)₃X^"; xii) -(CH₂)_nN(R³)₂; xiii) -(CH₂)_nN⁺(R³)₃X-; xiv) carbocyclic; xv) heterocyclic; xvi) nitrogen heterocycle quaternary ammonium; xvii) nitrogen heterocycle N-oxide; xviii) aromatic N-heterocyclic quaternary ammonium; xix) aromatic N-heterocyclic 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 anion; the index n is from 0 to 6 e) -(CH₂)_mCOR' wherein R' is i) -OR³; ϋ) -O(CH₂)_nN(R³)₂; iii) -O(CH₂)_nN⁺(R³)₃X^"; iv) -NR³(CH₂)_nN(R³)₂; v) -NR³(CH₂)„N⁺(R³)₃X-; vi) -(CH₂)_nN(R³)₂; vii) -(CH₂)_nN⁺(R³)₃X-; viii) or mixtures thereof; each R³ is independently hydrogen, C,-C₈ alkyl, C₂-C₈ hydroxyalkyl, and mixtures thereof; X is a water soluble anion; 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; and wherein said dye maintenance polymer is not an polyethyleneimine or alkoxylated derivative thereof; and b) the balance carriers and other adjunct ingredients.