MXPA02004614A

MXPA02004614A - Laundry detergent compositions comprising zwitterionic polyamines.

Info

Publication number: MXPA02004614A
Application number: MXPA02004614A
Authority: MX
Inventors: Nathan Price Kenneth
Original assignee: Procter & Gamble
Priority date: 1999-11-09
Filing date: 2000-11-07
Publication date: 2002-09-02
Also published as: KR20030011764A; KR100474794B1; AR027880A1; WO2001034748A1; JP2003523416A; AU1473101A; BR0015430A; CA2389768A1; MA25566A1; CN1455810A; TR200201248T2; AU774126B2; CZ20021612A3; CN1298828C; HUP0203066A2; HUP0203066A3; EP1228179A1

Abstract

The present invention relates to laundry detergent composition comprising: from about 0.01 %, most preferably from about 3 % to about 50 %, most preferably to about 7 % by weight, of a hydrophobically modified polyamine having formula (I): wherein R is C 5C 20 linear or branched alkylene, and mixtures thereof; R 1 is an alkyleneoxy unit having the formula: (R 2O)xR3 wherein R 2 is C 2C 4 linear or branched alkylene, and mixtures thereof; R 3 is hydrogen, C 1C 22 alkyl, C 7C 22 alkylenearyl, an anionic unit, and mixtures thereof; x is from about 15 to about 30; Q is a hydrophobic quaternizing unit selected from the group consisting of C 8C 30 linear or branched alkyl, C 6C 30 cycloalkyl, C 7C 30 substituted or unsubstituted alkylenearyl, and mixtures thereof; X is an anion present in sufficient amount to provide electronic neutrality; n is from 0 to 4, from about 0.01 % by weight, of surfactant; the balance carriers and adjunct ingredients.

Description

COMPOSITIONS DETERGENTS OF WASHING CLOTHES THAT COMPRISE ZWITERIONIC POLYAMINS FIELD OF THE INVENTION The present invention relates to laundry detergent compositions comprising one or more modified zwitterionic polyamines that provide improved lipid-free removal benefits, among others, the removal of hydrophilic, inter alia, clayey soils. The present invention additionally relates to methods for removing hydrophilic soiled garments.

BACKGROUND OF THE INVENTION Fabrics, especially clothing, can be soiled with a variety of foreign substances ranging from hydrophobic stains (grease, oil) to hydrophilic stains (clay). The level of cleanliness required to remove foreign substances depends greatly on the amount of stain that is present and the degree and manner in which the foreign substance has contacted the fibers of the fabric. The grass spots usually comprise a direct abrasive contact with vegetative matter, thereby producing very penetrating spots. Clay soil stains, although in some cases they contact fabric fibers with less force, however, they provide a different type of dirt removal problem due to the high degree of load associated with the clay itself. This high density of surface charge can act to repel some auxiliary ingredients to wash clothes, among others, clay dispersing agents, thereby resisting any appreciable peptization and dispersion of the clay into the washing solution. A surfactant by itself is not all that is required to remove dirty and unwanted clay spots. In fact, most surfactants by themselves in water are surprisingly deficient in removing clayey soils from fabrics. Not all surfactants work equally well on all types of stains. In addition to surfactants, polyamine-based hydrophilic soil dispersing agents are added to laundry detergent compositions to "carry" soiled clay away from the surface of the fabric and to stabilize the removed particles in solution sufficiently to minimize the possibility that the dirty clay is redeposited on the cloth. However, unless the clay can be removed initially from the dirty fabric, especially in the case of hydrophilic fibers, among others, cotton, there will be nothing in solution for the dispersing agents to settle and remain suspended. The need in the art for laundry detergent compositions that can effectively derail and remove embedded and other hydrophilic dirt from the fabric has long been perceived in the art.

Additionally, as the concentration of clay soil in the wash solution increases, there is a need for a surfactant agent system that is capable of handling this increased dirt load. Furthermore, for a long time the need for an active auxiliary ingredient has been perceived to the clay soils which can be improved to conform to the detergent embodiment of washing particular clothes, among others, granulates, liquids, and therefore can be adjusted to equal the agent system. surfactant. There has additionally been for some time the need for a method for cleaning hydrophilic soiled fabrics where the hydrophilic soils are effectively peptized, dispersed, and suspended in the washing solution.

BRIEF DESCRIPTION OF THE INVENTION It has now surprisingly been discovered that laundry detergent compositions comprising fully quaternized polyethoxylated polyamines wherein the aforementioned polyethoxy units are capped with anionic units and wherein the polyamine backbone comprises relatively hydrophobic main chain spacer units, the aforementioned polyamines they can be hydrophobically modified by selecting certain quaternization units to provide improved removal of dirty clothes. The laundry detergent compositions of the present invention are especially effective in the removal of clay soils and other dirty hydrophilic fellings. When used in conjunction with an appropriate surfactant agent system. , the hydrophobically modified polyamines of the present invention provide removal of stains that were previously considered ruinous for fabrics, especially fabrics comprising cellulose. The first aspect of the present invention further relates to laundry detergent compositions comprising: A) of about 0.01%, preferably about 0.1%, more preferably from about 3% to 50%, preferably about 20%, more preferably at about 10%, still more preferably at about 7% by weight, of a hydrophobically modified polyamine having the formula wherein R is linear or branched C5-C20 alkylene, and mixtures thereof; R 1 is an alkyleneoxy unit having the formula: - (R 2 O) * - R 3 wherein R 2 is linear or branched C 2 -C alkylene, and mixtures thereof; R3 is hydrogen, benzyl, and mixtures thereof; x is from about 15 to 30; Q is a hydrophobic quaternization unit selected from the group consisting of straight or branched C8-C30 alkyl, C6-C30 cycloalkyl, substituted or unsubstituted C -C3-alkylenearyl, and mixtures thereof; X is an anion that is present in an amount sufficient to provide electronic neutrality; n is from 0 to 4; B) of about 0.01% by weight, of a surfactant agent system comprising one or more surfactants that are selected from: i. from 0% to 100% by weight, of one or more anionic surfactants; ii. from 0% to 100% by weight, of one or more nonionic surfactants; iii. optionally from 0.1% to 80%, approximately by weight of one or more cationic surfactants; iv. optionally from 0.1% to 80%, approximately, by weight of one or more zwitterionic surfactants; v. optionally from 0.1% to 80%, approximately, by weight of one or more ampholytic surfactants; saw. or mixtures of these; C) the balance of carriers and auxiliary ingredients. The present invention relates to a method for washing fabrics, the aforementioned method comprises the step of contacting an article of manufacture comprising fabric, preferably clothing, with an aqueous solution of a laundry detergent composition comprising a hydrophobically modified polyamine of the present invention.

These and other purposes, attributes and advantages will be apparent to those of ordinary skill in the art of reading the following detailed description and the appended claims. All percentages, ratios and proportions in the present invention are by weight, unless otherwise specified. All temperatures are in degrees Celsius (° C) unless otherwise specified. All the cited documents are incorporated, in their pertinent part, in the present invention as a reference.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to hydrophobically modified quaternized zwitterionic polyamines which are suitable for use in laundry detergent compositions. The hydrophobically modified zwitterionic polyamines of the present invention provide increased benefits of removal of body and dirty from perspiration. It has surprisingly been found that the hydrophobically modified quaternized zwitterionic polyamines have increased efficiency when treating fabrics that are soiled with oils, perspiration, etc. of the human body. Without being limited by the theory, the hydrophobically modified zwitterionic quaternary polyamines of the present invention have an unexpected balance of properties that make the receptive compounds penetrate the fabric to solubilize oily, greasy stains while maintaining water solubility and retaining the suspension properties of water. dirty in particles that is required to direct the dirty away from the fabric thereby avoiding resedimentation. Additionally, the hydrophobically modified zwitterionic polyamines of the present invention reinforce the cleaning actions of high foam and high phosphate cleaning systems. When present in laundry detergent compositions, zwitterionic polyamines are effective in an amount of about 0.01, preferably about 0.1%, more preferably about 1%, even more preferably from about 3% to about 50%, more preferably still at about 20%, still more preferably at about 10%, more preferably still at about 7% by weight, of the aforementioned laundry detergent composition.

Zwiterionic Polyamines Quaternized Hydrophobically Modified For the purposes of the present invention, the term "hydrophobically modified" is defined in the present invention as the "reaction of a linear polyamine comprising from 2 to 5 nitrogens wherein each nitrogen has its main chain hydrogens replaced by a polyalkyleneoxy unit comprising at least about 15 alkyleneoxy units, with at least one equivalent per nitrogen of a quaternized agent, the aforementioned quaternized agents comprise a linear alkyl moiety having at least 8 carbon atoms, an alkyl moiety cyclic having at least 6 carbon atoms, an alkylearyl unit, inter alia, benzyl, having at least 7 carbon atoms, or mixtures thereof. " A "polyamine" for the purposes of the present invention is "an amine having less than 6 nitrogen atoms in the main chain and has no branching", while for the purposes of the present invention, amines comprising more than 5 nitrogens they are defined as "oligomeric amines" (oligoamines) or "polymeric amines" (polyalkyleneamines or polyalkyleneimines). The hydrophobically modified zwitterionic polyamines of the present invention have the formula: wherein R is a linear or branched C6-C-? 2 alkylene, and mixtures thereof, in one embodiment R is linear C6-C? 2 alkylene, in another embodiment R is linear C? -C alkylene, and in yet another embodiment each of the R units are hexylene units, typically linear hexylene units. R1 is a polyalkylenoxy unit capped with an anionic unit having the formula: - (R2O)? -R3 wherein R2 is straight or branched C2-C4 alkylene, and mixtures thereof. The term "straight" or "branched" as it relates to R2 includes any linear or branched alkylene unit comprising a total of 2 to 4 carbon atoms. In one embodiment R2 comprises ethylene, 1, 2-propylene, and mixtures thereof, in yet another embodiment each unit R2 is an ethylene unit. An embodiment of the present invention that provides advantages in a composition comprising bleach refers to hydrophobically modified zwitterionic polyamines comprising the first 1-6 alkyleneoxy units, preferably the first 1-3, as 1, 2-propyleneoxy units followed by the balance of ethyleneoxy units R3 is an anionic capping unit, and mixtures thereof. What one desires to mean as "an anionic capping unit, and mixtures thereof" is that the unit R3 may comprise a single anionic unit or each R3 may be a different anionic capping unit, or R3 may comprise any mixture of anionic units. " Non-limiting examples of anionic units comprising an embodiment of the present invention are anionic units which are selected from the group consisting of: a) - (CH2) fCO2M; b) -C (O) (CH2) fCO2M; c) - (CH2) fPO3M; d) - (CH2) fOPO3M; e) - (CH2) fSO3M; f) -CH2 (CHSO3M) (CH2) fSO3M; g) -CH2 (CHSO2M) (CH2) fSO3M; h) -C (O) CH2CH (SO3M) CO2M; i) -C (O) CH2CH (CO2M) NHCH (CO2M) CH2CO2M; j) and mixtures thereof; where M is hydrogen or a cation that provides charge neutrality. For the purposes of the present invention, all M units, associated with a hydrophobically modified zwitterionic polyamide, surfactant, or auxiliary ingredient, can be either a hydrogen atom or a cation depending on the form isolated by the technician or the pH relative to the system where the compound is used. Non-limiting examples of preferred cations include sodium, potassium, ammonium, and mixtures thereof. The index f is from about 0 to about 10, an embodiment of the present invention sets the scale of the index f from 0 to 2. The index x that describes the average number of alkylenoxy units attached to the nitrogen of the main chain is 15 to 30, approximately, preferably 15 to 25, more preferably 18 to 23, even more preferred the average value of alkylenoxy units is 20. The formulator will recognize that when a zwitterionic polyamine is ethoxylated, only an average number or statistical distribution of alkylenoxy units will be known. Therefore, depending on how "tightly" or how "exactly" a zwitterionic polyamine is alkoxylated, the average value can vary from realization to realization.

Q is a hydrophobic quaternization unit and each Q independently is C8-C or straight or branched alkyl, C6-C30 cycloalkyl, substituted or unsubstituted C7-C3-alkylenearyl, and mixtures thereof; in one embodiment of the present invention Q is a hydrophobic quaternization unit that is selected from the group consisting of substituted or unsubstituted C7-C30 alkylenearyl, and mixtures thereof; more preferably benzyl, substituted benzyl, naphthyl, substituted naphthyl, and mixtures thereof. For the purposes of the present invention the formulas: represents the term "naphthyl" depending on whether the aforementioned unit comprises a-substitution or β-substitution. The index w has the value from 0 to 20. Other alkylenearyl units include, in addition to benzyl, alkylearyl units having the formula: wherein the z-index is from 1 to 24. For the purposes of the present invention the term "substituted" as applied to suitable alkylenearyl units as units Q, are one or more linear or branched CrC-? 2 alkyl moieties, provided that the total number of carbon atoms including the aromatic ring does not exceed 30 carbon atoms . A non-limiting example of the substituted alkylenearyl unit according to the present invention has the formula: which is a half of 3,5-di-tert-butylbenzyl. The index n represents the number of secondary nitrogens in the main chain. The index n has the value of 0 to 4, preferably 0 to 2. X is an anion that is present in sufficient quantity to provide electronic neutrality. Non-limiting examples are anions are chlorine, bromine, iodine, methylisulfate, and mixtures thereof. An example of a preferred hydrophobically modified zwitterionic polyamine according to the present invention has the formula: wherein X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methylisulfate, and mixtures thereof. Surface-active Agent System The detergent composition of the present invention comprises about 0.01%, preferably about 1%, more preferably about 5%, and even more preferably about 10% to 80%, about, preferably about 50%, more preferably at about 30% by weight of a surfactant agent system, the aforementioned surfactant agent system comprises one or more surfactants which are selected from: i. from 0% to 100% weight, of one or more anionic surfactants; ii. from 0% to 100% by weight, of one or more nonionic surfactants; iii. optionally from 0.1% to 80%, approximately, by weight of one or more cationic surfactants; iv. optionally from 0.1% to 80%, approximately, by weight of one or more zwitterionic surfactants; v. optionally from 0.1% to 80%, approximately, by weight of one or more ampholytic surfactants; or vi. mixtures of these. A preferred surfactant agent system according to the present invention comprises about 0.01% by weight of one or more surfactants that are selected from: i. about 1% to 100% by weight of an anionic surfactant which is selected from: a) linear alkylbenzene sulfonates; b) Branched medium chain aryl sulfonate surfactants of the formula: wherein A is a branched medium chain alkyl unit having the formula: R R i CH3 (CH2) ^ CH (CH2) and CH (CH2) z- wherein R and R1 independently are each hydrogen, C? -C3 alkyl, and mixtures thereof, provided that the total number of carbon atoms in the unit The aforementioned alkyl is from 6 to 18 and at least one of R and R1 is not hydrogen; x is an integer from 0 to 13; and is an integer from 0 to 13; z is 0 or 1; R2 is hydrogen, d-C3 alkyl, and mixtures thereof; M 'is water soluble cation with enough charge to provide neutrality; c) branched alkyl sulfate surfactant agents having the formula: CH3CH2 (CH2) mCH2OSO3M; or the formula: CH3CH2 (CH2) mCH2 (OCH2CH2) and OS3M; d) Branched medium chain alkyl sulfate surfactants having the formula: R R 1 Rz I i 1 or the formula: R R1 R2 CH3CH2 (CH2) CH (CH2)? CH (CH2) vCH (CH2) zOROR3)? RpS? 3M wherein R, R1, and R2 each independently are hydrogen, C1-C3 alkyl, and mixtures thereof, provided that the total number of carbon atoms in the aforementioned surfactant is 14 to 20 and at least one of R, R1, and R2 is not hydrogen; the index w is a number between 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; provided that 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 0.01; M is a cation soluble in water of sufficient charge to provide electronic neutrality; ii. from 0% to 100% by weight, of one or more surfactants non-ionic; iii. optionally from about 0.1% to 80% by weight, of one or more cationic surfactants; V. optionally from about 0.1% to 80% by weight, of one or more zwitterionic surfactants; v. optionally from about 0.1% to 80% by weight, of one or more ampholytic surfactants; or vi. mixtures of these. Depending on the embodiment of the present invention, the formulator may select one or more categories of surfactants; however, at least one anionic surfactant and at least one nonionic surfactant must be present. Within each category, more than one type of surfactant can be selected. Non-limiting examples of surfactants useful in the present invention include: a) Cn-C? 8 alkylbenzene sulphonates (LAS); b) C 1 or C 2 o primary alkylsulfates, branched and random chain (AS); c) secondary C-io-Cis alkyl sulfates (2,3) having the formula: OSO3"M + OSO3" * CH3 (Cl? 2) yíCK) CH3 or C? 3 (CH2) and (CH) CH2CH3 wherein x and (y + 1) are integers of at least about 7, preferably at least about 9; the aforementioned surfactants are disclosed in U.S. Patent 3,234,258. Morris, issued on February 8, 1966; U.S. Patent 5,075,041, Lutz, issued December 24, 1991; U.S. Patent 5,349,101, Lutz et al., issued September 20, 1994; and U.S. Patent 5,389,277, Prieto, issued February 14, 1995, all are incorporated in the present invention as a reference; d) C 0 -C 18 alkyl alkoxy sulfates (AExS) wherein x is preferably 1-7; e) C10-C18 alkyl alkoxy carboxylates preferably comprising 1-5 ethoxy units; f) C12-C18 alkyl ethoxylates, C6-C2 alkoxylated alkyl phenols wherein the alkoxylated units with a mixture of ethyleneoxy and propyleneoxy units, C? 2-C? s alcohol and alkyl phenol condensates with oxide block polymers ethylene / propylene oxide, among others, Pluronic® ex BASF which is disclosed in U.S. Patent 3,929,678, Laughiin et al., issued March 30, 1975, which is incorporated herein by reference; g) alkylpolysaccharides as disclosed in U.S. Patent 4,565,647, Filling, issued January 26, 1986, which is incorporated herein by reference; h) polyhydroxy fatty acid amides having the formula: where R is C7-C2 alkyl? linear, C7-C2 alkyl? branched, C7-C2- alkenyl? linear, C7-C2 alkenyl? branched, and mixtures of these. R1 is ethylene; R2 is linear C3-C1 alkyl, branched C3-C alkyl, and mixtures thereof; preferably R2 is 1, 2-propylene. Nonionic surfactants comprising a mixture of units R1 and R2 preferably comprise from 4 to 12 ethylene units, approximately, in combination with 1 to 4 units of 1., 2-propylene, approximately. The units can be alternated, or put together in any suitable combination for the formulator. Preferably the ratio of units R1 to units R2 is from about 4: 1 to 8: 1. Preferably one unit R2 (i.e. 1, 2-propylene) is attached to the nitrogen atom followed by the chain balance comprising 4 to 8 ethylene units. R3 is hydrogen, linear C? -C alkyl, branched C3-C4 alkyl, and mixtures thereof, preferably hydrogen or methyl, more preferably hydrogen. R 4 is hydrogen, linear C 1 -C 4 alkyl, branched C 3 -C 4 alkyl, and mixtures thereof; preferably hydrogen. When the index m is equal to 2 the index n must be equal to 0 and the unit R4 is absent and instead it is replaced by a unit - [(R1O) x (R2O) and R3]. The index m is 1 or 2, the index n is 0 or 1, provided that when m is equal to 1, n is equal to one, resulting in a unit - [(R1O) x (R2O) and R3] and R4 is present in nitrogen. The index x is from about 0 to 50, preferably from about 3 to about 25, more preferably from about 3 to about 10. The index y is from about 0 to 10, preferably 0; however when the index y is not equal to 0, and it is from 1 to 4 approximately. Preferably all alkyleneoxy units are ethyleneoxy units. Those skilled in the ethoxylated polyoxyalkylenealkylamide surfactant technique will recognize that the values for the indices x and y with average values and true values can vary by several values depending on the process that is used to alkoxylate the amides. Suitable means for preparing the polyoxyalkylenealkylamide surfactants of the present invention can be found in Surfactant Science Series, Editor Martin Schick, Volume I, Chapter 8 (1967) and Volume XIX, Chapter 1 (1987) which is included in the present invention as reference.

Medium Chain Branched Alkylsulfates The surfactant agent systems of the present invention may comprise a medium chain branched alkyl sulfate surfactant and / or a medium chain branched alkyl alkoxy sulphate surfactant. Because the medium chain branched alkyl sulfate or alkyl alkoxy sulfate surfactants are not required when medium chain branched aryl sulfonate surfactants are present, the surfactant agent system comprises 0%, when present of 0.01%, preferably 0.1 % more preferably from 1% to 100%, approximately, preferably to approximately 80% by weight, preferably to approximately 60%, even more preferably to approximately 30% by weight, of the surfactant agent system. When the medium chain branched alkyl sulfate surfactant surfactants or medium chain branched alkyl alkoxy sulphate surfactants comprise 100% of the surface active agent system, the aforementioned surfactants will comprise up to 60% by weight of the final laundry detergent composition. The medium chain branched alkyl sulfate surfactants of the present invention have the formula: R R2 I CH3CH2 (CH2) wCH (CH2)? CH (CH2) and CH (CH2) 2pS? 3Mj the alkyl alkoxy sulfates have the formula: wherein R, R1, and R2 independently each is hydrogen, C1-C3 alkyl, and mixtures thereof; provided that at least one of R, R1, and R2 is not hydrogen; preferably R, R1, and R2 are methyl; preferably one R, R1, and R2 is methyl and the other units are hydrogen.

The total number of carbon atoms in the medium-chain branched alkyl alkylsulfate and alkyl alkoxy sulfate surfactants is from 14 to 20; the index w is an integer from 0 to 12; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; provided that 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 linear or branched C?-C 4 alkylene, preferably ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene, and mixtures thereof. However, a preferred embodiment of the present invention comprises from 1 to 3 units wherein R3 1,2-propylene, 1,3-propylene, or mixtures thereof followed by the balance of the R3 units comprising ethylene units. Another preferred embodiment comprises R3 units which are randomly units of ethylene and 1,2-propylene. The average value of the index m is at least 0.01 approximately. When the index m has low values the surfactant agent system comprises mainly alkyl sulfates with a small amount of alkyl alkoxy sulphate surfactant. Some tertiary carbon atoms may be present in the alkyl chain; however, this embodiment is not desired. M represents a cation, preferably hydrogen, a water soluble cation, and mixtures thereof. Non-limiting examples of water-soluble cations include sodium, potassium, lithium, ammonium, alkylammonium, and mixtures thereof. The preferred medium-chain branched alkyl alkylsulfate and alkyl alkoxy sulfate surfactants of the present invention are "substantially linear" surfactants. The term "substantially linear" is defined for the purposes of the present invention as "alkyl units comprising a branching unit or the chemical reaction products comprising mixtures of linear (unbranched) alkyl units and alkyl units which they comprise a unit that branches off. " The term "chemical reaction products" refers to the mixture obtained by a process wherein substantially linear alkyl units are the desired product but nevertheless some unbranched alkyl units are formed. When the definition is taken together with preferably one of R, R1, and R2 is methyl and the other units are hydrogen, the preferred alkyl chain-branched alkylsulfate and alkyl alkoxy sulfate surfactants comprise a methyl branch, preferably the aforementioned methyl strand is not in the a, ß, or in the penultimate carbon atom. Typically branched chains with a mixture of isomers. The following illustrates preferred examples of preferred medium-chain branched alkyl alkylsulfate and alkyl alkoxy sulfate surfactants. 8-Methylundecyl sulfate: 3-Methylundecyl sulfate: 3-Methyltridecyl sulfate: 8-Methyltridecyl sulfate: Branched Medium Chain Arylsulfonates The surfactant agent systems of the present invention may comprise a medium chain branched arylsulfonate surfactant agent. Because the medium chain branched arylsulfonate surfactants are not required when medium chain, branched alkyl alkylsulfate and / or alkyl alkoxy sulphate surfactants are present, the surfactant agent system comprises 0%, when 0.01% is present, preferably 0.1% approximately, more preferably from 1% to 100%, approximately, preferably to 80% approximately, preferably to 60% approximately, even more preferably to approximately 30% by weight, of the surfactant agent system. When the medium chain branched arylsulfonate surfactants comprise 100% of the surfactant system, the aforementioned medium chain branched arylsulfonate surfactants will comprise up to 60% by weight of the final laundry detergent composition. The medium chain branched arylsulfonate surfactants of the present invention have the formula: wherein A is a medium chain branched alkyl unit having the formula: R R 1 I I CH3 (CH2) xCH (CH2) and CH (CH2) i- wherein R and R1 are each independently hydrogen, C1-C3 alkyl, and mixtures thereof, provided that at least one of R and R1 is not hydrogen; preferably at least one of R or R1 is methyl; wherein the total number of carbon atoms in the aforementioned alkyl unit is from 6 to 18. Some tertiary carbon atoms may be present in the alkyl chain, however, this embodiment is not desired. The integer x is from 0 to 13. The integer y is from 0 to 13. The integer z is either 0 or 1, preferably 0.

R2 is hydrogen, C1-C3 alkyl, and mixtures thereof. Preferably R2 is hydrogen ..}. M 'represents a water-soluble cation with sufficient charge to provide neutrality, preferably hydrogen, a water-soluble cation, and mixtures thereof. Non-limiting examples of water-soluble cations include sodium, potassium, lithium, ammonium, alkylammonium, and mixtures thereof. In an important embodiment of the present invention, the preferred medium-chain branched arylsulfonate surfactants of the present invention are "substantially linear aryl" surfactants. The term "substantially linear aryl" is defined for the purposes of the present invention as "an alkyl unit which is taken together with an aryl unit wherein the aforementioned alkyl unit preferably comprises a branching unit; an unbranched linear alkyl unit having an aryl anity attached to the second carbon position as part of a mixture is included as a substantially linear aryl surfactant. " Preferred alkyl units do not have a methyl branch in the penultimate carbon atom. Typically the branched chains are a mixture of isomers. However, in the case of the medium chain branched arylsulfonates of the present invention, the relative position of the aryl moiety is key to the functionality of the surfactant. Preferably the aryl moiety is attached to the second carbon atom in the branched chain as illustrated in the present invention below.

In one or more embodiments the medium chain branched arylsulfonates of the present invention will comprise a mixture of branched chains. Preferably R1 is methyl, the z-index is equal to 0, and the sulfate moiety is for (1.4) the branched alkyl substituent thereby resulting in a "2-phenylarsulfonate" which is defined in the present invention by the General Formula: Typically the 2-phenylarsulfonates are formed as a mixture with each other with "3-phenylarylsulfonates" which is defined in the present invention by the general formula: The surfactant properties of the medium chain branched arylsulfonates of the present invention can be modified by varying the ratio of 2-phenyl to 3-phenyl isomers in the final surfactant mixture. A convenient means of describing the relative amounts of isomers that are present is the "2/3 phenyl index" which is defined in the present invention as "100 times the ratio of the amount of 2-phenyl isomer present divided by the amount of the 3-phenyl isomer that is present. " Any convenient means, NMR nuclear magnetic resonance, among others, can be used to determine the relative amounts of isomers that are present. A preferred 3/3 phenyl index is at least 275 which corresponds to at least 2.75 times more 2-phenyl isomer present than the 3-phenyl isomer in the surfactant mixture. The 2/3 preferred phenyl index according to the present invention is about 275, more preferably about 350, still more preferably about 500 to 10,000, about, preferably about 1200, more preferably about 700. Those of ordinary skill in the art will recognize that the chain branched surfactants of the present invention will be a mixture of isomers and the composition of the mixture will vary depending on the process is selected by the formulator to make the surfactants. For example, the following mixture is considered to comprise a mixture of substantially linear medium chain branched arisulfonate according to the present invention, sodium para- (7-methylnonan-2-yl) benzenesulfonate, para- (6-methylnonan-2-yl) sodium benzenesulfonate, sodium para- (7-methylnonan-3-yl) benzenesulfonate, sodium para- (7-methyldecan-2-yl) benzenesulfonate, sodium para- (7-methylnonanil) benzenesulfonate.

Formulations The compositions of the present invention can be in any form, among others, liquid, granulated, in paste. Depending on the specific form of the laundry composition, as well as the expected use thereof, the formulator may wish to use different combinations of surfactants and auxiliary ingredients. The Heavy-Duty Granular Compositions according to the present invention comprise: a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, even more preferably from 3% to 20%, approximately, preferably about 10%, more preferably to about 7% by weight, of a hydrophobically modified polyamine; and b) from about 0.01% by weight, preferably from about 0.1%, more preferably from about 1% to about 60%, preferably about 30% by weight, of the aforementioned composition of a surfactant agent system, the surfactant system aforementioned comprises: i. of 0.01%, preferably of 0.1%, approximately, more preferably from 1% to 100%, approximately, preferably to approximately 80% by weight, preferably to approximately 60%, more preferably to approximately 30% by weight, of a surfactant which is selected from the group of alkyl sulfate surfactants, alkoxy sulfate surfactants, medium chain branched alkyl sulfate surfactants, medium chain branched alkoxy sulfate surfactants, medium chain branched arylsulfonate surfactants, and mixtures thereof; ii. optionally and preferably of 0.01%, preferably of about 0.1%, more preferably from 1% to 100%, about, preferably to about 80% by weight, preferably to about 60%, even more preferably to about 30% by weight, of one or more anionic surfactants; iii. optionally, 0.01%, preferably about 0.1%, more preferably from 1% to 100%, approximately, preferably about 80% by weight, preferably about 60%, more preferably about 30% by weight, of one or more nonionic surfactants. Heavy-duty granular detergent compositions (HDG) will typically comprise more than anionic detersive surfactants. Therefore, the formulator will employ a zwitterionic polyamine having a greater number of anion units than the number of cationic units in the main chain. This balance of the net chart will improve the negative interaction of the surfactant molecules with the active hydrophilic zwitterionic polymers. In contrast, preferably the Heavy Use Liquid (HDL) compositions according to the present invention comprise: a) from about 0.01%, preferably from about 0.1%, more preferably from 1%, even more preferably from about 3% to about 20%; preferably about 10%, more preferably about 5% by weight, of a zwitterionic polyamine wherein the aforementioned polyamine comprises less than or equal number of anionic substituents than the number of main chain quaternary nitrogen units; and b) from about 0.01% by weight, preferably from about 0.1%, more preferably from about 1% to about 60%, preferably about 30% by weight, of the aforementioned composition of a surfactant agent system, the surfactant system aforementioned comprises: i. of 0.01%, preferably of about 0.1%, more preferably from about 1% to about 100%, preferably about 80% by weight, preferably about 60%, more preferably about 30% by weight, of a surfactant that is select from the group of medium chain branched alkyl sulfate surfactants, medium chain branched alkoxy sulfate surfactants, medium chain branched arylsulfonate surfactants, and mixtures thereof; ii. preferably 0.01%, preferably about 0.1%, more preferably about 1% to 100%, about, preferably about 80% by weight, preferably about 60%, even more preferably about 30%, by weight, of one or more nonionic surfactants, the nonionic surfactants are selected from the group consisting of alcohols, alcohol ethoxylates, polyoxyalkylenealkylamides, and mixtures thereof; iii. optionally, 0.01%, preferably about 0.1%, more preferably from 1% to 100%, about, preferably about 80% by weight, preferably about 60%, more preferably about 30% by weight, of one or more nonionic surfactants. Heavy-duty liquid laundry detergent (HDL) compositions will typically comprise more than a lesser amount of an anionic detersive surfactant and more nonionic surfactants. Therefore, the formulator will employ a zwitterionic polyamine having an equal number of anion units as the number of cationic units or a greater number of cationic main chain units than the number of anion units.

Bleach System Laundry detergent compositions comprising hydrophobically modified polyamine of the present invention optionally may comprise a bleach system. Bleaching systems typically comprise a "bleaching agent" (source of hydrogen peroxide) and an "initiator" or "catalyst".

Preferred laundry detergent compositions of the present invention comprising a bleaching system, comprise: a) from about 0.01% by weight of a hydrophobically modified polyamine according to the present invention; b) about 0.01% by weight, of a surfactant agent system comprising: i. from 0% to 100% by weight, of the surfactant agent system of one or more anionic surfactants; ii. from 0% to 100% by weight, of the surfactant agent system of one or more nonionic surfactants; iii. optionally from about 0.1% to 80% by weight, of the surfactant agent system of one or more cationic surfactants; iv. optionally 0.1% to 80% by weight, of the surfactant agent system of one or more zwitterionic surfactants; v. optionally 0.1% to 80% by weight, of the surfactant agent system of one or more ampholytic surfactants; or vi. mixtures of these; c) from about 1%, preferably from about 5% to about 80%, preferably about 50% by weight, of the laundry detergent composition, of a peroxygen bleach system comprising: i. about 40%, preferably about 50%, more preferably about 60% to about 100%, preferably about 95%, more preferably about 80%, by weight, of the bleach system, of a source of hydrogen peroxide; ii. optionally from about 0.1%, preferably from about 0.5% to about 60%, preferably about 40% by weight, of the bleach system, of a bleach activator; iii. optionally of about 1 ppb (0.0000001%), more preferably of 100 ppb (0.00001%) approximately, even more preferably of 500 ppb (0.00005%) approximately, more preferably still from 1 ppm (0.0001%) to 99.9%, approximately, more preferably at about 50%, still more preferably at about 5%, more preferably still at about 500 ppm (0.05%) by weight of the composition, of a transition metal bleach catalyst; iv. optionally about 0.1% by weight of a preformed peroxygen bleaching agent; and d) the balance of carriers and other auxiliary ingredients.

Bleaching Agents Sources of hydrogen peroxide are described in detail in the reference that is incorporated in the present Kirk Othmer's Encyclopedia of Chemical Technology, Fourth Edition (1992, John Wiley & Sons), Volume. 4, pp. 271-300"Bleaching Agents (Study)", and includes the different forms of sodium perborate and sodium percarbonate, including the different coated and modified forms. Sources of hydrogen peroxide which are suitable for use in the compositions of the present invention include, but are not limited to, perborates, percarbonates, perfosphates, persulfates, and mixtures thereof. Preferred sources of hydrogen peroxide are sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and sodium persulfate, more preferably sodium perborate monohydrate, sodium perborate tetrahydrate, and sodium percarbonate. When present the source of hydrogen peroxide is present at a level of about 40%, preferably about 50%, more preferably from about 60% to about 100%, preferably about 95%, more preferably about 80% by weight , of the bleaching system. Embodiments that are pre-bleach compositions comprising bleach may comprise from 5% to 99% of the source of hydrogen peroxide. A preferred percarbonate bleach comprises dry particles having an average particle size in the range of 500 micrometers to 1,000 micrometersapproximately no more than about 10% by weight of the aforementioned particles are smaller than about 200 microns and no more than about 10% by weight of the aforementioned particles are larger than about 1250 microns. Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactants.

Bleach Activators Preferably, the source of hydrogen peroxide (component of peroxygen bleach) in the composition is formulated with an activator (peracid precursor). The activator is present at levels of about 0.01%, preferably about 0.5%, more preferably from about 1% to about 15%, preferably about 10%, more preferably about 8%, by weight of the composition. In addition, the bleach activators will comprise from 0.1% to 60%, approximately, by weight, of the bleaching system. When the bleaching system described in the present invention comprises 60% by weight, of an activator (maximum amount) and the aforementioned composition (bleaching composition, laundry detergent, or otherwise) comprises 15% by weight of the activator mentioned above (the maximum amount by weight), the aforementioned composition will comprise 25% by weight of a bleaching system (60% of which is bleach activator, 40% a source of hydrogen peroxide). However, it is not the purpose to restrict the formulator to a 60:40 ratio of activator to hydrogen peroxide source. Preferably the molar ratio of the peroxygen bleach compound (as AvO) to bleach activator in the present invention generally ranges from at least 1: 1, preferably from about 20: 1, more preferably from 10: 1 to 1: 1, approximately , preferably at about 3: 1. Preferred activators are selected from the group consisting of tetraacetylethylenediamine (TAED), benzoylcaprolactam (BzCL), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzoyloxybenzenesulfonate (BOBS), nonanoyloxybenzenesulfonate (NOBS), phenylbenzoate (PhBz), decanoyloxybenzenesulfonate C10-OBS ), benzoylvalerolactam (BZVL), octanoyloxybenzenesulfonate (C8-OBS), perhydrolyzable esters and mixtures thereof, more preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators in the pH range of about 8 to 9.5 are those that are selected to have an OBS or VL output group. Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS) sodium salt of 4- [N- (nonanoyl) amino hexanoyloxy-benzene (NACA-OBS) an example of this is disclosed in U.S. Pat. No. 5,523,434, dodecanoyloxybenzenesulfonate (LOBS or C-? 2-OBS), 10-undecenoyloxybenzenesulfonate (UDOBS or Cn-OBS with unsaturation at the 10-position), and decanoyloxybenzoic acid (DOBA). Preferred bleach activators are those described in U.S. Patent 5,698,504, Christie et al., Issued December 16, 1997; U.S. Patent 5,686,401, Wiley et al., Issued November 11, 1997; U.S. Patent 5,686,014, Hartshorn et al., Issued November 11, 1997; U.S. Patent 5,405,412, Wiley et al., Issued April 11, 1995; U.S. Patent 5,405, 413, Wiley et al., Issued April 11, 1995; U.S. Patent 5,130,045, Michel et al., Issued July 14, 1992; and U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and the copending U.S. Patent Serial Nos. 08 / 709,072, 08 / 064,564; acyl lactam activators, as described in U.S. Patent 5,698,504, U.S. Patent 5,695,679 and U.S. Patent 5,686,014, all are cited above in the present invention, and are very useful in the present invention, especially acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams, U.S. Patent 5,503,639, Wiley et al., issued April 2, 1996, all are incorporated by reference in the present invention. Blanked quaternary bleach activators can also be included. The present detergent compositions preferably comprise a substid quaternary bleach activator (QSBA) or a substid quaternary peracid (QSP); more preferably, the last one. Preferred QSBA structures are further described in U.S. Patent 5,686,015, Wiley et al., Issued November 11, 1997; U.S. Patent 5,654,421, Taylor et al., Issued August 5, 1997; U.S. Patent 5,460,747, Gosselink et al., Issued October 24, 1995; U.S. Patent 5,584,888, Miracle et al., Issued December 17, 1996; and U.S. Patent 5,578,136, Taylor et al., issued November 26, 1996; all are incorporated by reference in the present invention. Most preferred bleach activators useful in the present invention are substituted amide as written in U.S. Patent 5,698,504, U.S. Patent 5,695,679, and U.S. Patent 5,686,014, all are cited above in the present invention. Preferred examples of such bleach activators include: (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate and mixtures thereof. Other useful activators, which are disclosed in the Patent of the United States 5,698,504, U.S. Patent 5,695,679, U.S. Patent 5,686,014 all are cited above with reference, and U.S. Patent 4,966,723, Hodge et al., Issued October 30, 1990, include benzoxazine activators. such as a CßH4 ring to which it is fused in the 1, 2-positions one half of -C (O) OC (R1) = N-. Depending on the activator and the precise application, good whitening results can be obtained from bleaching systems having a pH in use of from 6 to 13, approximately, preferably from 9.0 to 10.5, approximately. Typically, for example, activators with halves that withdraw electrons are used at pH scales near neutral or below neutral. Alkaline and buffering agents can be used to ensure such a pH.

Transition Metal Bleach Catalyst The laundry detergent compositions of the present invention optionally comprise a bleach system containing one or more bleach catalysts. Selected bleach catalysts, among others, 5,12-dimethyl-1, 5,8,12-tercaza-bicyclo [6.6.2] hexadecane manganese (II) chloride can be formulated in bleaching systems that do not require a source of peroxide of hydrogen or peroxygen bleach. The compositions comprise about 1 ppb (0.0000001%) approximately, more preferably about 100 ppb (0.00001%), even more preferably about 500 ppb (0.00005%), even more preferably from 1 ppm (0.0001%) to 99.9%, approximately , more preferably at about 50%, still more preferably at about 5%, more preferably still at about 500 ppm (0.05%) by weight of the composition, of a transition metal bleach catalyst. Non-limiting examples of suitable manganese-based catalysts are disclosed in U.S. Patent 5,576,282, Miracle et al., Issued November 19, 1996; U.S. Patent 5,246,621 Favre et al., Issued September 21, 1993; U.S. Patent 5,244,594 Favre et al., Issued September 14, 1993; U.S. Patent 5,194,416 Jureller et al., Issued March 16, 1993; U.S. Patent 5,114,606 van Vliet et al., Issued August 19, 1992; U.S. Patent 4,430,243 Bragg, issued February 7, 1984; U.S. Patent 5,114,611 van Kralingen, issued May 19, 1992; U.S. Patent 4,728,455 Rerek, issued March 1, 1988; U.S. Patent 5,284,944 Madison, issued February 8, 1994; U.S. Patent 5,246,612 van Dijk et al., Issued September 21, 1993; U.S. Patent 5,256,779 Kerschner et al., Issued October 26, 1993; U.S. Patent 5,280,117 Kerschner et al., Issued January 18, 1994; U.S. Patent 5,274,147 Kerschner et al., Issued December 28, 1993; U.S. Patent 5,153,161 Kerschner et al., Issued October 6, 1992; and U.S. Patent 5,227, 084 Martens et al., issued July 13, 1993; and European Patent Application Publication Nos. 549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1. Non-limiting examples of suitable cobalt-based catalysts are disclosed in U.S. Patent 5,597,936 Perkins et al., Issued January 28, 1997; U.S. Patent 5,595,967 Miracle et al., Issued January 21, 1997; U.S. Patent 5,703,030 Perkins et al., Issued December 30, 1997; U.S. Patent 4,810,410 Diakun et al., Issued March 7, 1989; M. L. Tobe, "Basic Hydrolysis of Transitional Metal Complexes" Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94; J. Chem. Ed. (1989), 66 (12), 1043-45; "The synthesis and characterization of inorganic compounds" W. L. Joliy (Prentice-Hall; 1970), pp. 461-3; Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); "Inorganic Synthesis", 173-176 (1960); and Journal of Physical Chemistry, 56, 22-25 (1952). Additional examples of bleach catalysts comprising preferred macrocyclic ligand are described in WO 98/39406 A1, published on September 11, 1998, and are included in the present invention as a reference. Suitable examples of these bleach catalysts include: Dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Diacuo-hydroxy-5,12-dimethyl-1 hexafluophosphate, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Acid-hydroxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Hexafluophosphate hexafluorophosphate aqueous-hydroxy-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (lll) Diacuo-5,12-dimethyl-1, 5,8,12-tetraazabicyclo tetrafluoroborate [6.6 .2] hexadecane manganese (II) Tetrafluophosphate dichloro-5,12-dimethyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (III) Dichloro-5,12-di-n-butyl-1 , 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Dichloro-5,12-dibenzyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Dichloro-5-n -butyl-12-methyl-1, 5,8,12-tetraazabicyclo [6.6.2] hexanecane Manganese (II) Dichloro-5-n-octii-12-methyl-1, 5,8,12-tetraazabicyclo [6.6 .2] manganese hexadecane ( ll) Dichloro-5-n-butyl-12-methyl-15,8,12-tetraazabicyclo [6.6.2] hexadecane manganese (II) Preformed Bleaching Agents The bleaching systems of the present invention may optionally further comprise 0.1%, prably 1%, more prably from 5% to 10%, prably about 7% by weight, of one or more preformed bleaching agents. Preformed whitening materials typically have the general formula: O li HO- O- C- R- Y wherein R is a CrC22 alkylene, C C22 substituted alkylene, phenylene, substituted C6-C22 phenylene, and mixtures thereof. And it is hydrogen, halogen, alkyl, aryl, -C (0) OH, -C (0) OOH, and mixtures thereof. The organic percarboxylic acids which may be used in the present invention may contain either one or two peroxy groups and may be either aliphatic or aromatic. When the organic percarboxylic acid is aliphatic, the unsubstituted acid has the general formula: OR II HO- O- C- (CH2) n ~ Y wherein Y can be hydrogen, methyl, methyl chloride, carboxylate, percarboxylate; and n is an integer that has the value of 1 to 20. When the organic percarboxylic acid is aromatic, the unsubstituted acid has the general formula: wherein Y can be hydrogen, alkyl, haloalkyl, carboxylate, percarboxylate, and mixtures thereof. Typical monoperoxypercarboxylic acids useful in the present invention include alkylpercarboxylic acids and arylpercarboxylic acids such as: i. peroxybenzoic acid and substituted peroxybenzoic acids, e.g., peroxy-o-naphthoic acid; ii. aliphatic, substituted aliphatic monoperoxy acids and arylkylmonoperoxy acids, e.g., peroxylauric acid, peroxystearic acid, and N, N-phthaloylaminoperoxycaproic acid (PAP). Typical diperoxypercarboxylic acids useful in the present invention include alkyldiperoxy acids and aryl peroxy acids such as: iii. 1,2-diperoxydecanedioic acid; iv. 1, 9-diperoxyazelaic acid; v. diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid; saw. 2-decyliperoxybutane-1,4-dioic acid; vii. 4,4'-sulfonbisperoxybenzoic acid. A non-limiting example of a highly prred preformed bleach bleach includes 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) as described in U.S. Patent No. 4,634,551, Burns et al., Issued January 6, 1987, which is included in the present invention as a rence. As well as the peroxygen bleach compositions described in the present invention, a chlorine bleach material can also be included as the bleaching agent. Such agents are well known in the art, and include for example sodium dichloroisocyanurate ("NaDCC"). However, chlorine bleaches are less prred for compositions comprising enzymes.

Auxiliary Ingredients The following are non-limiting examples of auxiliary ingredients useful in the laundry detergent compositions of the present invention, the aforementioned auxiliary ingredients include enhancers, optical brighteners, soil release polymers, dye transfer agents, dispersing agents, enzymes , foam suppressors, dyes, perfumes, dyes, filler salts, hydrotropes, photoactivators, fluorescers, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelating agents, stabilizers, anticaking agents, anti-wrinkle agents, germicides, fungicides, anti-corrosion agents, and mixtures of these.

Enzymes The term "enzyme" or "detersive enzyme", as used in the present invention, means any enzyme that has a cleansing, stain removal or otherwise advantageous effect in a laundry detergent formulation or composition, cleaning surfaces hard, or other formulation or cleaning composition as described in the present invention. In general, enzymes are present in the compositions of the present invention at a level of 0.0001%, more prably 0.0005%, still more prably from 0.001% to 2%, prably 0.1%, even more prably 0.02% by weight of pure enzyme. Prred enzymes are hydrolases such as proteases, amylases and lipases. Prred enzymes for laundry detergent purposes include, but are not limited to, among others, proteases, cellulases, lipases and peroxidases.

Protease Enzymes Preferred liquid laundry detergent compositions according to the present invention additionally comprise at least 0.001% by weight of a protease enzyme. However, an effective amount of protease enzyme is sufficient for use in liquid laundry detergent compositions that are described in the present invention. The term "effective amount" refers to any amount capable of producing a cleaning effect, removing stains, removing dirt, bleaching, deodorizing, or improving freshness on substrates such as fabrics. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01% mg to about 3 mg of active enzyme per gram of the detergent composition. Expressed in another way, the compositions in the present invention will typically comprise from 0.001% to 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. The protease enzymes of the present invention are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of the composition. Preferred liquid laundry detergent compositions of the present invention comprise modified protease enzymes derived from Bacillus amyloliquefaciens or Bacillus lentus. For the purposes of the present invention, protease enzymes derived from B. amyloliquefaciens are further referred to as "subtilisin BPN" which are further mentioned as "Protease A" and protease enzymes derived from B. Lentus which are additionally referred to as "subtilisin". 309". For the purposes of the present invention, the numeration of the subtilisin Bacillus amyloliquefaciens, as described in the patent applications of A. Baeck, et al., Entitled "Cleaner Compositions Containing Protease", US Patent Application Serial No. 08 / 322,676, serves as the numbering system for the amino acid sequence for both subtilisin BPN 'and subtilisin 309.

Subtilisin-BPN 'Enzyme Derivatives of Bacillus amylollauefaciens A preferred protease enzyme for use in the present invention is a variant of Protease A (BPN') which is a non-naturally occurring variant of carbonyl hydrolase having a different activity proteolytic, stability, substrate specificity, pH profile and / or performance characteristic compared to the precursor carbonyl hydrolase from which the amino acid sequence of the variant is derived. This variant of LBP 'is disclosed in EP 130,756 A, of January 9, 1985. Protease B A preferred protease enzyme for use in the present invention is Protease B. Protease B is a variant of carbonyl hydrolase which does not occurs naturally having a different proteolytic activity, stability, substrate specificity, pH profile and / or performance characteristics compared to the precursor carbonyl hydrolase from which the amino acid sequence of the variant is derived. Protease B is a variant of BPN 'in which tyrosine is replaced with leucine at position +217 and as further disclosed in EP 303,761 A, of April 28, 1987, and EP 130,756 A, of January 9, 1987. 1985 Protease C A preferred protease enzyme for use in the compositions of the present invention is Protease C. Protease C is a variant of serine alkaline protease from Bacillus in which lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine replaces asparagine at position 123, and alanine replaces threonine at 274. Protease C is described in EP 90915958: 4, which corresponds to WO 91/06637, published on May 16, 1991. Genetically modified variants , particularly of Protease C, are also included in the present invention.

Protease D A preferred protease enzyme for use in the present invention is Protease D. Protease C is a carbonyl hydrolase variant derived from subtilisin Bacillus lentus as described in WO 95/10615 published on April 20, 1995, by Genencor International. A further preferred protease enzyme for use with the modified polyamines of the present invention is ALCALASE® from Novo. Another suitable protease is obtained from a Bacillus strain, which has a maximum acfivity throughout the pH range of 8-12, developed and marketed as ESPERASE® by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1, 243,784 to Novo.

Other suitable proteases include SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands. See also a high pH protease from Bacillus sp. NCIMB 40338 which is described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble. When desired, a protease having reduced adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable in the present invention is described in WO 9425583 to Novo. Other particularly useful proteases are described in PCT Applications Nos. PCT / US98 / 22588, PCT / US98 / 22482 and PCT / US98 / 22486, all registered on October 23, 1998 from The Procter & Gamble Company. Also suitable for the present invention are proteases which are described in patent applications EP 251 446 and WO 91/06637, BLAP® protease which is described in WO91 / 02792 and its variants which are described in WO 95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 which is described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having reduced adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable for the present invention is described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 by Unilever. Commercially available proteases useful in the present invention are known as ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE® all from Novo Nordisk A / S of Denmark, and as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM ® all from Genencor International (formerly Gist-Brocades of The Netherlands). A preferred protease for use in the present invention is the protease enzyme as described in WO99 / 20771 published on April 29, 1999. In addition to the protease enzymes described above, other enzymes suitable for use in detergent compositions Laundry laundry liquids of the present invention are further described below in the present invention.

Other Enzymes Enzymes in addition to the protease enzyme may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based, or triglyceride-based spots from surfaces such as textiles, to prevent transfer of refugee dye, for example in the washing of clothes, and for the restoration of fabrics. Suitable enzymes include amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. Preferred selections are influenced by factors such as pH activity and / or stability optima, thermostability, stability to active detergents, improvers and the like. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred. Amylases suitable in the present invention include, for example, the α-amylases described in GB 1, 296, 839 to Novo.; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® by Novo is especially useful. Enzyme engineering is known to improve stability, e.g., oxidative stability. See for example J. Biological Chem., Vol. 260, No. 11, June 1985, pages 6518-6521 and WO 9402597 to Novo, of February 3, 1994, and WO 9509909 A to Novo. Cellulases usable in the present invention include both bacterial and fungal types, which preferably have an optimum pH of between 5 and 9.5. U.S. Patent 4,435,307, Barbesgoard et al., Issued March 6, 1984, discloses a fungal cellulase produced from Humicola insolens and the Humicola strain DSM 1800 or a fungus that produces cellulase 212 belonging to the Aeromonas genus, and a cellulase that is extracted from the hepatopancreas of a marine mollusk (Dolabella Auricular Solander). Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247-832. Especially useful is CAREZYME® (Novo). See also WO 9117243 to Novo. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as disclosed in British Patent 1, 372,034. See also lipases in Japanese Patent Application 53,20487, issued to the public on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trademark Lipasa P "Amano" or Amano -P "Other suitable commercial lipases include Amano-CES, ex Chromobacter viscosum lipases, eg, Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Jozo Co. Tagata, Japan; Chromobacter viscosum lipases from United States Patent Biochemical Corp., Patent of the United States A., and Disoynth Co., The Netherlands, and the lipases ex Pseudomonas gladioli.The enzyme LIPOLASE® which is derived from Humicola lanuginosa and commercially available from Novo, see also EP 341, 947, is a lipase Preferred for use in the present invention Variants of lipase and amylase stabilized against peroxidase enzymes are described in WO 9414951 A to Novo, see also WO 9205249 and RD 94359044. Cutinase enzymes suitable for used in the present invention are described in WO 8809367 A to Genencor. Enzymes of peroxidase can be used in combination with oxygen sources, eg, percarbonate, perborate, persulfate, hydrogen peroxide, etc., for "bleaching in solution" or avoid the transfer of dyes or pigments that are removed from substrates during operations of washing other substrates in the washing solution. Peroxidase enzymes known in the art include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are disclosed, for example, in WO89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo and WO 890813 A to Novo. A wide variety of enzyme materials and means for incorporation into synthetic detergent compositions are also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and in U.S. Patent 3,553,139 of 5 January 1971, to McCarty et al. Enzymes are further disclosed in U.S. Patent 4,101, 457, Place et al., July 18, 1978, and in U.S. Patent 4,507,219, Hughes, March 26, 1985. Enzymatic materials useful for Liquid detergent formulations and their incorporation into such formulations are disclosed in U.S. Patent 4,261, 868, Hora et al., April 14, 1981. Enzymes for use in the present invention can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319, August 17, 1971, to Gedge, et al., EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described in, for example, U.S. Patent 3,519,570. A Bacillus sp. Useful AC13 which provides proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme Stabilizing System Compositions containing enzymes including, but not limited to, liquid compositions, in the present invention may comprise from about 0.001%, preferably from about 0.005%, more preferably from about 0.01% to about 10%, preferably about 8% , more preferably about 6%, of an enzyme stabilizing system. The enzyme stabilizing system can be any enzyme stabilizing system that is compatible with the detersive enzyme. Such a system can be inherently provided by other active ingredients of the formulation, or can be added separately, e.g., by the formulator or by a manufacturer of detergent-ready enzymes. Such stabilizer systems may comprise, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to solve different stabilization problems depending on the type and physical form of the composition. Detergent. One method of stabilizing is the use of water soluble sources of calcium and / or magnesium in the finished compositions that provide such solutions to the enzymes. Calcium ions are generally more effective than magnesium ions and the present invention is preferred in case only one cation type is used. Typical detergent compositions, especially liquid, will comprise from 1 to 30, approximately, preferably from 2 to 20, approximately, more preferably from 8 to 12 millimoles, approximately, of calcium ion per liter of the finished detergent composition, although variation is possible depending on factors that include the multiplicity, the type and levels of enzymes that are incorporated. Preference is given to using water-soluble calcium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the example calcium salts. Increased levels additional levels of calcium and / or magnesium can of course be useful, for example to promote the fat-cutting action of certain types of surfactant. Another stabilizing method is by the use of borate species disclosed in U.S. Patent 4,537,706, Severson, issued August 27, 1985. Borate stabilizers, when used, may be at levels up to 10% or more. more of the composition although more typical levels of up to about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for use in liquid detergents. Substituted boric acids such as phenylboronic acid, butane boronic acid, p-bromophenylboronic acid or the like may be used in place of boric acid, and reduced total levels of boron in the detergent compositions may be possible by the use of such substituted boron derivatives .

Stabilizing systems of certain cleaning compositions additionally may comprise 0, preferably from 0.01% to 10%, approximately, preferably about 6% by weight, of chlorine bleach scrubbers, which are added to prevent bleach and chlorine species from are present in many water sources attack and deactivate enzymes, especially under alkaline conditions. Even though chlorine levels in water can be reduced, typically in the range of 0.5 ppm to 1.75 ppm, approximately, the available chlorine in the total volume of water that comes into contact with the enzyme during washing can be considerable; therefore, the stability of the enzyme in use can be problematic. In view of the fact that the perborate or percarbonate, which have the ability to react with the chlorine bleach, may be present in some of the present compositions in amounts that are taken into account separately from the stabilizing system, the use of additional stabilizers against chlorine may, in general terms, not be essential, although improved results of its use may be obtained. Anions of suitable chlorine scavengers are well known and readily available and, if used, can be salts containing ammonium cations are sulphite, bisulfite, thiosulphite, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or the alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof, can also be used. Also, special enzyme inhibitor systems can be incorporated so that different enzymes have maximum compatibility. Other conventional scrubbers such as bisulfate, nitrate, chloride, peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate , etc., and mixtures of these can be used if desired. In general, since the function of the chlorine scrubber can be performed by ingredients that are listed separately under better recognized functions (eg, sources of hydrogen peroxide), there is no absolute need to add a separate chlorine scrubber to less than in a compound that performs that function in the desired amount is absent from the enzyme-containing embodiment of the invention; even so, the debugger is added only to obtain optimal results. On the other hand, the formulator will proceed with the normal experience of a chemical technician to avoid the use of any enzyme scavenger or stabilizer that is mainly incompatible, in the way it is formulated, with other reactive ingredients, if used. In relation to the use of ammonium salts, such salts can be simply mixed with the detergent composition, but have a tendency to adsorb water and / or release ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in U.S. Patent 4,652,392, Baginski et al., Issued March 24, 1987.

Detergent Metering Agent The laundry detergent compositions of the present invention comprise one or more builders or builders. When present, the compositions will typically comprise from about 5%, preferably from about 10% to about 80%, preferably about 50%, more preferably about 30% by weight, of builder. The level of builder agent may vary widely depending on the final use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% of. The formulations typically comprise from about 5% to 50%, more typically, about 5% to 30%, by weight, of builder. Granulated formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the builder. However, it is not the purpose to exclude lower or higher levels of builder agent. Inorganic or phosphorus-containing builders include, but are not limited to, the alkali metal, ammonium and aikonammonium salts of polyphosphates ( exemplified by tripolyphosphates, pyrophosphates, and vitreous polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfates, aluminosilicates. However, phosphate-free builders are required in some locations. Importantly, the compositions in the present invention also function in the presence of so-called "weak" builders (as compared to phosphates) such as citrate, or in the so-called "sub-enhanced" situation that can occur with the builder agents. detergency of zeolite or layered silicates. Examples of silicate builder agents are alkali metal silicates, particularly those having a SiO2: Na2O ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates, such as layered sodium silicates. which are described in U.S. Patent 4,664,839. NaSKS-6 is the trademark of a layered crystalline silicate marketed by Hoechst (commonly abbreviated as "SKS-6"). Unlike zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. The NaSKS-6 has the morphological form delta-Na2SiO5 of the layered silicate. It can be prepared by methods such as those described in German Patent DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other such layered silicates can be used in the present invention, such as those having the general formula and H 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0. Different other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta forms and range. As noted above, the delta-Na2SiO5 form (NaSKS-6 form) is the most preferred form for use in the present invention. Other silicates may also be useful, such as, for example, magnesium silicate, which can serve as a creping agent in the granulated formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builder agents are the alkali metal and alkaline earth metal carbonates as disclosed in German Patent Application No. 2,321,001. The aluminosilicate builder agents are detergency builders useful in the present invention. The aluminosilicate builder agents are of great importance in most of the heavy duty granular detergent compositions currently marketed, and can also be a significant detergency enhancing ingredient in liquid detergent formulations. Aluminosilicate builders include those with the empirical formula: Mz [(zAIO2) and] xH2O where z and e are integers of at least 6, the molar ratio of zay is in the range of 1.0 to 0.5 and x is an integer from 15 to 264, approximately.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be of crystalline or amorphous structure and may be aluminosilicates that occur naturally or that are synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in the present invention are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the aluminosilicate ion exchange material crystalline has the formula: Na? 2 [(AIO2) i2 (SiO2) i2]? H2O where x is from 20 to 30, approximately, especially approximately 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0-10) can also be used in the present invention. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention include, but are not limited to, a wide variety of polycarboxylate compounds. As the present invention is used, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. The polycarboxylate builder generally can be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in the salt form, alkali metals, such as the sodium, potassium, and lithium, or alkalino-ammonium salts, are preferred. A variety of categories of useful materials are included among the polycarboxylate builder agents. An important category of polycarboxylate builder agents comprises ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, and U.S. Patent 3,635,830. See also detergent builders "TMS / TDS" of U.S. Patent 4,663,071. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patent 3,923,679, Rapko, issued December 2, 1975; U.S. Patent 4,158,635, Crutchfield et al., issued June 19, 1979; U.S. Patent 4,120,874, Crutchfield et al., issued October 17, 1978; and U.S. Patent 4,102,903, Crutchfield et al., issued July 25, 1978. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, acid 1, 3.5 -trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as methyl acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and the soluble salts thereof. Citrate builders, eg, citric acid and soluble salts thereof (particularly the sodium salt), are polycarboxylate builders of particular importance for heavy-duty laundry detergent formulations at their availability. sources of renewable resources and their biodegradable capacity. The citrates can also be used in granular compositions, especially in combination with zeolite builder and / or layered silicate. Oxydisuccinates are also especially useful in such compositions and combinations. The 3, 3-dicarboxy-4-oxa-1,6-hexanediotes and the related compounds disclosed in U.S. Patent 4,566,984 are also suitable in the detergent compositions of the present invention. Useful succinic acid builder agents include C5-C20 alkyl- and alkenyl-succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European Patent Application 86200690.5 / 0,200,263, published November 5, 1986. Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield. et al., issued March 13, 1979, and in United States Patent 3,308,067, Diehl, issued March 7, 1967. See also United States Patent 3,723,322. Fatty acids, e.g., C12-C18 monocarboxylic acids may also be incorporated into the compositions individually, or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional builder activity. Such uses of fatty acids will generally result in a decrease in foam production, which should be taken into account by the formulator. In situations where phosphorus-based detergency builders can be used, and especially in the formulation of sticks used in hand washing operations, the various alkali metal phosphates such as the well-known sodium tripolyphosphates can be used, sodium pyrophosphate and sodium orthophosphate. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

Dispersing Agents A description of other suitable polyalkyleneimine dispersing agents that can optionally be combined with the stable dispersing agents in the bleach of the present invention can be found in U.S. Patent 4,597,898 Vander Meer, issued July 1, 1986; European Patent Application 111, 965 Oh and Gosselink, published June 27, 1984; European Patent Application 111,984 Gosselink, published June 27, 1984; European Patent Application 112,592 Gosselink, published July 4, 1984; U.S. Patent 4,548,744 Connor, issued October 22, 1985; and U.S. Patent 5,565,145 Watson et al., issued October 15, 1996; all are included in the present invention for reference. However, any suitable clay / soil dispersant or anti-restraining agent can be used in the laundry detergent compositions of the present invention. Additionally, polymeric dispersing agents including polymeric polycarboxylates and polyethylene glycols are suitable for use in the present invention. Polymeric polycarboxylate materials can be prepared by the polymerization or copolymerization of suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence in the polymeric polycarboxylates in the present invention of monomeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that such segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers which are useful in the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form preferably ranges from 2,000 to 10,000, approximately, more preferably from 4,000 to 7,000, approximately, and more preferably even from 4,000 to 5,000, approximately. Water-soluble salts of such acrylic acid polymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type of detergent compositions has been disclosed in, for example, Diehl, U.S. Patent 3,308,067, issued March 7, 1967. Acrylic / maleic-based copolymers can be used as a preferred component of the agent dispersant / anti-settling. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic anhydride. The average molecular weight of such copolymers in the acid form preferably ranges from 2,000 to 100,000, approximately, more preferably from 5,000 to 75,000, approximately, more preferably even from 7,000 to 65,000, approximately. The ratio of acrylate to maleate segments in such copolymers generally ranges from about 30: 0 to 1: 1, more preferably from about 10: 1 to about 2: 1. The water-soluble salts of such acrylic acid / maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published on December 15, 1982, as well as EP 193,360, published on September 3, 1986, which describes also such polymers comprising hydroxypropyl acrylate. Still other dispersing agents include the terpolymers of maleic / acrylic / vinyl alcohols. Such materials are also disclosed in EP 193,360, including, for example, terpolymer 45/45/10 acrylic / maleic / vinyl alcohol. Other polymeric material that can be included in polyethylene glycol (PEG). The PEG can exhibit an operation of dispersing agent as well as it can also act as an agent for elimination / anti-settling of clay soil. Typical molecular weights vary for these purposes from 500 to 100,000, approximately, preferably from 1,000 to 50,000, approximately, more preferably from 1,500 to 10,000, approximately. Polyaspartate and polyglutamate dispersing agents can also be used, especially together with zeolite detergent builders. Dispersing agents such as polyaspartate preferably have a molecular weight (average) of about 10,000.

Dirty Release Agents The compositions according to the present invention may optionally comprise one or more dirt release agents. If used, the soil release agents will generally comprise about 0.01%, preferably about 0.1%, more preferably from 0.2% to 10%, about, preferably about 5%, more preferably about 3% by weight , of the composition. Polymeric soil release agents are characterized by having so many hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, as hydrophobic segments, to deposit on hydrophobic fibers and remain adhered to them until the end of the wash cycle clothes and, in this way, serve as an anchor for the hydrophilic segments. This may allow stains that occur after treatment with the release agent to be dirty to be more easily cleaned in subsequent washing procedures. The following, which are all included as reference in the present invention, describe suitable release polymers for use in the present invention. U.S. Patent 5,843,878 Gosselink et al., Issued December 1, 1998; U.S. Patent 5,834,412 Rohrbaugh et al., Issued November 10, 1998; U.S. Patent 5,728,671 Rohrbaugh et al., Issued March 17, 1998; U.S. Patent 5,691, 298 Gosseiink et al., Issued November 25, 1997; U.S. Patent 5,599,782 Pan al., Issued February 4, 1997; U.S. Patent 5,415,807 Gosselink et al., Issued May 16, 1995; U.S. Patent 5,182,043 Morrall et al., Issued January 26, 1993; U.S. Patent 4,956,447 Gosselink et al., Issued September 11, 1990; U.S. Patent 4,976,879 Maldonado et al., Issued December 11, 1990; U.S. Patent 4,968,451 Scheibel et al., Issued November 6, 1990; U.S. Patent 4,925,577 Borcher, Sr. et al., Issued May 15, 1990; U.S. Patent 4,861, 512 Gosselink, issued August 29, 1989; U.S. Patent 4,877,896 Maldonado et al., Issued October 31, 1989; U.S. Patent 4,771, 730 Gosselink et al., Issued October 27, 1987; U.S. Patent 711, 730 Gosselink et al., Issued December 8, 1987; U.S. Patent 4,721, 580 Gosselink issued January 26, 1988; United States Patent 4,000,093 Nicol et al., Issued December 28, 1976; U.S. Patent 3,959,230 Hayes, issued May 25, 1976; United States Patent 3,893,929 Basadur, issued July 8, 1975; and European Application 0 219 048, published April 22, 1987 by Kud et al.

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

Method of Use The present invention further relates to a method for removing hydrophobic soiled, among others, body oils, perspiration and other soiled human fabrics, preferably clothing, the aforementioned method comprises the step of contacting the fabric that requires cleaning with an aqueous solution containing at least 0.01% by weight of a laundry detergent composition comprising: A) from about 0.01% by weight of a hydrophobically modified polyamine having the formula: wherein R is linear or branched Cs-C2o alkylene, and mixtures thereof; R1 is an alkyleneoxy unit having the formula: - (R2O), -R3 wherein R2 is straight or branched C2-C4 alkylene, and mixtures thereof; R3 is hydrogen, C1-C22 alkyl, C7-C22 alkylenearyl. an anionic unit, and mixtures of these; x is from about 15 to 30; Q is a hydrophobic quaternization unit that is selected from the group consisting of straight or branched C8-C30 alkyl, C6-C3 cycloalkyl, substituted or unsubstituted C -C3-alkylenearyl, and mixtures thereof; X is an anion that is present in sufficient quantity to provide electronic neutrality; n is from 0 to 4; B) of about 0.01% by weight, of a surfactant agent system comprising one or more surface active agents that are selected from: i) from 0% to 100% by weight, of one or more anionic surfactants; ii) from 0% to 100% by weight, of one or more nonionic surfactants; iii) optionally from 0.1% to 80%, approximately by weight of one or more cationic surfactants; iv) optionally from 0.1% to 80%, approximately, by weight of one or more zwitterionic surfactants; v) optionally from 0.1% to 80%, approximately, by weight of one or more ampholytic surfactants; or vi) mixtures of these; C) the balance of carriers and auxiliary ingredients. Preferably the aqueous solution comprises at least about 0.01% (100 ppm), preferably at least 1% (1000 ppm), by weight, of the aforementioned laundry detergent composition. The compositions of the present invention can be suitably prepared by any process selected by the formulator, non-limiting examples of which are described in U.S. Patent 5,691, 297, Nassano et al., Issued November 11, 1997; U.S. Patent 5,691, 297 Nassano et al., issued November 11, 1997; U.S. Patent 5,574,005 Welch et al., issued November 12, 1996; U.S. Patent 5,569,645 Dinniwell et al., issued October 29, 1996; U.S. Patent 5,565,422 Del Greco et al., issued October 15, 1996; U.S. Patent 5,516,448 Capeci et al., issued May 14, 1996; U.S. 5,489,392 Capeci e al., Issued February 6, 1996; U.S. 5,486,303 Capeci et al., Issued on January 23, 1996; all are incorporated by reference in the present invention.

EXAMPLE 1 Synthesis of ethoxylated bis (hexamethylene) triamine tribencylammonium quaternary bromide (E20) The ethoxylation of Bis (hexamethylene) triamine at an average E20 by NH - The ethoxylation is carried out in a two gallon agitated stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum purge and inert gas, sampling, and for the introduction of ethylene oxide as a liquid. A cylinder of ~ 20 net pounds of ethylene oxide (ARC) is installed to supply ethylene oxide as a liquid by a pump to the autoclave with the cylinder positioned on a scale so that the change in cylinder weight can be monitored. A 362 g portion of Bis (hexamethylene) triamine (BHMT) molecular weight 215, (Aldrich), 1.58 moles, 5.04 moles of nitrogen, 8.4 moles of ethoxylatable sites (NH), is added to the autoclave. The autoclave is then closed and purged of air (by applying vacuum to minus 28"HG followed by pressurization with nitrogen at 250 pounds per square inch, then venting at atmospheric pressure). The contents of the autoclave are heated to 80 ° C while vacuum is applied. After approximately one hour, the autoclave is charged with nitrogen at approximately 250 pounds per square inch while the autoclave is cooled to approximately 105 ° C. Then, epylene oxide is added to the autoclave in increments over time while closely monitoring the pressure, temperature, and velocity of ethylene oxide circulation of the autoclave. The ethylene oxide pump is closed and cooling is applied to limit any temperature rise of any exothermic reaction. The temperature is maintained between 100 and 110 ° C while allowing the total pressure to increase gradually during the course of the reaction. After a total of 370 grams of ethylene oxide (8.4 moles) has been charged to the autoclave, the temperature is increased to 110 ° C and the autoclave is allowed to stir for an additional 2 hours. At this point, vacuum is applied to remove any residual unreacted ethylene oxide. Then vacuum is applied continuously while the autoclave is cooled to about 50 ° while introducing 181.5 g of a sodium methoxide in methanol solution (0.84 mole, to achieve a catalyst load based on the functions of the ethoxylate sites). The methoxide solution is removed from the autoclave under vacuum and then the reference temperature of the autoclave temperature controller is increased to 100 ° C. A device is used to monitor the energy consumed by the agitator. The energy of the agitator is monitored along with the temperature and pressure. The energy values of the agitator and temperature increase gradually as the methanol is removed from the autoclave and the viscosity of the mixture increases and stabilizes in about 1.5 hours indicating that most of the methanol has been removed. The mixture is further heated and stirred under vacuum for an additional 30 minutes.

The vacuum is removed and the autoclave is cooled to 105 ° C while charging with nitrogen at 250 pounds per square inch and then vented at ambient pressure. The autoclave is charged at 200 pounds per square inch with nitrogen. Ethylene oxide is again added to the autoclave in increments as before while closely monitoring the pressure, temperature, circulation velocity of the ethylene oxide in the autoclave while maintaining the temperature between 100 and 110 ° C and any temperature increase is limited due to exothermic reaction. After the addition of 4180 g of ethylene oxide (95 mol, resulting in a total of 20 moles of epylene oxide per mole of ethoxy sites on BHMT), the temperature is increased to 110 ° C and the mixture is stirred for 2 additional hours The reaction mixture is then collected into a 22 L three-necked round bottom flask purged with nitrogen. The strong alkaline catalyst is neutralized by the slow addition of 80.7 g of methanesulfonic acid (0.84 mol) with heating (100 ° C) and mechanical stirring. Then, residual ethylene oxide is removed from the reaction mixture and deodorized by irrigating an inert gas (argon or nitrogen) into the mixture through a gas dispersion frit while stirring and heating the mixture to a 120 ° C for 1 hour. The final reaction product is cooled slightly and stored in a glass container purged with nitrogen. The quaternization of BHMT E20 at 90 mol% (polymer of 3 mol N per mol) - A inside a heavy 3-neck round bottom flask, 1000ml, equipped with an argon inlet, condenser, addition funnel, thermometer, mechanical agitation and argon outlet (connected to a bubbling device) is added BHMT EO20 (522.8g, 0.333 mol N, 98% active, molecular weight - 4615) under argon. The material is heated to 80 ° C with stirring until melted. Then, benzyl bromide (61.6g, 0.36 mol, Aldrich, molecular weight - 171.04) is added slowly to molten BHMT EO20 using an addition funnel over a period of 10 minutes. The reaction is complete after stirring at 80 ° C for 6 hours. The reaction mixture is dissolved in 500 g of water and the pH is adjusted to > 9 using 1 N NaOH or 1 N HCl followed by transfer to a plastic container for storage. Sulfation of BHMT E20 at 90% - Under argon, the reaction mixture of the quaternization step is cooled to 5 ° C using an ice bath (BHMT E20 90 + mol% quaternization, 0.59 mol OH). Chlorosulfonic acid (72 g, 0.61 mol, 99%, molecular weight-116.52) is slowly added using an addition funnel. The temperature of the reaction mixture is allowed to rise above 10 ° C. After 6 hours the reaction ends. The reaction is again cooled to 5 ° C and sodium methoxide (264 g, 1.22 mol, Aldrich, 25% in methanol, molecular weight -54.02) is added slowly to the mixture which is stirred rapidly. The temperature of the reaction mixture is not allowed to be mild above 10 ° C. The reaction mixture is then transferred to a single-necked round bottom flask. Purified water (1300 ml) is added to the reaction mixture and the methylene chloride, methanol and some water are removed in a rotary evaporator at 50 ° C. The slightly yellow clear solution is transferred to a storage bottle. The pH of the final product conforms to > 9 using 1 N NaOH or 1N HCl as required. The following are non-limiting examples of the compositions according to the present invention.

TABLE I % by Weight 1. Polyamine hydrophobically modified according to Example 1. 2. Dichloride of 1,5-bis (hydroxylmethylene) -3,7-dimethyl-2,4-bs (2-pyridyl) -3 , 7-diazabicyclo [3.3.1] -nonan-9-ol manganese (II) 1 / 2H2O. 3. PEI 189 E15-18 according to U.S. Patent 4,597,898 Vander Meer, issued July 1, 1986. 4. Dirt release agent according to U.S. Patent 4,702,857 Gosselink, issued October 27, 1987. 5 Dirty release agent according to U.S. Patent 4,968,451, Scheibel et al., Issued November 6, 1990. The following examples include compositions comprising an auxiliary bleaching agent.

TABLE II% in Weight 1. 1, 5-bis (hydroxymethylene) -3,7-dimethyl-2,4-bis (2-pyridyl) -3,7-diazabicyclo [3.3.1] -nonan-9-ol manganese dichloride ( ll) 1 / 2H2O. 2. Nonyl ester of sodium p-hydroxybenzenesulfonate. 3. Dirt release agent according to U.S. Patent 5,415,807 Gosselink et al., Issued May 16, 1995. 4. Hydrophobically modified polyamine according to Example 1. 5. Balance to 100% may include, for example, minor ingredients such as optical brighteners, perfume, dirt dispersing agents, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc, silicates, etc.

The following is a non-limiting example of the bleaching system of the present invention in the absence of a source of hydrogen peroxide.

TABLE III % in weigh 1. 1, 5-bis (hydroxymethylene) -3,7-dimethyl-2,4-bis (2-pyridyl) -3,7-diazabicyclo [3.3.1] -nonan-9-ol manganese dichloride (l I) 1 / 2H2O. 2. Hydrophobically modified polyamine according to Example 1. 3. Potassium sulfite. 4. PEI 189 E15-18 according to U.S. Patent 4,597,898 Vander Meer, issued July 1, 1986. 6. Dirt release agent according to U.S. Patent 5,415,807 Gosselink et al., Issued May 16, 1995. 7. The 100% balance may include, for example, minor ingredients such as optical brighteners, perfume, dirt-dispersing agents, chelating agents, dye transfer inhibiting agents, additional water, and fillers, including CaCO3, talc. , silicates, etc. The compositions of the present invention can be suitably prepared by any process selected by the technical formulator, non-limiting examples of which are described in U.S. Patent 5,691, 297 Nassano et al., Issued November 11, 1997; U.S. Patent 5,574,005 Welch et al., Issued November 12, 1996; United States Patent 5,569,645 Dinniwell et al., Issued October 29, 1996; U.S. Patent 5,565,422 Del Greco et al., Issued October 15, 1996; U.S. Patent 5,516,448 Capeci et al., Issued May 14, 1996; U.S. Patent 5,489,392 Capeci et al., Issued February 6, 1996; U.S. Patent 5,486,303 Capeci et al., Issued January 23, 1996; all are incorporated by reference in the present invention.

Claims

NOVELTY OF THE INVENTION CLAIMS

1. The laundry detergent composition comprising: A) from 0.01% to 50%, approximately, by weight, of a hydrophobically modified polyamine having the formula: wherein R is linear or branched C6-C2o alkylene, and mixtures thereof; R1 is an alkyleneoxy unit having the formula: wherein R2 is linear or branched C2-C4 alkylene, and mixtures thereof; R3 is an anionic unit, and mixture of this; x is from about 15 to 30; Q is a hydrophobic quaternization unit that is selected from the group consisting of straight or branched C8-C30 alkyl, C6-C3o cycloalkyl. C7-C30 substituted or unsubstituted alkylenearyl and mixtures thereof; X is an anion that is present in sufficient quantity to provide electronic neutrality; n is from 0 to 4; B) from about 0.01% to 60% by weight of a surfactant agent system comprising one or more surface active agents that are selected from: i) from 0% to 100% by weight, of one or more anionic surfactants; I) from 0% to 100% by weight, of one or more nonionic surfactants; iii) optionally from about 0.1% to 80% by weight, one or more cationic surfactants; iv) optionally from about 0.1% to 80% by weight, of one or more zwitterionic surfactants; v) optionally from about 0.1% to 80% by weight, of one or more ampholytic surfactants; C) the balance of carriers and auxiliary ingredients.

2. The composition according to claim 1, further characterized in that R is hexylene, R2 is ethylene, 1, 2-propylene, and mixtures thereof.

3. The composition according to claim 1 or claim 2, further characterized in that R3 is selected from the group consisting of: a) - (CH2) fCO2M; b) -C (O) (CH2) fCO2M; c) - (CH2) fPO3M; d) - (CH2) fOPO3M; e) - (CH2) fSO3M; f) -CH2 (CHSO3M) (CH2) fSO3M; g) -CH2 (CHSO2M) (CH2) fSO3M; h) -C (O) CH2CH (SO3M) CO2M; i) C (O) CH2CH (CO2M) NHCH (CO2M) CH2CO2M; j) and mixtures thereof; where M is hydrogen or a cation that provides charge neutrality.

4. The composition according to any of claims 1-3, further characterized in that the index x is from 15 to 25.

5. The composition according to any of claims 1-4, further characterized in that Q is alkyl C? Linear 2-C-? 8, substituted or unsubstituted C7-C12 alkylene, and mixtures thereof.

6. The composition according to any of claims 1-5, further characterized in that the hydrophobically modified polyamine mentioned above has the formula: wherein M is a water-soluble cation; X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methylisulfate, and mixtures thereof. The composition according to any of claims 1-6, further characterized in that the aforementioned surfactant agent system comprises from 0.1% by weight to 100%, of one or more surfactants that are selected from: i) 1% to 80% by weight, of an anionic surfactant which is selected from: a) linear alkylbenzene sulfonates; b) medium chain branched arisulfonate surfactants having the formula: wherein A is a branched medium chain alkyl unit having the formula: wherein R and R1 independently are each hydrogen, C1-C3 alkyl, and mixtures thereof, provided that the total number of carbon atoms in the aforementioned 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; and is an integer from 0 to 13; z is 0 or 1; R2 is hydrogen, C1-C3 alkyl, and mixtures thereof; M 'is water soluble cation with enough charge to provide neutrality; c) branched alkyl sulfate surfactant agents having the formula: CH3CH2 (CH2) mCH2OSO3M; or the formula: CH3CH2 (CH2) mCH2 (OCH2CH2) and OS03M; d) Branched medium chain alkyl sulfate surfactants having the formula: or the formula: wherein R, R1, and R2 each independently are hydrogen, C3 alkyl, and mixtures thereof, provided that the total number of carbon atoms in the aforementioned surfactant is from 14 to 20 and at least one of R, R1, and R2 is not hydrogen; the index w is a number between 0 to 13; x is an integer from 0 to 13; and is an integer from 0 to 13; z is an integer of at least 1; provided that 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 0.01; M is a cation soluble in water of sufficient charge to provide electronic neutrality; ii. from 0% to 100% by weight, of one or more nonionic surfactants; iii. optionally from about 0.1% to 80% by weight, of one or more cationic surfactants; iv. optionally from about 0.1% to 80% by weight, of one or more zwitterionic surfactants; v. optionally from about 0.1% to 80% by weight, of one or more ampholytic surfactants; or vi. mixtures of these. The composition according to any of claims 1-7, further characterized in that it additionally comprises 1% by weight, of a peroxygen blocking system comprising: i) about 40% by weight, of the bleaching system, a source of hydrogen peroxide; I) optionally about 0.1% by weight, of the bleach system, a bleach activator; Ii) optionally of about 1 ppb of the composition, of a transition metal bleach catalyst; and v) optionally about 0.1% by weight, of a preformed peroxygen bleaching agent. 9. A laundry detergent composition characterized in that it comprises: A) of 0.01% by weight of a hydrophobically modified polyamine having the formula: wherein M is a water-soluble cation; X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methylisulfate, and mixtures thereof; B) from 0.01% to 60% by weight, of a surfactant agent system comprising one or more surfactants that are selected from: i) from 0% to 100% by weight, of one or more anionic surfactants; I) from 0% to 100% by weight, of one or more nonionic surfactants; Ii) optionally from about 0.1% to 80% by weight, of one or more cationic surfactants; iv) optionally from about 0.1% to 80% by weight, of one or more zwitterionic surfactants; v) optionally from about 0.1% to 80% by weight, of one or more ampholytic surfactants; or vi) mixtures of these; C) the balance of carriers and auxiliary ingredients. A method for cleaning fabrics characterized in that it comprises the step of contacting a fabric article with an aqueous solution containing at least 0.1% by weight of a composition comprising: A) from about 0.01% to 50% by weight of a hydrophobically modified polyamine having the formula: wherein R is C5-C20 linear or branched alkylene, mixtures thereof; R1 is an alkyleneoxy amount having the formula: wherein R2 is straight or branched C2-C4 alkylene, and mixtures thereof; R3 is an anionic unit selected from the group consisting of a) - (CH2) fCO2M; b) -C (O) (CH2) fCO2M; c) - (CH2) fPO3M; d) - (CH2) fOPO3M; e) - (CH2) fSO3M; f) -CH2 (CHSO3M) (CH2) fSO3M; g) -CH2 (CHSO2M) (CH2) fSO3M; h) -C (O) CH2CH (SO3M) CO2M; i) -C (O) CH2CH (CO2M) NHCH (CO2M) CH2CO2M; j) and mixtures thereof; wherein the index f is from about 0 to 10; M is hydrogen or a cation that provides charge neutrality; x is from about 15 to 30; Q is a hydrophobic quaternization unit selected from the group consisting of linear or branched C8-C3o alkyl, C6-C30 cycloalkyl, substituted or unsubstituted C7-C3-alkylenearyl, and mixtures thereof; X is an anion that is present in sufficient quantity to provide charge neutrality; n is from 0 to 4; B) from 0.01% to 60%, by weight, of a surfactant agent system comprising one or more surfactants that are selected from: i) from 0% to 100% by weight, of one or more anionic surfactants; ii) from 0% to 100% by weight, or from one or more nonionic surfactants; iii) optionally from about 0.1% to 80% by weight, of one or more cationic surfactants; iv) optionally from about 0.1% to 80% by weight, of one or more zwitterionic surfactants; v) optionally from about 0.1% to 80% by weight, of one or more ampholytic surfactants; or vi) mixtures of these; C) the balance of carriers and auxiliary ingredients.