EP1121408A1

EP1121408A1 - Laundry detergent compositions with a combination of cyclic amine based copolymers and hydrophobically modified carboxy methyl cellulose

Info

Publication number: EP1121408A1
Application number: EP99954739A
Authority: EP
Inventors: Rajan Keshav Panandiker; Jennifer Ann Leupin; William Conrad Wertz
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1998-10-13
Filing date: 1999-10-06
Publication date: 2001-08-08
Anticipated expiration: 2019-10-06
Also published as: ES2238854T3; BR9914520A; CA2346293A1; DE69923855D1; AR020794A1; CA2346293C; EP1121408B1; AU1101700A; ATE289627T1; JP2002527576A; CN1330704A; BR9914520B1; DE69923855T2; CN1163576C; WO2000022078A1

Abstract

Detergent compositions and fabric conditioning compositions which include from about 0.01 % to about 5.0 %, by weight of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.

Description

LAUNDRY DETERGENT COMPOSITIONS WITH A COMBINATION OF CYCLIC AMINE BASED POLYMERS AND HYDROPHOBICALLY MODIFIED CARBOXY

METHYL CELLULOSE

TECHNICAL FIELD

The present invention relates to compositions, m either liquid or granular form, for use in laundry applications, wherein the compositions compπse certain cyclic amine based polymer, ohgomer or copolymer materials m combination with hydrophobically modified carboxy methyl cellulose This combination imparts 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 laundering fabπcs and textiles, such as articles of worn clothing and apparel, will inevitably adversely affect the appearance and integrity of the fabric 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 during ordinary use. However, the laundeπng operation itself, over many cycles, can accentuate and contribute to the deterioration of the integrity and the appearance of such fabrics and textiles.

Deterioration of fabπc integrity and appearance can manifest itself in several ways. Short fibers are dislodged from woven and knit fabπc/textile structures by the mechanical action of laundering These dislodged fibers may form lint, fuzz or "pills" which are visible on the surface of fabrics and diminish the appearance of newness of the fabπc. Further, repeated laundeπng of fabπcs and textiles, especially with bleach-containing laundry products, can remove dye from fabrics and textiles and impart a faded, worn out appearance as a result of diminished color intensity, and m 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 detergent products that would associate themselves with the fibers of the fabπcs and textiles laundered using such detergent products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteπ orate in appearance. Any such detergent product additive mateπal should, of course, be able to benefit fabπc appearance and integπty without unduly interfeπng with the ability of the laundry detergent to perform its fabπc cleaning function. The present invention is directed to the use of a mixture of certain cyclic amme based polymer, oligomer or copolymer mateπals and hydrophobically modified carboxy methyl cellulose (CMC) in laundry applications that perform in this desired manner.

SUMMARY OF THE INVENTION

The present invention is directed to a detergent composition comprising: a) from about 1% to about 80% by weight of surfactants selected from the group consisting of noniomc, amonic, catiomc, amphoteπc zwittenonic surfactants and mixtures thereof; and b) at least about 0.01%, preferably at least about 0.1%, most preferably at least about 0.5% and less than about 50%, preferably less than about 25.0%, most preferably less than about 5.0%, by weight, of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. The cyclic am e based polymer, oligomer or copolymer mateπals which are suitable for use in laundry operations and provide the desired fabπc appearance and mtegπty benefits can be characterized by the following general formula:

wherein, each T is independently selected from the group consisting of H, C\ -Cj2 alkyl, substituted alkyl, C7-C12 alkylaryl, -(CH₂)hCOOM, -(CH₂)hS0₃M, CH₂CH(OH)SO₃M, -(CH₂)hOSO₃M,

-wherein W compπses at least one cyclic constituent selected from the group consisting of:

in addition to the at least one cyclic constituent, W may also comprise an aliphatic or substituted aliphatic moiety of the general structure;

-each B is independently Cι-Cι₂ alkylene, Cι-C_j2 substituted alkylene, C3-C1₂ alkenylene, Cg- C_{j 2} dialkylarylene, Cg-Cι ₂ dialkylarylenediyl, and -(R5O)_nR5- ;

-each D is independently C -Cg alkylene;

-each Q is independently selected from the group consisting of hydroxy, g alkoxy, C₂-Cι g hydroxyalkoxy, ammo, Cj-Ci g alkylamino, dialkylamino, tπalkylamino groups, heterocyc c monoamino groups and diammo groups;

-each R_j is independently selected from the group consisting of H, Cj-Cg alkyl and Ci -Cg hydroxyalkyl;

-each R₂ is independently selected from the group consisting of C1 -Ci ₂ alkylene, Cj-C j₂ alkenylene, -CH -CH(ORι)-CH₂, Cg-Cι alkarylene, C4-Cj₂ dihydroxyalkylene, poly(C₂-C alkyleneoxy)alkylene, H₂CH(OH)CH₂OR₂OCH₂CH(OH)CH₂-, and C₃- C 12 hydrocarbyl moieties; provided that when R₂ is a C₃-Cι ₂ hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:

OH

- - OR₅ -^ O— CH₂-CH— CH₂T-[w — R^- W - T -each R₃ is independently selected from the group consisting of H, O, R2, C 1-C20 hydroxyalkyl, C1-C20 alkyl, substituted alkyl, Cg-Cj \ aryl, substituted aryl, C7-C1 \ alkylaryl, C1-C20 ammoalkyl, -(CH₂)hCOOM, -(CH₂)hS0₃M, CH₂CH(OH)SO₃M, -(CH₂) OSO₃M,

COOM

CH COOM COOM ^NCH-COOM - COOM __CH2 I nooM — CH . .COOM \

CH₂-COOM ^"CH2 ^V , and COOM

-each R4 is independently selected from the group consisting of H, C 1-C22 alkyl, Ci -C22 hydroxyalkyl, aryl and C -C22 alkylaryl; -each R5 is independently selected from the group consisting of C2-C alkylene, C2-Cg alkyl substituted alkylene; and

A is a compatible monovalent or di or polyvalent anion; M is a compatible cation; b = number necessary to balance the charge; each x is independently from 3 to about 1000; each c is independently 0 or 1 ; each h is independently from about 1 to about 8; each q is independently from 0 to about 6; each n is independently from 1 to about 20, each r is independently from 0 to about 20; and each t is independently from 0 to 1.

Cellulosic based polymer or oligomer materials which are suitable for use laundry operations and provide the desired fabric appearance and mtegπty benefits can be characteπzed by the following general formula:

wherein each R is selected from the group consisting of R2, Re, and

wherein: - each R₂ is independently selected from the group consisting of H and C 1-C4 alkyl;

O - each Rcs -(^CH2) -C-OZ wherein each Z is independently selected from the group consisting of M, R , Re, and R_H; each R_H is independently selected from the group consisting of C5 -C₂o alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1 -C20 alkoxy-2 -hydroxyalkyl, C7-C₂Q alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2- hydroxyalkyl, (R4)₃ N-alkyl, ( 4)₃ N-2 -hydroxyalkyl, aryloxy-2 -hydroxyalkyl,

O R₅ O R₅ O R₅ O

II I II I II I II

— C CH C CH, — C CH, CH C-OM , a _and ,

O R₅ O

II I II

— C — CH— CH₂— C-OM. each R4 is independently selected from the group consisting of H, C 1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C₂Q arylalkyl, aminoalkyl, alkylammoalkyl, dialkylaminoalkyl, pipeπdinoalkyl, morphohnoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C\ -C Q alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R4)₂N-alkyl, and (R^ N-alkyl; wherein:

M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that: the Degree of Substitution for group R_H is between about 0.0005 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group Re wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7; if any R_H bears a positive charge, it is balanced by a suitable amon; and two R4's on the same nitrogen can together form a ring structure selected from the group consisting of pipeπdme and morphohne. The cyclic amme based polymer, oligomer or copolymer matenals defined above can be used, along with the hydrophobically modified cellulosic based polymers or oligomers, as a washing solution additive m either granular or liquid form. Alternatively, they can be admixed to granular detergents, dissolved in liquid detergent compositions or added to a fabπc softening composition.

The ratio of the hydrophobically modified cellulosic to cyclic amme based polymer, oligomer or copolymer mateπals is within the range of 1000:1 to 1 :1000 and is preferably between 100: 1 to 50: 1, more preferably between 50: 1 to 1 : 1, even more preferably between 10:1 to 1.1

The laundry detergent compositions herein comprise from about 1% to 80% by weight of a detersive surfactant, from about 0.01% to 80% by weight of an organic or inorganic detergency builder and from about 0.01% to 5% by weight of the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers based fabπc treatment mateπals of the present invention. The detersive surfactant and detergency builder mateπals can be any of those useful in conventional laundry detergent products. Aqueous solutions of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the subject invention compπse from about 0.01% to 80% by weight of the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers fabric treatment mateπals dissolved in water and other ingredients such as stabilizers and pH adjusters.

In its method aspect, the present invention relates to the laundeπng or treating of fabπcs and textiles in aqueous washing or treating solutions formed from effective amounts of the detergent compositions described herein, or formed from the individual components of such compositions Laundeπng of fabπcs and textiles m such washing solutions, followed by raising and drying, imparts fabric appearance benefits to the fabπc and textile articles so treated Such benefits can include improved overall appearance, pill/fuzz reduction, antifading, improved abrasion resistance, and/or enhanced softness It has been surprisingly determined that the a mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers according to this invention imparts fabπc appearance and integrity benefits that are greater than the benefits achieved by a corresponding amount of either component by itself

DETAILED DESCRIPTION OF THE INVENTION

As noted, when fabric or textiles are laundered in wash solutions which compπse the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the present invention fabric appearance and integrity are enhanced The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers 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 mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers are descπbed herein pπmaπly as liquid or granular detergent additives but the present invention is not meant to be so limited T e mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, detergent composition components, optional ingredients for such compositions and methods of using such compositions, are described in detail below. All percentages are by weight unless other specified.

A) Cyclic amme Based Polymer. Oligomer or Copolymer Matenals

An essential component of the compositions of the present invention compπses one or more cyclic amine based polymer, oligomer or copolymer Such mateπals have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers fabπc treatment mateπals. 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 cyclic amme based fabπc treatment mateπals used in the compositions and methods herein can provide such fabπc appearance benefits with acceptably little or no loss m cleaning performance provided by the laundry detergent compositions into which such mateπals are incorporated.

The cyclic amine based polymer, oligomer or copolymer component of the compositions herein may comprise combinations of these cyclic amme based matenals. For example, a mixture of piperadine and epihalohydπn condensates can be combined with a mixture of morphohne and epihalohydπn condensates to achieve the desired fabric treatment results. Moreover, the molecular weight of cyclic amine based fabric treatment matenals can vary within the mixture as is illustrated m the Examples below.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers compnse 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 polymeπzed from a mixture of a pπmary cyclic amine based monomer, e.g., piperadine, and a secondary cyclic amine monomer, e.g., morphohne.

The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers of the detergent compositions herein will generally compπse from about 0.01% to about 5% by the weight of the detergent composition. More preferably, the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers will compπse from about 0.1% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3% However, as discussed above, when used as a washing solution additive, i.e. when mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers is not incorporated into a detergent composition, the concentration of mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers can compnse from about 0.1% to about 80% by weight of the additive matenal Cyclic amme based polymer, oligomer or copolymer mateπals which are suitable for use in laundry operations and provide the desired fabnc appearance and integrity benefits can be charactenzed by the general formula given in the Summary of the Invention.

Preferred compounds that fall within this general structure include compounds:

- wherein each R_j is H; and

-at least one W is selected from the group consisting of:

Even more preferred compounds for the fabric appearance and integrity benefits are those

-wherein each K\ is H; and

-at least one W is selected from the group consisting of:

And most preferred compounds for the fabnc appearance and mtegnty benefits are those: -wherein each R_j is H; and

-at least one W is selected from the group consisting of:

Preferred compounds to be used as the linking group R₂ include, but are not limited to: polyepoxides, ethylenecarbonate, propylenecarbonate, urea, α, β-unsaturated carboxylic acids, esters of α, β-unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids, anhydrides of α, β-unsaturated carboxylic acids, di- or polycarboxylic acids, esters of di- or polycarboxy c acids, amides of di- or polycarboxylic acids, anhydndes of di- or polycarboxylic acids, glycidylhalogens, chloroformic esters, chloroacetic esters, denvatives of chloroformic esters, derivatives of chloroacetic esters, epihalohydnns, glycerol dichlorohydπns, bis- (halohydπns), polyetherdihalo-compounds, phosgene, polyhalogens, functionalized glycidyl ethers and mixtures thereof Moreover, R2 can also comprise a reaction product formed by reacting one or more of polyetherdiamines, alkylenediammes, polyalkylenepolyamines, alcohols, alkyleneglycols and polyalkyleneglycols with α, β-unsaturated carboxylic acids, esters of α, β- unsaturated carboxylic acids, amides of α, β-unsaturated carboxylic acids and anhydrides of α, β- unsaturated carboxylic acids provided that the reaction products contain at least two double bonds, two carboxylic groups, two amide groups or two ester groups

Additionally preferred cyclic amme based polymer, oligomer or copolymer materials for use herein include adducts of two or more compositions selected from the group consisting of piperazme, piperadine, epichlorohydπn, epichlorohydnn benzyl quat, epichlorohydπn methyl quat, morphohne and mixtures thereof.

These cyclic amine based polymers can be linear or branched. One specific type of branching can be intorduced using a polyfunctional crosslinkmg agent. An example of such such polymer is exemplified below

B) Hydrophobically Modified Cellulosic Based Polymers or Oligomers

The essential component of the compositions of the present invention compnses one or more cellulosic based polymer or oligomer. Such matenals have been found to impart a number of appearance benefits to fabrics and textiles laundered in aqueous washing solutions formed from detergent compositions which contain such cellulosic based fabπc treatment matenals.

Such fabπc appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc. The cellulosic based fabric treatment matenals used in the compositions and methods herein can provide such fabπc appearance benefits with acceptably little or no loss in cleaning performance provided by the laundry detergent compositions into which such mateπals are incorporated.

As will be apparent to those skilled in the art, an oligomer is a molecule consisting of only a few monomer units while polymers compπse 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. One suitable type of cellulosic based polymer or oligomer fabnc treatment mateπal for use herein has an average molecular weight of from about 5,000 to about 2,000,000, preferably from about 50,000 to about 1 ,000,000.

The cellulosic based fabnc treatment component of the detergent compositions herein will generally compnse from about 0.1% to about 5% by the weight of the detergent composition. More preferably, such cellulosic based fabnc treatment mateπals will compnse from about 0.5% to about 4% by weight of the detergent compositions, most preferably from about 0.75% to about 3% However, as discussed above, when used as a washing solution additive, i.e. when the cellulosic based fabric treatment component is not incorporated into a detergent composition, the concentration of the cellulosic based component can compπse from about 0.1% to about 80% by weight of the additive material.

One suitable group of cellulosic based polymer or oligomer matenals for use herein is characterized by the following formula:

wherein each R is selected from the group consisting of R2, Re, and

wherein: each R2 is independently selected from the group consisting of H and C1 -C4 alkyl;

O

- each Re , -(^CH2)y-^C-°^Z, wherein each Z is independently selected from the group consisting of M, R₂, Re, and R_H; each R_H IS independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, Cι -C₂o alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2 -hydroxyalkyl, (R4)2N-alkyl, (R4>2N-2- hydroxyalkyl, (R4)₃ N-alkyl, (R4)₃ N-2-hydroxyalkyl, Cg-C^ aryloxy-2 -hydroxyalkyl,

O O O O II ^■f⁵ II II II — C- -CH- -C- -CH₂ -C- -CH₂- -CH- -C-OM , and

O R₅ O

II I II

— C — CH— CH₂— C-OM. each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, ammoalkyl, alkylammoalkyl, dialkylammoalkyl, pφeπdinoalkyl, mo holmoalkyl, cycloalkylammoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C\ -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, (R₄)₂N-alkyl, and (R4)₃ N-alkyl; wherein:

M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg; each x is from 0 to about 5; each y is from about 1 to about 5; and provided that: the Degree of Substitution for group R_H is between about 0.0005 and 0.1, more preferably between about 0.005 and 0.05, and most preferably between about 0.01 and 0.05; the Degree of Substitution for group Re wherein Z is H or M is between about 0.2 and 2.0, more preferably between about 0.3 and 1.0, and most preferably between about 0.4 and 0.7; if any R_H bears a positive charge, it is balanced by a suitable anion; and two R4's on the same nitrogen can together form a nng structure selected from the group consisting of pipendme and morphohne.

The "Degree of Substitution" for group R_H, which is sometimes abbreviated herein "DS_RH", means the number of moles of group R_H components that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered πng as shown in the repeating unit of the general structure above.

The "Degree of Substitution" for group Re, which is sometimes abbreviated herein "DS_Rc", means the number of moles of group Re components, wherein Z is H or M, that are substituted per anhydrous glucose unit, wherein an anhydrous glucose unit is a six membered nng as shown in the repeating unit of the general structure above. The requirement that Z be H or M is necessary to insure that there are a sufficient number of carboxy methyl groups such that the resulting polymer is soluble. It is understood that in addition to the required number of Re components wherein Z is H or M, there can be, and most preferably are, additional Re components wherein Z is a group other than H or M.

The production of materials according to the present invention is further defined in the Examples below. C) Detersive Surfactant

The detergent compositions herein compnse from about 1% to 80% by weight of a detersive surfactant. Preferably such compositions compnse from about 5% to 50% by weight of surfactant. Detersive surfactants utilized can be of the anionic, noniomc, zwittenomc, ampholytic or catiomc type or can compπse compatible mixtures of these types. Detergent surfactants useful herein are described U.S. Patent 3,664,961, Noms, issued May 23, 1972, U.S. Patent 3,919,678, Laughlm et al , issued December 30, 1975, U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980. All of these patents are incorporated herein by reference. Of all the surfactants, a onics and nomonics are preferred.

Useful anionic surfactants can themselves be of several different types. For example, water-soluble salts of the higher fatty acids, i.e., "soaps", are useful anionic surfactants in the compositions herein This includes alkali metal soaps such as the sodium, potassium, ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms.

Additional non-soap anionic surfactants which are suitable for use herein include the water- soluble salts, preferably the alkali metal, and ammonium salts, of organic sulfuπc reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfunc acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 1 1 to 13 , abbreviated as C \ \ . \ ₃ LAS.

Preferred noniomc surfactants are those of the formula R. (OC2H4)_nOH, wherein R. is a

C_{] ()}-Ci6 alkyl group or a C -Ci 2 alkyl phenyl group, and n is from 3 to about 80. Particularly preferred are condensation products of C 12-C15 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, e.g., Ci2-Cι alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.

Additional suitable surfactants, including polyhydroxy fatty acid amides and amme based surfactants, are disclosed in co-pendmg PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al. The entire disclosure of the Panandiker et al. reference is incorporated herein by reference D) Detergent Builder

The detergent compositions herein may also compnse from about 0.1% to 80% by weight of a detergent builder. Preferably such compositions in liquid form will compnse from about 1% to 10% by weight of the builder component. Preferably such compositions granular form will compπse from about 1% to 50% by weight of the builder component. Detergent builders are well known in the art and can compnse, for example, phosphate salts as well as vaπous 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 described in 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 oxydisuccinates and the ether carboxylate builder compositions comprising a combination of tartrate monosuccmate and tartrate disuccinate descnbed 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 nonphosphorus, inorganic builders include the silicates, aluminosihcates, borates and carbonates. Particularly preferred are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having 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 aluminosihcates 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 in U. S. Patent No. 4,605,509 are crystalline layered silicates which are suitable for use in the detergent compositions of this invention.

E) Optional Detergent Ingredients

In addition to the surfactants, builders and mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers hereinbefore described, 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.

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-oxoperoxybutyπc acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354, Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al, Issued November 1, 1983 Highly preferred bleaching agents also include 6-nonylamιno-6-oxoperoxycaproιc acid (NAPAA) as described m U.S. Patent 4,634,551, Issued January 6, 1987 to Burns et al.

Inorganic peroxygen bleaching agents may also be used, generally in particulate form, the detergent compositions herein Inorganic bleaching agents are in 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 bleaching agents can also include 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 in aqueous solution (i.e., during use of the compositions herein for fabric laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various non-limit g 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(0)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 nucleophihc attack on the bleach activator by the perhydrolysis anion. 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 descnbed in 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, including benzoyl caprolactam, adsorbed into sodium perborate.

If utilized, peroxygen bleaching agent will generally comprise from about 2% to 30% by weight of the detergent compositions herein. More preferably, peroxygen bleaching 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 comprise from about 2% to 10% by weight of the detergent compositions herein. Frequently, activators are employed such that the molar ratio of bleaching 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 co-pending

PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent

Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, m the name of

Panandiker et al. The entire disclosure of the Panandiker et al. reference was incorporated by reference above.

Another highly preferred optional ingredient m the detergent compositions herein is a detersive enzyme component. Enzymes can be included in the present detergent compositions for a vanety of purposes, including removal of protem-based, carbohydrate-based, or tπglyceπde-based stains from substrates, for the prevention of refugee dye transfer in fabπc laundermg, and for fabπc restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable oπgm, such as vegetable, animal, bacteπal, 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 bacteπal amylases and proteases, and fungal cellulases.

"Detersive enzyme", as used herein, means any enzyme having a cleaning, stam removing or otherwise beneficial effect in a laundry detergent composition. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases, amylases and peroxidases. Enzymes are normally incorporated into detergent compositions at levels sufficient to provide a "clean g-effective amount" The term "cleaning-effective amount" refers to any amount capable of producing a cleaning, stam removal, soil removal, whitening, deodoπzmg, or freshness improving effect on substrates such as fabncs. 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 comprise 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 in 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 stabilizing system can be any stabilizing system which is compatible with the detersive enzyme. Such a system may be inherently provided by other formulation actives, or be added 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 carboxylic 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. The compositions of the present invention may also include dye transfer inhibiting agents such as polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrroIidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. These agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: - NC(O)-, -C(O)O-, -S-, -O-, -N=; x is 0 or 1; and R is aliphatic, ethoxylated aliphatics, aromatics, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group can be represented by the following general structures:

O O

I I

(Rι)χ-N— (R₂)_y; =N— (R,)χ

(R₃)z wherein R_j, R₂, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa <10, preferably pKa <7, more preferred pKa <6.

Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N- oxidation. The polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.

The most preferred polyamine N-oxide useful in the detergent compositions herein is poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4. This preferred class of materials can be referred to as "PVNO".

Further suitable dye transfer inhibitors can be found in U. S. Pat. No. 5,466,802, issued Nov. 14, 1995 to Panandiker et al., which is hereby incorporated by reference. F) Detergent Composition Preparation The detergent compositions according to the present invention can be 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 mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers 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 mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, can be admixed in granular powder form with the spray dned granules in a rotary mixing drum. The liquid ingredients, e.g., solutions of the essential mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, 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 in "compact form", i.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 chlondes, typically sodium sulphate; "compact" detergents typically compπse 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 mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers to liquid detergent or other aqueous compositions of this invention may be accomplished by simply mixing into the liquid solutions the desired mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers

The methods and compositions heretofore disclosed may also be applied towards the production of particles that may be used as one of the component detergent granules in a granular detergent composition

G) Fabnc Laundenng Method

The present invention also provides a method for laundering fabncs m a manner which imparts fabnc appearance benefits provided by the mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers used herein Such a method employs contacting these fabncs with an aqueous washing solution formed from an effective amount of the detergent compositions hereinbefore descnbed or formed from the individual components of such compositions Contacting of fabncs 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 fabπc cleaning and treatment

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

H) Fabric Conditioning and Softening

The mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers hereinbefore described as components of the laundry detergent compositions herein may also be used to treat and condition fabrics and textiles in the absence of the surfactant and builder components of the detergent composition embodiments of this invention Thus, for example, a fabnc conditioning composition compπsing only the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers themselves, or compnsmg an aqueous solution of the mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers, may be added dunng the nnse cycle of a conventional home laundenng operation in order to impart the desired fabnc appearance and mtegnty benefits hereinbefore descnbed

Additional suitable fabric softening agents are disclosed in co-pending PCT Application WO98/14300, Published March 25, 1999, entitled Laundry Detergent Compositions with Cyclic Amine Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith, which was filed on September 15, 1997, in the name of Panandiker et al The entire disclosure of the Panandiker et al reference was incorporated by reference above The compositions of the present invention compπse at least about 1%, preferably from about 10%, more preferably from about 20% to about 80%, more preferably to about 60% by weight, of the composition of one or more fabπc softener actives.

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 1 Synthesis of the adduct of imidazole and epichlorohydin (Ratio of imidazole:epichlorohydrin 1:1):

The polycatio c condensate is prepared by reacting imidazole and epichlorohydπn. To a round bottomed flask equipped with a magnatic stirrer, condenser and a thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is heated to 50°C followed by dropwise addition of epichlorohydπn (0.68 moles). After all the epichlorohydπn is added, the temperature is raised to 80°C until all the alkylatmg agent is consumed. The condensate produced had molecular weight of about 12,500.

EXAMPLE 2 Synthesis of the adduct of imidazole and epichlorohydin (Ratio of imidazole:epichlorohydrin 1.4:1)

To a round bottomed flask equipped with a magnatic stirrer, condenser and a thermometer are added imidazole (0.68 moles) and 95 mL water. The solution is heated to 50°C followed by dropwise addition of epichlorohydπn (0.50 moles). After all the epichlorohydπn is added, the temperature is raised to 80°C until all the alkylatmg agent is consumed. The condensate produced had molecular weight of about 2000.

EXAMPLE 3 Synthesis of the adduct of piperazine, morpholine and epichlorohydin (Ratio 1.8/0.8/2.0) Into a round bottom flask equipped with stirrer, thermometer, dropping funnel and reflux condenser 154.8 g (1.8 mole) of piperazme and 69.6 g (0.8 mole) of morphohne and 220 ml of water are added. After a clear solution at 40°C is obtained, the solution is heated to 55-65°C and with vigorous stirπng 185 g (2 mole) of epichlorohydπn is added at such a rate, that the temperature does not exceed 80°C. After all the epichlorohydπn is added the reaction mixture is heated to 85°C until all of the alkylatmg agents is consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water are added and the reaction mixture is stirred for another hour at 85°C. Then an additional 47 g of water is added and the mixture is allowed to cool to room temperature.

EXAMPLE 4 Synthesis of the adduct of piper azine/morpholine/epi, in a ratio of 1.8/0.8/2.0

Into a round bottom flask equipped with stirrer, thermometer, dropping funnel and reflux condenser 154.8 g (1.8 mole) of piperazme and 69.6 g (0.8 mole) of morphohne and 220 ml of water are added. After a clear solution at 40°C is obtained, the solution is heated to 55-65°C and with vigorous stirring 185 g (2 mole) of epichlorohydnn is added at such a rate, that the temperature does not exceed 80°C After all the epichlorohydπn is added the reaction mixture is heated to 85 °C until all of the alkylatmg agents has been consumed (negative Preussmann test after 4 hours). 108.8 g (0.68 mole) of 25% NaOH and 40 g of water is added and the reaction mixture is stirred for another hour at 85°C. Then an additional 47 g of water are added and the mixture is allowed to cool to room temperature.

EXAMPLE 5 Adduct of piperazine/morpholine/epi from Example 4, 100% oxidized 233.6 g (equivalent to 1,292 mole oxidizable nitrogen atoms) of the mateπal from

Example 4 above is mixed with 22.1 g (0.276) of 50% NaOH and then heated to 55-65°C. At that temperature 102.4 g (1,421 mole) of H202 (47.2%) is added dropwise over a penod of 3.5 hours. After the addition is complete, the reaction mixture is held at the same temperature for 3 more hours and is then stirred at room temperature overnight. Pt/C was added, unreacted H2O2 destroyed and the solution then filtered.

The reaction product is characterized as follows: water content 58% pH 5.6 chloride contentl .593 mmole/g

EXAMPLE 6 Synthesis of the adduct of imidazole/piperazine/epi, in a ratio 1.0/3.0/4.0 68.8g (1.0 mole) of midazole and 260.6 g (3.0 mole) of piperazme are dissolved m 700.2 g of water and at a temperature of 50-60°C, 370 g (4.0 mole) of epichlorhydπn is added dropwise. After the addition is complete, the reaction mixture is stirred for additional 5 hours at 80°C.

EXAMPLE 7 Adduct of imidazole/piperazine/epi from Example 6, 100% oxidized

To 237 g of the product from Example 6 above (equivalent to 1,022 mole of oxidizable nitrogen atoms) 80.7 g (1.12 mole) of a 47.2% solution of H2O2 water is added over a period of 5 hours at 40°C. After that, the mixture is heated to 50-60°C until the theoretical amount of

H202 has been consumed Unreacted H202 is destroyed by using Pt/C and the solution is then filtered

The reaction product is characterized as follows: water content' 58.6% pH 2.86 chloride content: 3.694 mmole/g

Mn (GPC) 340

Mw (GPC) 940

Mn/Mw: 2.8+/-0.1

EXAMPLE 8

Synthesis of hydrophobically modified CMC Materials

The carboxylation of cellulose to produce CMC is a procedure that is well known to those skilled in the art. One method of producing the modified CMC mateπals of this invention, is to add dunng the CMC making process the material, or matenals, to be substituted. An example of such as procedure is given below. This same procedure can be utilized with the other substituent mateπals descnbed herein by replacing the hexylchloπde with the substituent material, or mateπals, of interest, for example, cetylchlonde. The amount of mateπal that should be added to the CMC making process to achieve the desired degree of substitution will be easily calculated by those skilled in the art in light of the following Examples.

EXAMPLE 9 Synthesis of Hexylether of CMC This example illustrates the preparation of a hydrophobically modified carboxymethyl cellulose and is representative of preparation of all of the cellulose ether derivatives of this invention.

Cellulose (20 g), sodium hydroxide (10 g), water (30 g), and ethanol (150 g) are charged into a 500 ml glass reactor. The resulting alkali cellulose is stirred 45 minutes at 25°C. Then monochloroacetic acid (15 g) and hexylchoride (1 g) are added and the temperature raised over time to 95°C and held at 95°C for 150 minutes. The reaction is cooled to 70°C, and then cooled to 25°C Neutralization is accomplished by the addition of a sufficient amount of nitric acid/acetic acid to achieve a slurry pH of between 8 and 9. The slurry is filtered to obtain a hexylether of CMC.

EXAMPLE 10 Cellulosic Polymers Used in Test Detergent Compositions

Representative modified cellulosic polymers for use in the liquid and granular detergent compositions described below are charactenzed in Tables 10 A and 10 B. The General Polymer Parameters are common to all of the polymers, while the specific chemical structure of the mateπals tested are listed under the Specific Polymer Parameters.

Table 10 A General Polymer Parameters

Molecular Parameters Description

Polvmer Backbone Carboxymethylcellulose

Degree of Carboxymethylation DS_Rc = 0.3 - 2 0; preferred DS_RC = 0.5 - 0.70.

Distribution of Even and random distπbution of carboxylmethyls Carboxvmethvls along the backbone

Molecular Weight Mw: 5,000 - 2,000000. Preferred: medium (approx 250,000 g/mol)

Type of Modification Ether modification (m addition to carboxymethylation). Mixed cellulose ether

Level of Modification DS_RH = about 0.001 to about 0.1 Table 10 B Table Specific Polymer Parameters

ID Polymer Type of Types of Chemistry Modification***

*A Hexyl CMC Hexyl ether Chlorohexane added to CMC making process

*B Decyl CMC Decyl ether Chlorodecane added to CMC making process

** C12-C13 alkoxy-2 C12-C13 alkoxy-2 C12-C13 alkyl glycidyl ether hydroxypropyl CMC hydroxypropyl added to CMC making ether process

*D Hexadecyl CMC Hexadecyl ether Chlorohexadecane added to CMC making process

*E Chloride salt of 3- chloride salt of 3- 2,3-epoxypropyltπmethyl tπmethylammonιo-2- tnmethylammonio- ammonium chloπde added to hydroxypropyl ether 2-hydroxypropyl the CMC making process of CMC ether

*p [-(C(O)- Cetyl Ketene Dimer added to

CH(C16H33)- CMC making process.

C(0)CH2(C16H33) ] ester of CMC or 1 ,3- dιoxo-2- hexadecyloctadecyl ester of CMC

CMC = Carboxymethylcellulose

* Manufactured by Metsa Specialty Chemicals

** Manufactured by Akzo

***DS_RH for these materials was in the range of from about 0.001 to about 0.1

EXAMPLE 11 The following are idealized chemical structures for certain cyclic amme based polymers, oligomers or copolymers of this invention. Side reactions expected to occur dunng the condensation are not shown.

Table 11

Example Matenal

Adduct of Imidazole-epichlorohydπn

(Ratio of ιmιdazole:epιchlorohydπn 1:1, Polymer from Example

(Idealized Structure) Adduct of imidazole, piperazme and epichlorohydnn (Ratio- 1.0: 1.0:2.0) quat with 0.22 moles of chloroacetate

Adduct of imidazole, piperazme and epichlorohydnn (Ratio-

Adduct of imidazole, piperazme andepichlorohydnn (Ratio-

Adduct of imidazole and epichlorohdrin, (ratio 1.75: 1) oxidized

Adduct of piperazme and epichlorohydnn (ratio 1 : 1) 100% oxidized

Adduct of piperazme and epichlorohydπn (ratio 1 : 1) 50% oxidized

Adduct of piperazme, moφho ne and epichlorohydπn (ratio 1 :0.2:1) 100% oxidized

Adduct of piperazme, moφholme and epichlorohydπn (ratio 1 :0.2: 1)25% methyl quat and oxidized

Adduct of imidazole, piperazme and epichlorohydnn (ratio 1 :3 ;4) 100%, oxidized

Adduct of imidazole, dimethylaminopropylamine and epichlorohydnn (ratio 1.02:0.34: 1.0) oxidized

EXAMPLE 12 Granular Detergent Test Composition Preparation

Several heavy duty granular detergent compositions are prepared containing a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. These granular detergent compositions all have the following basic formula:

Table 12

Component Wt. %

Ci Linear alkyl benzene sulfonate 9.31

Ci4.ι ς alkyl ether (0.35 EO) sulfate 12.74

Zeolite Builder 27.79

Sodium Carbonate 27.31

PEG 4000 1.60

Dispersant 2.26

Ci 2.1 Alcohol Ethoxylate (9 EO) 1.5

Sodium Perborate 1.03

Soil Release Polvmer 0.41

Enzvmes 0.59

Cyclic Amine Based Polymers or Oligoi mers 3.0

Hydrophobically Modified Cellulosic Based 1.0 Polymers or Oligomers

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

100%

EXAMPLE 13 Liquid Detergent Test Composition Preparation

Several heavy duty liquid detergent compositions are prepared a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. These liquid detergent compositions all have the following basic formula:

Table 13

Component Wt. %

Ci 2.ι ς alkyl ether (2.5) sulfate 38

C1 glucose amide 6.86

Citric Acid 4.75

Ci -1 Fatty Acid 2.00

Enzvmes 1.02

MEA 1.0

Propanediol 0.36

Borax 6.58

Dispersant 1.48

Na Toluene Sulfonate 6.25 Cyclic Amine Based Polymers or Oligomers 1.0

Hydrophobically Modified Cellulosic Based 0.1 Polymers or Oligomers

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

100%

EXAMPLE 14 Granular Detergent Test Composition Preparation

Several granular detergent compositions are prepared containing a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers. Such granular detergent compositions all have the following basic formula:

Table 14

Example Comparative

Component Wt. % Wt%

Na Cj 2 Linear alkyl benzene sulfonate 9.40 9.40

Na Ci _ι ς alkyl sulfonate 1 1.26 1 1.26

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 2.1 T, alkyl ethoxylate (E9) 1.5 1.5

Sodium Perborate 1.03 1.03

Cyclic Amine Based Polymers or 0.8 0 Oligomers

Hydrophobically Modified Cellulosic 0.3 0 Based Polymers or Oligomers

Other Adjunct ingredients Balance Balance

100% 100%

EXAMPLE 15

A detergent agglomerate which may be used as a particulate component in a detergent composition is prepared according to the following formulas and ranges. The granule may be manufactured by agglomeration methods known to those skilled in the art; some of which are described in the present application.

1 : Dispersant is Na Polyacrylate 4500, Polyethylene Glycol or a mixture of both.

Claims

WHAT IS CLAIMED IS :

1. A detergent composition charactenzed by: a) from 1% to 80% by weight of surfactants selected from the group consisting of noniomc, amonic, cationic, amphotenc zwitterionic surfactants and mixtures thereof; and b) at least 0.01%, preferably at least 0.1%, most preferably at least 0.5% and no more than 50%, preferably no more than 25.0%, most preferably no more than 5.0%, by weight, of a mixture of cyclic amme based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.

2. The detergent composition of claim 1 , wherein the hydrophobically modified cellulosic based polymers or oligomers are of the general foimula:

wherein each R is selected from the group consisting of R2, R and

O - each Rc _is →^y-C-OZ wherein each Z is independently selected from the group consisting of M, R2, Re, and R_H; each R_H is independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2 -hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2- hydroxyalkyl, ^4)3 N-alkyl, ^4)3 N-2 -hydroxyalkyl, C₍$-Ci 2 aryloxy-2 -hydroxyalkyl,

O R₅ O R₅ O R₅ O

II I II I II I II

— C CH C CH₂ — C CH₂ CH C-OM _and

O R₅ O

I I I II

— C — CH— CH₂— C-OM. each R4 is independently selected from the group consisting of H, C1-C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, ammoalkyl, alkylaminoalkyl, dialkylammoalkyl, pipeπdinoalkyl, moφhohnoalkyl, cycloalkylaminoalkyl and hydroxyalkyl; each R5 is independently selected from the group consisting of H, C\ -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-C20 arylalkyl, substituted alkyl, hydroxyalkyl,

(R₄)₂N-alkyl, and (1*4)3 N-alkyl; wherein:

M is a suitable cation selected from the group consisting of Na, K, l/2Ca, and l/2Mg;

provided that: the Degree of Substitution for group R_H is between 0.0005 and 0.1, more preferably between

0 005 and 0.05, and most preferably between 0.01 and 0.05; the Degree of Substitution for group Re wherein Z is H or M is between 0.2 and 2.0, more preferably between 0.3 and 1.0, and most preferably between 0.4 and 0.7; if any R_H bears a positive charge, it is balanced by a suitable anion; and two R4's on the same nitrogen can together form a πng structure selected from the group consisting of pipeπdine and moφhohne.

3 The detergent composition of any of claims 1-2, wherein the cyclic amine based polymers, oligomers or copolymers are of the general formula:

wherem; each T is independently selected from the group consisting of H, Ci -Ci 2 alkyl, substituted alkyl,

C7-C 12 alkylaryl,

-(CH₂)hCOOM, -(CH₂)hS0₃M, CH₂CH(OH)S0₃M, -(CH₂)hOSO₃M,

-wherein W is characterized by at least one cyclic constituent selected from the group consisting of

in addition to the at least one cyclic constituent, W may also compπse an aliphatic or substituted aliphatic moiety of the general structure;

-each B is independently C1-C12 alkylene, C\-C\2 substituted alkylene, C3-C12 alkenylene, Cg- Cj2 dialkylarylene, Cg-Ci2 dialkylarylenediyl, and -(R5θ)_nR5- ;

-each D is independently C2-C.5 alkylene; -each Q is independently selected from the group consisting of hydroxy, C j-Cjg alkoxy, C2-C^ hydroxyalkoxy, ammo, C_j-C^ g alkylamino, dialkylammo, tnalkylammo groups, heterocyclic monoammo groups and diamino groups; -each R\ is independently selected from the group consisting of H, Ci -Cg alkyl and Cj-Cg hydroxyalkyl; -each R2 is independently selected from the group consisting of C\ -Cj2 alkylene, C]-Ci2 alkenylene, -CH -CH(ORι )-CH2, Cg-C₁₂ alkarylene, C -C₁₂ dihydroxyalkylene, poly(C₂-C₄ alkyleneoxy)alkylene, H₂CH(OH)CH₂OR₂OCH2CH(OH)CH2-, and C3- C 12 hydrocarbyl moieties; provided that when R₂ is a C3-C12 hydrocarbyl moiety the hydrocarbyl moiety can comprise from about 2 to about 4 branching moieties of the general structure:

OH -(-OR5 -) O— CH₂-CH-CH₂T-[w— R₂3~ W- T

Λ

-each R3 is independently selected from the group consisting of H, O, R2, C 1-C20 hydroxyalkyl, Cj -C20 alkyl, substituted alkyl, C6-C 1 j aryl, substituted aryl, C7-C1 \ alkylaryl, C1-C20 aminoalkyl,

-(CH₂)hCOOM, -(CH₂) S0₃M, CH₂CH(OH)S0₃M, -(CH₂)hOS0₃M,

-each R4 is independently selected from the group consisting of H, C1-C22 alkyl, C1-C22 hydroxyalkyl, aryl and C7-C22 alkylaryl;

-each R5 is independently selected from the group consisting of C2-C alkylene, C2-Cg alkyl substituted alkylene; and

A is a compatible monovalent or di or polyvalent anion;

M is a compatible cation; b = number necessary to balance the charge; each x is independently from 3 to 1000; each c is independently 0 or 1 , each h is independently from 1 to 8; each q is independently from 0 to 6; each n is independently from 1 to 20; each r is independently from 0 to 20; and each t is independently from 0 to 1.

4. The detergent composition of any of claims 1-3, wherein each K\ is H and at least one W is selected from the group consisting of:

5. The detergent composition of any of claims 1-4, wherein each R_j is H and at least one W is selected from the group consisting of:

6. The detergent composition of any of claims 1-5, wherein each R\ is H and at least one W is selected from the group consisting of:

7. The detergent composition of any of claims 1-6, wherein each R_H is independently selected from the group consisting of C5 -C20 alkyl, C5-C7 cycloalkyl, C7-C20 alkylaryl, C7-

C20 arylalkyl, substituted alkyl, hydroxyalkyl, C1-C20 alkoxy-2-hydroxyalkyl, C7-C20 alkylaryloxy-2-hydroxyalkyl, (R4)2N-alkyl, (R4)2N-2-hydroxyalkyl, (R4)3 N-alkyl, ^4)3 N-2- hydroxyalkyl, and C -C12 aryloxy-2 -hydroxyalkyl

8 A laundry additive composition characterized by: a) from 1% to 80% by weight of water; and b) from 0.01 % to 5.0%, preferably from 0.1% to 4.0%, by weight of a mixture of cyclic amine based polymers, oligomers or copolymers and hydrophobically modified cellulosic based polymers or oligomers.

9. The detergent composition of any of claims 1-8, wherein the composition further is characterized by an inorganic peroxygen bleaching compound, which is preferably selected from the group consisting of alkali metal salts of perborate, percarbonate and mixtures thereof, and a bleach activator, which is preferably nonanoyloxybenzene sulfonate.

10. The detergent composition of any of claims 1 -9, wherein the composition further is charactenzed by a cellulase enzyme.