The present invention relates to laundry detergent compositions which provide enhanced hydrophilic soil, inter alia, clay, removal benefits. The laundry detergent compositions of the present invention combine polyamines and a surfactant system which comprises mid-chain branched surfactants inter alia mid-chain branched alkyl sulfates. The laundry detergent compositions of the present invention may take any form, inter alia, solid, including granular, powder, tablet, bar, or liquid, including gels, paste, thixotropic liquids. The present invention further relates to methods for cleaning fabric having heavy clay soil deposits.
Fabric, especially clothing, can become soiled with a variety of foreign substances ranging from hydrophobic stains (grease, oil) to hydrophilic stains (clay). The level of cleaning which is necessary to remove said foreign substances depends to a large degree upon the amount of stain present and the degree to which the foreign substance has contacted the fabric fibers. Grass stains usually involve direct abrasive contact with vegetative matter thereby producing highly penetrating stains. Clay soil stains, although in some instances contacting the fabric fibers with less force, nevertheless provide a different type of soil removal problem due to the high degree of charge associated with the clay itself. This high surface charge density may act to repel some laundry adjunct ingredients, inter alia, clay dispersants, thereby resisting any appreciable peptization and dispersal of the clay into the laundry liquor.
A surfactant per se is not all that is necessary to remove unwanted clay soils and stains. In fact, most surfactants by themselves in water are surprisingly poor at removing clay soils from fabric not all surfactants work equally well on all types of stains. In addition to surfactants, polyamine-based hydrophilic soil dispersants are added to laundry detergent compositions to xe2x80x9ccarry awayxe2x80x9d clay soils from the fabric surface and to stabilize the removed particles in solution sufficiently to minimize the possibility that the clay soil will be re-deposited upon the fabric. However, unless the clay can be initially removed from the soiled fabric, especially in the case of hydrophilic fibers, inter alia, cotton, there will be nothing in solution for the dispersants to bind to and keep suspended.
There is a long felt need in the art for laundry detergent compositions which can effectively break up and remove embedded clay and other hydrophilic soils from fabric. In addition, as the concentration of hydrophilic soil increases in the laundry liquor, there is a need for a surfactant system which will be able to handle this increased soil load. Also there is a long felt need for a clay soil active adjunct ingredient which can be optimized to fit the particular laundry detergent embodiment, inter alia, granular, liquid, and which can be therefore tailored to match the surfactant system. There has further been a long felt need for a method for cleaning hydrophilic soils from fabric wherein the hydrophilic soils are effectively peptized, dispersed, and suspended in the laundry liquor.
The present invention meets the aforementioned needs in that it has been surprisingly discovered that certain polyamine-based agents, also referred to herein as xe2x80x9cpolyaminesxe2x80x9d, in combination with a surfactant system comprising one or more mid-chain branched surfactants provides enhanced removal of clay and other hydrophilic soils from fabric.
The first aspect of the present invention relates to a laundry detergent composition comprising:
a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 2% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of a polyamine, said polyamine selected from the group consisting of:
i) polyamines comprising two or more backbone nitrogens;
ii) polyamines comprising one or more cationic backbone nitrogens;
iii) polyamines comprising one or more alkoxylated backbone nitrogens;
iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and
v) mixtures thereof;
b) from about 0.01%, preferably from about 0.1% more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% by weight, of a surfactant system comprising:
i) from 0% to 80% by weight, of a mid-chain branched alkyl sulfate surfactant selected from the group consisting of surfactants having the formula: 
xe2x80x83and mixtures thereof; wherein R, R1, and R2 are each independently hydrogen, C1-C3 alkyl, and mixtures thereof, provided the total number of carbon atoms in said surfactant is from 14 to 20 and at least one of R, R1, and R2 is not hydrogen; 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 ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; the average value of the index m is at least about 0.01;
ii) from 0% to 80% by weight, of a mid-chain branched aryl sulfonate surfactant having the formula: 
xe2x80x83wherein A is a mid-chain branched alkyl unit having the formula: 
xe2x80x83wherein R and R1 are each independently hydrogen, C1-C3 alkyl, and mixtures thereof, provided the total number of carbon atoms in said alkyl unit is from 6 to 18 and at least one of R and R1 is not hydrogen; x is an integer from 0 to 13; y is an integer from 0 to 13; z is 0 or 1; R2 is hydrogen, C1-C3 alkyl, and mixtures thereof; Mxe2x80x2 is a water soluble cation with sufficient charge to provide neutrality;
iii) optionally from 0.01% by weight, of a surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, ampholytic surfactants, and mixtures thereof; and
c) the balance carriers and adjunct ingredients.
The present invention also relates to hydrophilic soil cleaning systems which comprise polyamines which can be tailored to the specific surfactant system or laundry detergent form, i.e., liquid, granular.
The present invention further relates to laundry detergent compositions which are effective in removing clay-like soils under circumstances of high soil loading or high water hardness.
The present invention also relates to a method for removing hydrophilic stains from fabric by contacting fabric in need of cleaning with a composition according to the present invention.
These and other objects, features and advantages will become apparent to those of ordinary skill in the art from a reading of the following detailed description and the appended claims. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All temperatures are in degrees Celsius (xc2x0 C.) unless otherwise specified. All documents cited are in relevant part, incorporated herein by reference.
The present invention relates to the surprising discovery that the combination of a polyamine and a surfactant system which comprises at least one mid-chain branched surfactant provides enhanced benefits for removal of clay soil from fabric especially clothing. It has been surprisingly discovered that the formulator, by selecting the molecular weight of the parent backbone, relative degree of quaternization, relative amount of N-oxide formation of the polyamine backbone, the type and relative degree of units which substitute the polyamine backbone, inter alia, cationic, anionic, and the nature of the amine backbone itself, inter alia, polyhexyleneimine, the formulator is able to form a polymer which can be tailored for optimization depending upon the desired execution. For example, the formulator may opt to use one type of polymer for a liquid embodiment targeted for use in a high soil loading context and another polymer for use in a granular detergent used for washing fabric in cold water.
Without wishing to be bound by theory it is believed the polyamines of the present invention interact with the mid-chain branched surfactants in a manner which makes the adsorption in the clay more efficacious by changing the anionic nature of the surface. It is believed this system is more effective in peptizing or breaking up the clay aggregates on the surface, thus allowing the inherent agitation associated with the laundry process (for example, the agitation provided by an automatic washing machine) act to break the surface-modified particles loose from the fabric surface and disperse them into solution. The clay and other hydrophilic particles which are removed by the compositions of the present invention are those types of stains or particles which are not well removed by normal surfactant/dispersant systems.
Although other surfactants, inter alia, non mid-chain branched sulphonates and sulphates, nonionic surfactants, are highly desirable components of the herein described granular laundry detergent compositions, their absence or presence does not affect the ability of the polyamine/mid-chain branched surfactant system to enhance clay soil removal.
The laundry detergent compositions of the present invention may take any form, for example, solid, including granular, powder, tablet, or liquid, including gels, paste, thixotropic liquids, etc.
The following is a detailed description of the required elements of the present invention.
The polyamines of the present invention comprise from 0.01%, preferably from about 0.1%, more preferably from 1%, most preferably from 2% to about 20%, preferably to about 10%, more preferably to about 5% by weight, of the compositions of the present invention. Suitable polyamines for use with mid-chain branched surfactants are polyamines selected from the group consisting of:
i) polyamines comprising two or more backbone nitrogens;
ii) polyamines comprising one or more cationic backbone nitrogens;
iii) polyamines comprising one or more alkoxylated backbone nitrogens;
iv) polyamines comprising one or more cationic backbone nitrogens and one or more alkoxylated backbone nitrogens; and
v) mixtures thereof.
The polymers of the present invention are suitable for use in compositions which may take any form, for example, solids (i.e., powders, granules, extrudates, tablets), gels, thixotropic liquids, and pourable liquids (i.e., dispersions, isotropic solutions).
The polymers of the present invention are comprised of a polyamine backbone wherein the backbone units which connect the amino units can be modified by the formulator to achieve varying levels of product enhancement, inter alia, boosting of clay soil removal by surfactants, greater effectiveness in high soil loading usage. In addition to modification of the backbone compositions, the formulator may preferably substitute one or more of the backbone amino unit hydrogens by other units, inter alia, alkyleneoxy units having a terminal anionic moiety. In addition, the nitrogens of the backbone may be oxidized to the N-oxide. Preferably at least two of the nitrogens of the polyamine backbones are quaternized.
For the purposes of the present invention xe2x80x9ccationic unitsxe2x80x9d are defined as xe2x80x9cunits which are capable of having a positive chargexe2x80x9d. For the purposes of the polyamines of the present invention the cationic units are the quaternary ammonium nitrogens of the polyamine backbones or quaternary ammonium units which comprise the units which substitute the polyamine backbone. For the purposes of the present invention xe2x80x9canionic unitsxe2x80x9d are defined as xe2x80x9cunits which are capable of having a negative chargexe2x80x9d. For the purposes of the polyamines of the present invention the anionic units are xe2x80x9cunits which alone, or as a part of another unit, substitute for hydrogens along the polyamine backbonexe2x80x9d a non-limiting example of which is a xe2x80x94(CH2CH2O)20SO3Na which is capable of replacing a backbone hydrogen on a nitrogen or oxygen atom.
One type of preferred polyamine according to the present invention are polyalkyleneimines having the formula:
[Jxe2x80x94R]nxe2x80x94J
wherein the [Jxe2x80x94R] units represent the amino units which comprise the main backbone and any branching chains. Preferably the polyamines prior to modification, inter alia, quaternization, substitution of a backbone unit hydrogen with an alkyleneoxy unit, have backbones which comprise from 3 to about 100 amino units. The index n which describes the number of backbone units present is further described herein below.
J units are the backbone amino units, said units are selected from the group consisting of:
i) primary amino units having the formula:
(R1)2N;
ii) secondary amino units having the formula:
xe2x80x94R1N;
iii) tertiary amino units having the formula: 
iv) primary quaternary amino units having the formula: 
v) secondary quaternary amino units having the formula: 
vi) tertiary quaternary amino units having the formula: 
vii) primary N-oxide amino units having the formula: 
viii) secondary N-oxide amino units having the formula: 
ix) tertiary N-oxide amino units having the formula: 
x) and mixtures thereof.
B units which have the formula:
[Jxe2x80x94R]xe2x80x94
represent a continuation of the polyamine backbone by branching. The number of B units present, as well as, any further amino units which comprise the branches are reflected in the total value of the index n.
For the purpose of the present invention the term xe2x80x9csubstitutedxe2x80x9d is defined herein as xe2x80x9ccompatible moieties which replace a hydrogen atomxe2x80x9d. Non-limiting examples of substituents are hydroxy; nitrilo; oximino; halogen; nitro; carboxyl, inter alia, xe2x80x94CHO, CO2H, xe2x80x94CO2Rxe2x80x2, xe2x80x94CONH2, xe2x80x94CONHRxe2x80x2; xe2x80x94CONRxe2x80x22, wherein Rxe2x80x2 is C1-C12 linear or branched alkyl; amino; C1-C12 mono and di-alkylamino; xe2x80x94OSO3M; xe2x80x94SO3M; xe2x80x94OPO3M; xe2x80x94ORxe2x80x3 wherein Rxe2x80x3 is C1-C12 linear or branched alkyl; and mixtures thereof.
The backbone amino units of the polymers are connected by one or more R units, said R units are selected from the group consisting of:
i) C2-C12 linear alkylene, C3-C12 branched alkylene, C6-C16 substituted or unsubstituted arylene, C7-C40 substituted or unsubstituted alkylenearylene having the formula: 
xe2x80x83or mixtures thereof. When R is linear alkylene R is preferably C2-C6 alkylene. However, preferred embodiments of the present invention combine R units which are linear alkylene with one or more of the other R units listed herein below. When R is branched alkylene R is preferably 1,2-propylene, 1,2-butylene, 1,2-hexylene, and mixtures thereof. When R is substituted or unsubstituted phenylene, R is preferably 1,4-phenylene. When two adjacent nitrogens of the polyamine backbone are N-oxides, preferably the alkylene backbone unit which separates said units are C4 units or greater. When R units comprise only linear or branched alkylene units, a preferred embodiment of the present invention relates to mixed linear and branched units, for example, units having backbones with the repeating formula: 
xe2x80x83wherein the hydrogen atoms bonded to the backbone nitrogens may be substituted by any of the herein below described units. The formulator may also wish to provide lower molecular weight highly branched backbones by incorporating units having, for example, branched units having the formula: 
xe2x80x83wherein said backbone branching is not provided by a secondary amino unit, secondary quaternary amino unit, or secondary N-oxide J unit as described herein above but instead is branched in the R backbone unit itself.
ii) alkyleneoxyalkylene units having the formula:
xe2x80x94(R2O)w(R3)xe2x80x94
xe2x80x83wherein R2 is selected from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof; R3 is C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof; the index w is from 0 to about 25. R2 and R3 units may also comprise other backbone units. When comprising alkyleneoxyalkylene units R2 and R3 units are preferably mixtures of ethylene, propylene and butylene and the index w is from 1, preferably from about 2 to about 10, preferably to about 6. An example of a backbone comprising a mixture of R2 units has the formula: 
iii) hydroxyalkylene units having the formula: 
xe2x80x83wherein R4 is hydrogen, C1-C6 alkyl, xe2x80x94(CH2)u(R2O)t(CH2)uY, and mixtures thereof. When R units comprise hydroxyalkylene units, R4 is preferably hydrogen or xe2x80x94CH2)u(R2O)t(CH2)uY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is preferably hydrogen or an anionic unit, more preferably xe2x80x94SO3M. The indices x, y, and z are each independently from 0 to 20, preferably the indices are each at least equal to 1 and R4 is hydrogen (2-hydroxypropylene unit) or (R2O)tY, or for polyhydroxy units y is preferably 2 or 3. A preferred hydroxyalkylene unit is the 2-hydroxypropylene unit which can, for example, be suitably formed from glycidyl ether forming reagents, inter alia, epihalohydrin. An example of an R unit which comprises the index y greater than 1 has the formula: 
iv) hydroxyalkylene/oxyalkylene units having the formula: 
xe2x80x83wherein R2, R4, and the indices w, x, y, and z are the same as defined herein above. X is oxygen or the amino unit xe2x80x94NR4xe2x80x94, the index r is 0 or 1. The indices j and k are each independently from 1 to 20. When alkyleneoxy units are absent the index w is 0. Non-limiting examples of preferred hydroxyalkylene/oxyalkylene units have the formula: 
xe2x80x83wherein R2, R3, X, r, and w are the same as defined herein above. Non-limiting examples of preferred carboxyalkyleneoxy units include: 
xe2x80x83wherein R4 is hydrogen, C1-C6 alkyl, xe2x80x94(CH2)u(R2O)t(CH2)uY, and mixtures thereof. When R units comprise backbone branching units, R4 is preferably hydrogen or xe2x80x94(CH2)u(R2O)txe2x80x94(CH2)uY wherein the index t is greater than 0, preferably from 10 to 30; the index u is from 0 to 6; and Y is hydrogen, C1-C4 linear alkyl, xe2x80x94N(R1)2, an anionic unit, and mixtures thereof; preferably Y is hydrogen, or xe2x80x94N(R1)2. A preferred embodiment of backbone branching units comprises R4 equal to xe2x80x94(R2O)tH. The indices x, y, and z are each independently from 0 to 20. vii) The formulator may suitably combine any of the above described R units to make a polyamine having a greater or lesser degree of hydrophilic character.
R1 units are the units which are attached to the backbone nitrogens. R1 units are selected from the group consisting of:
i) hydrogen; which is the unit typically present prior to any backbone modification.
ii) C1-C22 alkyl, preferably C1-C4 alkyl, more preferably methyl or ethyl, most preferably methyl. A preferred embodiment of the present invention in the instance wherein R1 units are attached to quaternary units (iv) or (v), R1 is the same unit as quaternizing unit Q. For example a J unit having the formula: 
iii) C7-C22 arylenealkyl having the general formula: 
xe2x80x83wherein R5 is C1C16 linear or branched alkyl, nxe2x80x2 is 0 or 1.
iv) C7-C22 alkylenearyl having the general formula: 
xe2x80x83wherein R6 is hydrogen, C1-C15 alkyl, and mixtures thereof; a preferred R1 unit which is an alkylenearyl unit is benzyl; mxe2x80x2 is from 1 to 16.
v) xe2x80x94[CH2CH(OR4)CH2O]s(R2O)tY; wherein R2 and R4 are the same as defined herein above, preferably when R1 units comprise R2 units, R2 is preferably ethylene. The value of the index s is from 0 to 5. For the purposes of the present invention the index t is expressed as an average value, said average value from about 0.5 to about 100. The formulator may lightly alkyleneoxylate the backbone nitrogens in a manner wherein not every nitrogen atom comprises an R1 unit which is an alkyleneoxy unit thereby rendering the value of the index t less than 1. For one embodiment herein the average value of the index t is from about 0.5 to 30, wherein for others the average value of the index t is from about 10 to about 30, for another embodiment from about 5 to about 15. The value of the index t allows the formulator to adjust the amount of alkyleneoxy units which are present and, therefore, may change due to the simple addition of a specific adjunct ingredient to the formulation.
vi) Anionic units as described herein below.
The formulator may suitably combine one or more of the above described R1 units when substituting the backbone of the polymers of the present invention.
Q is a quaternizing unit selected from the group consisting of C1-C4 linear alkyl, benzyl, and mixtures thereof, preferably methyl. As described herein above, preferably Q is the same as R1 when R1 comprises an alkyl unit. For each backbone N+ unit (quaternary nitrogen) there will be an anion to provide charge neutrality. The anionic groups of the present invention include both units which are covalently attached to the polymer, as well as, external anions which are present to achieve charge neutrality. Non-limiting examples of anions suitable for use include halogen, inter alia, chloride; methyl sulfate; hydrogen sulfate, and sulfate. The formulator will recognize by the herein described examples that the anion will typically be a unit which is part of the quaternizing reagent, inter alia, methyl chloride, dimethyl sulfate, benzyl bromide.
X is oxygen, xe2x80x94NR4xe2x80x94, and mixtures thereof, preferably oxygen.
Y is hydrogen, C1-C4 linear alkyl, xe2x80x94N(R1)2, or an anionic unit. Y is xe2x80x94N(R1)2 preferably when Y is part of an R unit which is a backbone branching unit. Anionic units are defined herein as xe2x80x9cunits or moieties which are capable of having a negative chargexe2x80x9d. For example, a carboxylic acid unit, xe2x80x94CO2H, is neutral, however upon de-protonation the unit becomes an anionic unit, xe2x80x94CO2xe2x88x92, the unit is therefore, xe2x80x9ccapable of having a negative charge. Non-limiting examples of anionic Y units include xe2x80x94(CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94(CH2)fPO3M, xe2x80x94(CH2)tOPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH2CO2M, xe2x80x94CH2CH(OZ)CH2O(R1O)tZ, xe2x80x94(CH2)tCHxe2x80x94[O(R2O)tZ]CHfO(R2O)tZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include xe2x80x94(CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94(CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality.
Y units may also be oligomeric or polymeric, for example, the anionic Y unit having the formula: 
may be oligomerized or polymerized to form units having the general formula: 
wherein the index n represents a number greater than 1.
Further non-limiting examples of Y units which can be suitably oligomerized or polymerized include: 
Certain embodiments of the present invention may require polyamines which comprise one or more anionic units which are substituted on the polyamine backbone. In general, for granular laundry detergent compositions which require a high degree of anionic charge, especially when the polyamine backbones are highly quaternized, preferably greater than about 40%, more preferably greater than 50%, yet more preferably more than 75%, most preferably greater than 90% of said Y units are xe2x80x94SO3M comprising units. For liquid laundry detergent compositions preferably less than about 90%, more preferably less than 75%, yet more preferably less than 50%, most preferably less than 40% of said Y units comprise an anionic moiety, inter alia, xe2x80x94SO3M comprising units. The number of Y units which comprise an anionic unit will vary from embodiment to embodiment. M is hydrogen, a water soluble cation, and mixtures thereof; the index f is from 0 to 6.
The index n represents the number of backbone units wherein the number of amino units in the backbone is equal to n+1. For the purposes of the present invention the index n is from 2 to about 1000. Branching units B are included in the total number of backbone units. For example, a backbone having the formula: 
has an index n equal to 4. The following is a non-limiting example of a polyamine backbone which is fully quaternized. 
One class of polyamines which are suitable for use with the mid-chain branched surfactants of the present invention are the polymers comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, xe2x80x94(CH2CH2O)20H, having the formula: 
Another example of this type of polyamine is the polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, xe2x80x94(CH2CH2O)7H, having the formula 
However, the formulator may desire a polyamine which will not be adulterated by the presence of bleach. One means available to mitigate against the effects of bleaching agents is to form N-oxides of the backbone nitrogens. The example below illustrates a polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, xe2x80x94(CH2CH2O)7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides having the formula 
The presence of charged backbones, in the form of quaternary ammonium units, in many instances will enhance the performance of mid-chain branched surfactant comprising compositions. Illustrated below is a polymer which comprises a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized. The substituents are polyoxyalkyleneoxy units, xe2x80x94(CH2CH2O)7H, or methyl groups. The modified, cationicly charged backbone polymer has the formula: 
The following is a non-limiting example of a polyamine according to the present invention. 
A preferred polyamine polymer according to the present invention, is the bleach stable polyamine which comprises no N-oxide units, having the formula: 
wherein each R unit is an ethylene or propylene unit; R1 units are xe2x80x94[CH2CH(OR4)CH2O]sxe2x80x94(R2O)tY units; wherein R2 is ethylene, 1,2-propylene, and mixtures thereof; Y is hydrogen, and the value of the index s is 0. Preferably the values of the indices wxe2x80x2, xxe2x80x2, and yxe2x80x2 are such that the polyamine has a backbone molecular weight prior to modification of from 600 daltons to about 3000 daltons. Preferred backbone molecular weights are 600 daltons, 1200 daltons, 1800 daltons, and 3000 daltons.
An example of a preferred polyalkylene amine according to the present invention is a polyamine wherein each R is ethylene and the backbone has a molecular weight of about 3000 daltons and each hydrogen of the backbone amino units are substituted by a polyalkylene R1 unit wherein either one or three 1,2-propyleneoxy units are directly attached to the polyamine chain followed by sufficient ethyleneoxy units to provide an R1 units which has an average of 30 alkyleneoxy units present.
Preferred polymers of the present invention have the formula: 
wherein R units have the formula xe2x80x94(R2O)wR3xe2x80x94 wherein R2 and R3 are each independently selected from the group consisting of C2-C8 linear alkylene, C3-C8 branched alkylene, phenylene, substituted phenylene, and mixtures thereof. The R2 units of the formula above, which comprise xe2x80x94(R2O)tY units, are each ethylene; Y is hydrogen, xe2x80x94SO3M, and mixtures thereof, the index t is from 15 to 25; the index m is from 0 to 20, preferably from 0 to 10, more preferably from 0 to 4, yet more preferably from 0 to 3, most preferably from 0 to 2; the index w is from 1, preferably from about 2 to about 10, preferably to about 6.
An example of a preferred R unit having the formula xe2x80x94(R2O)wR3xe2x80x94 is the backbone:
xe2x80x94CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2xe2x80x94
wherein R2 is propylene and butylene, R3 is propylene, w is equal to 2.
Non-limiting examples of backbones according to the present invention include 1,9-diamino-3,7-dioxanonane; 1,10-diamino-3,8-dioxadecane; 1,12-diamino-3,10-dioxadodecane; 1,14-diamino-3,12-dioxatetradecane. However, backbones which comprise more than two nitrogens may comprise one or more repeating units having the formula:
H2Nxe2x80x94[Rxe2x80x94NH]xe2x80x94
for example a unit having the formula:
H2Nxe2x80x94[CH2CH2OCH2CH2NH]xe2x80x94
is described herein as 1,5-diamino-3-oxapentane. A backbone which comprises two 1,5-diamino-3-oxapentane units has the formula:
H2NCH2CH2OCH2CH2NHCH2CH2OCH2CH2NH2.
Further suitable repeating units include 1,8-diamino-3,6-diaxaoctane; 1,11-diamino-3,6,9-trioxaundecane; 1,5-diamino-1,4-dimethyl-3-oxaheptane; 1,8-diamino-1,4,7-trimethyl-3,6-dioxaoctane; 1,9-diamino-5-oxanonane; 1,14-diamino-5,10-dioxatetradecane.
The present invention affords the formulator with the ability to optimize the polymer for a particular use or embodiment. Not wishing to be limited by theory, it is believed that the backbone quaternization (positive charge carriers) interact with the hydrophilic soils, inter alia, clay, and the anionic capping units of the R1 units ameliorate the ability of surfactant molecules to interact, and therefore occupy, the cationic sites of the polymers. It is surprisingly found that the amount of anionic moieties needed vary from embodiment to embodiment. Heavy Duty Granular (HDG) compositions which comprise a high amount of linear alkylbenzene sulfonate (LAS) surfactant require a greater number of anionic units per se to be present in the polymers. However, unexpectedly the polymers of the present invention provide a greater degree of clay removal when used with the same amount of a non-mid chain branched surfactant. Preferably, in HDG formulations, the polymer will have a net negative charge. For example, three quaternized backbone nitrogens will be present for every 5 xe2x80x94SO3M capping units.
Surprisingly, liquid embodiments (HDL) of the present invention are more effective in removing hydrophilic soils when the backbones comprise R units having a greater degree of alkylene unit character and which comprise a lower number of anionic units which cap the R1 units than the backbones in their HDG counterpart embodiments.
The polymers of the present invention preferably comprise polyamine backbone which are derivatives of two types of backbone units:
i) normal oligomers which comprise R units of type (i), which are preferably polyamines having the formula:
H2Nxe2x80x94(CH2)n+1xe2x80x94[NHxe2x80x94(CH2)x]mxe2x80x94[NBxe2x80x94(CH2)x]nxe2x80x94NH2
xe2x80x83wherein B is a continuation of the polyamine chain by branching, n is preferably 0, m is from 0 to 3, x is 2 to 8, preferably from 3 to 6; and
ii) hydrophilic oligomers which comprise R units of type (ii), which are preferably polyamines having the formula:
H2Nxe2x80x94[(CH2)xO]y(CH2)x]xe2x80x94[NHxe2x80x94[(CH2)xO]y(CH2)x]mxe2x80x94NH2
xe2x80x83wherein m is from 0 to 3; each x is independently from 2 to 8, preferably from 2 to 6; y is preferably from 1 to 8.
Depending upon the degree of hydrophilic character needed in the backbones, the formulator may assemble higher oligomers from these constituent parts by using R units of types
(iii), (iv), and (v). Non-limiting examples include the epihalohydrin condensate having the formula: 
xe2x80x83or the hybrid oligomer having the formula: 
xe2x80x83wherein each backbone comprises a mixture of R units.
As described herein before, the formulator may form polymers which have an excess of charge or an equivalent amount of charge type. An example of a preferred polyamine according to the present invention which has an excess of anionic charged units, has the formula: 
wherein R is a 1,3-propyleneoxy-1,4butyleneoxy-1,3-propylene unit, w is 2; R1 is xe2x80x94(R2O)tY, wherein R2 is ethylene, each Y is xe2x80x94SO3xe2x88x92, Q is methyl, m is 0, n is 0, t is 20. For polyamines of the present invention, it will be recognized by the formulator that not every R1 unit will have a xe2x80x94SO3xe2x88x92 moiety capping said R1 unit. For the above example, the final polyamine mixture comprises at least about 90% Y units which are xe2x80x94SO3xe2x88x92 units.
Another preferred class of polyamine suitable for use in the present invention, are polyamines which may be present as a formulated admixture or a product by process composition, or a mixture of both. These preferred compounds can be represented by the formulae:
i) (PA)w(T)x;
ii) (PA)w(L)z;
iii) [(PA)w(T)x]y[L]z;
wherein PA is a grafted or non-grafted, modified or unmodified polyamine backbone unit, T is an amide-forming polycarboxylic acid crosslinking unit, and L is a non-amide forming crosslinking unit. For compounds of type (i) and (iii) the relative amounts of PA units and T units which are present are such that the molar ratio of PA units to T units is from 0.8:1 to 1.5:1. For compounds of type (ii) the relative amounts of PA units and L units which are present are such that the (PA)w(L)z comprises from about 0.05, preferably from about 0.3 to 2 parts by weight of said L units. Therefore, 1 part of a grafted or non-grafted, modified or unmodified polyamine backbone unit may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound. Likewise, for compounds of type (iii), crosslinked polyamines having the formula PA)w(T)x may be combined with from about 0.05, preferably from about 0.3 parts by weight of an L unit to about 2 parts by weight of an L unit to form a suitable modified polyamine compound having the formula [(PA)w(T)x]y[L]z.
The modified polyamine compounds of the present invention comprise a Polyamine Backbone, PA unit, which can be optionally, but preferably grafted. The following are non-limiting examples of suitable PA units according to the present invention.
A preferred PA unit according to the present invention are polyalkyleneimines and polyalkyleneamines having the general formula: 
wherein R is C2-C12 linear alkylene, C3-C12 branched alkylene, and mixtures thereof; B representing a continuation of the chain structure by branching. The indices w, x, and y have various values depending upon such factors as molecular weight and relative degree of branching. The polyalkyleneimines and polyalkyleneamines which comprise PA units of the present invention are divided into three categories based upon relative molecular weight. The terms polyalkyleneimine and polyalkyleneamines are used interchangeably throughout the present specification and are taken to mean polyamines having the general formula indicated above regardless of method of preparation.
For low molecular weight polyalkyleneimines having the formula: 
R is C2-C12 linear alkylene, C3-C12 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and 1,6-hexylene, more preferred is ethylene. The indices w, x, and y are such that the molecular weight of said polyamines does not exceed about 600 daltons. For example, for an entirely linear polyethyleneimine having a molecular weight of about 600 daltons, the index w=1, x=13, and y=0. For an entirely branched polyethyleneimine having a molecular weight of approximately 600 daltons, w=8, x=0 and y=7. (This combination of indices results in a material having an average molecular weight of about 646 daltons, which, for the purposes of the present invention is a low molecular weight polyalkyleneimine.) The index w typically has the value of y+1. The simplest of the low molecular weight polyamines of this type is ethylene diamine which may be present up to about 10% by weight of the PA unit mixture. Non-limiting examples of low molecular weight polyalkyleneimine PA units include diethylene triamine, triethylene tetramine, tetraethylene pentamine, dipropylene triamine, tripropylene tetramine, and dihexamethylene triamine. PA units may be used as crude products or mixtures, and if desired by the formulator, these PA units may be used in the presence of small amounts of diamines as described herein above, wherein the amount of diamines, inter alia, ethylene diamine, hexamethylene diamine may be present up to about 10% by weight, of the PA unit mixture.
For medium range molecular weight polyalkyleneimines having the formula: 
R is C2-C4 linear alkylene, C3-C4 branched alkylene, and mixtures thereof; preferably R is ethylene, 1,3-propylene, and mixtures thereof, more preferred is ethylene wherein said polyamines are polyethyleneimines (PEI""s). The indices w, x, and y are such that the molecular weight of said polyamines is from about 600 daltons to about 50,000 daltons. The indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone.
High Molecular Weight Polyalkyleneimines
For high molecular weight polyalkyleneimines having the formula: 
R is C2-C3 linear alkylene, preferably R is ethylene. The indices w, x, and y are such that the molecular weight of said polyamines is from about 50,000 daltons to about 1,000,000 (1 million) daltons. The indices w, x, and y will indicate not only the molecular weight of the polyalkyleneimines but also the degree of branching present in the PA unit backbone.
Another example of a preferred PA unit according to the present invention are the polyvinyl amine homo-polymers or co-polymers having the formula: 
wherein V is a co-monomer, non-limiting examples of which include vinyl amides, vinyl pyrrolidone, vinyl imidazole, vinyl esters, vinyl alcohols, and mixtures thereof, all of which can be taken together or in combination with polyvinyl amine to form suitable co-polymerization products suitable for use in the fabric enhancement systems of the present invention. The indices m and n are such that the copolymers comprise at least 10%, more preferably at least about 30% of units derived from vinyl amine and wherein further the molecular weight of said copolymers if from about 500 daltons, preferably from about 5,000 daltons to about 50,000 daltons, preferably to about 20,000 daltons.
Optionally, but preferably, the PA units of the present invention are modified either before or after reaction with a T unit or L unit crosslinking agent. The two preferred types of modifications are grafting and capping.
Preferably the PA units of the present invention are grafted, that is the PA unit is further reacted with a reagent which elongates said PA unit chain, preferably by reaction of the nitrogens of the PA backbone unit with one or more equivalents of aziridine (ethyleneimine), caprolactam, and mixtures thereof. Grafting units, in contrast to the xe2x80x9ccappingxe2x80x9d units described herein below, can further react on themselves to provide PA unit chain propagation. An example of a preferred grafted PA unit of the present invention has the formula: 
wherein R, B, w, x, and y are the same as defined herein above and G is hydrogen or an extension of the PA unit backbone by grafting. Non-limiting examples of preferred grafting agents are aziridine (ethyleneimine), caprolactam, and mixtures thereof. A preferred grafting agent is aziridine wherein the backbone is extended by units having the formula: 
wherein Bxe2x80x2 is a continuation by branching wherein the graft does not exceed about 12 units, preferably xe2x80x94CH2CH2NH2 and the value of the indices p+q have the value from 0, preferably from about 1, more preferably from about 2 to about 7, preferably to about 5. Another preferred grafting unit is caprolactam.
The PA units of the present invention can be grafted prior to or after crosslinking with one or more T units described herein below, preferably the grafting is accomplished after crosslinking with said T unit. This allows the formulator to take advantage of the differential reactivity between the primary and secondary amino units of the PA unit backbone thereby allowing the formulator to controllably link said PA units and to also control the amount of subsequent branching which results from the grafting step.
Another optional but preferred PA unit modification is the presence of xe2x80x9ccappingxe2x80x9d units. For example, a PA unit is reacted with an amount of a monocarboxylic acid, non-limiting examples of which are C1-C22 linear or branched alkyl, preferably C10-C18 linear alkyl inter alia lauric acid, myristic acid. The amount of capping unit which is reacted with the PA unit is an amount which is sufficient to achieve the desired properties of the formula. However, the amount of capping unit used is not sufficient to abate any further crosslinking or grafting which the formulator may choose to perform.
T crosslinking units are preferably carbonyl comprising polyamido forming units. The T units are taken together with PA units to form crosslinked modified polyamine compounds having the formula (PA)w(T)x or [(PA)w(T)x]y[L]z.
A preferred embodiment of the present invention includes crosslinked PA units wherein a T unit provides crosslinking between two or more PA units to form a (PA)w(T)x polyamido crosslinked section. A preferred crosslinking T unit has the general formula: 
wherein R1 is methylene, phenylene, and mixtures thereof; preferably methylene. The index k has the value from 2 to about 8, preferably to about 4. Preferred values of k are 2, 3, and 4. R2 is xe2x80x94NHxe2x80x94 thereby forming a urethane amide linkage when said R2 comprising T units react with the backbone nitrogens of the PA units. The value of the index j is independently 0 or 1. The presence of R2 units can result, for example, from the use of diisocyanates as crosslinking agents. Non-limiting examples of dibasic acids which are used as a source for T units in the above formula include succinic acid, maleic acid, adipic acid, glutaric acid, suberic acid, sebacic acid, and terephthalic acid. However, the formulator is not limited to crosslinking T units deriving from dibasic acids, for example, tribasic crosslinking T units, inter alia, citrate, may be used to link the PA units of the present invention.
Examples of (PA)w(T)x compounds according to the present invention are obtained by condensation of dicarboxylic acids inter alia succinic acid, maleic acid, adipic acid, terephthalic acid, with polyalkylene polyamines inter alia diethylenetriamine, triethylenetetranine, dipropylenetriamine, tripropylenetetramine wherein the ratio of the dicarboxylic acid to polyalkyleneimine is from 1:0.8 to 1:1.5 moles, preferably a ratio of from 1:0.9 to 1:1.2 moles wherein the resulting crosslinked material has a viscosity in a 50% by weight, aqueous solution of more than 100 centipoise at 25xc2x0 C.
Non-amide Forming L Crosslinking Units
Another preferred embodiment of the polyamines of the present invention are (PA)w(T)x units which are further crosslinked by L units to form polyamido amines having the formula [(PA)w(T)x]y[L]2 or are reacted with PA units to form non-amide polyamines having the formula (PA)w(L)z.
The L units of the present invention are any unit which suitably crosslinks PA units or (PA)w(T)x units. Preferred L linking units comprise units which are derived from the use of epihalohydrins, preferably epichlorohydrin, as a crosslinking agent. The epihalohydrins can be used directly with the PA units or suitably combined with other crosslinking adjuncts non-limiting examples of which include alkyleneglycols, and polyalkylene polyglycols inter alia ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol-1,6-glycerol, oligoglycerol, pentaerythrites, polyols which are obtained by the reduction of carbohydrates (sorbitol, mannitol), monosaccharides, disaccharides, oligosaccharides, polysaccharides, polyvinyl alcohols, and mixtures thereof.
For example, a suitable L unit is a dodecylene unit having the formula:
xe2x80x94(CH2)12xe2x80x94
wherein an equivalent of 1,12-dichlorododecane is reacted, for example, with a suitable amount of a PA unit to produce a polyamine which is crosslinked via dodecylene units. For the purposes of the present invention, L crosslinking units which comprise only carbon and hydrogen are considered to be xe2x80x9chydrocarbylxe2x80x9d L units. Preferred hydrocarbyl units are polyalkylene units have the formula:
xe2x80x94(CH2)nxe2x80x94
wherein n is from 1 to about 50.
Hydrocarbyl L units may be derived from hydrocarbons having two units which are capable of reacting with the nitrogen of the PA units. Non-limiting examples of precursors which result in the formation of hydrocarbyl L units include 1,6-dibromohexane, 1,8-ditosyloctane, and 1,14-dichlorotetradecane.
Further examples of preferred non-amide forming crosslinking L units are the units which derive from crosslinking units wherein epihalohydrin is used as the connecting unit. For example, 1,12-dihydroxydodecane is reacted with epichlorohydrin to form the bis-epoxide non-amide forming L unit precursor having the formula: 
which when reacted with one or more PA units or (PA)w(T)x units results in an L crosslinking unit having the formula: 
however, it is not necessary to pre-form and isolate the bis-epoxide, instead the crosslinking unit precursor may be formed in situ by reaction of 1,12-dihydroxydodecane or other suitable precursor unit with epihalohydrin in the presence of grafted or ungrafted PA units or (PA)w(T)x units.
Other crosslinking L units which utilize one or more epihalohydrin connecting units include polyalkyleneoxy L units having the formula: 
wherein R1 is ethylene, R2 is 1,2-propylene, x is from 0 to 100 and y is from 0 to 100. Another preferred unit which can comprise an L unit and which can be suitably combined with epihalohydrin connecting units include polyhydroxy units having the formula: 
wherein the index t is from at least 2 to about 20 and the index u is from 1 to about 6. The formulator may also combine units to form hybrid L crosslinking units, for example, units having the formula: 
wherein the indexes w and y are each independently from 1 to 50, z is units are present in a sufficient to suitably connect the polyhydroxy units and the polyalkyleneoxy units into the backbone without the formation of ether linkages.
The following is an example of an L linkidng group which comprises both a polyalkyleneoxy and a polyhydroxy unit. 
A further example of a preferred crosslinking L units are units which comprises at least two aziridine groups as connecting groups, for example an L unit having the formula: 
which can be used to link two (PA)w units, two (PA)w(T)x units, or mixtures thereof.
The polyamines of the present invention may have varying final compositions, for example, (PA)w(T)x, [(PA)w(T)x]y[L]z, [(PA)]w[L]z, and mixtures thereof, wherein each PA unit may be grafted or ungrafted. The indices w and x have values such that the ratio of w to x is from 0.8:1 to 1.5:1; y and z have values such that said polyamido compound comprises from about 0.05, preferably to about 0.3 to 2 parts by weight of said L unit. In the cases wherein no crosslinking takes place the indices w and y will be equal to 1 and x and z will be equal to 0. In the case wherein no crosslinking occurs using L units, the index y is equal to 1 and z is equal to 0. In the case wherein no crosslinking occurs using T units, the indices w and y are equal to 1 and x is equal to 0.
An preferred embodiment of the present invention which comprises PA units, T units, and L units includes the reaction product of:
a) 1 part by weight, of a polyamine obtained by condensation of 1 mole of a dicarboxylic acid with a polyalkylene polyamine (i.e., diethylenetriamine) to the extent wherein at least about 10% of the xe2x80x94NH backbone hydrogens are unmodified by reaction with said dicarboxylic acid, then optionally reacting the obtained polyamine condensation product with up to 12 ethyleneimine units (i.e., grafting of the backbone using aziridine) per basic nitrogen atom; and
b) further reacting the product obtained in (a) with from 0.05, preferably from about 0.3 to about 2 parts by weight, of an L units, inter alia the reaction product of a polyalkylene oxide having from 8 to 100 alkylene oxide units with epichlorohydrin at a temperature of form about 20xc2x0 C. to about 100xc2x0 C.
A preferred embodiment of the present invention are the water-soluble condensation products which can be obtained by the reaction of
a) polyalkyleneimines and polyalkyleneimines grafted with ethyleneimines, and mixtures thereof; with
b) at least bifunctional halogen-free cross-linking agents, said agents selected from the group consisting of:
i) ethylene carbonate, propylene carbonate, urea, and mixtures thereof;
ii) mono-carboxylic acids comprising one olefin moiety inter alia acrylic acid, methacrylic acid, crotonic acid; and the esters, amides, and anhydrides thereof; polycarboxylic acids inter alia oxalic acid, succinic acid, tartaric acid, itaconic acid, maleic acid; and the esters, amides, and anhydrides thereof;
iii) reaction products of polyetherdiamines, alkylenediamines, polyalkylene-diamines, and mixtures thereof, with mono-carboxylic acids comprising one olefin moiety wherein the resulting polyamine comprises a functional units which is selected from the group consisting of at least two ethylenically unsaturated double bonds, carbonamide, carboxyl group, ester group, and mixtures thereof;
iv) at least two aziridine group-containing reaction products of dicarboxylic acid esters with ethyleneimine and mixtures of the cross-linking agents.
However, prior to reaction of (PA)w(T)x units formed herein above, the (PA)w(T)x polyamine compound may be partially amidated (xe2x80x9ccappedxe2x80x9d as described herein above) by treatment with a mono carboxylic acid or the esters of mono carboxylic acids. The formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final Fabric Enhancement Polymer. Non-limiting examples of suitable mono-carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
The high molecular weight modified polyamine condensation products of the present invention (also referred to herein as xe2x80x9cresinsxe2x80x9d) are preferably formed from the reaction of one or more grafted, cross-linked polyethyleneimines and one or more polyethylene and/or polypropylene glycol copolymers, wherein the resulting crosslinked modified polyamines (resins) have a final viscosity of more than or equal to 300 mPa-sec., preferably from 400 to 2,500 mPa-sec. when measured at 20xc2x0 C. in a 20% aqueous solution. The modified polyamine compounds of the present invention are suitably described in U.S. Pat. No. 3,642,572 Eadres et al., issued Feb. 15, 1972, U.S. Pat. No. 4,144,123 Scharf et al., issued Mar. 13, 1979 and U.S. Pat. No. 4,371,674 Hertel et al., issued Feb. 1, 1983, NE 6,612,293, DT 1,946,471, DT 36386, DT 733,973, DE 1,771,814, all of which are included herein by reference.
A further example of preferred polyamines according to the present invention are polyamines derived from amino acid residues. For the purposes of the present invention the term xe2x80x9cresiduexe2x80x9d is defined as xe2x80x9cone unit which comprises the polymeric material of the present inventionxe2x80x9d. A non-limiting example of a residue which comprises the polymeric material is a lysine residue having the formula: 
wherein preferably said lysine residue forms the backbone of said polymeric material by forming a bond to the xcfx89-amino unit, however, the lysine residue may be suitably incorporated into the backbone via the xcex1-amino unit; or an ornithine residue having the formula: 
wherein preferably said ornithine residue forms the backbone of said polymeric material by forming a bond to the xcfx89-amino unit, however, the ornithine residue may be optionally incorporated into the backbone via the xcex1-amino unit; and said lysine residue or ornithine residue may have any optical isomer form, i.e., dextrorotatory, levorotatory.
The amino acid-based polymers of the present invention comprise at least about 5% by weight of lysine, ornithine, or mixtures thereof, preferably at least about 10%, more preferably at least about 20%, most preferably at least about 40% by weight of lysine, ornithine, or mixtures thereof.
For the purposes of the present invention the terms xe2x80x9cN-termxe2x80x9d and xe2x80x9cC-termxe2x80x9d are defined as an xe2x80x9camino terminating unitxe2x80x9d and a xe2x80x9ccarboxyl terminating unitxe2x80x9d respectively and are used throughout the present specification to indicate the capping units of the main polymeric chain as well as any branching chains.
The polymeric material of the present invention has the formula:
xe2x80x83N-termxe2x80x94[Lys]xxe2x80x94[Orn]yxe2x80x94[AA]zxe2x80x94C-term
wherein Lys represents a residue of the amino acid lysine, Orn represents a residue of the amino acid ornithine, and AA represents a residue of a non-lysine or non-ornithine amino acid, carboxylic acid, or other chain propagating residue.
In general, the lysine and ornithine residues are preferably incorporated into the polymeric chain via the xcfx89-amino residue and the carboxylate residue. However, this xe2x80x9cnormalxe2x80x9d incorporation does not preclude incorporation of a lysine or ornithine residue into the backbone or branch chain via two amino units whereby the carboxyl unit remains un-incorporated into any chain.
AA units are amino acid or other chain propagating residues having the formula: 
wherein the index n is from 0 to 10, preferably 1, 2 and 4; the preferred R units are independently selected from the group consisting of:
i) hydrogen;
ii) xe2x80x94(CH2)mCOR2 wherein:
R2 is xe2x80x94OH, for example wherein said amino acid, AA residue is glutamic acid, aspartic acid, etc.;
R2 is an amino lactam C-terminal capping group, preferably a unit having the formula: 
R2 is an N-terminal residue of a cross-linking chain comprising one or more residues which provides cross-linking between two polymeric material chains, for example, R2 may comprise one end of a diamine inter alia hexamethylene diamine, an N-terminal residue which links the main polymeric chain to a branched chain, for example, a branched chain having the general formula: 
xe2x80x83preferably, when R2 is an amide-forming unit, R2 is derived from the reaction of the lysine/ornithine polymeric material with caprolactam, amino caproic acid, and mixtures thereof; the index m is from 0 to 3, preferably the index m is 1 or 2, more preferably 1;
iii) benzyl;
iv) 4-hydroxybenzyl;
v) 3-(guanidinyl)propyl;
vi) (1H-indol-3-yl)methyl;
vii) (1H-imidazol-5-yl)methyl;
viii) is mixtures thereof.
R1 units are independently selected form the group consisting of:
i) hydrogen; preferred unit;
ii) the C terminal end of a cross-linking chain comprising one or more residues which provides either cross-linking between two polymeric material chains or a branching of the polymer chain, preferably when R1 is a C terminal unit, said unit is derived from the reaction of the lysine/ornithine polymeric material with caprolactam, amino caproic acid, and mixtures thereof;
iii) C1-C18 linear or branched alkyl, preferably methyl;
iv) C2-C18 linear or branched alkenyl;
v) C2-C18 linear or branched hydroxyalkyl;
vi) C3-C8 cycloalkyl;
vii) aryl;
viii) C6-C18 substituted or unsubstituted alkylenearyl, preferably benzyl;
ix) one end of a di-carboxylic acid linking group wherein two polymeric chains are linked by reaction of the lysine/ornithine polymeric material with a di-carboxylic acid or di-carboxylic acid ester; and
x) mixtures thereof.
Non-limiting examples of preferred AA amino acid residues are arginine, tryptophan, tyrosine, histidine, aspartic acid, glutamic acid, asparagine, glutamine, serine, threonine, and mixtures thereof. More preferred AA amino acid residues are selected form the group consisting of arginine, tryptophan, and mixtures thereof.
N-term amino terminal capping groups terminate, truncate or end the amine terminus of the main polymeric chain or branch chains. Preferred amino terminal capping groups are selected from the group consisting of:
i) hydrogen (most preferred);
ii) C1-C18 linear or branched alkyl, preferably methyl;
iii) C2-C18 linear or branched alkenyl;
iv) C3-C8 cycloalkyl;
v) aryl;
vi) C6-C18 substituted or unsubstituted alkylenearyl, preferably benzyl;
vii) C1-C18 linear or branched acyl, preferably the N-terminal units of the polymer are capped (partially amidated) with an acyl unit inter alia lauric acid, myristic acid, behenic acid;
viii) C2-C22 diacyl units, for example units derived from dicarboxylic acids or esters thereof, which can serve to cap two separate N-terminal units at the same time: and
ix) mixtures thereof.
C-term carboxy terminal capping groups terminate, truncate, or end the carboxy terminus of the main polymeric chain or branch chains. Preferred carboxy terminal capping groups are selected from the group consisting of:
i) xe2x80x94OM wherein M is hydrogen or a salt forming cation, most preferred capping unit is xe2x80x94OH;
ii) xe2x80x94N(R3)2 wherein each R3 is independently C1-C18 linear or branched alkyl; C2-C18 linear or branched hydroxyalkyl, C3-C8 cycloalkyl, and mixtures thereof, preferably methyl;
iii) preferably an amino lactam unit having the formula: 
iv) preferably an amino lactam unit having the formula: 
v) units having an amine function, including:
a) mono amines having the formula:
R1R2NH
xe2x80x83wherein R1 and R2 are each independently hydrogen or a hydrocarbyl unit comprising from 1 to 22 carbon atoms;
b) polyamines having the formula: 
xe2x80x83wherein R is C2-C22 alkylene, m is from 0 to about 5; e.g. ethylene diamine, hexamethylenediamine;
c) preferably the C terminal end of the lysine/ornithine polymeric materials are truncated by reacting said polymeric materials with one or more equivalents of caprolactam and/or amino caproic acid; and
vi) mixtures thereof.
The polyamines which serve as carbonyl end units may serve to cap one or more carboxy terminal units of the same chain or two or more different chains. The preferred polymer chains of the present invention have the amino terminus (N-term unit) of the main chain and branch chains capped with hydrogen and the carboxy terminus (C-term unit) of the main chain and branch chains capped with xe2x80x94OH.
As described herein above, the formulator may, preferably partially amidate the compounds of the present invention by treatment with a mono carboxylic acid or the esters of mono carboxylic acids. The formulator may vary the degree to which the backbone nitrogens are amidated according to the desired properties of the final Fabric Enhancement Polymer. Non-limiting examples of suitable mono-carboxylic acids include formic acid, acetic acid, propionic acid, benzoic acid, salicylic acid, lauric acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, and mixtures thereof.
In a preferred embodiment of the present invention an amino acid having two amine moieties inter alia lysine, ornithine is co-condensed with caprolactam or aminocaproic acid to form a co-condensation product. Other preferred co-condensates include reaction of lysine or ornithine with lauric acid to form the amidated polymer.
The amino units of any lysine, ornithine, or AA unit may be optionally quaternized, preferably quaternized by one or more units selected from the group consisting of C1-C4 linear or branched alkyl, benzyl, and mixtures thereof.
In addition, N-terminal or C-terminal capping units which have more than one functionality inter alia two carboxy units of a diacid (succinic acid), may crosslink two or more poly lysine or poly ornithine comprising chains. Therefore, in addition to capping, and therefore truncating the N-terminal ends of two separate polyamine backbones, a unit such as succinic acid may crosslink two polyamine chains.
The molecular weight of the amino acid-based polymeric materials of the present invention are preferably from about 400 daltons, more preferably from about 1000 daltons, most preferably from about 2000 daltons to preferably about 500,000 daltons, more preferably to about 25,000 daltons, most preferably to about 10,000 daltons.
Another suitable class of polyamines of the present invention are the polyamines wherein the amine nitrogen is tethered to an alkylene backbone. The following are non-limiting examples of tethered polymeric amines according to the present invention.
The tethered polymeric amines of the present invention have the general formula: 
wherein Rxe2x80x2 and Rxe2x80x3 are each independently hydrogen, C1-C6 alkyl, phenyl, substituted phenyl, C7-C22 alkylenearyl, and mixtures thereof, R3 is an amine comprising unit, non-limiting examples of which include: xe2x80x94N(R)2, xe2x80x94N+(R)3, xe2x80x94C(O)N(R)2, xe2x80x94C(O)N+(R)3, and mixtures thereof; wherein R is hydrogen, C1-C12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R1O)zY, wherein R1 is C1-C6 linear or branched alkylene, Y is hydrogen or an anionic unit. Each caution nitrogen will have an anionic unit X which provides charge neutrality to the polymer. The index x is from about 5 to about 1,000,000 (one million) depending upon the properties which the formulator may wish to provide via the tethered polyamine.
One class of tethered polymeric amines are the quaternized and non-quaternized polyvinylamines having the formula: 
wherein R is hydrogen, C1-C12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R1O)zY, wherein R1 is C1-C6 linear or branched alkylene, Y is hydrogen or an anionic unit, non-limiting examples of which include, xe2x80x94CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH2CO2M, xe2x80x94CH2CH(OZ)CH2O(R1O)tZ, xe2x80x94(CH2)fCH[O(R2O)tZ]CH2O(R2O)tZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include xe2x80x94CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality; and the index f is from 0 to 6, t is 0 or 1, z is from 1 to 50.
The index x has the value from about 50 to about 1,500; preferably the index x has a value such that the resulting polymeric suds stabilizer has an average molecular weight of from about 2,500, preferably from about 10,000, more preferably from about 20,000 to about 150,000, preferably to about 90,000, more preferably to about 80,000 daltons.
One class of polymeric suds stabilizer according to the present invention are the alkyl acrylamides having the formula: 
wherein R is hydrogen, C1-C12 linear or branched alkyl, benzyl, or alkyleneoxy having the formula (R1O)zY, wherein R1 is C1-C6 linear or branched alkylene, Y is hydrogen or an anionic unit, non-limiting examples of which include, xe2x80x94CH2)fCO2M, xe2x80x94C(O)(CH2)fCO2M, xe2x80x94(CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH2CO2M, xe2x80x94CH2CH(OZ)CH2O(R1O)tZ, xe2x80x94(CH2)fCH[O(R2O)tZ]CH2O(R2O)tZ, and mixtures thereof, wherein Z is hydrogen or an anionic unit non-limiting examples of which include xe2x80x94(CH2)fCO2M, xe2x80x94(O)(CH2)fCO2M, xe2x80x94CH2)fPO3M, xe2x80x94(CH2)fOPO3M, xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO3M)xe2x80x94(CH2)fSO3M, xe2x80x94CH2(CHSO2M)(CH2)fSO3M, xe2x80x94C(O)CH2CH(SO3M)CO2M, xe2x80x94C(O)CH2CH(CO2M)NHCH(CO2M)CH2CO2M, and mixtures thereof, M is a cation which provides charge neutrality; and the index f is from 0 to 6, t is 0 or 1, z is from 1 to 50.
The index x has the value from about 50 to about 1,500; preferably the index x has a value such that the resulting polymer has an average molecular weight of from about 2,500, preferably from about 10,000, more preferably from about 20,000 to about 150,000, preferably to about 90,000, more preferably to about 80,000 daltons.