BRPI0820448B1 - DETERGENT COMPOSITIONS FOR WASHING CLOTHES OR COMPOSITIONS FOR CLEANING, AND IMPLEMENTING CLEANING - Google Patents

Description

Report of the Invention Patent for "DETERGENT COMPOSITIONS FOR WASHING CLOTHES OR CLEANING COMPOSITIONS, AND CLEANING IMPLEMENT".

FIELD OF INVENTION

The present invention relates to laundry cleaning compositions and cleaning compositions containing a multi-polymer system comprising an amphiphilic alkoxylated grease-cleaning polymer and also a clay dirt-cleaning polymer or a polymer for dirt suspension.

BACKGROUND OF THE INVENTION

Consumers want laundry detergents that include, but are not limited to, liquid and gel products with excellent overall cleanability. The detergent industry typically uses surfactants, among other substances, to provide this benefit. Due to the growing concern about the environment as well as the high cost, the widespread use of surfactants may be losing popularity. Accordingly, detergent manufacturers are studying ways to reduce the dosage of surfactant in the washing liquid, while still offering the consumer a product with excellent overall cleanability. However, it has been found that the reduction in surfactant levels, especially oil-derived surfactants such as linear alkyl benzene sulfonate, leads to erosion in the removal of grease stains.

Dirt and stains to be removed from fabrics and other surfaces range from polar soils such as proteinaceous, clay and inorganic soils to nonpolar soils such as soot, carbon black, byproducts of incomplete combustion of hydrocarbons and organic soils. The less surfactant available for cleaning these soils and stains, the other cleaning mechanisms need to be discovered. One approach to reducing surfactant dosage is to formulate polymeric laundry detergents. As with surfactants, polymers can be useful as dirt release agents in fabrics. In addition, or alternatively, some polymers provide suspension of dispersed soils in the wash liquid, which in turn prevents redeposition onto the fabric to be washed.

Therefore, it would be desirable to provide laundry detergent compositions comprising polymer systems which provide good cleaning of surface and wide band fabrics as well as suspension of the soils. It would be even more desirable for such laundry detergent compositions to provide good cleaning even when formulated with low surfactant and organic solvent contents. It would also be desirable to provide such laundry detergent compositions in the form of granules, liquids or gels.

SUMMARY OF THE INVENTION

The present invention relates to laundry detergent compositions and cleaning compositions which provide optimized cleaning benefits comprising a novel polymer system. The polymer system comprises one or more alkoxylated grease cleaning amphiphilic polymers, and also a clay dirt cleaning polymer; or a dirt suspension polymer.

The amphiphilic alkoxylated grease cleaning polymer comprises a central structure and a plurality of alkoxylate groups. The central structure may comprise either i) a polyalkylenimine structure comprising, in condensed form, repeating units of formulas (I), (II), (III) and (IV): where, # in each case denotes half a bond between a nitrogen atom and the free bond position of an A1 group of two adjacent repeating units of formulas (I), (II), (III) or (IV); * in each case denotes half of a bond to one of the alkoxylate groups; and A1 is independently selected from C2 -C6 alkylene; wherein the imine polyalkylimine structure consists of 1 repeating unit of formula (I), x repeating units of formula (II), y repeating units of formula (III) and y + 1 repeating units of formula (IV) where x and y in each case have a value in the range of 0 to about 150; wherein the weight average molecular weight, Mw, of the central polyalkylenimine structure is a value in the range of about 60 to about 10,000 g / mol; or ii) a polyalkanolamine structure of the condensation products of at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein A is independently selected from C1-4 alkylene. -C6; R1 Ru, R2, R2 *, R3, R3 *, R4, R4 *, R5 and R5 * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, the last three mentioned radicals being optionally substituted; and R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, the last three mentioned radicals may be optionally substituted. The plurality of alkylenoxy groups are independently selected from alkylenoxy units of the following formula (V) (V) where: * in each case denotes half of a nitrogen atom bond of the repeating unit with the following formulas (I ), (II) or (IV); A2 is in each case independently selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene; A3 is 1,2-propylene; R is in each case independently selected from hydrogen and C1 -C4 alkyl; m has an average value in the range from 0 to about 2; n has an average value in the range of about 20 to about 50; and p has an average value in the range of about 10 to about 50.

The clay dirt cleaning polymer is selected from the group consisting of ethoxylated oligamines, quaternary methyl ethoxylated oligamines, quaternary benzyl ethoxylated oligamines, propoxylated-ethoxysulfated quaternary methyl quaternary ethoxysulfated oligamines , quaternary benzyl propoxylated-ethoxysulfated oligoamines, quaternary methyl ethoxylated oligoetherines, quaternary benzyl ethoxylated oligoetherines, quaternary ethoxysulfated oligoetheramines, quaternary ethoxysulfated oligoetheramines, and mixtures thereof of the same group to 00 consists of i) alkoxylated polyethyleneimine having from about 5 to 24 ethoxylate groups per -NH group and from zero to about 12 propoxylate groups per -NH group; and (ii) random graft copolymers having a hydrophilic backbone comprising monomers selected from the group consisting of Ct.6 unsaturated acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols; and mixtures thereof; and hydrophobic side chains selected from the group comprising C 4-25 alkyl, polypropylene groups; polybutylene, a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms; a C1-6 alkyl ester of acrylic or methacrylic acid; and iii) a mixture thereof. DETAILED DESCRIPTION OF THE INVENTION

Laundry Detergent Compositions and Cleaning Compositions The laundry detergent compositions and cleaning compositions of the present invention comprise a polymer system comprising one or more amphiphilic alkoxylated grease polymers, and also a polymer for cleaning clay dirt; or a dirt suspension polymer.

Amphiphilic Grease Cleaning Alkoxylated Polymers The compositions of the present invention comprise one or more amphiphilic grease cleaning alkoxylated polymers. Alkoxylated grease-cleaning amphiphilic polymers of the present invention refer to any alkoxylated polymers having balanced hydrophilic and hydrophobic properties such that they remove grease particles from fabrics and surfaces. Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers of the present invention comprise a core structure and a plurality of alkoxylate groups attached to the core structure.

The central structure may comprise a polyalkylenimine structure comprising, in condensed form, repeating units having the following formulas (I), (II), (III) and (IV): where, # in each case denotes half of a bond between a nitrogen atom and the free bond position of an A1 group of two adjacent repeating units of formulas (I), (II), (III) or (IV); * in each case denotes half of a bond to one of the alkoxylate groups; and A1 is independently selected from C2 -C6 alkylene; wherein the polyalkylenimine structure consists of 1 repeating unit of formula (I), x repeating units of formula (II), y repeating units of formula (III) and y + 1 repeating units of formula (IV), where x and y in each case have a value in the range of 0 to about 150; wherein the weight average molecular weight, Mw, of the polyalkylenimine core structure is a value in the range from about 60 to about 10,000 g / mol;

The core structure may alternatively comprise a polyalkanolamine structure of condensation products of at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein A is independently selected from C1 -C6 alkylene; R \ R1 *, R2, R2 *, R3, R3 *, R4, R4 *, R5 and R5 * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, the last three mentioned radicals being optionally substituted. ; and R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, the last three mentioned radicals being optionally substituted.

The plurality of alkylenoxy groups attached to the central structure are independently selected from alkylenoxy units of the following formula (V) where, * in each case denotes half a bond of a repeat atom nitrogen atom with the following formulas (I), (II) or (IV); A2 is in each case independently selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene; A3 is 1,2-propylene; R is in each case independently selected from hydrogen and C1 -C4 alkyl; m has an average value in the range from 0 to about 2; n has an average value in the range of about 20 to about 50; and p has an average value in the range of about 10 to about 50.

Specific embodiments of the amphiphilic alkoxylated polymers for grease cleaning may be selected from alkoxylated polyalkylenimines which have an internal polyethylene oxide block and an external polypropylene oxide block, ethoxylation degree and non-propoxylation degree. above or below specific limiting values. Specific embodiments of alkoxylated polyalkylenimines according to the present invention have a minimum ratio of polyethylene blocks to polypropylene blocks (n / w) of about 0.6 and a maximum of about 1 5 (x + 2y +). 1) 12. Alkoxylated polyalkylenimines which have an n / w ratio of about 0.8 to about 1.2 (x + 2y + 1) 1/2 have been found to have especially beneficial properties.

Alkoxylated polyalkylenimines according to the present invention have a backbone consisting of nitrogen atoms of primary, secondary and tertiary amines which are attached to each other by alkylene A radicals and are arranged randomly. Primary amine moieties that initiate or terminate the main chain and side chains of the polyalkylenimine main chain and whose remaining hydrogen atoms are subsequently substituted by alkylenoxy units are referred to as repeating units of the following formula (I) or (IV) respectively. Secondary amine moieties whose remaining hydrogen atoms are subsequently substituted by alkylenoxy units are termed repeating units of the following formula (II). Tertiary amine moieties having branching in the main chain and side chains are called repeating units of the following formula (III).

Since cyclization may occur in the formation of the polyalkylenimine backbone, it is also possible that cyclic amine moieties may be present in small amounts in the backbone. Such polyalkylenimines which contain cyclic amine moieties are of course alkoxylated, as are those consisting of primary non-cyclic amine moieties and secondary amine moieties.

The polyalkylenimine backbone consisting of nitrogen atoms and groups A1 has an average molecular weight Mw of from about 60 to about 10,000 g / mol, preferably from about 100 to about 8,000 g / mol. more preferably from about 500 to about 6,000 g / mol.

The sum corresponds (x + 2y + 1) to the total number of alkylene imine units present in an individual polyalkylenimine backbone and thus is directly related to the molecular weight of the polyalkylenimine backbone. The values given in the descriptive report, however, refer to the average number of all polyalkylenimines present in the mixture. The sum (x + 2y + 2) corresponds to the total number of amino groups present in an individual polyalkylenimine backbone.

The A1 radicals connecting the nitrogen atoms of the amino group may be identical or different, linear or branched C2 -C6 alkylene radicals such as 1,2-ethylene, 1,2-propylene, 1,2-butylene, 1,2-isobutylene, 1,2-pentanediyl, 1,2-hexanediyl or hexamethylene. A preferred branched alkylene is 1,2-propylene. Preferred linear alkyls are ethylene and hexamethylene. A more preferred alkylene is 1,2-ethylene.

Hydrogen atoms of the primary and secondary amino groups of the polyalkylenimine backbone are substituted by alkylenoxy units of the following formula (V).

In this formula, the variables preferably have one of the meanings given below: A2 in each box is selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene; preferably A2 is 1,2-propylene. A3 is 1.2-propylene; R in each case is selected from hydrogen and C1-C4 alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; preferably R is hydrogen. The index m in each case has a value from 0 to about 2; preferably m is 0 or approximately 1; more preferably me. The index n has an average value in the range of about 20 to about 50, preferably in the range of about 22 to about 40, and more preferably in the range of about 24 to about 30. The index p has an average value in the range from about 10 to about 50, preferably in the range from about 11 to about 40, and more preferably in the range from about 12 to about 30.

Preferably, the alkylenoxy moiety of formula (V) is a non-random alkoxylate block sequence. By non-random sequence is meant that [-A2-0-] m is added first (i.e., closer to the nitrogen atom bond of the repeating unit of formula (I), (II), or (III) ), [-CH2-CH2-0-] n is added second, and [-A3-0-] p is added third. This orientation provides the alkoxylated polyalkylenimine with an inner polyethylene oxide block and an outer polypropylene oxide block.

The substantial part of these units of formula (V) is formed by the ethylenoxy units - [CH2-CH2-0)] n- and propylene units - [CH2-CH2 (CH3) -0] p-. Alkenyloxy units may additionally also have a small proportion of propylene or butylene - [A2-0] m- units, that is, the hydrogen-saturated polyalkylenimine backbone may initially react with small amounts of about 2 mmol, especially from about 0.5 to about 1.5 mol, in particular from about 0.8 to about 1.2 mol, of propylene oxide or butylenoxide per mol of NH-present moieties, i.e. incipient.

This initial modification of the polyalkylenimine backbone allows, if necessary, to reduce the viscosity of the reaction mixture on alkoxylation. However, the modification generally does not influence the performance properties of alkoxylated polyalkylenimine and is therefore not a preferred measure.

Alkoxylated polyalkylenimines may be prepared by a known method. Exemplary procedures are described in US Patent Application No. 10953, filed November 9, 2007. Specific alkoxylated polyalkylenimine embodiments include the 600 g / mol polyethyleneimine core with 24 NH ethoxylate groups and 16 propoxylates per -NH, the 600 g / mol polyethyleneimine core with 24 NH-ethoxylate groups and 24 NH-propoxylate groups, diethylene triamine with 24 NH-ethoxylate groups and 24 NH-propoxylates, and hexamethylene diamine with 24 -NH ethoxylate groups and 16 -NH propoxylate groups described therein.

Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers may alternatively be selected from alkoxylated polyalkanolamine polymers are obtained by a process which includes the steps of: a) condensing at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein A is independently selected from C1 -C6 alkylene; R 1, R 1 *, R 2, R 2 *, R 3, R 3 *, R 4, R 4 *, R 5 and R 5 * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, the last three mentioned radicals being optionally substituted; and R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and b) reacting at least a portion of the remaining hydroxy groups and / or, if present, at least a portion of the secondary amino groups of the polyether provided in step a) with at least one alkylene oxide.

Examples of N- (hydroxyalkyl) amines (1a) are N-tri- (2-hydroxyalkyl) -amines. N-tri- (2-hydroxyalkyl) amines are obtained by reacting ammonia with three equivalents of alkylene oxides (amonolysis). Preferred examples of such compounds (1a) are triethanol amine, triisopropanol amine and tributan-2-olamine. Examples of N- (hydroxyalkyl) amines (1b) are N-di- (2-hydroxyalkyl) -amines which are obtainable by reacting a primary amine of the following formula H2N-R6, where R6 has one of the meanings given above with two equivalents of an alkylene oxide (aminolysis). Examples of such compound (1b) are, for example, N-methyldiethanolamine, N, N-bis- (2-hydroxypropyl) -N-methylamine, N, N-bis- (2-hydroxybutyl) -N-methylamine, N-isopropyldiethanolamine , Nn-butyldiethanolamine, N-sec-butyldiethanolamine, N-cyclohexyldiethanolamine, N-benzyldiethanolamine, N-4-tolyldiethanolamine, N, N-Bis- (2-hydroxyethyl) anilin and the like.

[0029] Modalities of polyalkanolamine alkoxylated polymers are obtained from compounds selected from N- (hydroxyalkyl) amines of the following formulas (la) and / or (lb), where A is a methylene group which is non- substituted or bearing a substituent selected from C1-4 alkyl. Specific polymers are obtained from compounds (1a) and / or (1b), wherein A is methylene or methylene which carries a methyl group. Particularly preferred polymers are those obtained from compounds (1a) and / or (1b), wherein A is unsubstituted methylene.

Other embodiments of the alkoxylated polyalkanolamine polymers are obtained from compounds selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein R 1, R 1 *, R 2, R 2 * , R3, R3 *, R4, R4 *, R5 and R5 * are independently of each other selected from hydrogen and C1 -C4 alkyl, ie hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec -butyl and tert-butyl. More preferably R1, R1 *, R2, R2 *, R3, R3 *, R4, R4 *, R5 and R5 * are independently of each other selected from hydrogen and methyl.

A preferred embodiment of the invention relates to polymers obtained from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein R 1 *, R 2 *, R 3 *, R 4 * and R 5 * are hydrogen and R 1, R 2, R 3, R 4, and R 5 are independently from each other selected from hydrogen and C 1 -C 4 alkyl. More preferably R1 *, R2 *, R3 *, R4 * and R5 * are hydrogen and R1, R2, R3, R4, and R5 are independently of one another selected from hydrogen and methyl.

The polymer according to the invention is obtained from N- (hydroxyalkyl) amines of the following formula (lb), wherein R6, if present, is preferably selected from hydrogen and C1 -C4- alkyl.

The polymer according to the invention is preferably obtained by a process wherein in step b) at least one alkylene oxide is selected from epoxyethane, epoxypropane, 1,2-epoxybutane, 2,3- epoxybutane, 1,2-epoxy-2-methylpropane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxy-2-methylbutane, 2,3-epoxy-2-methylbutane, 1,2- epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane and 1,2-epoxyethylene benzene. More preferably at least one alkylene oxide is selected from epoxyethane and / or epoxypropane.

The polymer according to the invention is preferably obtained by the reaction of 1 to 100 mmol, preferably 2 to 80 mmol of at least one alkylene oxide with 1 mol of hydroxy groups and, if present, of the secondary amino groups of the polyether obtained by the condensation of at least one compound of the following formulas (1a) and / or (1b).

The polymer according to the invention preferably has a number average molecular weight in the range of 500 to 100,000 g / mol, more preferably in the range of 1000 to 80,000 g / mol, and in particular in the range of 2,000 to 50,000 g / mol. The polymer according to the invention preferably has a polydispersity (Mw / Mn) in the range from 1 to 10, and in particular in the range from 1 to 5.

In a specific embodiment, the polymer according to the invention is obtained by a process wherein in step a) less than 5 wt%, preferably less than 1 wt%, and more preferably substantially none, i.e., less than 0.1% by weight of the cocondensible compounds other than the compounds of the following formulas (la) and / or (lb), are employed (i.e. cocondensate) based on the amount of the compounds with the following formulas (la) and / or (lb).

The term "cocondensible compound" for use in the present invention comprises compounds which carry at least one, preferably at least two acidic hydrogen atoms, such as diols or diamines. Examples of such cocondensible compounds are provided below.

In another specific embodiment, the polymer according to the invention is obtained by a process wherein in step a) at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (la) and / or (lb) is being co-condensed with at least one compound selected from polyols of formula Y (OH) n, where n is an integer from 2 to 4 and Y denotes a bivalent, trivalent or tetravalent, cycloaliphatic or aromatic radical having 2 to 10 carbon atoms.

Suitable polyols of the following formula Y (OH) n are aliphatic polyols, such as ethylene glycol, propylene glycol, butylene glycol, glycerin, tri (hydroxymethyl) ethane, tri (hydroxymethyl) propane or pentaerythritol polyols, cycloaliphatic polyols, such as 1. , 4-dihydroxycyclohexane, arylaliphatic polyols such as 1,4-bis (hydroxymethyl) benzene, and the like.

If present, polyols of the following formula Y (OH) n are generally co-condensed in an amount of 50% by weight or less based on the amount of the compounds of the following formulas (la) and / or ( 1b), that is, in an amount from 0.1 to 50% by weight, and more preferably in an amount from 1 to 25% by weight.

In yet another specific embodiment of the invention the polymer is obtained by a process wherein in step a) at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b) is being co-condensed with at least one compound selected from polyamines of the following formula Y '(NHRy) m, where m is an integer from 2 to 4, Y denotes a bivalent, trivalent or tetravalent, cycloaliphatic or radical aliphatic radical aromatic having 2 to 10 carbon atoms and Ry has one of the meanings given for R 6 or two radicals Ry together may form a C 1 -C 6 alkylene group.

Suitable polyamines of the following formula Y '(NHRy) m are ethylenediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminocyclo hexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine and the like.

If present, polyamines of the following formula Y '(NHRy) m are generally co-condensed in an amount of 50% by weight or less based on the amount of the compounds of the following formulas (la) and / or (1b), that is, in an amount from 0.1 to 50% by weight, and more preferably in an amount from 1 to 25% by weight.

Alkoxylated polyalkanolamines may be prepared by any known method. Exemplary procedures are described in U.S. Patent Application No. 10951, filed November 9, 2007.

Amphiphilic alkoxylated grease cleaning polymers are present in the detergent and cleaning compositions of the present invention in contents ranging from about 0.05% to 10% by weight of the composition. Modalities of the compositions may comprise from about 0.1% to about 5% by weight. More specifically, the embodiments may comprise from about 0.25 to about 2.5% of the grease cleaning polymer.

Clay Dust Cleaning Polymer The polymer system of the detergent and cleaning compositions of the present invention may comprise a clay dirt cleaning polymer. As discussed in LJS Patent No. 4,661,288, a clay dirt cleaning polymer with the ability to remove particulate clay fabrics during washing. Without sticking to theory, clay cleaners must have the ability to adsorb onto the negatively charged layers of the clay particle and repel negatively charged layers of clay to the clay particle which loses its cohesive force and can be removed in wash water.

Specific grades of the clay dirt cleaning polymers that may be used in the present invention may include, but are not limited to, ethoxylated oligamine, quaternary methyl ethoxylated oligamine, quaternary benzyl ethoxylated oligoamine, methyl quaternary ethoxysulfated oligoamine, propoxylated oligoamine, methyl quaternary ethoxysulfated, quaternary benzyl ethoxysulfated oligoamine, quaternary benzyl propoxylated-ethoxysulfated oligoamine, quaternary methyl ethoxylated oligoetheramine, benzyl quaternary ethoxylated sulfate ethoxylated oligoetheramine oligosaccharide

Specific embodiments of clay dirt cleaning polymers may be selected from the group consisting of ethoxylated tetraethylene pentaimine; quaternary dimethyl ethoxylated hexamethylene diamine; quaternary dimethyl ethoxysulfated hexa-methylene diamine; hexahymethyl tri (quaternary methyl amine) ethoxysulfated; quaternary dimethyl quaternary ethoxypropoxysulfated hexamethylene diamine; poly (quaternary benzyl amine) ethoxy hexamethylene; poly (quaternary benzyl amine) ethoxysulfated hexamethylene; bis (hexamethylene) triamine ethoxylated about 30 times by -NH group and about 90% quaternized; ethoxylated tetrasulfate 4,9-dioxa-1,12-dodecanediamine dimethyl quaternary; transsulfated propoxylated-ethoxylated bis (hexamethylene) triamine transsulfated; 50% sulfonated, propoxylated, ethoxylated methyl quaternary hexamethylene diamine, and mixtures thereof. Such polymers and the processes for making them have been described in US 4551506, US 4622378, US 46661288, US 4897898, EP 0137615B, US 6525012, US 6846791, EP 1228035, EP 1228179.

Clay dirt cleaning polymers are optional in the polymer system of the detergent and cleaning compositions of the present invention. However, when used, they are used in contents in the range of about 0.05% to 10% by weight of the composition. Modalities of the compositions may comprise from about 0.1% to about 5% by weight. More specifically, the embodiments may comprise from about 0.25 to about 2.5% of the clay cleaning polymer.

Other polymers useful for cleaning are polyacrylates, which preferably have a molecular weight in the range from about 2000 to about 20,000 g / mol. Due to its superior solubility, preference in this group may in turn be given to the short chain polyacrylates having molar mass in the range of 2000 to 10,000 g / mol and more preferably in the range of 3000 to 5000 g / mol. Useful polymers may also include substances consisting partially or completely of vinyl alcohol units or derivatives thereof.

Useful polymeric polycarboxylates further include copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Of particular utility are acrylic acid-maleic acid copolymers which comprise from about 50% to about 90% by weight acrylic acid and from about 10% to about 50% by weight maleic acid. Their relative molecular weight based on free acids is generally in the range of 2000 to 70,000 g / mol, preferably in the range of 20,000 to 50,000 g / mol and especially in the range of 30,000 to 40,000 g / mol.

To optimize water solubility, polymers may further comprise allylsulfonic acids, such as allyloxybenzenesulfonic acid and metallylsulfonic acid, or as a monomer. Preference is also given in particular to biodegradable polymers composed of more than two different monomer units, for example those comprising acrylic acid and maleic acid salts and also vinyl alcohol or vinyl alcohol derivatives as monomers, or comprising acid salts. acrylic and 2-alkylallylsulfonic acid and also sugar derivatives as monomers. Preferred copolymers further include those which as monomers preferably comprise acrolein and acrylic acid / acrylic acid or acrolein salts and vinyl acetate.

Another useful class of polycarboxylate copolymers are copolymers of acrylic acid or methacrylic acid and ethylenically unsaturated hydrophobic monomers containing alkyl, aryl, or alkoxy groups or combinations thereof.

Preferred polymers further include amino polymeric dicarboxylic acids, their salts or their precursor substances. Particular preference is given to polyaspartic acids or salts and derivatives thereof, which are known to have a stabilizing-stabilizing effect. as well as co-builder properties. Dirt Suspension Polymers The polymer system of the detergent and cleaning compositions of the present invention may comprise a dirt suspension polymer. A dirt suspension polymer is any dirt suspension polymer removed, thereby preventing redeposition of the dirt particles onto the surface. Specific dirt suspension polymers which may be used in the present invention may include alkoxylated polyethyleneimine. which have a polyethyleneimine backbone having a molecular weight of from about 300 to about 10,000 weight average molecular weight, preferably from about 400 to about 7500 weight average molecular weight, preferably about 500 to about 1900 weight average molecular weight, and preferably from about 3000 to 6000 weight average molecular weight. The polyethyleneimine backbone is modified by either: (1) one or two modifications by nitrogen atom alkoxylation, depending on whether modification occurs in an inner nitrogen atom or a terminal nitrogen atom in the polyethyleneimine backbone, the Alkylation modification is the replacement of a hydrogen atom with a polyalkoxyene chain with an average of about 1 to about 40 alkoxy moieties per modification, and the terminal alkoxy portion of the alkoxylation modification is terminated with hydrogen, an alkyl C1-C4, or mixtures thereof; (2) a substitution of a C 1 -C 4 alkyl moiety and one or two modifications by nitrogen atom alkoxylation, depending on whether the substitution occurs on an internal nitrogen atom or a terminal nitrogen atom in the polyethyleneimine backbone, the modification being by alkoxylation is the substitution of a hydrogen atom with a polyalkoxyene chain having an average of about 1 to about 40 alkoxy moieties per modification, and wherein the terminal alkoxy moiety is terminated with hydrogen, a C1 -C4 alkyl, or mixtures thereof; or (3) a combination thereof.

The alkoxylation modification of the polyethyleneimine backbone consists of replacing a hydrogen atom with a polyalkoxyethylene chain having an average of from about 1 to about 40 alkoxy moieties, preferably from about 5 to about 20 moieties. alkoxy The alkoxy moieties are selected from ethoxy (EO), 1,2-propoxy (1,2-PO), 1,3-propoxy (1,3-PO), butoxy (BO) and combinations thereof. In some embodiments, the polyalkoxyene chain is selected from ethoxy moieties and ethoxy / propoxy block moieties. The polyalkoxyene chain may be ethoxy moieties having an average degree of about 5 to about 15 or the polyalkoxyene chain may be ethoxy / propoxy block moieties having an average degree of ethoxylation of about 5 to about 15 and average degree of propoxylation from about 1 to about 16.

A specific alkoxylated polyethyleneimine has the general structure of formula (I): formula (!) Wherein the polyethyleneimine backbone has a weight average molecular weight of 600, n of formula (I) has an average of 20 and R of formula (I) is selected from hydrogen, a C1-C4 alkyl and mixtures thereof.

Such alkoxylated polyethyleneimines and the processes for making them have been described in US 3489686, US 5565145, US 6004922, and WO 2006/108857.

The dirt suppression polymers may alternatively be a random amphiphilic graft copolymers having a hydrophilic backbone comprising monomers selected from the group consisting of C1-6 unsaturated acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols, and mixtures thereof; and hydrophobic side chains selected from the group comprising C 4-25 alkyl, polypropylene groups; polybutylene, a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms; an alkyl ester of acrylic or methacrylic acid; or mixture thereof. A specific useful embodiment of the dirt suspension polymers is a random graft copolymer having a hydrophilic backbone comprising polyethylene glycol having a molecular weight of from 4,000 to 15,000, and from 50% to 65% by weight of hydrophobic side chains formed. by polymerizing at least one monomer selected from a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or alkyl ester of acrylic acid or methacrylic acid. Another embodiment of the dirt suspension polymer is a random graft copolymer having a hydrophilic backbone comprising polyethylene glycol having a molecular weight of from 4,000 to 15,000, and from 50% to 65% by weight of hydrophobic side chains formed by polymerization of at least one monomer selected from vinyl acetate, vinyl propionate and / or butyl acrylate. An example of such polymers would be a water-soluble graft-based polyalkylene oxide having side chains formed by polymerization of a vinyl ester component, said polymers having an average of one graft site per 50 oxide units. alkylene and average molar masses Mp <F> from 3,000 to 100,000 g / mol. This example polymer could have a polydispersity, Mw / Mn, less than or equal to about 3.

Amphiphilic graft polymers for use in the present invention as well as methods of preparing them are described in detail in European Patent Application No. 06114756, EP A-219048, EP A-358474, and WO 2006/130442. They may be present in the detergent or cleaning composition in weight percentages of from about 0.05% to about 10%, from about 0.1% to about 5%, from about 0.2% to about 10%. 3%, or from about 0.3% to about 2%.

Amphiphilic graft polymers are water-soluble polyalkylene oxide-based substances as a graft base and side chains formed by polymerization of a vinyl ester component. These polymers have an average graft site per 50 alkylene oxide units and average molar masses (Mw) of from about 3000 to about 100,000.

A method of preparing the amphiphilic graft polymers comprises the steps of: polymerizing a vinyl ester component (B) composed of vinyl acetate and / or vinyl propionate (B1) and, if desired, a more monomer ethylenically unsaturated (B2) in the presence of a water-soluble polyalkylene oxide (A), a free radical forming initiator (C) and, if desired, up to 40% by weight based on the sum of the components (A ), (B) and (C), of an organic solvent (D), at an average polymerization temperature at which initiator (C) has a decomposition half-life of 40 to 500 min, such that the fraction the unconverted graft monomer (B) and the initiator (C) in the reaction mixture is constantly maintained at a quantitative deficiency with respect to polyalkylene oxide (A).

Graft polymers are characterized by their low degree of branching (degree of grafting); these have, on average and based on the reaction mixture obtained, no more than 1 graft site, preferably no more than 0.6 graft site, no more than 0.5 graft site, or no more than 0, 4 graft site per 50 alkylene oxide units. They comprise, on average and based on the reaction mixture obtained, at least 0.05, or at least 0.1 graft site per 50 alkylene oxide units. The degree of branching can be determined, for example, by 13 C NMR spectroscopy from graft site signal integrals and polyalkylene oxide -CH 2 groups.

According to their low degree of branching, the molar ratio between ungrafted grafted alkylene oxide units in the graft polymers of the invention is from about 0.002 to about 0.05, from about 0.002 to about about 0.035, about 0.003 to about 0.025, or about 0.004 to about 0.02.

In some embodiments, the graft polymers of the invention have a narrow molar mass distribution and therefore a polydispersity Mw / Mn generally less than or equal to about 3, less than or equal to about 2.5, or less. or equal to about 2.3. In some embodiments, their polydispersity Mw / Mn is in the range of about 1.5 to about 2.2. The polydispersity of the graft polymers may be determined, for example, by gel permeation chromatography using narrowly distributed polymethyl methacrylates as standard. The weight average molecular weight Mw of the graft polymers of the invention is from about 3000 to about 100,000, from about 6,000 to about 45,000, or from about 8,000 to about 30,000.

Other embodiments of the graft polymers of the invention also have a low content of ungrafted polyvinyl ester (B). In general, they comprise an amount less than or equal to about 10% by weight, less than or equal to about 7.5% by weight, or less than or equal to about 5% by weight of non-polyvinyl ester. -graft (B).

Due to the low ungrafted polyvinyl ester content and the balanced ratio of components (A) and (B), the graft polymers of the invention may be soluble in water or in water / alcohol mixtures (e.g. 25 wt.% solution of diethylene glycol monobutyl ether in water). Such polymers may have pronounced low fog points that, for graft polymers that are water soluble at a temperature of up to about 50 ° C, less than or equal to about 95 ° C, less than or equal to about 85 ° C, or less than or equal to at about 75 ° C, and for the other graft polymers at about 25 wt% diethylene glycol monobutyl ether, are generally less than or equal to about 90 °, or about 45 ° to about 8513.

In some embodiments, the amphiphilic graft polymers of the invention have: (A) from about 20 to about 70% by weight of a water soluble polyalkylene oxide as a graft base, and (B) side chains formed by free radical polymerization of from about 30 to about 80% by weight of a vinyl ester component composed of: (B1) from about 70 to about 100% by weight of vinyl acetate and / or vinyl propionate, and (B2) from 0 to about 30% by weight of a more ethylenically unsaturated monomer in the presence of (A).

In some embodiments, they comprise from about 25 to about 60% by weight of the graft base (A) and from about 40 to about 75% by weight of the polyvinyl ester component (b). .

Water-soluble polyalkylene oxides suitable for graft base formation (A) are, in principle, all C 2 -C 4 alkylene oxide based polymers comprising at least about 50 wt.% Or at least about 60 wt.% or at least about 75 wt.% of the ethylene oxide in copolymerized form.

Polyalkylene oxides (A) may have a low polydispersity, Mw / Mn. In some embodiments, their polydispersity is less than or equal to about 1.5.

The polyalkylene oxides (A) may be the corresponding polyalkylene glycols in their free form, that is, with OH terminal groups, but may also be terminated at one or both terminal groups. Suitable terminal groups are, for example, C1 -C25 alkyl, phenyl and C1 -C14 alkyl phenyl.

Some non-limiting examples of particularly suitable polyalkylene oxides (A) include: (A1) polyethylene glycols which may be terminated at one or both terminal groups, especially by C1 -C4 alkyl groups, which in some embodiments are non-etherified, and have average molar masses Mn of from about 1500 to about 20,000, or from about 2500 to about 15,000; (A2) copolymers of ethylene oxide and propylene oxide and / or butylene oxide having an ethylene oxide content of at least about 50% by weight, which may similarly be terminated at one or both terminal groups by for example C1-C25 alkyl groups, but which are non-etherified and have average molar masses Mn of from about 1,500 to about 20,000, or from about 2,500 to about 15,000; (A3) chain extended products with average molar masses from about 2,500 to about 20,000, which may be obtained by reacting polyethylene glycols (A1) with average molar masses Mn from about 200 to about 5000 or copolymers (A2) with average molar masses Mn of from about 200 to about 5000 with C 2 -C 12 dicarboxylic acids or dicarboxylic esters - or C 6 -C 18 diisocyanates.

In some embodiments, the graft bases (A) are polyethylene glycols (A1). The side chains of the graft polymers of the invention are formed by polymerizing a vinyl ester component (B) in the presence of the graft base (A). The vinyl ester component (B) may comprise (B1) vinyl acetate or vinyl propionate, or in mixtures of vinyl acetate and vinyl propionate, in some embodiments, preferably vinyl acetate as the vinyl ester component ( B). However, the graft polymer side chains may also be formed by copolymerization of vinyl acetate and / or vinyl propionate (B1) and another ethylenically unsaturated monomer (B2). The fraction of monomer (B2) in the vinyl ester component (B) may be up to about 30 wt%, which corresponds to a graft polymer content of (B2) about 24 wt%.

Suitable comonomers (B2) are, for example, monoethylenically unsaturated carboxylic acids and dicarboxylic acids and their derivatives, such as esters, amides and anhydrides, and styrene. Of course it is also possible to use mixtures of different comonomers.

Some non-mimicking examples include: (meth) acrylic acid, C1-C12-alkyl and (meth) acrylic acid hydroxy-C2-C12 alkyl ester, (meth) acrylamide, N-C1 -C12- (meth) ) alkyl acrylamide, N, N-di (C1 -C6 alkyl) (meth) acrylamide, maleic acid, maleic anhydride and mono (C1 -C2 alkyl) maleic acid esters.

In some embodiments, monomers (B2) are C1 -C8 alkyl esters of (meth) acrylic acid and hydroxyethyl acrylate. In some embodiments, preference may be given for C1 -C4 alkyl esters of (meth) acrylic acid. In some embodiments, preference may be given to monomers (B2) which are methyl acrylate, ethyl acrylate and in particular n-butyl acrylate. When the graft polymers of the invention comprise monomers (B2) as a constituent of the vinyl ester component (B), the content of graft polymers in (B2) may range from about 0.5 to about 20% by weight, from about 1 to 15% by weight, or from about 2 to about 10% by weight.

The dirt suspension polymer may also be selected from quaternized and sulfated derivatives of alkoxylated polyalkanolamine polymers that act as grease cleaning polymers. By definition, alkoxylated non-quaternized, non-sulfated polyalkanolamine acts as the grease-cleaning polymers of the present invention, however, quaternized and sulfated derivatives are less satisfactory grease cleaners, but are good dirt-suspending polymers.

Quaternized, alkoxylated sulfated polyalkanolamines are obtained by a process which includes the steps of: a) condensing at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (La) and / or (Tb), wherein A is independently selected from C 1 -C 6 alkylene, R 1 R 1 *, R 2, R 2 *, R 3, R 3 *, R 4, R 4 *, R 5 and R 5 * are independently selected from hydrogen alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted: and R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and b) reacting at least a portion of the remaining hydroxy groups and / or, if present, at least a portion of the secondary amino groups of the polyether provided in step a) with at least one alkylene oxide and or derivatives of said polymers. alkoxylated polyalkanolamine obtained by the addition of step c) quartenization, rotation, sulfation and / or phosphating of said polymer.

The derivatives obtained from step c) quartenization, protrination, sulfation and / or phosphating of the polymers are obtained by taking the polymer obtained in step b) and subjecting it to derivatization or, thus, the derivatives obtained may be obtained. be subjected to further derivatisation such as quartenization, protrination, sulphation and / or phosphatation.

Derivatives of alkoxylated polyalkanolamine polymers containing quaternary ammonium groups, i.e. charged cationic groups, can be produced from amine nitrogen atoms by quaternization with alkylating agents. This includes C1-C4 alkyl halides or sulfates such as ethyl chloride, ethyl bromide, methyl chloride, methyl bromide, dimethyl sulfate and diethyl sulfate. A preferred quaternizing agent is dimethyl sulfate.

Derivatives of polymers containing charged cationic groups (other than quaternary ammonium groups) can also be produced from amine nitrogen atoms by acid protonation. Suitable acids are, for example, carboxylic acid such as lactic acid or mineral acids such as phosphoric acid, sulfuric acid and hydrochloric acid.

Sulfation of the polymers may be conducted by a reaction with sulfuric acid or a sulfuric acid derivative. In this way, acid alkyl ether sulfate is obtained. Suitable sulfating agents are, for example, sulfuric acid (preferably 75 to 100% strength, more preferably 85 to 98% strength), oil, SO3, chlorosulfuric acid, sulfur chloride, amidosulfuric acid and the like. If sulfur chloride is used as a sulfating agent, the remaining chlorine is replaced by hydrolysis after sulfation.

The sulfating agent is often used in equimolar, or proportions, or in excess, for example, 1 to 1.5 mmol per mol of OH group present in the polymer according to the invention. But the sulfating agent may also be used in subequimolar proportions. Sulfation may be conducted in the presence of a solvent or by dragging. A suitable drag or solvent is, for example, toluene. After sulfation, the reaction mixture is generally neutralized and developed in a conventional manner.

Phosphating of the polymers may be conducted by a reaction with phosphoric acid or a phosphoric acid derivative. In this way, alkyl ether acid phosphates are obtained. Phosphating of polymers is generally performed in a manner analogous to the sulfation described above. Suitable phosphating agents are, for example, phosphoric acid, polyphosphoric acid, phosphorus pentoxide, POCl 3 and the like. If POCI3 is used as a sulfating agent, the remaining chlorine is replaced by hydrolysis after sulfation.

The dirt suspension polymer can also be selected from the zwitterionic and ethoxylated polyaminoamine of W02005 / 093030. Modified polyaminoamine comprising formula (I) (I) wherein n having the following formula (I) is an integer from 1 to 500; R 3 of formula (I) is selected from a C 2 -C 8 alkanediyl, preferably 1,2-ethanediyl or 1,3-propanediol; R4 of formula (I) is selected from a chemical bond, C1 -C20 alkanediyl, Cr C20 alkanediyl comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, CrC20alcanodiyl comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical, and mixtures thereof; wherein (I) comprises secondary amino groups of the polymer backbone, secondary amino groups comprise amino hydrogens, amino hydrogens are selectively substituted by modified polyaminoamide, so that modified polyaminoamide comprises partial quaternization of secondary amino groups. by selectively substituting at least one amino hydrogen with at least one alkoxy moiety of the following formula (II): - (CH2-CR1R2-0-) pA (N) wherein A of formula (II) is selected from from a hydrogen or an acid group, the acid group being selected from -B1-PO (OH) 2, -B1-S (0) 20H and -B2-COOH; such that B1 of formula (II) has a single bond or C1 -C6 alkanediyl; and B2 having the following formula (II) is C1 -C6 alkanediyl; R 1 of the following formula (II) is independently selected from hydrogen, C 1 -C 12 alkyl, C 2 -C 8 alkenyl, C 6 -C 16 aryl or C 6 -C 16 aryl-C 1 -C 4 alkyl; R2 of the following formula (II) is independently selected from hydrogen or methyl; and p having the following formula (II) is an integer comprising a numerical average of at least 10; with the amino hydrogen balance of the secondary amino groups being selected from the group comprising electron pairs, hydrogen, C1 -C6 alkyl, C6 -C6 aryl-C1 -C4 alkyl and formula (III) Alk-OA, where A with a following formula (III) is hydrogen or an acid group, the acid group being selected from -B1-PO (OH) 2, -B1-S (0) 20H and -B2-COOH; such that B1 of formula (III) is selected from a single bond or C1 -C6 alkanediyl; and B2 of formula (III) is selected from a C1 -C6 alkanediyl, and Alk of formula (III) is C2 -C6 alkane-1,2-diol; the secondary amino groups of formula (I) are further selected to comprise at least one alkylating moiety of formula (IV): wherein R of formula (IV) is selected from the group consisting of: C1 -C6 alkyl, C6 -C16 -aryl-C1 -C4 alkyl and formula (III) Alk-OA, formula (II) - (CH2-CR1 R2-0-) pA; and X of formula (IV) is a leaving group selected from a halogen, an alkyl halogen, a sulfate, an alkyl sulfonate, an aryl sulfonate, an alkyl sulfate and mixtures thereof.

The polyaminoamide may further comprise cycloaliphatic or aromatic diamines to yield the general formula of (VII): wherein R 3, R 4, and n of formula (VI) are the same as formula (I); R7 of formula (VI) is a bivalent organic radical carrying from 1 to 20 carbon atoms, CrC20alcanodiyl comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen, CrC20alcanodiyl, CrC20alcanodiyl comprising from 1 to 6 heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen further comprising one or more hydroxyl groups, a substituted or unsubstituted divalent aromatic radical, and mixtures thereof.

The modified polyaminoamide may further comprise an esterification moiety for the alkoxy moiety, the alkylating moiety, and mixtures thereof, provided that the hydroxy group is present in the alkoxy moiety and the alkylating moiety. The esterification moiety may be selected from chlorosulfonic acid, sulfur trioxide, amidosulfonic acid, polyphosphate, phosphoryl chloride, phosphorus pentoxide and mixtures thereof.

The polyaminoamide may comprise primary amino groups of the polymer backbone, preferably primary amino groups comprise amino hydrogens, amino hydrogens are modified comprising at least one alkoxy portion of formula (II) with the remainder of the amino acids. amino hydrogens of the secondary amino groups being further modified from the group consisting of electron pairs, hydrogen, C1 -C6 alkyl, C6 -C16 aryl-C1 -C4 alkyl and formula (III) Alq-OA, and the primary amino groups are further modified comprising at least one alkylating moiety of formula (II). Such modified polyaminoamide may further comprise an esterification moiety for the alkoxy moiety, the alkylating moiety, and mixtures thereof, when the hydroxy group is present on the alkoxy moiety and the alkylating moiety. The etherification moieties may be selected from formula (XV) L-B3-A ', where A' from formula (XV) is selected from -COOH, -SO03H, and -PO (OH) 2, B3 of formula (XV) is selected from C1 -C6 alkanediyl; and L of formula (XV) is a leaving group which may be substituted by nucleophiles.

In one embodiment, the detergent composition comprises a modified polyaminoamide of formula (IX): wherein x of formula (IX) is from 10 to 200, preferably from about 15 to about 150, with the following formula. Most preferably, from about 21 to about 100. Most preferably, the numerical average of x of formula (IX) is in the range of 15 to 70, especially from 21 to 50. EO in formula (IX) , represents ethoxy moieties.

In another embodiment, the detergent composition comprises a modified polyamino amide of formula (X): wherein x of formula (X) is from 10 to 200, from about 15 to about 150, or from about 21 to about 100. The numerical average of x of formula (X) is in the range of 15 to 70, especially 21 to 50. EO in formula (X) represents ethoxy moieties. The ratio of dicarboxylic acid: polyalkylene polyamines in formula (X) is 4: 5 and 35:36.

Other suspended soils contemplated for use as dirt suspension polymers include the class of polyacrylate polymers, such as the (meth) acrylic and condensed ethylene (meth) acrylic oxide copolymers disclosed in US Patent No. 3,719,647 , and carboxy methyl cellulose derivatives in US Patent Nos. 3,597,416 and 3,523,088.

Clay dirt suspension polymers are optional in the polymer system of the detergent and cleaning compositions of the present invention. However, when used, they are incorporated in contents in the range of from about 0.05% to 10% by weight of the composition. Modalities of the compositions may comprise from about 0.1% to about 5% by weight. More specifically, the embodiments may comprise from about 0.25 to about 2.5% of the clay dirt suspension polymer.

Multi-Polymer System The laundry detergent compositions and cleaning compositions of the present invention comprise a polymer system comprising at least one of the amphiphilic grease-cleaning polymers, and also at least one dirt-cleaning polymer clay or at least one polymer for suspending clay dirt.

In addition, for the polymer system described above, laundry detergent compositions and cleaning compositions generally comprise surfactants and, if appropriate, other polymers as washing substances. " builders "and other customary ingredients, for example" cobuilders ", complexing agents, bleaches, patterners, greyish inhibitors, dye transfer inhibitors, enzymes and perfumes.

The multimeric system of the present invention may be used in laundry detergent compositions or cleaning compositions comprising a surfactant system comprising C10 -C16 alkyl benzene sulfonates (LAS) and one or more co-additives selected from nonionic, cationic, anionic or mixtures thereof. Alternatively, the multipolymer system of the present invention may be used in laundry detergent compositions or cleaning compositions comprising surfactant systems comprising any anionic surfactant or admixture thereof with optionally supplemented nonionic surfactants and / or fatty acids with zwitterionic surfactants or also known as semipolar surfactants such as C12-C16 alkyl dimethyl amine. N-oxides may also be used. In other embodiments, the surfactant used may be exclusively anionic or exclusively nonionic. Suitable surfactant contents are from about 0.5% to about 80% by weight of the detergent composition, more typically from about 5% to about 60% by weight.

A preferred class of anionic surfactants are the sodium, potassium and ammonium alkanol salts of the C10 -C16 alkyl benzene sulfonates, which may be prepared by sulfonation (using SO2 or SO3) of alkyl benzene, followed by neutralization. . Suitable alkyl benzene feedstocks may be produced from olefins, paraffins or mixtures thereof using any alkylation scheme, including sulfuric and HF-based processes. Any suitable catalyst may be used for alkylation, including solid acid catalysts such as solid DETAL®, acid catalyst commercially available from UOP, a Honeywell company. Such solid acid catalysts include DETAL® DA-114 catalysts and other solid acid catalysts described in UOP, Petresa, Huntsman and others. It should be understood and appreciated that by precisely varying the alkylation catalyst it is possible to vary widely the position of the covalent bond of benzene to an aliphatic hydrocarbon chain. Accordingly, alkyl benzene sulfonates usable herein may vary widely in the content of the 2-phenyl isomer and / or the internal isomer content.

The selection of co-active may be dependent on the desired benefit. In one embodiment, the co-active is selected as a nonionic surfactant, preferably C12-C18 alkyl ethoxylates. In another embodiment, the co-active is selected as an anionic surfactant, preferably C10-C18 alkylalkoxy sulfates (AEXS), where x is from 1 to 30. In another embodiment, the co-active is selected as a cationic surfactant, preferably chloride. of dimethyl hydroxyethyl lauryl ammonium. If the surfactant system comprises C10 -C15 alkyl benzene sulfonates (LAS), LAS is used in contents in the range of from about 9% to about 25%, or from about 13% to about 25%, or about 15% to about 23% by weight of the composition.

In one embodiment, the surfactant system may comprise from 0% to about 7%, or from about 0.1% to about 5%, or from about 1% to about 4%, by weight. composition, a co-active selected from a non-ionic co-active, cationic co-active, anionic co-active and any mixture of these materials.

Some non-limiting examples of nonionic co-activeants include: C 12 -C 18 alkyl ethoxylates, such as NEODOL® nonionic surfactants, available from Shell; C 6 -C 12 alkyl phenol alkoxylates, wherein the alkoxylate units are a mixture of oxyethylene and oxypropylene units; C 12 -C 18 alcohol and C 6 -C 12 alkyl phenol condensates with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates, such as PLURONIC®, available from BASF; branched medium chain alcohols, BA, C14-C22, as discussed in US 6,150,322; C1 -C22 branched chain middle alkyl alkoxylates, BAEX wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkyl polysaccharides as discussed in US 4,565,647 Llenado, issued January 26, 1986; specifically alkyl polyglycosides as discussed in US 4,483,780 and US 4,483,779; the fatty acid polyhydroxy amides as discussed in US 5,332,528; and ether capped with poly (oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408. Also useful herein as nonionic or co-active surfactants are alkoxylated ester surfactants such as those having the formula R 1 C (O) 0 (R 20) n R 3, wherein R 1 is selected from C 6 -C 22 straight and branched alkyl or alkylene moieties; R 2 is selected from C 2 H 4 and C 3 H 6 moieties and R 3 is selected from H, CH 3, C 2 H 5 and C 3 H 7 moieties; and n has a value between 1 and 20. Such alkoxylated ester surfactant includes fatty ethoxylate methyl esters (ESM) and are well known in the art; see for example US 6,071,873, US 6,319,887, US 6,384,009, US 5,753,606, WO 01/10391, WO 96/23049.

Some nonlimiting examples of semipolar nonionic co-activeants include: water-soluble amine oxides, with an alkyl moiety containing from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; water soluble phosphine oxides having an alkyl moiety containing from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms; and water soluble sulfoxides, with an alkyl moiety containing from 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681,704 and US 4,133,779.

Some nonlimiting examples of cationic co-additives include: Quaternary ammonium surfactants that can have up to 26 carbon atoms include: Quaternary ammonium alkoxylate (AQA) surfactants as discussed in US 6,136,769; quaternary dimethyl hydroxyethyl ammonium as discussed in 6,004,922; Dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US Pat. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amine surfactants as discussed in US Patent No. 6,221,825 and WO 00/47708, specifically dimethyl propylamine starch (APA).

Some nonlimiting examples of anionic co-activeants usable herein include: primary, branched chain and random C10 -C20 alkyl sulfates (AS); C 1 -C 18 secondary alkyl (2,3) sulfates; C10 -C18 alkyl alkoxy sulfate (AEXS), wherein x is from 1 to 30; C10 -C18 alkyl alkoxy carboxylates comprising from 1 to 5 ethoxy units; branched middle chain alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; branched chain alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkyl benzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha olefin sulfonate (AOS). Anionic surfactants of the present invention may be used in the form of their sodium, potassium or ammonium alkanol salts.

The present invention may also relate to compositions comprising the multipolymer system of the invention and a surfactant system comprising linear C8 -C18 alkyl sulfonate surfactant and a cohesive. The compositions may be in any form, especially in liquid form; a solid such as powder, granules, agglomerates, paste, tablet, small shells, bar, gel; an emulsion; types supplied in containers with two compartments; a spray or detergent foam; pre-moistened wipes (i.e. the cleaning composition in combination with a nonwoven material such as that discussed in US Patent No. 6,121,165, Mackey, et al.); dry wipes (i.e. the cleaning composition in combination with nonwoven materials, such as that discussed in US 5,980,931, Fowler, et al.) activated by water by a consumer; and other homogeneous or multiphase forms of consumer cleaners. The composition may be in the form of a tablet or containment bag, including small multi-compartment shells.

[00106] In one embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition. In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition wherein preferably the hard surface cleaning composition is impregnated with a nonwoven substrate. For use in the present invention, the term "impregnating" means that the hard surface cleaning composition is contacted with a non-woven substrate so that at least a portion thereof is penetrated by said cleaning composition wherein, preferably said composition saturates said nonwoven substrate. The cleaning composition can also be used in car care compositions for cleaning various surfaces such as hardwood, tile, ceramics, plastic, leather, metal and glass. Such a cleaning composition could also be formulated for use in personal care and pet care compositions, such as shampoo, body wash, liquid or solid soap, and other cleaning compositions wherein surfactant comes in contact with free hardness elements as well as in all compositions that require a hardness tolerant surfactant system such as oil well drilling compositions.

[00107] In another embodiment, the cleaning composition is a dish cleaning composition, such as liquid manual dishwashing compositions, solid dishwashing liquid compositions, automatic dishwashing liquid compositions, and compositions under pressure. tablet or dish washer units in automatic washer.

Quite typically, the cleaning compositions of the present invention, such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic soap-based laundry bars, fabric softeners and liquids or solids for tissue treatment as well as treatment articles of all types require various auxiliary compounds, although certain formulated products such as bleach additives may only require, for example, an oxygen-based bleaching agent and a surfactant. as described in the present invention. A comprehensive list of suitable auxiliary materials for laundry or cleaning can be found in WO 99/05242.

Common cleaning adjuncts include builders, enzymes, polymers not discussed above, bleaches, bleach activators, catalytic materials and the like, excluding any materials previously defined herein. Other cleaning aids of the present invention may include sweat suppressants, foam (antifoam) suppressors and the like, miscellaneous active ingredients or specialized materials such as dispersing polymers (e.g. from BASF Corp. or Rohm & Haas) in addition to those described above, splashing. colored, silvercare, anti-fogging and / or anti-corrosion agents, dyes, fillers, germicides, alkalinity source, hydrotropes, antioxidants, enzyme stabilizing agents, properfumes, perfumes, solubilizing agents, vehicles, processing aids, pigments, and for formulations liquids, solvents, chelating agents, dye transfer inhibiting agents, dispersants, bleaches, suds suppressors, dyes, structure elasticizing agents, fabric softeners, anti-abrasion agents, hydrotropes, processing aids, and other tissue care agents , surface and skin care agents. Suitable examples of these other cleaning aids, as well as their contents of use, are found in US Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1. Method of Use The present invention includes a method for cleaning a target surface. For use in the present invention, the term "target surface" may encompass surfaces such as fabrics, plates, cups and other cooking surfaces, hard surfaces, hair or skin. For use in the present invention, the term "hard surface" encompasses hard surfaces that are found in a typical home such as hardwood, tile, ceramics, plastic, leather, metal and glass. Such a method includes the steps of contacting the composition comprising the modified polyol compound, in its pure form or diluted in a washing liquid, with at least a portion of a target surface and then optionally rinsing the target surface. Preferably, the target surface is subjected to a washing step prior to the optional rinsing step mentioned above. For purposes of the present invention, washing includes, but is not limited to, scrubbing, drying and mechanical agitation.

As will be appreciated by one of skill in the art, the cleaning compositions of the present invention are ideal for use in home care (hard surface cleaning) and / or laundry applications.

The solution pH of the composition is chosen to be most complementary to a target surface to be cleaned, spanning a wide pH range from about 5 to about 11. In the case of personal care compositions as for skin and hair cleaning, the pH of the composition is preferably in the range of about 5 to about 8, while the laundry cleaning compositions have a pH in the range of about 8 to about 10. The compositions are preferably used at concentrations of from about 200 ppm to about 10,000 ppm in solution. Water temperatures are preferably from about 5 ° C to about 100 ° C.

Preferably for use in laundry cleaning compositions, concentrations in the range of about 200 ppm to about 10,000 ppm in solution (or washing liquid) are used. Water temperatures are preferably in the range of about 5 ° to about 60 ° C. The water to tissue ratio is preferably from about 1: 1 to about 20: 1.

The method may include the step of contacting an impregnated non-woven substrate with an embodiment of the composition of the present invention. For use in the present invention "nonwoven substrate" may comprise any conventionally made nonwoven sheet or mat having suitable weight, gauge (thickness), absorbency and strength characteristics. Examples of suitable commercially available nonwoven substrates include those available under the trade names SONTARA® from DuPont and POLYWEB® from James River Corp.

As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally intended for use in liquid dish cleaning compositions. The method for using a liquid dishwashing composition of the present invention comprises the steps of bringing dirty dishes into contact with an effective amount, typically from about 0.5 ml to about 20 ml (per 25 dishes being treated). of the liquid dish cleaning composition of the present invention diluted with water.

Examples Example 1 - Oranular laundry detergent 600 g / mol molecular weight polyethyleneimine core with 24 -NH ethoxylate groups and 16 -NH propoxylate groups. 2 Core triethanol amine core of 13,600 g / mol with 24 ethoxylate groups by -OH and 16 propoxylate groups by -OH. 3 600 g / mol molecular weight polyethyleneimine core with 20 ethoxylate groups by -NH. The PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with one polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. Example 2 - Qranular laundry detergent Aqueous slurry composition. Polyethyleneimine core is 600 g / mol molecular weight with 24 NH-ethoxylate groups and 16 NH-propoxylate groups. The PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. Preparation of a dry powder or atomization.

An aqueous slurry of composition as described above is prepared to have a moisture content of 25.89%. The aqueous slurry is heated to 72 ° and pumped under high pressure (5.5x106 Nm'2 to 6.0x106 Nnrf2) in a countercurrent flow spray drying tower with an inlet air temperature in the range of 270 ° C. * 0 3000. The aqueous slurry is atomized and then dried to produce a solid mixture, which is cooled and sieved to remove large (> 1.8 mm) materials to form a dried powder. by atomization, which has free flow. The thin material (<0.15 mm) is eluted with the exhaust air in the spray drying tower and collected in a post tower containment system. The spray dried powder has a moisture content of 1.0 wt%, an apparent density of 427 g / l, and a particle size distribution of up to 95.2 wt% of the spray dried powder. has a particle size in the range of 150 to 710 micrometers. The composition of the spray dried powder is shown below.

Spray-dried powder composition. Polyethyleneimine core is 600 g / mol molecular weight with 24 -NH ethoxylate groups and 16 -NH propoxylate groups. 4 PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. Preparation of an Anionic Surfactant Particle 1 The anionic detersive surfactant particle 1 is produced from a batch of 520 g, first using a Tilt-A-Pin type mixer and then a type mixer. Tilt-A-Plow (both available from Processall). 108 g of sodium sulphate are added to the Tilt-A-Pin mixer together with 244 g of sodium carbonate, 168 g of 70% active C25E3S paste (C12.15 alcohol-based sodium ethoxy sulphate and ethylene oxide ) are added to the Tilt-A-Pin mixer. The components are then mixed at 1200 rpm for 10 seconds. The resulting powder is then transferred into a Tilt-A-Plow mixer and mixed at 200 rpm for 2 minutes to form particles. The particles are then dried in a fluid bed dryer at a rate of 2500 l / min at 120 ° C until the equilibrium relative humidity of the particles is less than 15%. The dried particles are then sieved and the fraction through 1180 pm and at 250 pm is retained. The composition of the anionic detersive surfactant particle 1 is as follows: 25.0 wt% sodium ethoxy sulfate C25E3S 18.0 wt% sodium sulfate 57.0 wt% sodium carbonate a cationic detersive surfactant particle 1 [00118] The cationic surfactant particle 1 is produced from a 14.6 kg batch in a Morton FM-50 Loedige mixer. 4.5 kg of micronized sodium sulfate and 4.5 kg of micronized sodium carbonate are premixed in the Morton FM-50 Loedige mixer. 4.6 kg of 40% active aqueous C12-14 monohydroxyethyl dimethyl ammonium (cationic surfactant) monoalkyl chloride solution (cationic surfactant) is added to the Morton FM-50 Loedige mixer while both the main motor and cutter are running. After approximately two minutes of mixing, 1.0 kg of a 1: 1 weight ratio mixture of micronized sodium sulfate and micronized sodium carbonate is added to the mixer. The resulting agglomerate is collected and dried in a fluid bed drier at a base of 2,500 l / min of air at a temperature of 100 ° C to 140 ° C for 30 minutes. The resulting powder is sieved, and the fraction up to 1,400 pm is collected as the cationic surfactant particle 1. The composition of the cationic surfactant particle 1 is as follows: 15% by weight of C12-14 monohydroxyethyl monoalkyl chloride quaternary ammonium dimethyl 40.76 wt% sodium carbonate 40.76 wt% sodium sulfate 3.48 wt% moisture and other components Preparation of a qranular laundry detergent composition [00119] 10.84 kg of the spray dried powder of example 2, 4.76 kg of anionic detersive surfactant particle 1, 1.57 kg of cationic detersive surfactant particle 1 and 7.83 kg (total amount) of other individually dosed materials added to Dry materials are dosed in a 1 m diameter concrete batch mixer operating at 24 rpm. Once all materials have been metered into the mixer, the mixture is processed for 5 minutes to form a specific composition. granular for washing clothes. The formulation of the granular laundry detergent composition is described below: A laundry detergent orange composition.

Example 3 - Liquid laundry detergent 600 g / mol molecular weight polyethyleneimine core with 24 NH-ethoxylate groups and 16 NH-propoxylate groups. 2 Core triethanol amine core of 13,600 g / mol with 24 ethoxylate groups by -OH and 16 propoxylate groups by -OH. 3 600 g / mol molecular weight polyethyleneimine core with 20 ethoxylate groups by -NH, 4 PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide eopolymer with a polyethylene oxide backbone and multiple chain polyvinyl acetate side bitches The molecular weight of the polyethylene oxide main bitch is about 6.000 and the ratio of the weight of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and not more than 1 point. of 50 units of ethylene oxide, 5 diethylene triamine pentaacetic acid, sodium salt diethylene triamine acid pentaquisical methylphosphonic acid, sodium salt 7 ethylenediamine tetraacetic acid, sodium salt 8 Acusol OP 301 1 Polyethyleneimine core with a molecular weight of 600 g / mol with 24 ethoxylate groups by -NH and 16 propoxylate groups by -NH. 2 Core triethanol amine nucleus of 13,600 g / mol with 24 ethoxylate groups by -OH and 16 propoxylate groups by -OH. 3 600 g / mol molecular weight polyethyleneimine core with 20 ethoxylate groups by -NH. The PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. 600 g / mol molecular weight polyethyleneimine nucleus with 24 NH-ethoxylate groups and 16 NH-propoxylate groups. 2 Core triethanol amine core of 13,600 g / mol with 24 ethoxylate groups by -OH and 16 propoxylate groups by -OH. 3 600 g / mol molecular weight polyethyleneimine core with 20 ethoxylate groups by -NH, 4 PEG-PVA graft polymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and not more than 1 graft point per 50 ethylene oxide units, 5 Alco 725 (styrene / acrylate) Example 4 - Liquid dishwashing detergents 1 600 g / mol molecular weight polyethyleneimine core with 24 NH-ethoxylate groups and 16 propoxylate groups by -NH. 2 13,600 g / mol molecular weight triethanol amine nucleus with 24 -OH ethoxylate groups and 16 -OH propoxylate groups, 4 PEG-PVA graft polymer is a polyvinyl acetate grafted polyethylene oxide copolymer with one polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. Non-phonic may be any ethoxylated Cn alkyl surfactant containing 9 ethoxy groups, 1,3, BAC is 1,3 bis (methylamine) cyclohexane. Ethyl methacrylate (β, Ν-dimethylamino) homopolymer Example 5 - Dishwashing dishwashing detergent 1 600 g / mol molecular weight polyethyleneimine core with 24 NH-ethoxylate groups and 16 NH-propoxylate groups. 2 Core triethanol amine core of 13,600 g / mol with 24 ethoxylate groups by -OH and 16 propoxylate groups by -OH. The PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the weight ratio of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene. 5 As ACUSOL® 445N available from Rohm & Haas or ALCOSPERSE® available from Alco. 6 As SLF-18 POLY TERGENT from Olin Corporation. Example 6: A liquid laundry detergent composition in the form of a bag, encapsulated by a polyvinyl alcohol film 1 ........................ ....................................................................................................................................................................................................................................................................................................................................... PAP = Phthaloyl amino acid caproic acid as a 70% wet compact asset 2 Polyethyleneimine core with molecular weight of 600 g / mol with 24 NH-ethoxylate groups and 16 NH-propoxylate groups. 3 600 g / mol molecular weight polyethyleneimine core with 20 ethoxylate groups by -NH. The PEG-PVA graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer with a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6.000 and the ratio of the weight of polyethylene oxide to the weight of polyvinyl acetate is about 40 to 60 and no more than 1 graft point per 50 oxide units. of ethylene.

Unless otherwise specified, all component or composition contents refer to the active content of the component or composition and exclude impurities, such as residual solvents or by-products, which may be present in commercially available sources.

All percentages and ratios are calculated by weight unless otherwise indicated. All percentages and ratios are calculated based on the total composition except where otherwise indicated.

It should be understood that each maximum numerical limit mentioned in this specification includes all lower numerical limits, as if such lower numerical limits were expressly recorded herein. Each minimum numerical limit mentioned in this specification includes each of the upper numerical limits, as if such upper numerical limits were expressly recorded herein. Each numeric range mentioned in this specification includes each narrower numeric range that is within this broader numerical range, as if such narrower numeric ranges were expressly recorded herein.

The dimensions and values set forth in the present invention should not be construed as being strictly limited to the exact numerical values mentioned. Instead, unless otherwise specified, each of these dimensions is intended to mean both the declared value and a functionally equivalent range of values around that value. For example, a dimension displayed as "40 mm" is intended to mean "about 40 mm".

All documents cited in the detailed description of the invention are, in their relevant part, incorporated herein by reference. Citation of any document should not be construed as an admission that it represents prior art with respect to the present invention.

While specific embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various other changes and modifications may be made without departing from the character and scope of the invention. Therefore, it is intended to cover in the appended claims all such changes and modifications that fall within the scope of the present invention.

Claims (14)

A laundry detergent composition or cleaning composition, characterized in that it comprises a polymer system comprising: a) one or more alkoxylated grease cleaning polymers comprising a central structure and a plurality of alkoxylate groups, wherein The central structure may comprise: i) a polyalkylenimine structure comprising, in condensed form, repeating units of formulas (I), (II), (III) and (IV): wherein # in each case denotes half a bond between a nitrogen atom and the free bond position of an A1 group of two adjacent repeating units of formula (I), (II), (III) or (IV); * in each case denotes half of a bond to one of the alkoxylate groups; and A1 is independently selected from straight or branched C2 -C6 alkylene; wherein the polyalkylenimine structure consists of 1 repeating unit of formula (I), x repeating units of formula (II), y repeating units of formula (III) and y + 1 repeating units of formula (IV), where x and y in each case have a value in the range of 0 to about 150; wherein the weight average molecular weight, Mw, of the central polyalkylenimine structure is a value in the range of about 60 to about 10,000 g / mol; or ii) a polyalkanolamine structure of the condensation products of at least one compound selected from N- (hydroxyalkyl) amines of the following formulas (1a) and / or (1b), wherein A is independently selected from C1 -C6 alkylene; R 1 R 1 *, R 2, R 2 *, R 3, R 3 ** R 4, R 4 *, R 5 and R 5 * are independently selected from hydrogen, alkyl, cycloalkyl or aryl, wherein the last three mentioned radicals may be optionally substituted; and R 6 is selected from hydrogen, alkyl, cycloalkyl or aryl wherein the last three mentioned radicals may be optionally substituted; and the plurality of alkylenoxy groups are independently selected from alkylenoxy units of formula (V) wherein: * in each case denotes half a bond of a nitrogen atom of the repeating unit with the following formulas (I), ( II) or (IV); A2 is in each case independently selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene; A3 is 1,2-propylene; R is in each case independently selected from hydrogen and C1-C4 alkyl; m has an average value in the range from 0 to about 2; n has an average value in the range of about 20 to about 50; and p has an average value in the range from about 10 to about 50, and also b) a clay dirt cleaning polymer which is selected from the group consisting of ethoxylated oligamines, methyl quaternary ethoxylated oligamines, benzyl ethoxylated oligamines quaternary, oligoamines etoxissulfatadas methyl quaternary, oligoamines propoxylated-etoxissulfatadas methyl quaternary, oligoamines etoxissulfatadas benzyl quaternary, propoxylated-etoxissulfatada oligoamines benzyl quaternary, oligoeteraminas ethoxylated methyl quaternary, oligoeteraminas ethoxylated benzyl quaternary, oligoeteraminas etoxissulfatadas methyl quaternary, oligoeteraminas etoxissulfatadas benzyl quaternary, and mixtures thereof ; or c) a dirt suspension polymer. Laundry detergent composition or cleaning composition according to claim 1, characterized in that the clay dirt cleaning polymer is selected from the group consisting of ethoxysulfated quaternary dimethyl diamine dimethyl diamine; ethoxylated tetraethylene pentaimine; quaternary dimethyl ethoxylated hexamethylene diamine; bis (hexamethylene) triamine ethoxylated about 30 times by -NH group and about 90% quaternized; ethoxylated tetrasulfate 4,9-dioxa-1,12-dodecanediamine dimethyl quaternary; propoxylated ethoxylated bis (hexamethylene) triamine; benzyl quaternized bis (hexamethylene) triamine; trans-sulfated bis (hexamethylene) triamine; propoxylated, 50% sulfonated hexa-methylene diamine methyl quaternary ethoxylate. Laundry detergent composition or cleaning composition according to claim 1, characterized in that the dirt suspension polymer is selected from the group consisting of: i) alkoxylated polyethyleneimine having from about 5 to about 24 ethoxylate groups per -NH group and from zero to about 12 propoxylate groups per -NH group; and ii) random graft copolymers having a hydrophilic backbone comprising monomers selected from the group consisting of C1-6 unsaturated acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols, and mixtures thereof; and hydrophobic side chains selected from the group comprising C4.25 alkyl, polypropylene groups; polybutylene, a vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms; a C 1-6 alkyl ester of acrylic or methacrylic acid; and iii) a mixture thereof. Laundry detergent composition or cleaning composition according to claim 3, characterized in that the hydrophobic dirt suspension polymer is a random graft copolymer having a hydrophilic backbone comprising polyethylene glycol by weight. molecular weight of 4,000 to 15,000, and 50% to 65% by weight of hydrophobic side chains formed by polymerizing at least one monomer selected from vinyl ester of a saturated monocarboxylic acid containing from 1 to 6 carbon atoms and / or a C1-6 alkyl ester of acrylic acid or methacrylic acid. Laundry detergent composition or cleaning composition according to Claim 4, characterized in that the hydrophobic dirt suspension polymer is a random graft copolymer having a hydrophilic backbone comprising molecular weight polyethylene glycol. from 4,000 to 15,000, and from 50% to 65% by weight of hydrophobic side chains formed by polymerizing at least one monomer selected from vinyl acetate, vinyl propionate and / or butyl acrylate. Laundry detergent composition or cleaning composition according to claim 3, characterized in that the hydrophobic dirt suspension polymer is a water-soluble graft-based polyalkylene oxide having side chains formed by the polymerization of a vinyl ester component, said polymer having an average of 1 graft site per 50 alkylene oxide units and average molar masses Mw of 3,000 to 100,000 g / mol. Laundry detergent composition or cleaning composition according to claim 6, characterized in that the graft polymer has an Mw / Mn polydispersity of ≤ 3 µm. Laundry detergent composition or cleaning composition according to Claim 1, characterized in that the detergent or composition further comprises a surfactant system. Laundry detergent composition or cleaning composition according to claim 8, characterized in that the surfactant system comprises C10 -C16 alkyl benzene sulfonates. Laundry detergent composition or cleaning composition according to claim 8, characterized in that the surfactant system comprises a C8-C18 linear alkyl sulfonate surfactant. Laundry detergent composition or cleaning composition according to claim 9, characterized in that the surfactant system further comprises one or more co-active agents selected from the group consisting of nonionic surfactants, cationic surfactants, surfactants anions and mixtures thereof. Laundry detergent composition or cleaning composition according to Claim 8, characterized in that the detergent or composition further comprises cleaning auxiliary additives. Cleaning implement, characterized in that it comprises a nonwoven substrate and the laundry detergent composition or cleaning composition as defined in claim 1. A laundry detergent composition or cleaning composition, characterized in that it comprises a polymer system comprising: a) one or more alkoxylated grease cleaning polymers comprising a central structure and a plurality of alkoxylate groups, wherein : the central structure may comprise: a polyalkylenimine structure comprising, in condensed form, repeating units of formulas (I), (II), (III) and (IV): wherein # in each case denotes half of a bonding between a nitrogen atom and the free bonding position of an A1 group of two adjacent repeating units of formula (I), (II), (III) or (IV); * in each case denotes half of a bond to one of the alkoxylate groups; and A1 is independently selected from straight or branched C2 -C6 alkylene; wherein the polyalkylenimine structure consists of 1 repeating unit of formula (I), x repeating units of formula (II), y repeating units of formula (III) and y + 1 repeating units of formula (IV), where x and y in each case have a value in the range of 0 to about 150; wherein the weight average molecular weight, Mw, of the polyalkylenimine core structure is a value in the range from about 60 to about 10,000 g / mol; and the plurality of alkylenoxy groups are independently selected from alkylenoxy units of formula (V) wherein: * in each case denotes half a bond of a nitrogen atom of the repeating unit with the following formulas (I), ( II) or (IV); A2 is in each case independently selected from 1,2-propylene, 1,2-butylene and 1,2-isobutylene; A3 is 1,2-propylene; R is in each case independently selected from hydrogen and C1 -C4 alkyl; m has an average value in the range from 0 to about 2; n has an average value in the range of about 20 to about 50; and p has an average value in the range from about 10 to about 50, and also b) a polymer for cleaning clay dirt; or c) a dirt suspension polymer.