WO2024115754A1

WO2024115754A1 - Aqueous compositions containing polyalkoxylates, polyalkoxylates, and use

Info

Publication number: WO2024115754A1
Application number: PCT/EP2023/083966
Authority: WO
Inventors: Stephan Hueffer; Ivette Garcia Castro; Yannick MATT; Rainer Klopsch; Jessica Eleanor Bean
Original assignee: Basf Se
Priority date: 2022-12-02
Filing date: 2023-12-01
Publication date: 2024-06-06

Abstract

The present invention is directed towards aqueous compositions comprising at least one (A) compound that comprises at least one alkoxylated aliphatic or cycloaliphatic mono- or polyamine comprising (a) a backbone that is derived from a compound bearing at least one primary amino group per molecule, (b) polyalkylenoxide chains comprising a (b1) polyethylene oxide chain with 15 to 50 ethylene oxide groups attached to each nitrogen atom, (b2) capped with a polypropylene oxide or polybutylene oxide chain comprising from 0.5 to 4 PO or BuO groups and amounting to 2.5 to 20 % by weight of the respective polyethylene oxide chain.

Description

Aqueous compositions containing polyalkoxylates, polyalkoxylates, and use

The present invention is directed towards aqueous compositions comprising at least one compound (A) that comprises at least one alkoxylated aliphatic or cycloaliphatic mono- or polyamine comprising

(a) a backbone (a) that is derived from a compound bearing at least one primary amino group per molecule,

(b) polyalkylenoxide chains (b) comprising a

(b1) polyethylene oxide chain with 15 to 50 ethylene oxide (“EO”) groups attached directly or indirectly to each nitrogen atom,

(b2) capped with a polypropylene oxide or polybutylene oxide chain comprising from 0.5 to 4 PO or BuO groups and amounting to 2.5 to 20 % by weight of the respective polyethylene oxide chain.

Said aqueous compositions are preferably detergent compositions, in particular laundry detergent compositions. These compounds (A) are useful for such aqueous compositions. Furthermore, the present invention relates to compounds (A) and to a process for making such compounds (A). The present invention also relates to compounds (A’).

Laundry detergents have to fulfil several requirements. They need to remove all sorts of soiling from laundry, for example all sorts of pigments, clay, fatty soil, and dyestuffs including dyestuff from food and drinks such as red wine, tea, coffee, and fruit including berry juices. Laundry detergents also need to exhibit a certain storage stability. Especially laundry detergents that are liquid or that contain hygroscopic ingredients often lack a good storage stability, e.g., enzymes tend to be deactivated.

In laundry detergents, among others, pigments need to be dispersed so they remain the washing liquor instead of being re-deposited on the laundry. In addition, a good biodegradability of key components is required in the market, for example at least 60% according to the OECD 301 F method, and it was an objective to provide such components.

Accordingly, the aqueous compositions as defined at the outset have been found, hereinafter also referred to as inventive compositions, inventive aqueous compositions or (aqueous) compositions according to the present invention. Inventive compositions comprise at least one compound (A). Inventive compositions and compounds (A) shall be described in more detail below. Inventive compositions are aqueous compositions, thus, they contain water, and they are geltype or preferably liquid at ambient temperature. Preferably, inventive aqueous compositions are liquid at ambient temperature, and they typically have a dynamic viscosity in the range of 120 to 1200 mPa s, preferably in the range of 150 to 300 mPa s, determined according to Brookfield at 20°C, spindle S62, 100 rpm.

In the context of the present invention, the term “aqueous” means that at least the majority by weight of the solvents present in said aqueous compositions is water. Up to 20% by weight of non-aqueous solvent may be present, e.g., ethanol, isopropanol, ethylene glycol, 1 ,2-propylene glycol, diethylene glycol, or combinations of at least two of the aforementioned.

Inventive compositions are preferably phosphate-free, also referred to as “free from phosphate”. "Free from phosphate" and “phosphate-free” are used interchangeably in the context of this invention, and the terms should be understood as meaning that the content of phosphate and polyphosphate in inventive compositions range of from detection level to 1% by weight, preferably from 10 ppm to 0.2% by weight, determined by gravimetry.

Phosphate may be added deliberately. Due to environmental concerns, though, it is preferred to not add phosphate deliberately. However, phosphate may involuntarily be present as an impurity of various ingredients.

Compound (A) bears a backbone (a), hereinafter also referred to as backbone (a) or simply as (a). Backbone (a) is preferably an aliphatic or cycloaliphatic compound. This means that the backbone has one or more, e. g. 1 to 200, in particular 2 to 150 groups which are aliphatic groups, cycloaliphatic groups or combinations thereof, where in case of 2 or more groups, the groups are linked to each other by heteroatoms or heteroatom groups such as -O-, -NH-, - C(O)NH- (= carboxamide) and/or -C(O)O- (carboxylic ester groups). Backbone (a) is derived from a compound bearing at least one primary amino group (NH2) per molecule, preferably at least two primary amino groups per molecule or at least one primary amino group and at least one secondary amino group (NH) per molecule. The NH2 group may also be present in the form of a guanidine group, i. e. a group NH-N(=NH)-NH2.

The compound which forms the polymer backbone (a) or from which the backbone (a) is derived, respectively, is typically selected from low molecular weight compounds, i. e. compounds or compound mixtures, where the respective compound has a defined molecular weight, which is typically in the range of 80 to 400 g/mol. These compounds are aliphatic or cycloaliphatic and bear at least one primary amino group (NH2) per molecule, preferably at least two primary amino groups per molecule or at least one primary amino group and at least one secondary amino group (NH) per molecule. The compound which forms the polymer backbone (a) or from which the backbone (a) is derived, respectively, may be also be selected from oligomers and polymers having not a defined molecular weight but an average molecular weight which is higher than that of the low molecular compounds. Typically, the number average molecular weight of the oligomers and polymers forming the backbone (a) is in the range of 200 to 10,000 g/mol. The weight average molecular weight of polymers forming the backbone (a) is in the range of 1 ,000 to 50,000 g/mol. The polydispersity Q = M_w/M_n of the oligomer or polymer forming the backbone is typically at least 1 .5, preferably in the range of from 1 .5 to 50, in particular in the range of from 2 to 40 and even more preferably from 3 to 35.

Here, the term “derived from” is understood, that the compound bearing at least one primary amino group per molecule, in particular at least one primary amino group and at least one secondary amino group or at least two primary amino groups and optionally 1 or more secondary amino groups itself forms the backbone or is reacted to from an oligomer or polymer, e. g. by a condensation reaction, e. g. by an amidation, or by a addition reaction, e. g. by an alkoxylation reaction, or by combinations thereof. Of course, resulting backbone typically has still functional groups, such as hydroxyl groups and/or primary or secondary amino groups which are capable of being alkoxylated.

Thus, in the compound A, typically at least a part of the hydrogen atoms in NH groups of the compound bearing at least one primary amino group per molecule are replaced by poly- alkylenoxide chains (b) while the remainder can be modified, e. g. by a carbonyl group to form a carboxamide group, a carbonyloxy group, a C2-C4-alkyleneoxy group or a C2-C4-alkyleneoxycar- bonyl group, which themselves are attached to further structural units of the backbone which may stem derived from further molecules, aliphatic di- and/or tricarboxylic acid molecules, diol compounds, triol compounds and combinations thereof.

The molecular weights given here refer to the molecular weight as determined by performing a gel permeation chromatography (GPC) of the respective oligomer or polymer forming the backbone (a) at 20°C using hexafluoroisopropanol (HFIP) as an eluent and polymethylmethacrylate of defined molecular weight as standards for calibration and using a refractive index detector. For further details we refer to the experimental part.

As used herein, M_n refers to the number average molecular weight and M_w refers to the weight average molecular weight or the respective polymer or oligomer. In this context, the term aliphatic groups refer to acyclic hydrocarbon groups having typically 1 to 20 carbon atoms, in particular 1 to 10 carbon atoms. Aliphatic groups in particular relates to linear or branched alkyl having typically 1 to 20 carbon atoms (C1-C20 alkyl), in particular 1 to 10 carbon atoms (C1-C10 alkyl), more particularly 1 to 6 carbon atoms (Ci-Cs alkyl), linear or branched alkandiyl having typically 2 to 20 carbon atoms (C2-C20 alkandiyl), in particular 2 to 10 carbon atoms (C2-C10 alkandiyl) and linear or branched alkantriyl having typically 3 to 20 carbon atoms (C3-C20 alkantriyl), in particular 3 to 10 carbon atoms (C3-C10 alkantriyl). The aliphatic groups may be unsubstituted or substituted by 1 or 2 hydroxyl groups. In aliphatic groups 1 , 2, 3, 4 or 5 non-adjacent carbon atoms may be replaced by O or N, e. g. CH2 groups may be replaced by O or NH and CH groups may be replaced by N. Examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methyl- butyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, 2-heptyl, 1- octyl, 2-octyl, 2-ethylhexyl, 1-nonyl, 2-nonyl and 1-decyl. Examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, tert.-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methyl- butyl, 2,2-dimethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, n-heptyl, 2-heptyl, 1- octyl, 2-octyl, 2-ethylhexyl, 1-nonyl, 2-nonyl and 1-decyl. Examples of alkandiyl, which is also referred to as alkylene, are 1 ,2-ethanediyl, 1 ,3-propanediyl, 1 ,2-propanediyl, 1 ,4 butanediyl, 2,3- butanediyl, 1 ,2-butanediyl, 1 ,5-pentanediyl, 1 ,2-pentanediyl, 1 ,6-hexanediyl, 1 ,2-hexanediyl, 1 ,2-heptanediyl, 1 ,2-octanediyl, 1 ,2-nonanediyl and 1 ,2-decanediyl. Examples of aliphatic groups bearing one or more N-atoms and or O-atoms include 3-azapentan-1 ,5-diyl, 3,6-di- azaoctan-1 ,8-diyl, 3,7-diazanonan-1 ,9-diyl, 3,6,9-triazaundecandiyl, 3,6,9, 11 -tetraza- 1 ,13-tride- candiyl, 3-oxapentan-1 ,5-diyl, 3,6-dioxaoctan-1 ,8-diyl, 3,7-dioxanonan-1 ,9-diyl, 3,6,9-trioxaun- decandiyl and 3,6,9, 11-tetraoxa-1 ,13-tridecandiyl.

In this context, the term cycloaliphatic groups relate to mono- or bicyclic cycloalkyl having typically 5 to 10 carbon atoms (C5-C10 cycloalkyl), in particular 5 to 6 carbon atoms (Cs-Ce cycloalkyl), and mono- or bicyclic cylcoalkandiyl having typically 5 to 10 carbon atoms (C5-C10 cycloal- kandiyl), in particular 2 to 6 carbon atoms (Cs-Ce alkandiyl). The cycloaliphatic groups may be unsubstituted or substituted by 1 or 2 hydroxyl groups, and/or 1 to 4 C1-C4 alkyl groups. Examples of cycloalkyl include in particular cyclopenyl, cyclohexyl, cycloheptyl, bicycloheptyl isomers, such as bicycle[2,2,1]heptyl and cyclooctyl and the like. Examples of cycloalkandiyl include in particular 1 ,2- and 1 ,3-cyclopentandiyl, 1 ,2-, 1 ,3 and 1 ,4-cyclohexandiyl, methyl-2,4-hexandiyl, methyl-2,5-cyclohexandiyl and the like. In cycloaliphatic groups 1 , 2 or 3 non-adjacent carbon atoms may be replaced by O or N, e. g. CH2 groups may be replaced by O or NH and CH groups may be replaced by N. Backbone (a) is frequently derived from low molecular compounds having typically 2 primary aminogroups, such as cycloaliphatic diamines, e. g. 1 ,2-, 1 ,3- or 1 ,4-diaminocyclohexane, 1 ,3- diamino-4-methylcyclohexane (= methylcyclohexane-2,4-diamine) or 3-aminomethyl-3,5,5-tri- methylcyclohexylamine (isophoron diamine), C2-C6 alkylene diamines, such as 1 ,2-ethylene diamine, 1 ,3-propylene diamine, 1 ,4-diaminobutane or 1 ,6-diaminohexane, and oligoamines of the general formula (I)

H₂N-(CH2)Z1-[NH(CH2)Z2]Z4-NH(CH₂)Z3-NH2 (I) wherein the variables z1 , z2 and z3 are independently from each other selected from 2 to 4 and wherein z4 is selected from zero to 6, in particular 0 to 4, and wherein each CH₂-group may be non-substituted or substituted with one to 2 methyl or methoxy groups. Examples of oligoamines are H₂N-(CH2)3-NH(CH2)2-NH(CH₂)3-NH2 (“N4-amine”, also called N,N'-Bis-(3-aminopro- pyl)-ethylenediamine), H₂N-(CH2)3-NH(CH₂)2-NH2 (“N3-amine”) and mixtures thereof, for example in a molar ratio of 9:1. Further examples of said aliphatic amine oligomers include diethylene triamine (H₂N-(CH2)2-[NH(CH2)2]-NH(CH₂)2-NH2 = N,N'-bis-(2-aminoethyl)-ethylenediamine), tetraethylene pentamine (H₂N-(CH2)2-[NH(CH2)2]2-NH(CH₂)2-NH2 = N,N'-bis-(2-aminoethyl)-diethy- lenetriamine) and pentaethylene hexamine (H₂N-(CH2)2-[NH(CH2)2]3-NH(CH₂)2-NH2 = N'-[2-[2- [2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine). Further examples of low molecular compounds include aliphatic amino acids having at least one primary group and at least one further amino group selected from primary and secondary amino groups. Examples include arginine and lysine.

Thus, the backbone (a) in particular comprises at least one structural unit derived a polyamine compound selected from methylcyclohexane-2,4-diamine, a compound of the formula (I), such as N,N'-bis-(3-aminopropyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-ethylenediamine, N,N'- bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethyla- mino]ethyl]ethane-1 ,2-diamine, an amino acid from arginine and lysine, and polylysine. In this context, the term “structural element derived from” is understood, that at least a part of the hydrogen atoms in NH groups of the polyamine compound are replaced by polyalkylenoxide chains (b) while the remainder can be modified by a carbonyl group, a carbonyloxy group, a C₂- C4-alkyleneoxy group or a C₂-C4-alkyleneoxycarbonyl group, which themselves are attached to further structural units of the backbone which may stem derived from further polyamine molecules, aliphatic di- and/or tricarboxylic acid molecules, diol compounds, triol compounds and combinations thereof.

Backbone (a) may be derived from an organic polymer, for example polyethylenimine or poly- propylenimine or polyvinylamine or polylysine, preferably branched polyethylenimine with a weight average molecular weight Mw in the range of from 800 to 3,000 g/mol, determined by gel permeation chromatography in 1% by weight solution in HFIP.

In one embodiment of the present invention, branched polyethylenimines display a polydispersity Q = M_w/Mn of at least 3.5, preferably in the range of from 3.5 to 10, more preferably in the range of from 4 to 9 and even more preferably from 4.0 to 5.5. In other embodiments of the present invention, branched polyalkylenimines display a polydispersity Q = M_w/M_n of 3.4 at most, for examples in the range of from 1.1 to 3.0, more preferably in the range of from 1.3 to 2.5 and even more preferably from 1.5 to 2.0.

A preferred backbone (a) may also be derived from polylysine. Polylysines are polypeptides preferably bearing an average of 3 to 50, preferably 25 to 35 lysine units per molecule, for example 3 to 9 or 25 to 35 lysine units. Polylysine may be selected from a-polylysine and e-polyly- sine, with e-polylysine being preferred. Polylysine may be based on D-lysine or on L-lysine and mixtures thereof, the L-enantiomer being preferred. Another embodiment of polylysine are so- called branched polylysines. In this context, a branched polylysine contains a lysine moiety in which both amino groups form an amide bond with another lysine moiety.

During manufacture, partial racemization of lysine or the lysine units in polylysine may occur but the L-enantiomer is prevailing. Furthermore, the term polylysine in the context of the present invention includes polypeptides that contain lysine and at least one further amino acid such as alanine, glycine, valine, threonine and the like, with the majority of the amino acids in said polylysine being lysine. However, polylysines that contain lysine as sole amino acid building block are preferred.

Further examples of suitable backbones (a) are derived from aliphatic amine oligomers, hereinafter also referred to as oligoamines, according to the general formula (I) as described above. Preferred oligoamines are H2N-(CH2)3-NH(CH2)2-NH(CH2)3-NH2 (“N4-amine”, also called N,N'- Bis-(3-aminopropyl)-ethylenediamine), H2N-(CH2)3-NH(CH2)2-NH2 (“N3-amine”) and mixtures thereof, for example in a molar ratio of 9:1 . Further examples of preferred aliphatic amine oligomers include diethylene triamine, tetraethylene pentamine and pentaethylene hexamine.

Preferred backbones are derived from compounds selected from methylcyclohexane-2,4-dia- mine, methylcyclohexane-2,6-diamine, mixtures of methylcyclohexane-2,6-diamine and methyl- cyclohexane-2,4-diamine, N,N'-bis-(3-aminopropyl)-ethylenediamine (N4-amine), lysine and polylysine, in particular polylysine having on average 3 to 50, preferably 25 to 35 lysine units per molecule, for example 3 to 9 or 25 to 35 lysine units. Methylcyclohexane-2,4-diamine is usually provided as a mixture of isomers including methylcy- clohexane-2,6-diamine:

After alkoxylation, compound (A) does not bear any primary amino group anymore as measured by amine number determination. This is why - in the context of inventive compounds (A) and of inventive compositions - the expression “based on” is chosen.

In one embodiment of the present invention, backbone (a) comprises ester and/or amide groups, preferably more ester groups than amide groups, and/or backbone (a) contains carbonate and urethane groups, preferably more carbonate than urethane groups. In particular, the backbone (a) comprises ester and/or amide groups, preferably more ester groups than amide groups. Here and in the following ester groups refer to carboxylic ester groups of the formula -C(O)O-. Here and in the following amide groups refer to carboxamide groups of the formula -C(O)NH-.

Typically, backbones having at least one of carboxylic ester groups, carboxamide groups, carbonate groups and/or urethane groups are condensates of

(i) at least one of polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3- aminopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-aminoethyl)- ethylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethyla- mino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine, arginine, lysine or polylysine or a combination of at least two of the foregoing or a combination of one of the foregoing with an aliphatic di- or polyol having in particular 3, 4, 5 or 6 OH groups, where the polyamine compound is optionally converted with 0.01 to 1 moles, in particular 0.05 to 0.6 moles, of C2-C4-alkylene oxide, such as ethylene oxide or propylene oxide, per N-H group and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid, or an organic carbonate.

In this context, examples of aliphatic diols include neopentylglycol, 1,5-pentanediol, 1,6-hex- anediol and 1,4-butynediol. In this context, examples of preferred aliphatic polyols include triethanolamine, glycerol, 1,1,1 -trimethylolpropane (“TMP”), pentaerythrol, sorbit and combinations thereof, in particular triethanolamine or pentaerythrol and combinations thereof. Particluarly preferred aliphatic polyol comprise triethanolamine. Als preferred are combinations of triethanolamine and pentaerythrol. Combinations of at least one aliphatic diol and at least one aliphatic polyol are also possible.

For example, ester groups may be introduced into backbone (a) by converting an amine compound, in particular a polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, in particular selected from cycloaliphatic diamines such as methylcyclohexane-2,4-diamine, and aliphatic diamines, preferably an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, arginine, lysine, or polylysine first with a stoichiometric or in particular a substoichiometric amount, e. g. 0.01 to 1 moles, in particular 0.1 to 0.6 moles per N- H, of a C2-C4-alkylene oxide, such as ethylene oxide or propylene oxide, followed by conver- sion/condensation with an aliphatic di- or tricarboxylic acid, in particular a mixture of an aliphatic dicarboxylic acid with an aliphatic tricarboxylic acid, with or without an acidic catalyst, and distilling off the water formed. During condensation an aliphatic polyol having in particular 3, 4, 5 or 6 hydroxyl groups, such as triethanolamine, glycerol, 1,1,1 -trimethylolpropane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, may be present.

Here and in the following examples of aliphatic dicarboxylic acids are in particular those having 3 to 10 carbon atoms, such as adipic acid, sebacic acid, glutamic acid or citric acid or with a mixture from a dicarboxylic and a tricarboxylic acid. For producing the backbone, the acids may be used also be used as their alkyl esters, in particular their di- or tri-Ci-C2-alkyl esters. Mixtures of aliphatic dicarboxylic acid with an aliphatic tricarboxylic acid are e. g. mixtures containing citric acid as a tricarboxylic acid and one of adipic acid, sebacic acid or glutamic acid.

Ester groups may be introduced into backbone (a) by converting an amine compound, in particular a cycloaliphatic diamine such as methylcyclohexane-2,4-diamine, or an aliphatic diamine, in particular an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, arginine, lysine or polylysine first with a stoichiometric or in particular a substoichiometric amount, e. g. 0.01 to 1 moles, in particular 0.1 to 0.6 moles per N-H, of a C2-C4-alkylene oxide such as ethylene oxide or propylene oxide, followed by conversion with an alkyl ester of an aliphatic di- or tri-carboxylic acid, in particular a di- or tri-Ci-C2-alkyl ester of a di- or tri-carboxylic acid or in particular a mixture of an ester of a dicarboxylic acid and an ester of a tricarboxylic acid, with or without an acidic catalyst, and distilling off the alcohol, e. g. methanol or ethanol, formed. During condensation an aliphatic polyol having in particular 3, 4, 5 or 6 hydroxyl groups, such as triethanolamine, glycerol, 1,1,1 -trimethylolpropane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, may be present.

Amide groups may be introduced into backbone (a) by converting an amine compound, in particular a cycloaliphatic diamine such as methylcyclohexane-2,4-diamine, or an aliphatic diamine, in particular an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, lysine, arginine or polylysine with an aliphatic di- or tricarboxylic acid or in particular with a dicarboxylic acid, with or without an acidic catalyst, and distilling off the water formed. Instead of the di- and/or tri-carboxylic acid, the alkyl esters, in particular the di- or tri-Ci-C2-alkyl esters can be used. During condensation an aliphatic polyol having in particular s, 4, 5 or 6 hydroxyl groups, such as triethanolamine, glycerol, 1,1,1-trime- thylolpropane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, may be present.

In another embodiment, ester and carbonate groups are introduced into backbone (a) by mixing an amine such as methylcyclohexane-2,4-diamine, or an aliphatic diamine, in particular an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, lysine, arginine or polylysine with an aliphatic di- or polyol, such as triethanolamine, glycerol, 1,1,1 -trimethylolpropane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, and with or without prior alkoxylation with a stoichiometric or substoichiometric amount of a C2-C4-alkylene oxide such as ethylene oxide or propylene oxide, converting said mixture with an organic carbonate, with phosgene or with a chlorocarboxylic ester. Since the formation of chlorides is undesirable, the conversion with organic carbonate such as dimethyl carbonate or diethyl carbonate is preferred.

In one embodiment of the present invention, a backbone is prepared starting from a combination of (i) at least one amine such as methylcyclohexane-2,4-diamine, or an aliphatic diamine, in particular an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, arginine, lysine or polylysine with (iii) at least one aliphatic polyol having preferably 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, 1,1,1- trimethylolpropane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, for example in a weigh ratio of 5:1 to 1 :5, preferably 2:1 to 1 :2. The mixture is condensed with an aliphatic di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or with a mixture said aliphatic di- or tricarboxylic acids, in particular with a mixture of a dicarboxylic acid such as sebacic acid. Instead of the di- and/or tri-carboxylic acid, the alkyl esters, in particular the di- or tri-Ci-C2-alkyl esters can be used.

In one further preferred embodiment of the present invention, a backbone is prepared starting from a combination of (i) at least one of arginine or lysine with (iii) at least one aliphatic polyol having preferably 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, 1 , 1 , 1 -trimethylolpro- pane (“TMP”), pentaerythrol, or sorbit, in particular triethanolamine or pentaerythrol, for example in a weigh ratio (i):(iii) of 5:1 to 1 :5, preferably 2:1 to 1 :2. The mixture is condensed with an aliphatic di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or with a mixture said aliphatic di- or tricarboxylic acids, in particular with a dicarboxylic acid such as sebacic acid. Instead of the di- and/or tri-carboxylic acid, the alkyl esters, in particular the di- or tri-Ci-C2-alkyl esters can be used.

In one embodiment of the present invention, compounds (A) are selected from compounds (A1) wherein backbone (a) is a condensate which is obtainable as follows:

At least one of methylcyclohexane-2,4-diamine, an oligoamine of the formula (I), such as N4- amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, lysine, arginine and polylysine - alone or in combination with an aliphatic polyol having in particular 3, 4, 5 or 6 hydroxyl groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, or with an aliphatic or alicyclic diol such as neopentylglycol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,4-butynediol - is

(a1) converted with 0.01 to 1 equivalents, or 0.01 to 0.3 equivalents, in particular 0.05 to 0.6 equivalents or 0.05 to 0.25 equivalents or 0.4 to 1 equivalent or 0.4 to 0.6 equivalents of C2-C4-alkylene oxide per N-H group, for example with 1 ,2-butylene oxide or propylene oxide, or preferably with ethylene oxide, thereby forming an intermediate,

(a2) the intermediate from step (a1) is then converted with a di- or tricarboxylic acid selected from adipic acid, sebacic acid, glutamic acid or citric acid or with a mixture from a dicarboxylic and a tricarboxylic acid or with a carbonate to backbone (a1). Instead of the di- and/or tri-carboxylic acid, the alkyl esters, in particular the di- or tri-Ci-C2-alkyl esters can be used. A skilled person will readily understand that the term “equivalent per N-H group” refers to mol per 1 mol of N-H group. A skilled person will also understand that a primary amino group (NH2) counts as 2 N-H groups while a secondary amino group (NH) counts as 1 N-H group.

In particular, backbone (a) is selected from

(a1) condensates formed from

(i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as methylcyclo- hexane-2,4-diamine, an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, lysine or arginine, where the polyamine compound has been converted with 0.01 to 1 moles or 0.01 to 0.3 moles, in particular 0.05 to 0.6 moles or 0.05 to 0.25 moles or 0.4 to 1 moles or 0.4 to 0.6 moles of a C2-C4-alkylene oxide, such as ethylene oxide or propylene oxide, per 1 mol of N-H groups;

(ii) at least one di- or tricarboxylic acids, such as adipic acid, sebacic acid, glutamic acid or citric acid, in particular a combination of at least one dicarboxylic acid and at least one tricarboxylic acid, or an alkylester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; and

(iii) optionally an aliphatic diol, such as neopentylglycol, 1,5-pentanediol, 1,6-hexanediol or 1 ,4-butynediol, or an aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of (i) to (iii) is in particular in the range of 5:1 to 1 :5, especially in the range of 2:1 to 1 :2;

(a2) condensates formed from (i¹)

(i¹) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as methylcyclo- hexane-2,4-diamine, an oligoamine of the formula (I), such as N4-amine, diethylene triamine, tetraethylene pentamine or pentaethylene hexamine, lysine or arginine;

(iii) optionally at least one of aliphatic diols, such as neopentylglycol, 1,5-pentanediol, 1,6- hexanediol or 1 ,4-butynediol, and aliphatic polyols having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of (i) to (iii) is in particular in the range of 5:1 to 1 :5, especially in the range of 2: 1 to 1 :2;

(a3) condensates formed from lysine, arginine or polylysine and at least one aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, especially triethanolamine, and optionally an aliphatic dicarboxylic acid, such as adipic acid, sebacic acid or glutamic acid and optionally at least one of aliphatic diols, such as neopentylglycol, 1 ,5-pentanediol, 1 ,6-hexanediol or 1 ,4-butynediol;;

(a4) condensates formed from (i”) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 1 moles or 0.01 to 0.3 moles, in particular 0.05 to 0.6 moles or 0.05 to 0.25 moles or 0.4 to 1 moles or 0.4 to 0.6 moles of a C2-C4- alkylene oxide, such as ethylene oxide or propylene oxide, per 1 mol of N-H groups, followed by self-condensation of the converted product, and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid and (iii) optionally at least one of aliphatic diols, such as neopentylglycol, 1 ,5-pentanediol, 1 ,6-hexanediol or 1 ,4-butynediol, and aliphatic polyols having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of (i) to (iii) is in particular in the range of 5: 1 to 1 :5, especially in the range of 2: 1 to 1 :2.

Compounds (A) further comprise

(b) polyalkylenoxide chains comprising a

(b1) polyethylene oxide chain with 15 to 50 EO groups attached directly or indirectly to each nitrogen atom, which means that a polyethylene oxide chain is directly attached to each amino group of backbone (a). Said polyethylene oxide chains may have the same or different lengths. Since in most manufacturing methods such chains are made by ethoxylation with ethylene oxide, the lengths of the polyethylene oxide chains (b1) usually follow a molecular weight distribution. Said chains are then (b2) capped with a polypropylene oxide or polybutylene oxide chain comprising from 0.5 to 4 PO or BuO groups and amounting to 2.5 to 20 % by weight of the respective polyethylene oxide chain, preferably 3 to 15% by weight. Preferred are PO groups, and more preferred are 2 to 4 PO groups per polyethylene oxide chain.

In the context of the present invention, the following abbreviations are used: EO as ethylene oxide, PO: 1 ,2-propylene oxide, BuO: 1 ,2-butylene oxide.

The values of 0.5 to 4 correspond to average values (number average).

Indirectly attached means that the polyethylene oxide chains are not directly linked to a nitrogen atom but through some spacer other than ethylene oxide. In one embodiment the polyethylene oxide chains are attached indirectly to a majority or preferably to each of the nitrogen atoms through one propylene oxide group per polyethylene oxide chain.

Intermediate compounds (A’), which bear uncapped polyethylene oxide chains with 15 to 50 ethylene oxide groups attached directly or indirectly to each nitrogen atom are novel, if the backbone (a) is selected from condensates of

(i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3-ami- nopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-aminoethyl)-eth- ylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethyla- mino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine, arginine, lysine or polylysine or a combination of at least two of the foregoing, where the polyamine compound is optionally converted with 0.01 to 0.3 moles, in particular 0.05 to 025 moles of C2-C4-alkylene oxide, such as ethyleneoxide or propyleneoxide, per 1 mole of N-H groups,

(ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid;

(iii) optionally at least one of an aliphatic diols, such as neopentylglycol, 1 ,5-pentanediol, 1 ,6- hexanediol or 1 ,4-butynediol, or aliphatic polyols having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of (i) to (iii) is in particular in the range of 5:1 to 1 :5, especially in the range of 2: 1 to 1 :2.

Therefore, intermediate compounds (A’), their aqueous compositions as described from the compound (A) and their use in laundry care are also part of the present invention. Particularly preferred embodiments are those, where the backbone (a) is selected from the following backbones (a’.1), (a’.2) and (a’.3):

(a'.1) condensates formed from (i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 0.3 moles of a C2-C4-alkylene oxide per 1 mol of N-H groups, and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid, and optionally an aliphatic polyol having at least 3 OH groups;

(a¹.2) condensates formed from (i¹) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C4-alkyl ester of said di- or tricarboxylic acid, and optionally an aliphatic polyol having at least 3 OH groups;

(a¹.3) condensates formed from lysine, arginine or polylysine and at least one aliphatic polyol having at least 3 OH groups and optionally an aliphatic dicarboxylic acid.

In one embodiment of the present invention, inventive compositions comprise in the range of from 0.1 to 10 % by weight of compound (A) or (A’), respectively, based on the total solids content, preferred are 0.5 to 5% b weight. The total solids content is determined by evaporation of the volatiles at a maximum temperature of 100°C, in vacuo.

In one embodiment of the present invention, inventive compositions comprise at least one enzyme. Enzymes are identified by polypeptide sequences (also called amino acid sequences herein). The polypeptide sequence specifies the three-dimensional structure including the “active site” of an enzyme which in turn determines the catalytic activity of the same. Polypeptide sequences may be identified by a SEQ ID NO. According to the World Intellectual Property Office (WIPO) Standard ST.25 (1998) the amino acids herein are represented using three-letter code with the first letter as a capital or the corresponding one letter.

Any enzyme according to the invention relates to parent enzymes and/or variant enzymes, both having enzymatic activity. Enzymes having enzymatic activity are enzymatically active or exert enzymatic conversion, meaning that enzymes act on substrates and convert these into products. The term “enzyme” herein excludes inactive variants of an enzyme. A “parent” sequence (of a parent protein or enzyme, also called “parent enzyme”) is the starting sequence for introduction of changes (e.g., by introducing one or more amino acid substitutions, insertions, deletions, or a combination thereof) to the sequence, resulting in “variants” of the parent sequences. The term parent enzyme (or parent sequence) includes wild-type enzymes (sequences) and synthetically generated sequences (enzymes) which are used as starting sequences for introduction of (further) changes.

The term “enzyme variant” or “sequence variant” or “variant enzyme” refers to an enzyme that differs from its parent enzyme in its amino acid sequence to a certain extent. If not indicated otherwise, variant enzyme “having enzymatic activity” means that this variant enzyme has the same type of enzymatic activity as the respective parent enzyme.

In describing the variants of the present invention, the nomenclature described as follows is used:

Amino acid substitutions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by the substituted amino acid. Amino acid deletions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by *. Amino acid insertions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by the original amino acid and the additional amino acid. For example, an insertion at position 180 of lysine next to glycine is designated as “Gly180GlyLys” or “G180GK”. In cases where a substitution and an insertion occur at the same position, this may be indicated as S99SD+S99A or in short S99AD. In cases where an amino acid residue identical to the existing amino acid residue is inserted, degeneracy in the nomenclature arises. If for example a glycine is inserted after the glycine in the above example this would be indicated by G180GG. Where different alterations can be introduced at a position, the different alterations are separated by a comma, e.g., “Arg170Tyr, Glu” represents a substitution of arginine at position 170 with tyrosine or glutamic acid. Alternatively, different alterations or optional substitutions may be indicated in brackets, e.g., Arg170[Tyr, Gly] or Arg170{Tyr, Gly}; or in short R170 [Y,G] or R170 {Y, G}; or in long R170Y, R170G.

Enzyme variants may be defined by their sequence identity when compared to a parent enzyme. Sequence identity usually is provided as “% sequence identity” or “% identity”. For calculation of sequence identities, in a first step a sequence alignment has to be produced. According to this invention, a pairwise global alignment has to be produced, meaning that two sequences have to be aligned over their complete length, which is usually produced by using a mathematical approach, called alignment algorithm. According to the invention, the alignment is generated by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453). Preferably, the program “NEEDLE” (The European Molecular Biology Open Software Suite (EMBOSS)) is used for the purposes of the current invention, with using the programs default parameter (gap open=10.0, gap extend=0.5 and matrix=EBLOSUM62).

According to this invention, the following calculation of %-identity applies: %-identity = (identical residues I length of the alignment region which is showing the respective sequence of this invention over its complete length) *100.

According to this invention, enzyme variants may be described as an amino acid sequence which is at least n% identical to the amino acid sequence of the respective parent enzyme with “n” being an integer between 10 and 100. In one embodiment, variant enzymes are at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, or at least 99% identical when compared to the full-length amino acid sequence of the parent enzyme, wherein the enzyme variant has enzymatic activity.

“Enzymatic activity” means the catalytic effect exerted by an enzyme, which usually is expressed as units per milligram of enzyme (specific activity) which relates to molecules of substrate transformed per minute per molecule of enzyme (molecular activity). Variant enzymes may have enzymatic activity according to the present invention when said enzyme variants exhibit at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at 10 least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or 100% of the enzymatic activity of the respective parent enzyme.

In one embodiment, enzyme is selected from hydrolases, preferably from proteases, amylases, lipases, cellulases, and mannanases.

In one embodiment of the present invention, inventive compositions comprise

(A) at least one hydrolase, hereinafter also referred to as hydrolase (B), preferably selected from lipases, hereinafter also referred to as lipase (B).

“Lipases”, “lipolytic enzyme”, “lipid esterase”, all refer to enzymes of EC class 3.1.1 (“carboxylic ester hydrolase”). Such a lipase (B) may have lipase activity (or lipolytic activity; triacylglycerol lipase, EC 3.1.1.3), cutinase activity (EC 3.1.1.74; enzymes having cutinase activity may be called cutinase herein), sterol esterase activity (EC 3.1.1.13) and/or wax-ester hydrolase activity (EC 3.1.1.50). Lipases (B) include those of bacterial or fungal origin.

Commercially available lipase (B) include but are not limited to those sold under the trade names Lipolase™, Lipex™, Lipolex™ and Lipoclean™ (Novozymes A/S), Preferenz™ L (DuPont), Lumafast (originally from Genencor) and Lipomax (Gist- Brocades/ now DSM).

In one aspect of the present invention, lipase (B) is selected from the following: lipases from Hu- micola (synonym Thermomyces), e.g., from H. lanuginosa (T. lanuginosus) as described in EP 258068, EP 305216, WO 92/05249 and WO 2009/109500 or from H. insolens as described in WO 96/13580; lipases derived from Rhizomucor miehei as described in WO 92/05249; lipase from strains of Pseudomonas (some of these now renamed to Burkholderia), e.g., from P. alcali- genes or P. pseudoalcaligenes (EP 218272, WO 94/25578, WO 95/30744, WO 95/35381, WO 96/00292), P. cepacia (EP 331376), P. stutzeri (GB 1372034), P. fluorescens, Pseudomonas sp. strain SD705 (WO 95/06720 and WO 96/27002), P. wisconsinensis (WO 96/12012), Pseudomonas mendocina (WO 95/14783), P. glumae (WO 95/35381 , WO 96/00292); lipase from Streptomyces griseus (WO 2011/150157) and S. pristinaespiralis (WO 2012/137147), GDSL-type Streptomyces lipases (WO 2010/065455); lipase from Thermobifida fusca as disclosed in WO 2011/084412; lipase from Geobacillus stearothermophilus as disclosed in WO 2011/084417; Bacillus lipases, e.g., as disclosed in WO 00/60063, lipases from B. subtilis as disclosed in Dartois et al. (1992), Biochemica et Biophysica Acta, 1131, 253-360 or

WO 2011/084599, 8. stearothermophilus (JP S64-074992) or 8. pumilus (WO 91/16422); lipase from Candida antarctica as disclosed in WO 94/01541. Suitable lipases (B) include also those which are variants of the above described lipases which have lipolytic activity.

Suitable lipases (B) include also those that are variants of the above described lipases which have lipolytic activity. Suitable lipase variants include variants with at least 40 to 100% identity when compared to the full length polypeptide sequence of the parent enzyme as disclosed above. In one embodiment lipase variants having lipolytic activity may be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full length polypeptide sequence of the parent enzyme as disclosed above.

Lipases (B) have “lipolytic activity”. The methods for determining lipolytic activity are well-known in the literature (see e.g., Gupta et al. (2003), Biotechnol. Appl. Biochem. 37, p. 63-71). E.g., the lipase activity may be measured by ester bond hydrolysis in the substrate para-nitrophenyl palmitate (pNP-Palmitate, C:16) and releases pNP which is yellow and can be detected at 405 nm.

In one embodiment, lipase (B) is selected from fungal triacylglycerol lipase according to EC class 3.1.1.3. Fungal triacylglycerol lipase may be selected from lipases of Thermomyces lanuginosa. In one embodiment, at least one Thermomyces lanuginosa lipase is selected from triacylglycerol lipase according to amino acids 1-269 of SEQ ID NO: 2 of US5869438 and variants thereof having lipolytic activity.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity which are at least 90%, at least 91 %, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising conservative mutations only, which do not pertain the functional domain of amino acids 1- 269 of SEQ ID NO: 2 of US 5,869,438. Lipase variants of this embodiment having lipolytic activity may be at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the following amino acid substitutions when compared to amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438: T231 R and N233R. Said lipase variants may further comprise one or more of the following amino acid exchanges when compared to amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438: Q4V, V60S, A150G, L227G, P256K.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the amino acid substitutions T231 R, N233R, Q4V, V60S, A150G, L227G, P256K within the polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438and are at least 95%, at least 96%, or at least 97% similar when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising the amino acid substitutions T231 R and N233R within amino acids 1-269 of SEQ ID NO: 2 of US5869438 and are at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% similar when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438.

Thermomyces lanuginosa lipase may be a variant of amino acids 1-269 of SEQ ID NO: 2 of US5869438 having lipolytic activity, wherein the variant of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438is characterized in containing the amino acid substitutions T231 R and N233R. Said lipase may be called Lipex herein.

In one embodiment of the present invention, a combination of at least two of the foregoing lipases (B) may be used.

In one embodiment of the present invention, lipases (B) are included in inventive composition in such an amount that a finished inventive composition has a lipolytic enzyme activity in the range of from 100 to 0.005 LU/mg, preferably 25 to 0.05 LU/mg of the composition. A Lipase Unit (LU) is that amount of lipase which produces 1 pmol of titratable fatty acid per minute in a pH stat, under the following conditions: temperature 30° C.; pH=9.0; substrate is an emulsion of 3.3 wt. % of olive oil and 3.3% gum arabic, in the presence of 13 mmol/l Ca²⁺ and 20 mmol/l NaCI in 5 mmol/l Tris-buffer.

In one embodiment of the present invention, inventive compositions comprise (B) at least one protease (B), hereinafter also referred to as protease (B).

In one embodiment, at least one protease (B) is selected from the group of serine endopeptidases (EC 3.4.21), most preferably selected from the group of subtilisin type proteases (EC 3.4.21.62). Serine proteases or serine peptidases are characterized by having a serine in the catalytically active site, which forms a covalent adduct with the substrate during the catalytic reaction. A serine protease in the context of the present invention may be selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC 3.4.21.78 or EC 3.4.21.79), kallikrein (e.g., EC 3.4.21.34, EC 3.4.21.35, EC 3.4.21.118, or EC 3.4.21.119,) plasmin (e.g., EC 3.4.21.7), trypsin (e.g., EC 3.4.21.4), thrombin (e.g., EC 3.4.21.5), and subtilisin. Subtilisin is also known as sub- tilopeptidase, e.g., EC 3.4.21.62, the latter hereinafter also being referred to as “subtilisin”. The subtilisin related class of serine proteases shares a common amino acid sequence defining a catalytic triad which distinguishes them from the chymotrypsin related class of serine proteases. Subtilisins and chymotrypsin related serine proteases both have a catalytic triad comprising aspartate, histidine and serine. Proteases are active proteins exerting “protease activity” or “proteolytic activity”. Proteolytic activity is related to the rate of degradation of protein by a protease or proteolytic enzyme in a defined course of time.

The methods for analyzing proteolytic activity are well-known in the literature (see e.g., Gupta et al. (2002), Appl. Microbiol. Biotechnol. 60: 381-395). Proteolytic activity may be determined by using Succinyl-Ala-Ala-Pro-Phe-p-nitroanilide (Suc-AAPF-pNA, short AAPF; see e.g., DelMar et al. (1979), Analytical Biochem 99, 316-320) as substrate. pNA is cleaved from the substrate molecule by proteolytic cleavage, resulting in release of yellow color of free pNA which can be quantified by measuring OD405.

Proteolytic activity may be provided in units per gram enzyme. For example, 1 II protease may correspond to the amount of protease which sets free 1 pmol folin-positive amino acids and peptides (as tyrosine) per minute at pH 8.0 and 37°C (casein as substrate).

Proteases of the subtilisin type (EC 3.4.21.62) may be bacterial proteases originating from a microorganism selected from Bacillus, Clostridium, Enterococcus, Geobacillus, Lactobacillus, Lactococcus, Oceanobacillus, Staphylococcus, Streptococcus, or Streptomyces protease, or a Gram-negative bacterial polypeptide such as a Campylobacter, E. coli, Flavobacterium, Fuso- bacterium, Helicobacter, llyobacter, Neisseria, Pseudomonas, Salmonella, and Ureaplasma.

In one aspect of the invention, at least one protease (B) is selected from Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus circulans, Bacillus clausii, Bacillus coagu- lans, Bacillus firmus, Bacillus gibsonii, Bacillus lautus, Bacillus lentus, Bacillus licheniformis, Bacillus megaterium, Bacillus pumilus, Bacillus sphaericus, Bacillus stearothermophilus, Bacillus subtilis, or Bacillus thuringiensis protease.

In one embodiment of the present invention, at least one protease (B) is selected from the following: subtilisin from Bacillus amyloliquefaciens BPN' (described by Vasantha et al. (1984) J. Bacteriol. Volume 159, p. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11, p. 7911-7925); subtilisin from Bacillus licheniformis (subtilisin Carlsberg; disclosed in EL Smith et al. (1968) in J. Biol Chem, Volume 243, pp. 2184-2191, and Jacobs et al. (1985) in Nucl. Acids Res, Vol 13, p. 8913-8926); subtilisin PB92 (original sequence of the alkaline protease PB92 is described in EP 283075 A2); subtilisin 147 and/or 309 (Esperase®, Savinase®, respectively) as disclosed in WO 89/06279; subtilisin from Bacillus lentus as disclosed in WO 91/02792, such as from Bacillus lentus DSM 5483 or the variants of Bacillus lentus DSM 5483 as described in WO 95/23221; subtilisin from Bacillus alcalophilus (DSM 11233) disclosed in DE 10064983; subtilisin from Bacillus gibsonii (DSM 14391) as disclosed in WO 2003/054184; sub- tilisin from Bacillus sp. (DSM 14390) disclosed in WO 2003/056017; subtilisin from Bacillus sp. (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003/054184; subtilisin having SEQ ID NO: 4 as described in WO 2005/063974; subtilisin having SEQ ID NO: 4 as described in WO 2005/103244; subtilisin having SEQ ID NO: 7 as described in WO 2005/103244; and subtilisin having SEQ ID NO: 2 as described in application DE 102005028295.4.

In one embodiment, at least one protease (B) has a sequence according to SEQ ID NO:22 as described in EP 1921147, or a protease which is at least 80% identical thereto and has proteolytic activity. In one embodiment, said protease is characterized by having amino acid glutamic acid, or aspartic acid, or asparagine, or glutamine, or alanine, or glycine, or serine at position 101 (according to BPN’ numbering) and has proteolytic activity. In one embodiment, said protease comprises one or more further substitutions: (a) threonine at position 3 (3T), (b) isoleucine at position 4 (4I), (c) alanine, threonine or arginine at position 63 (63A, 63T, or 63R), (d) aspartic acid or glutamic acid at position 156 (156D or 156E), (e) proline at position 194 (194P), (f) methionine at position 199 (199M), (g) isoleucine at position 205 (205I), (h) aspartic acid, glutamic acid or glycine at position 217 (217D, 217E or 217G), (i) combinations of two or more amino acids according to (a) to (h).

At least one protease (B) may be at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and is characterized by comprising one amino acid (according to (a)-(h)) or combinations according to (i) together with the amino acid 101 E, 101 D, 101 N, 101Q, 101A, 101G, or 101S (according to BPN’ numbering). In one embodiment, said protease is characterized by comprising the mutation (according to BPN’ numbering) R101E, or S3T + V4I + V205I, or R101 E and S3T, V4I, and V205I, or S3T + V4I + V199M + V205I + L217D, and having proteolytic activity. A protease having a sequence according to SEQ ID NO: 22 as described in EP 1921147 with 101 E may be called Lavergy herein.

In one embodiment, protease according to SEQ ID NO:22 as described in EP 1921147 is characterized by comprising the mutation (according to BPN’ numbering) S3T + V4I + S9R + A15T + V68A + D99S + R101S + A103S + 1104V + N218D, and by having proteolytic activity.

Inventive compositions may comprise a combination of at least two proteases (B), preferably selected from the group of serine endopeptidases (EC 3.4.21), more preferably selected from the group of subtilisin type proteases (EC 3.4.21.62) - all as disclosed above. It is preferred to use a combination of lipase (B) and protease (B) in compositions, for example 1 to 2% by weight of protease (B) and 0.1 to 0.5% by weight of lipase (B), both referring to the total weight of the composition.

In the context of the present invention, lipase (B) and/or protease (B) is deemed called stable when its enzymatic activity “available in application” equals at least 60% when compared to the initial enzymatic activity before storage. An enzyme may be called stable within this invention if its enzymatic activity available in application is at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 98%, at least 99%, or at least 99.5% when compared to the initial enzymatic activity before storage.

Subtracting a% from 100% gives the “loss of enzymatic activity during storage” when compared to the initial enzymatic activity before storage. In one embodiment, an enzyme is stable according to the invention when essentially no loss of enzymatic activity occurs during storage, i.e. loss in enzymatic activity equals 0% when compared to the initial enzymatic activity before storage. Essentially no loss of enzymatic activity within this invention may mean that the loss of enzymatic activity is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%.

In one embodiment of the present invention, inventive compositions comprise

(C) at least one anionic surfactant, hereinafter also being referred to as anionic surfactant (C).

Examples of anionic surfactants (C) are alkali metal and ammonium salts of Cs-Cis-alkyl sulfates, of Cs-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4- Ci2-alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of Ci2-Ci8-alkylsulfonic acids and of C -Ci8-alkylarylsulfonic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

Further examples of anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, and ether carboxylates.

In a preferred embodiment of the present invention, anionic surfactant (C) is selected from compounds according to general formula (III)

R¹-O(CH₂CH₂O)xi-SO₃M (HI) wherein

R¹ n-C -Ci8-alkyl, especially with an even number of carbon atoms, for example n-decyl, n- dodecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl, preferably C -C -alkyl, and even more preferably n-Ci2-alkyl, x1 being a number in the range of from 1 to 5, preferably 2 to 4 and even more preferably 3.

M being selected from alkali metals, preferably potassium and even more preferably sodium.

In anionic surfactant (C), x1 may be an average number and therefore n is not necessarily a whole number, while in individual molecules according to formula (III a), x denotes a whole number.

In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of anionic surfactant (C), preferably 5 to 50 % by weight.

Inventive compositions may comprise ingredients other than the aforementioned. Examples are non-ionic surfactants, fragrances, dyestuffs, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.

Preferred inventive compositions may contain one or more non-ionic surfactants.

Preferred non-ionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III a)

in which the variables are defined as follows: R² is identical or different and selected from hydrogen and linear Ci-C -alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

R³ is selected from Cs-C22-alkyl, branched or linear, for example n-CsHn, n-C H2i, n-Ci2H25, n-Ci4H29, n-CieH33 or n-CisHs?,

R⁴ is selected from Ci-Cw-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

The variables e and f are in the range from zero to 300, where the sum of e and f is at least one, preferably in the range of from 3 to 50. Preferably, e is in the range from 1 to 100 and f is in the range from 0 to 30.

Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (III b)

in which the variables are defined as follows:

R² is identical or different and selected from hydrogen and linear Ci-Co-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl,

R⁵ is selected from Ce-C2o-alkyl, branched or linear, in particular n-CsHn, n-C H2i, n-Ci2H25, n-Ci3H27, n-CisHsi, n-Ci4H29, n-CieH33, n-CisHs?, a is a number in the range from zero to 10, preferably from 1 to 6, b is a number in the range from 1 to 80, preferably from 4 to 20, d is a number in the range from zero to 50, preferably 4 to 25. The sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.

Compounds of the general formula (Ill a) and (III b) may be block copolymers or random copolymers, preference being given to block copolymers.

Further suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-Ci6-alkyl polyglucosides and branched Cs-Ci4-alkyl polyglycosides such as compounds of general average formula (IV) are likewise suitable.

wherein:

R⁶ is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

R⁷ is -(CH₂)₂-R⁶,

G¹ is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose, y1 in the range of from 1.1 to 4, y1 being an average number,

Further examples of non-ionic surfactants are compounds of general formula (V) and (VI)

AO is selected from ethylene oxide, propylene oxide and butylene oxide, EO is ethylene oxide, CH2CH2-O,

R⁸ selected from Cs-Cis-alkyl, branched or linear, and R⁵ is defined as above.

A³O is selected from propylene oxide and butylene oxide, w is a number in the range of from 15 to 70, preferably 30 to 50, w1 and w3 are numbers in the range of from 1 to 5, and w2 is a number in the range of from 13 to 35.

An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE- A 198 19 187.

Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.

Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

Examples of amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions. Preferred examples of amphoteric surfactants are so- called betaine-surfactants. Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).

Examples of amine oxide surfactants are compounds of the general formula (VII)

R⁹R¹⁰R¹¹N^O (VII) wherein R⁹, R¹⁰, and R¹¹ are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene C -C2o-alkylamido moieties. Preferably, R⁹ is selected from Cs-C2o-al- kyl or C2-C4-alkylene C -C2o-alkylamido and R¹⁰ and R¹¹ are both methyl.

A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide. In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from non-ionic surfactants, amphoteric surfactants and amine oxide surfactants.

In a preferred embodiment, inventive solid detergent compositions for cleaners and especially those for automatic dishwashing do not contain any anionic surfactant.

Inventive compositions may contain at least one bleaching agent, also referred to as bleach. Bleaching agents may be selected from chlorine bleach and peroxide bleach, and peroxide bleach may be selected from inorganic peroxide bleach and organic peroxide bleach. Preferred are inorganic peroxide bleaches, selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.

In inventive compositions, alkali metal percarbonates, especially sodium percarbonates, are preferably used in coated form. Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the foregoing, for example combinations of sodium carbonate and sodium sulfate.

Suitable chlorine-containing bleaches are, for example, 1 ,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Inventive compositions may comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.

Inventive compositions may comprise one or more bleach catalysts. Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthe- nium-amine complexes can also be used as bleach catalysts. Inventive compositions may comprise one or more bleach activators, for example N-methylmor- pholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).

Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

Examples of fragrances are benzyl salicylate, 2-(4-tert.-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

Examples of dyestuffs are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101 , Acid Green 1 , Solvent Green 7, and Acid Green 25.

Inventive compositions may contain one or more preservatives or biocides. Biocides and preservatives prevent alterations of inventive liquid detergent compositions due to attacks from microorganisms. Examples of biocides and preservatives are BTA (1 ,2,3-benzotriazole), benzalkonium chlorides, 1 ,2-benzisothiazolin-3-one (“BIT”), 2-methyl-2H-isothiazol-3-one („MIT“) and 5-chloro-2-methyl-2H-isothiazol-3-one („CIT“), benzoic acid, sorbic acid, iodopropynyl butylcarbamate (“IPBC”), dichlorodimethylhydantoine (“DCDMH”), bromochlorodimethylhydantoine (“BCDMH”), and dibromodimethylhydantoine (“DBDMH”). Another example of biocides is 2-phe- noxyethanol, especially in combination with BIT or IPBC.

Examples particularly of interest are the following antimicrobial agents and/or preservatives: 4,4’-dichloro 2-hydroxydiphenyl ether (CAS-No. 3380-30-1), further names: 5-chloro-2-(4-chlo- rophenoxy) phenol, Diclosan, DCPP, which is commercially available as a solution of 30 wt% of 4,4’-dichloro 2-hydroxydiphenyl ether in 1 ,2 propyleneglycol under the trade name Tinosan® HP 100; and

2-Phenoxyethanol (CAS-no. 122-99-6, further names: phenoxyethanol, methylphenylglycol, Phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE);

2-bromo-2-nitropropane-1 ,3-diol (CAS-No. 52-51-7, further names: 2-bromo-2-nitro-1 ,3-pro- panediol, Bronopol®, Protectol® BN, Myacide AS);

Glutaraldehyde (CAS-No. 111-30-8, further names: 1-5-pentandial, pentane-1 , 5-dial, glutaral, glutardialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); Glyoxal (CAS No. 107-22-2; further names: ethandial, oxylaldehyde, 1 ,2-ethandial, Protectol® GL);

2-butyl-benzo[d]isothiazol-3-one (BBIT, CAS No. 4299-07-4); 2-methyl-2H-isothiazol-3-one (MIT, CAS No 2682-20-4); 2-octyl-2H-isothiazol-3-one (OIT, CAS No. 26530-20-1); 5-Chloro-2- methyl-2H-isothiazol-3-one (CIT, CMIT, CAS No. 26172-55-4); mixtures of 5-chloro-2-methyl- 2H- isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (Mixture of CMIT/MIT, CAS No. 55965-84-9); 1 ,2-benzisothiazol-3(2H)-one (BIT, CAS No. 2634-33-5);

Hexa-2,4-dienoic acid (Sorbic acid, CAS No. 110-44-1) and its salts, e.g., calcium sorbate, sodium sorbate, Potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate, CAS No. 24634-61-5);

Lactic acid and its salts; especially sodium lactate, L-(+)-lactic acid (CAS No. 79-33-4);

Benzoic acid (CAS No 65-85-0, CAS No. 532-32-1) and salts of benzoic acid, e.g., sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate;

Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS Nos 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1 , 68391-01-5, 61789-y71-7, 85409-22-9);

Didecyldimethylammonium chloride (DDAC, CAS No. 68424-95-3 and CAS No. 7173-51-5);

N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine, CAS No. 2372-82-9);

Peracetic acid (CAS No. 79-21-0);

Hydrogen peroxide (CAS No. 7722-84-1);

Biocide or preservative may be added to the inventive composition in a concentration of 0.001 to 10% relative to the total weight of the composition. Preferably, inventive compositions contain 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%. The invention thus further pertains to a method of preserving an inventive composition against microbial contamination or growth, which method comprises addition of 2-phenoxyethanol.

The invention thus further pertains to a method of providing an antimicrobial effect on textiles after treatment with an inventive composition containing 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP).

Examples of viscosity modifiers are agar-agar, carrageen, tragacanth, gum arabic, alginates, pectins, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, for example polyacrylic acid cross-linked with bis-(meth)acrylamide, furthermore silicic acid, clay such as - but not limited to - montmorillonite, zeolite, dextrin, and casein.

Hydrotropes in the context with the present invention are compounds that facilitate the dissolution of compounds that exhibit limited solubility in water. Examples of hydrotropes are organic solvents such as ethanol, isopropanol, ethylene glycol, 1 ,2-propylene glycol, and further organic solvents that are water-miscible under normal conditions without limitation. Further examples of suitable hydrotropes are the sodium salts of toluene sulfonic acid, of xylene sulfonic acid, and of cumene sulfonic acid.

Examples of polymers other than compound (A) are especially polyacrylic acid and its respective alkali metal salts, especially its sodium salt. A suitable polymer is in particular polyacrylic acid, preferably with an average molecular weight M_w in the range from 2,000 to 40,000 g/mol. preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol, each partially or fully neutralized with alkali, especially with sodium. Suitable as well are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. Polyacrylic acid and its respective alkali metal salts may serve as soil anti-redeposition agents.

Further examples of polymers are polyvinylpyrrolidones (PVP). Polyvinylpyrrolidones may serve as dye transfer inhibitors.

Further examples of polymers are polyethylene terephthalates, polyoxyethylene terephthalates, and polyethylene terephthalates that are end-capped with one or two hydrophilic groups per molecule, hydrophilic groups being selected from CH2CH2CH2-SO3Na, CH2CH(CH2-SC>3Na)2, and CH₂CH(CH₂SO2Na)CH2-SO3Na.

Examples of buffers are monoethanolamine and N,N,N-triethanolamine. Examples of defoamers are silicones.

Inventive compositions are not only good in cleaning soiled laundry with respect to organic fatty soil such as oil. Inventive liquid detergent compositions are very useful for removing non- bleachable stains such as, but not limited to stains from red wine, tea, coffee, vegetables, and various fruit juices like berry juices from laundry. They still do not leave residues on the clothes.

A further aspect of the present invention is therefore the use of inventive compositions for laundry care. Laundry care in this context includes laundry cleaning.

In another aspect, inventive compositions are useful for hard surface cleaning. A further aspect of the present invention is therefore the use of inventive compositions for hard surface cleaning.

In the context of the present invention, the term “composition for hard surface cleaning” includes cleaners for home care and for industrial or institutional applications. The term “composition for hard surface cleaning” includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, but not laundry detergent compositions. A special embodiment of compositions for hard surface cleaning are automatic dishwashing compositions.

In the context of the present invention, the terms “compositions for hard surface cleaning” and “compositions for hard surface cleaners” are used interchangeably.

In the context of the present invention and unless expressly stated otherwise, percentages in the context of ingredients of laundry detergent compositions are percentages by weight and refer to the total solids content of the respective laundry detergent composition. In the context of the present invention and unless expressly stated otherwise, percentages in the context of ingredients of detergent composition for hard surface cleaners are percentages by weight and refer to the total solids content of the detergent composition for hard surface cleaning.

Inventive compositions when used for automatic dishwashing preferably contain (D) at least one builder component selected from aminopolycarboxylic acids and preferably their alkali metal salts, in the context of the present invention also referred to as complexing agent (D) or sequestrant (D). In the context of the present invention, the terms sequestrants and chelating agents are used interchangeably.

Examples of sequestrants (D) are alkali metal salts of MGDA (methyl glycine diacetic acid), GLDA (glutamic acid diacetic acid), IDS (iminodisuccinate), EDTA, and polymers with complexing groups like, for example, polyethylenimine in which 20 to 90 mole-% of the N-atoms bear at least one CH2COO' group, and their respective alkali metal salts, especially their sodium salts, for example MGDA-Nas, GLDA-Na4, or IDS-Na4.

Preferred sequestrants are those according to general formula (IX a)

[CH3-CH(COO)-N(CH2-COO)2]M₃-X2HX2 (IX a) wherein M is selected from ammonium and alkali metal cations, same or different, for example cations of sodium, potassium, and combinations of at least two of the foregoing. Ammonium may be substituted with alkyl but non-substituted ammonium NH₄ ⁺ is preferred. Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium, and even more preferred in compound according to general formula (II a) all M are the same and they are all Na; and x2 in formula (II a) is in the range of from zero to 1 .0, or (IX b)

[OOC-CH₂CH2-CH(COO)-N(CH2-COO)2]M4-X3HX3 (IX b) wherein M is as defined above, and x3 in formula (IX b) is in the range of from zero to 2.0, preferably to 1.0, or (IX c)

[OOC-CH2-CH(COO)]-N-CH(COO)-CH2-COO]M₄-X4HX4 (IX c) wherein M is as defined above, and x4 in formula (IX c) is in the range of from zero to 2.0, preferably to 1.0. In one embodiment of the present invention, said inventive composition contains a combination of at least two of the foregoing, for example a combination of chelating agent according to general formula (IX a) and a chelating agent according to general formula (IX b).

Chelating agents according to the general formulae (IX a) and (IX b) are preferred. Even more preferred are chelating agents according to the general formula (IX a).

In one embodiment of the present invention, compound according to general formula (IX a) is selected from ammonium or alkali metal salt of racemic MGDA and from ammonium and alkali metal salts of mixtures of L- and D-enantiomers according to formula (IX a), said mixture containing predominantly the respective L-isomer with an enantiomeric excess (ee) in the range of from 5 to 99%, preferably 5 to 95%, more preferably from 10 to 75% and even more preferably from 10 to 66%.

In one embodiment of the present invention, compound according to general formula (IX b) is selected from at least one alkali metal salt of a mixture of L- and D- enantiomers according to formula (IX b), said mixture containing the racemic mixture or preferably predominantly the respective L-isomer, for example with an enantiomeric excess (ee) in the range of from 5 to 99%, preferably 15 to 95%.

The enantiomeric excess of compound according to general formula (IX a) may be determined by measuring the polarization (polarimetry) or preferably by chromatography, for example by HPLC with a chiral column, for example with one or more cyclodextrins as immobilized phase or with a ligand exchange (Pirkle-brush) concept chiral stationary phase. Preferred is determination of the ee by HPLC with an immobilized optically active amine such as D-penicillamine in the presence of copper(+ll) salt. The enantiomeric excess of compound according to general formula (IX b) salts may be determined by measuring the polarization (polarimetry).

In one embodiment of the present invention, inventive compositions contain in the range of from 0.5 to 50% by weight of sequestrant (D), preferably 1 to 35% by weight, referring to the total solids content.

In order to be suitable as liquid laundry compositions, inventive compositions may be in bulk form or as unit doses, for example in the form of sachets or pouches. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol. In a preferred embodiment of the present invention, inventive compositions are liquid or gel-type at ambient temperature. In another preferred embodiment of the present invention, inventive compositions are solid at ambient temperature, for example powders or tabs.

In one embodiment of the present invention, inventive compositions are liquid or gel-type and have a pH value in the range of from 7 to 9, preferably 7.5 to 8.5. In embodiments where inventive compositions are solid, their pH value may be in the range of from 7.5 to 11 , determined after dissolving 1 g/100 ml in distilled water and at ambient temperature. In embodiments where inventive compositions are used for hard surfaces like tiles, for example bathroom tiles, their pH value may even be acidic, for example from 3 to 6.

In one embodiment of the present invention, inventive compositions are liquid or gel-type and have a total solids content in the range of from 8 to 80%, preferably 10 to 50%, determined by drying under vacuum at 80°C.

Another aspect of the present invention is related to polymers (A), hereinafter also referred to as inventive compounds (A) or simply as compounds (A). Inventive compounds (A) have been described above.

In one embodiment of the present invention, the weight ratio of backbone (a) to side chains (b) is in the range of from 1 : 5 to 1 : 100.

In one embodiment of the present invention, inventive compounds (A) have an average molecular weight M_n in the range of from 2,500 to 100,000 g, preferably 5,000 to 50,000 g/mol. A preferred average molecular weight M_w is in the range of from 7,500 to 75,000 g/mol.

In one embodiment of the present invention, inventive compounds (A) have a polydispersity M_w/Mn in the range of from 2.0 to 6.0, preferably from 2.5 to 5.0, more preferably from 2.5 to 4.5.

Inventive compounds may have a phosphate content of from 1 to 100 ppm by weight. Said phosphate content may be determined by gravimetry.

In one aspect, the invention is directed to a method of improving the cleaning performance of a liquid detergent composition, by adding a compound (A) according to the invention to a detergent composition preferably comprising at least one lipase and/or at least one protease.

The term "improved cleaning performance" herein may indicate that polymers (A) provide better, i.e. improved, properties in stain removal under relevant cleaning conditions, when compared to the cleaning performance of a detergent composition lacking compound (A). In one embodiment, “improved cleaning performance” means that the cleaning performance of a detergent comprising compound (A) and at least one enzyme, preferably at least one hydrolase (B), especially at least one lipase (B) and/or at least one protease (B), is improved when compared to the cleaning performance of a detergent comprising compound (A) and no enzyme. In one embodiment, “improved cleaning performance” means that the cleaning performance of a detergent comprising compound (A) and an enzyme, preferably lipase (B), more preferably hydrolase (B) and/or protease (B), is improved when compared to the cleaning performance of a detergent comprising at least one enzyme, preferably at least one hydrolase (B), preferably lipase (B) and/or at least one protease (B) and no compound (A).

The term "relevant cleaning conditions" herein refers to the conditions, particularly cleaning temperature, time, cleaning mechanics, suds concentration, type of detergent and water hardness, actually used in laundry machines, automatic dish washers or in manual cleaning processes.

Inventive compounds (A) are excellently suited as and particularly for the manufacture of inventive compositions. Inventive compounds (A) show good biodegradability according to OECD. A further aspect of the present invention relates to a process for making inventive compounds (A), hereinafter also referred to as inventive process or inventive synthesis. The inventive process comprises step (a) and step (P). Both steps (a) and step (P) may comprise two or more sub-steps.

Step (a) includes providing a backbone molecule that is derived from a compound bearing at least one primary amino group per molecule. Such backbone molecules correspond to the non- alkoxylated backbones (a), and they may be referred to as backbone molecules (a).

In one embodiment, the reaction is preferably carried out in solution, and it is advantageous to provide backbone molecule (a) in solution. Suitable solvents are water and mixtures of water and alcohols like, e.g., methanol and ethanol, glycols like ethylene glycol, propylene glycol, and diethylene glycol as well as polyethylene glycol, for example with an average molecular weight M_n up to 500 g/mol, with a water content of preferably at least 70% by weight. In a preferred embodiment of the present invention, backbone molecule (a) is provided in bulk, and the reaction is performed in the absence of a solvent.

In one group (1) of embodiments of the present invention, step (a) comprises the following substeps: (a1) converting a polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3-ami- nopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-aminoethyl)-eth- ylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethyla- mino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine, arginine, lysine or polylysine with 0.01 to 1 moles or 0.01 to 0.3 moles, in particular 0.05 to 0.6 moles or 0.05 to 0.25 moles or 0.4 to 1 moles or 0.4 to 0.6 moles of a C2-C4-alkylene oxide, per 1 mole of N-H group, for example with 1,2-butylene oxide or propylene oxide, or preferably with ethylene oxide, thereby forming an intermediate,

(a2) converting the intermediate resulting from step (cd) with a di- or tricarboxylic acid which is in particular selected from adipic acid, sebacic acid, glutamic acid or citric acid or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a mixture from a dicarboxylic and a tricarboxylic acid, e. g. a mixture of sebacid acid or adipic acid with citric acid, or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a carbonate, such as diethyl carbonate; to backbone (a1). In step (a2) an aliphatic diol, such as neopentylglycol, 1,5-pentanediol, 1,6- hexanediol or 1 ,4-butynediol, or an aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of the converted polyamine to the total amount of the di- and polyol is in particular in the range of 5:1 to 1:5, especially in the range of 2:1 to 1 :2.

In one particular subgroup of group (1) of embodiments of the present invention, step (a) comprises the following sub-steps:

(a1) converting at least one of methylcyclohexane-2,4-diamine, N4-amine, lysine and polylysine with 0.4 to one equivalent of C2-C4-alkylene oxide per N-H group, for example with 1 ,2-butylene oxide or propylene oxide, or preferably with ethylene oxide, thereby forming an intermediate,

(a2) converting the intermediate resulting from step (a1) with a di- or tricarboxylic acid selected from adipic acid, sebacic acid, glutamic acid or citric acid, or with a mixture from a dicarboxylic and a tricarboxylic acid, or with a carbonate, to backbone (a1). In this subgroup of group (1) of embodiments alkyl ester, in particular C1-C2- alkyl esters of said di- or tricarboxylic acids can be used instead of the di- or tricarboxylic acids can be used.

In one other group (2) of embodiments of the present invention, step (a) comprises the following sub-steps:

(a1) converting a polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3-ami- nopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-aminoethyl)-eth- ylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethyla- mino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine, arginine, lysine or polylysine with 0.01 to 1 moles or 0.01 to 0.3 moles, in particular 0.05 to 0.6 moles or 0.05 to 0.25 moles or 0.4 to 1 moles or 0.4 to 0.6 moles of a C2-C4-alkylene oxide, per 1 mole of N-H group, for example with 1 ,2-butylene oxide or propylene oxide, or preferably with ethylene oxide, thereby forming an intermediate,

(a2) subjecting the intermediate from step (a1) to polycondensation - preferably under catalysis of at least one acidic catalyst, for example methylsulfonic acid (“MSA”), sulfuric acid or p-toluene sulfonic acid - thereby obtaining a polycondensate,

(a3) converting the polycondensate resulting from step (a2) with a di- or tricarboxylic acid which is in particular selected from adipic acid, sebacic acid, glutamic acid or citric acid or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a mixture from a dicarboxylic and a tricarboxylic acid, e. g. a mixture of sebacid acid or adipic acid with citric acid, or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a carbonate, such as diethyl carbonate; to backbone (a4). In step (a3) an aliphatic diol, such as neopentylglycol, 1 ,5-pentanediol, 1 ,6- hexanediol or 1 ,4-butynediol, or an aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of the converted polyamine to the total amount of the di- and polyol is in particular in the range of 5:1 to 1 :5, especially in the range of 2:1 to 1 :2.

In one particular subgroup of group (2) of embodiments of the present invention, step (a) comprises the following sub-steps:

(a3) converting the polycondensate resulting from step (a2) with a di- or tricarboxylic acid selected from adipic acid, sebacic acid, glutamic acid or citric acid or with a mixture from a dicarboxylic and a tricarboxylic acid, or with a carbonate, to backbone (a4). In this subgroup of group (2) of embodiments alkyl ester, in particular C1-C2- alkyl esters of said di- or tricarboxylic acids can be used instead of the di- or tricarboxylic acids can be used.

In one other group (3) of embodiments of the present invention, step (a) comprises the following steps:

(a1) condensing at least one a polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3-aminopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2- aminoethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2- aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine, arginine, lysine or polylysine with a di- or tricarboxylic acid which is in particular selected from adipic acid, sebacic acid, glutamic acid or citric acid or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a mixture from a dicarboxylic and a tricarboxylic acid, e. g. a mixture of sebacid acid or adipic acid with citric acid, or an alkyl ester, in particular a Ci-C2-alkyl ester of said di- or tricarboxylic acid; or with a carbonate, such as diethyl carbonate; to backbone (a2). In step (a1) an aliphatic diol, such as neopentylglycol, 1 ,5-pentanediol, 1 ,6- hexanediol or 1 ,4-butynediol, or an aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of the converted polyamine to the total amount of the di- and polyol is in particular in the range of 5:1 to 1 :5, especially in the range of 2:1 to 1 :2.

In particular subgroup of group (3) of embodiments of the present invention, step (a) comprises the following sub-steps:

(cd) converting at least one of methylcyclohexane-2,4-diamine, N4-amine, lysine and polylysine with a di- or tricarboxylic acid selected from adipic acid, sebacic acid, glutamic acid or citric acid or with a mixture from a dicarboxylic and a tricarboxylic acid, or with a carbonate, to backbone (a2).

In one other group (4) of embodiments of the present invention, step (a) comprises the following sub-steps:

(cd) reacting arginine, lysine or polylysine with a polyol, preferably under catalysis of at least one acidic catalyst, for example methylsulfonic acid (“MSA”), sulfuric acid or p-toluene sulfonic acid, thereby obtaining a polycondensate,

(a2) converting the polycondensate resulting from step (a2) with a dicarboxylic acid which is in particular selected from adipic acid, sebacic acid and glutamic acid acid or an alkyl ester, in particular a Ci-C2-alkyl ester of said dicarboxylic acid; to backbone (a3). In step (a2) an aliphatic diol, such as neopentylglycol, 1,5-pentanediol, 1,6- hexanediol or 1 ,4-butynediol, or an aliphatic polyol having at least 3 OH groups, in particular 3, 4, 5 or 6 OH groups, such as triethanolamine, glycerol, trimethylolpropane (TMP), pentaerythrol, or sorbit, in particular pentarerythrol or triethanolamine, or a combination thereof, the relative amount of the converted polyamine to the total amount of the di- and polyol is in particular in the range of 5:1 to 1:5, especially in the range of 2:1 to 1 :2. In group 4 of embodiments, the polyol may of course also be an intermediate as obtained in step (a1) of group (1) of embodiments.

In step (a2) of group 1 of embodiments and likewise in step (a3) of group 2 of embodiments, the intermediate from step (a1) or (a2), respectively, is reacted with at least one dicarboxylic or tri- carboxlic acid or with a mixture of the foregoing, or, in each case, with their respective anhydrides or Ci-C4-alkylesters, thereby obtaining an ester.

In each case, such amine provided in step (a1) or (a2) may be provided as such or as mixture with a diol or polyol such as triethanolamine, glycerol, TMP pentaerythrol, or sorbit, or a mixture thereof.

Step (a2) may be carried out at temperatures in the range of from 20 to 180°C. In embodiments wherein ester(s), in particular Ci-C2-alkyl esters are used, such as adipic acid diethyl ester, diethyl succinate, adipic acid dimethyl ester, dimethyl succinate, triethyl citrate or the like, temperatures in the range of from 25 to 150°C are preferred. In embodiments wherein anhydride(s) are applied, for example succinic anhydride, 25 to 150°C are preferred. In embodiments wherein the respective free acid(s) are used, temperatures in the range of from 100 to 180°C are preferred. Especially in embodiments wherein temperatures of 100°C or more are applied it is preferred to ramp up the temperature.

Step (a2) may be performed at any pressure, for example from 10 mbar to 10 bar. Preferred are ambient pressure and pressures below, for example 10 to 500 mbar.

In the course of step (a2), water or an alcohol is formed, for example methanol or ethanol. It is preferred to remove such byproducts, for example by distilling them off. Suitable tools are Dean- Stark apparatuses, distillation bridges, water eliminators, and other apparatuses that may serve for removal of water or alcohols by distillation.

Step (a2) may be performed in the absence or presence of a solvent. Suitable solvents are aromatic solvents like toluene, aliphatic hydrocarbons or cycloaliphatic solvents, for example decane, cyclohexane, n-heptane and the like. It is preferred, though, to perform step (P) in the absence of a solvent, especially when the reaction mixture is liquid at the reaction temperature. In one embodiment of the present invention, step (a2) is performed in the presence of a catalyst. Examples of suitable catalysts are especially acidic catalysts, for example inorganic acids and organic acids.

Acidic inorganic catalysts for the purposes of the present invention include for example sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH value 5 to 6) and acidic alumina. Suitable are as well, for example, aluminum compounds of the general formula AI(OR⁵)3 and titanates of the general formula Ti(OR⁵)4 as acidic inorganic catalysts, the residues R⁵ each being identical or different and being chosen independently of one another from

Ci-Cw-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n- pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sechexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl,

C3-Ci2-cycloalkyl, examples being cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopentyl, cyclohexyl and cycloheptyl.

Preferably the residues R⁵ in AI(OR⁵)3 and Ti(OR⁵)4 are each identical and chosen from isopropyl or 2-ethylhexyl.

Preferred acidic organometallic catalysts are chosen for example from dialkyltin oxides (R⁵)2SnO with R⁵ being as defined above. One particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, available commercially in the form of oxo-tin.

Preferred acidic organic catalysts are acidic organic compounds containing, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particular preference is given to sulfonic acids such as para-toluenesulfonic acid, or methanesulfonic acid for example. Acidic ion exchangers can also be used as acidic organic catalysts, examples being polystyrene resins which contain sulfonic acid groups and have been crosslinked with about 2 mol % of divinylbenzene. Particularly preferred is methanesulfonic acid.

Combinations of two or more of the aforementioned catalysts can also be used. Another possibility is to use those organic or organometallic or else inorganic catalysts which are in the form of discrete molecules, in an immobilized form. If the use of acidic inorganic, organometallic or organic catalysts is desired, the amount of catalyst used in accordance with the invention is from 0.005 to 5% by weight, preferably from 0.02 to 1 % by weight, each based on the total amount of the reactants.

In another embodiment of the present invention, step (a2) is performed without a catalyst.

In one embodiment of the present invention, step (a2) has a duration in the range of from 30 minutes up to 24 hours.

By performing step (a2), an ester is obtained that may bear amide groups.

In one embodiment of the present invention, the reaction in step (a2) leads to a complete conversion of all carboxylic acid or ester or anhydride groups of the respective dicarboxylic or tricar- boxlic acid or with a mixture of the foregoing, or, in each case, with their respective anhydrides or Ci-C4-alkylesters. It is observed, though, that in many embodiments the conversion of ester or carboxylic acid groups or anhydride groups is incomplete, which results in the ester still bearing carboxylic acid groups or Ci-C4-alkylester groups. The completeness of the reaction may be assessed by determining the acid number, for example according to EN ISO 660: 2009).

In one embodiment of the present invention, further groups of, e.g., citric acid or its Ci-C4-esters may react, for example the hydroxyl group.

The ester resulting from step (a2) may be isolated and purified, for example by removal of solvent, if applicable, or by neutralization of acid. Especially in embodiments of step (a2) in which neither a catalyst nor a solvent was used it is preferred to transfer the resultant ester to step (P) without further purification steps.

Examples of carbonates are diethyl carbonate, dimethyl carbonate, and methylethyl carbonate, as well as phosgene and monoethyl chlorocarbonate (C2Hs-O-(CO)CI). Preferred are diethyl carbonate and dimethyl carbonate, and more preferred is diethyl carbonate.

Backbone (a) is usually a mixture of compounds and bears N-H groups, COOH groups and CH2CH2-OH groups. The amount of N-H groups, COOH groups and CH2CH2-OH groups may be measured by determination of the amine value, the acid number and the hydroxyl value, respectively. Hydroxyl values are advantageously determined according to DIN EN ISO 4629-1 (2016). Step (P) then includes reacting said backbone molecule (a) with ethylene oxide and then with either of propylene oxide or butylene oxide. It is, for example, possible to subject backbone (a) to a first alkoxylation (pi) with ethylene oxide and to subject the product from step (pi) to a second alkoxylation (p2) , with propylene oxide or butylene oxide.

In one embodiment of the present invention, in step (pi) 15 to 40 molecules of ethylene oxide are reacted per sum of N-H groups, COOH groups and CH2CH2-OH groups of backbone (a), preferably 25 to 30 molecules. In step (p2), propylene oxide or butylene oxide are added to an amount that corresponds to 2.5 to 20 weight-% of the sum of backbone molecule (a) and EO.

In one embodiment of the present invention, step (P) includes a pre-alkoxylation step before step (pi) with a maximum of one equivalent of PO per N-H function, with or without catalyst.

Said pre-alkoxylation may be carried out at a temperature in the range of from 25 to 150°C, preferred are 120 to 140°C.

Step (P) - especially (p 1 ) and (p2) - is preferably carried out in the presence of a catalyst, for example a base or a double-metal cyanide.

In one embodiment of the present invention, step (P) is carried out in the presence of a base. Suitable bases such as potassium hydroxide, sodium hydroxide, sodium or potassium alkoxides such as potassium methylate (KOCH3), potassium tert-butoxide, sodium ethoxide and sodium methylate (NaOCHs), preferably from potassium hydroxide and sodium hydroxide. Further examples of catalysts are alkali metal hydrides and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preference is given to the alkali metal hydroxides, preference being given to potassium hydroxide and sodium hydroxide, and to alkali metal alkoxides, particular preference being given to potassium t-butoxide in t-butanol, sodium n-hexanolate in n-hexanol, and to sodium methanolate in n-nonanol. Typical use amounts for the base are from 0.05 to 10% by weight, in particular from 0.5 to 2% by weight, based on the total amount of backbone (a) and C2-C4-alkylene oxide.

No phosphate is preferably used as catalyst.

In one embodiment of the present invention, step (P) is carried out in the presence of a doublemetal cyanide. Double-metal cyanides, hereinafter also referred to as double metal cyanide compounds or DMC compounds, usually comprise at least two different metals, at least one of them being selected from transition metals and the other one being selected from transition metals and alkali earth metals, and furthermore cyanide counterions. Particularly suitable catalysts for the alkoxylation are double-metal cyanide compounds which contain zinc, cobalt or iron or two thereof. Berlin blue, for example, is particularly suitable.

Preference is given to using crystalline DMC compounds. In a preferred embodiment, a crystalline DMC compound of the Zn-Co type which comprises zinc acetate as further metal salt component is used as catalyst. Such compounds crystallize in monoclinic structure and have a platelet-like habit.

In one embodiment of the present invention, the inventive synthesis is carried out in the presence of at least one double-metal cyanide selected from hexacyano cobaltates.

Double-metal cyanide compounds can be used as powder, paste or suspension or be moulded to give a moulding, be introduced into mouldings, foams or the like or be applied to mouldings, foams or the like.

Preferably, a DMC catalyst used for step (P), based on backbone (a), is from 5 to 2000 ppm (i.e. mg of catalyst per kg of product), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm; ppm referring to mass-ppm (parts per million) of backbone (a)

Step (P) may be carried out in bulk, embodiment (i), or in an organic solvent, embodiment (ii). In embodiment (i), water can be removed from backbone (a). Such water removal can be done by heating to a temperature in the range of from 80 to 150°C under a reduced pressure in the range of from 0.01 to 0.5 bar and distilling off the water.

In one embodiment of the present invention, step (P) is carried out at a reaction temperature in the range of from 70 to 200°C and preferably from 100 to 180°C.

In one embodiment of the present invention, step (P) is carried out at a pressure of up to 10 bar and in particular up to 8 bar, for example 1 to 8 bar.

In one embodiment of the present invention, the reaction time of step (P) is generally in the range of from 0.5 to 12 hours. Examples of suitable organic solvents for embodiment (ii) of step (P) are nonpolar and polar aprotic organic solvents. Examples of particularly suitable nonpolar aprotic solvents include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. Examples of particularly suitable polar aprotic solvents are ethers, in particular cyclic ethers such as tetrahydrofuran and 1,4-dioxane, furthermore N,N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyllactams such as N-methylpyrrolidone. It is as well possible to use mixtures of at least two of the above organic solvents. Preferred organic solvents are xylene and toluene.

In embodiment (ii), the solution obtained in the first step, before or after addition of catalyst and solvent, is dewatered before being subjected to alkylene oxide, said water removal advantageously being done by removing the water at a temperature in the range of from 120 to 180°C, preferably supported by a stream of nitrogen. The subsequent reaction with alkylene oxide may be effected as in embodiment (i). In embodiment (i), inventive polymer (A) is obtained directly in bulk and may be dissolved in water, if desired. In embodiment (ii), for work-up organic solvent is typically replaced by water. Inventive polymer (A) according to the invention may alternatively be isolated in bulk.

An - optional - step of work-up may include the deactivation of catalyst used in step (P), in the case of basic catalysts by neutralization.

In one embodiment of the present invention, when the step (P) is completed, residual alkylene oxide can be removed, for example by stripping with nitrogen or by steam distillation.

By carrying out the inventive process, inventive compounds (A) are obtained.

The present invention is further illustrated by working examples.

General remarks:

Reactions were carried out under nitrogen atmosphere unless expressly noted otherwise. Percentages refer to % by weight unless expressly stated otherwise.

GPC measurements were performed in HFIP (hexafluoro-isopropanol) at ambient temperature by PSS Agilent 1200 Series. The nominal solvent flow rate was 1 mL/min. Two SEC columns with a pore size of 100 and 1000 for HFIP and 2x1000 and 2x10000 A for DMAc from PSS Polymer Standards were used for fractionation. The refractive index detector G136A and UV/Vis detector G1314B from Agilent Technologies were used for HFIP. The calibration was carried out with poly(methyl methacrylate) for samples in HFIP. The results were evaluated using WinGPC UniChrom V 8.20 software from Polymer Standards Service GmbH Hydroxyl values (OH values) were determined according to DIN EN ISO 4629-1 (2016).

Amine values were determined according to DIN EN ISO 9702 (1998).

Acid values were determined according to DIN EN ISO 2114 (2000).

The Hazen colour number was determined according to DIN ISO 6271 , ASTM D 1209, with spectrophotometric detection. (2° norm observer, normal light, layer thickness 11 mm, against distilled water). rpm: revolutions per minute. Nl: norm liter, volume determined at ambient pressure and 23°C

I. Syntheses of inventive compounds (A)

Step (a1): The following backbone molecules (a) were provided from commercial sources:

The following starting materials were used:

(a.1): N4-amine, commercially available from BASF SE (a.2): MCDA, 4:1 molar mixture of 2,4-isomer and 2,6-isomer (a.3): triethanolamine and L-lysine mixture

1.1 Synthesis of backbone (a1.1)

Step (a.1.1) Conversion of N4-amine (a.1) with ethylene oxide, 0.5 mol per N-H group

A 5-liter steel autoclave was charged with 1.22 kg (a.1) (7 mol) N4-amine in 122 g de-ionized water and then heated to 100 °C. Then, 50 g of ethylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 876 g of ethylene oxide (“EO”) were fed into the autoclave within 12 hours, 0.5 EO/mol/N-H group. The reaction mixture was stirred at 100 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 2.15 kg of intermediate ITM.1 were obtained as a pale yellow viscous liquid.

Analytics: total amine value: 710 mg KOH/g OH value: 1013 mg KOH/g

Step (a2.1): ITM.1 : citric acid : sebacic acid: 1 : 0.1 : 0.9

A 2-liter flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with ITM.1 (784.7 g, 2.56 mol), citric acid (49.2 g, 256 mmol) and sebacic acid (466.1 g, 2.31 mol) and warmed to 60 °C. Then, the resulting liquid was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C over a period of 90 minutes. The stirring speed was adjusted to 270 rpm as the viscosity decreased with rising temperature. The reaction mixture was then heated to 120 °C (inside temperature). Mild foaming was observed. Water distilled off and was collected. Stirring at 140°C was continued under nitrogen for 19.5 hours. Then, the reaction mixture was slowly cooled down. The resultant ester (a1 .1) was collected as a clear amber viscous material.

GPC in HFIP: M_n 1622 g/mol, M_w 17564 g/mol

Acid number: 61.5 mg KOH/g

OH value: 392 mg KOH/g

1.2 Synthesis of backbone (a1 .2)

Step (a.1.2) Conversion of MCDA (a.2) with ethylene oxide, 0.5 mol per N-H group

A 5-liter steel autoclave was charged with 1.6 kg (a.2) (12.5 mol, 50 mol N-H) in 160 g de-ion- ized water and then heated to 100 °C. An amount of 2.6 g of KOH was added. Then, 50 g of ethylene oxide were fed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 1 ,050 g of ethylene oxide (“EO”) were fed into the autoclave within 18 hours, 0.5 mol EO/N-H group. The reaction mixture was stirred at 100 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 2.7 kg of intermediate ITM.2 were obtained as a yellow viscous liquid.

Analytics: total amine value: 510 mg KOH/g

OH value: 863 mg KOH/g

Step (a2.2): ITM.2 : citric acid : sebacic acid: pentaerythrol : 1 : 0.1 : 0.9 : 0.1

A 500-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged ITM.2 (79.1 g, 0.45 mol), citric acid (17.2 g, 90 mmol) and sebacic acid (163.1 g, 808 mmol), 12.22 g pentaerythrol (90 mmol) and warmed to 60 °C. Then, the resulting liquid was stirred at 60 rpm under nitrogen atmosphere and heated to 120 °C over a period of 75 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. The reaction mixture was then heated to 120 °C (inside temperature). Mild foaming was observed. Water distilled off and was collected. Stirring at 120°C was continued under nitrogen for 6.5 hours. Then, the reaction mixture was slowly cooled to ambient temperature. The resultant ester (a1.2) was collected as a clear brown material.

GPC in HFIP: M_n233 g/mol, M_w 4860 g/mol

Acid number: 207 mg KOH/g

OH value: 230 mg KOH/g

1.3 Synthesis of backbone (a1.3)

Step (a.1.3) Conversion of triethanolamine and L-lysine mixture (a.3), with sebacic acid:

A 500-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with L-lysine (81.5 g, 558 mmol) and 83.16 g of triethanolamine (558 mmol). Then, the resulting liquid was stirred at 60 rpm under nitrogen atmosphere and heated to 120 °C. At a temperature of 110°, sebacic acid was added (135.3 g, 669 mmol). The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. The reaction mixture was then heated to 120 °C (inside temperature). Mild foaming was observed. Water distilled off and was collected. Stirring at 120°C was continued under nitrogen for 3 hours. Then, the reaction mixture was slowly cooled to ambient temperature. The resultant ester (a1.3) was collected as a clear red viscous material.

GPC in HFIP: M_n 694 g/mol, M_w9086 g/mol

Acid number: 126 mg KOH/g

OH value: 341 mg KOH/g

1.4 Synthesis of backbone (a1.4)

A 250-ml three-necked flask was charged with 37.04 g (248 mmol) triethanolamine, 11.5 g (110 mmol) 1 ,5-pentanediol and 37.2 g N4-amine that had been converted with 1 mol EO/N-H function. The resulting mixture was heated to 120°C under a reduced pressure of 10 mbar. The flask was flushed with nitrogen. A Vigreux column and a dropping funnel were added to the flask, and 0.3 g 1 ,5,7-triazabicyclo[4.4.0]dec-5-ene were added as a catalyst. Under ambient pressure, 52.95 g of diethyl carbonate were added within 60 minutes. Then, heating was set to 175°C, and the ethanol formed was distilled off over a period of time of 15 minutes. Then, the pressure was reduced stepwise to 10 mbar and reacted for 9 hours. Then, another 10 g of diethyl carbonate were added and volatiles ere again distilled off under reduced pressure. After cooling to ambient temperature, a dark brown residue was obtained, (a1.4). GPC in HFIP: M_n 5580 g/mol, M_w 10000 g/mol

OH value: 572 mg KOH/g

1.5 Synthesis of backbone (a1 .5)

Step (a.1.5) Conversion of N4-amine (a.1) with propylene oxide, 0.5 per N-H group

A 5-liter steel autoclave was charged with 955 kg (a.1) (5.5 mol) N4-amine in 122 g de-ionized water and then heated to 100 °C. Then, 50 g of propylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 907 g of propylene oxide (“PO”) were fed into the autoclave within 15 hours, 0.5 PO/mol/N-H group. The reaction mixture was stirred at 100 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual PO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 1.9 kg of intermediate ITM.5 were obtained as a pale yellow viscous liquid. Amine value: 675 mg KOH/g, OH value: 925 mg KOH/g

A 2 L flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with intermediate ITM.5 (755.1 g, 2.17 mol), citric acid (52.0 g, 0.271 mol) and se- bacic acid (492.9 g, 2.44 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 60 minutes. The stirring speed was adjusted to 270 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 19 hours. Then, the reaction mixture was slowly cooled down and the resulting backbone (a1.5) was collected as a clear, amber, viscous material.

GPC in HFIP: M_n 409 g/mol, M_w 13133 g/mol

Acid number:98 mg KOH/g

OH value: 312 mg KOH/g

1.6 Synthesis of backbone (a1 .6)

MCDA : citric acid : adipic acid: 1 : 0.18 : 0.27

A 2 L flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with MCDA (430.8 g, 3.36 mol), citric acid (115.3 g, 0.60 mol) and adipic acid (131.5 g, 0.90 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 160 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 270 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 8 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a clear, amber, solid material.

GPC in HFIP: M_n 1212 g/mol, M_w 4485 g/mol

Acid number: 76 mg KOH/g

OH value: 443 mg KOH/g

II. Ethoxylation and end-capping, step (P)

Some exemplified examples are found below. In related examples, the amounts of propylene oxide were varied mutatis mutandis.

11.1 Synthesis of polymers (A1.2) to (A1.6)

Ethoxylation:

A 5-liter steel autoclave was charged with 350 g backbone (a1 .1). An amount of 14.3 g of KOH (50%) was added and the mixture was heated to 130°C under stirring. Then, 50 g of ethylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 3,180 g of ethylene oxide were fed into the autoclave within 35 hours, total amount of EO: 30 mol/OH or NH or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 3.59 kg of an ethoxylate was obtained as a brown solid, total amine value: 35.0 mg KOH/g, OH value: 132.0 mg KOH/g.

11.1.1 End-capping with 0.5 equivalents PO

A 2-liter steel autoclave was charged with 300 g of the above ethoxylate and 1 .22 g of KOH (50%), and the resultant mixture was heated to 130°C under stirring with 100 rpm. Then, 6 g of propylene oxide were added within 10 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down to ambient temperature. Inventive polymer (A1.2) was collected as a brown solid (307 g). Total amine value: 34 mg KOH/g, OH value: 129 mg KOH/g, corresponding to 0.5 PO. 11.1.2 End-capping with one equivalent PO

The above protocol (11.1.1) was followed but with 1.26 g of KOH (instead of 1.22 g) and with 12 g of PO instead of 6 g. Inventive polymer (A1 .3) was collected as a brown solid (315 g). Total amine value: 33 mg KOH/g, OH value: 127 mg KOH/g, corresponding to 1 PO.

11.1.3 End-capping with 3 equivalents PO

The above protocol (11.1.1) was followed but with 1.3 g of KOH (instead of 1.22 g) and with 36 g of PO instead of 6 g. Inventive polymer (A1.4) was collected as a brown solid (348 g). Total amine value: 31 mg KOH/g, OH value: 125 mg KOH/g, corresponding to 3 PO.

11.1.4 End-capping with 5 equivalents PO

The above protocol (11.1.1) was followed but with 1.44 g of KOH (instead of 1.22 g) and with 60 g of PO instead of 6 g. Inventive polymer (A1 .5) was collected as a brown solid (360 g). Total amine value: 28 mg KOH/g, OH value: 116 mg KOH/g, corresponding to 5 PO.

11.1.5 End-capping with 9 equivalents PO (comparative)

The above protocol (11.1.1) was followed but with 1.6 g of KOH (instead of 1.22 g) and with 108 g of PO instead of 6 g. Comparative polymer C-(A1.6) was collected as a brown solid (407 g). Total amine value: 22 mg KOH/g, OH value: 110 mg KOH/g, corresponding to 9 PO.

II.2 Synthesis of polymer (A2.2) and related polymers

Ethoxylation:

A 2-liter steel autoclave was charged with 140 g backbone (a1 .2). An amount of 2.6 g of KOH (50%) was added and the mixture was heated to 130°C under stirring. Then, 50 g of ethylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 456 g of ethylene oxide were fed into the autoclave within 8 hours, total amount of EO: 20 mol/OH or NH or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 652 g of an ethoxylate was obtained as a brown liquid, total amine value: 27.0 mg KOH/g, OH value: 127.0 mg KOH/g. The above procedure was repeated on larger scale to yield some 1 .2 kg of ethoxylate.

End-cappings:

A 2-liter steel autoclave was charged with 400 g of the above ethoxylate and 1.7 g of KOH (50%) and heated to 130°C under stirring with 100 rpm. Then, 33 g of propylene oxide were added within 60 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. Inventive polymer (A2.2) was collected as a brown solid (435 g). Total amine value: 25.5 mg KOH/g, OH value: 126 mg KOH/g.

The above procedure was repeated with 55 g of PO instead of 33 g. Inventive polymer (A2.3) was collected as a brown solid (455 g). Total amine value: 24 mg KOH/g, OH value: 122 mg KOH/g.

The above procedure was repeated with 2.0 g of KOH (instead of 1.7 g) and with 110 g of PO instead of 33 g. Inventive polymer (A2.4) was collected as a brown solid (510 g). Total amine value: 23 mg KOH/g, OH value: 120 mg KOH/g.

11.3 Synthesis of polymer (A3.2) and related polymers:

Ethoxylation:

A 2-liter steel autoclave was charged with 150 g backbone (a1 .3). An amount of 3.9 g of KOH (50%) was added and the mixture was heated to 130°C under stirring. Then, 50 g of ethylene oxide were fed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 753 g of ethylene oxide were fed into the autoclave within 12 hours, total amount of EO: 25 mol/OH or NH or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 959 g of an ethoxylate was obtained as a brown solid, total amine value: 25.0 mg KOH/g, OH value: 133.0 mg KOH/g. End cappings:

A 2-liter steel autoclave was charged with 500 g of the above ethoxylate and 2.2 g of KOH (50%), and the resultant mixture was heated to 130°C under stirring with 100 rpm. Then, 28 g of propylene oxide were added within 10 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. Inventive polymer (A3.2) was collected as a brown solid (530 g). Total amine value: 23.0 mg KOH/g, OH value: 120 mg KOH/g.

The above procedure was repeated with 2.4 g of KOH (instead of 2.2 g) and with 84 g of PO instead of 28 g. Inventive polymer (A3.3) was collected as a brown solid (435 g). Total amine value: 21 mg KOH/g, OH value: 118 mg KOH/g.

The above procedure was repeated with 3 g of KOH (instead of 2.2 g) and with 252 g of PO instead of 28 g. Inventive polymer (A3.4) was collected as a brown solid (753 g). Total amine value: 20 mg KOH/g, OH value: 115 mg KOH/g.

11.4 Synthesis of polymer (A4.2) and related polymers

Ethoxylation:

A 2-liter steel autoclave was charged with 34.4 g backbone (a1.4) in 55.66g methyl ethyl ketone. An amount of 2.0 g of KOH (50%) was added and the mixture was heated to 130°C under stirring. Then, 50 g of ethylene oxide were fed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 398 g of ethylene oxide were fed into the autoclave within 8 hours, total amount of EO: 30 mol/OH or N-H or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 484 g of an ethoxylate was obtained as a brown wax, total amine value: 25.0 mg KOH/g, OH value: 82.0 mg KOH/g.

A 2-liter steel autoclave was charged with 218 g of the above ethoxylate and 1.7 g of KOH (50%), and the resultant mixture was heated to 130°C under stirring with 100 rpm. Then, 7 g of propylene oxide were added within 10 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. Inventive polymer (A4.2) was collected as a brown solid (255 g). Total amine value: 14.0 mg KOH/g, OH value: 65.0 mg KOH/g. End cappings:

A 2-liter steel autoclave was charged with 218 g of the above ethoxylate and 0.9 g of KOH (50%), and the resultant mixture was heated to 130°C under stirring with 100 rpm. Then, 7 g of propylene oxide were added within 10 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. Inventive polymer (A4.2) was collected as a brown solid (235 g). Total amine value: 24 mg KOH/g, OH value: 80 mg KOH/g.

The above procedure was repeated with 1 g of KOH (instead of 0.9 g) and with 28 g of PO instead of 7 g. Inventive polymer (A4.3) was collected as a brown solid (250 g). Total amine value: 22 mg KOH/g, OH value: 77 mg KOH/g.

The above procedure was repeated with 1.3 g of KOH (instead of 0.9 g) and with 98 g of PO instead of 7 g. Inventive polymer (A4.4) was collected as a brown solid (332 g). Total amine value: 19 mg KOH/g, OH value: 72 mg KOH/g.

11.5 Ethoxylation and end-capping of (a1.5)

Ethoxylation:

A 2-liter steel autoclave was charged with 150 g backbone (a1.5). An amount of 395 mg of KOH (50%) was added and the mixture was heated to 130°C under stirring (100 rpm). Then, 50 g of ethylene oxide were fed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 1344 g of ethylene oxide were fed into the autoclave as follows: 30 g within 10 minutes, then the stirring speed was increased to 200 rpm and the remaining 1314 g were within 9 hours, total amount of EO: 30 mol/OH or N-H or COOH group. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 1556 g of an ethoxylate was obtained as a brown wax, total amine value: 25.0 mg KOH/g, OH value: 82.0 mg KOH/g.

A 2-liter steel autoclave was charged with 440 g of the above ethoxylate and 1.8 g of KOH (50%), and the resultant mixture was heated to 130°C under stirring with 100 rpm. Then, 9 g of propylene oxide were added within 10 minutes and stirred at 130°C under increased stirrer speed, 200 rpm, for another 6 hours. Then, the reaction mixture was slowly cooled down. Inventive polymer (A5.2) was collected as a brown solid (451 g). Total amine value:30 mg KOH/g, OH value: 75 mg KOH/g (0.5 PO).

The above procedure was repeated with 1 .9 g of KOH (instead of 1.8 g) and with 36 g of PO instead of 9 g. Inventive polymer (A5.3) was collected as a brown solid (476 g). Total amine value: 27 mg KOH/g, OH value: 72 mg KOH/g.

The above procedure was repeated with 2.3 g of KOH (instead of 1 .8 g) and with 126 g of PO instead of 9 g. Inventive polymer (A5.4) was collected as a brown solid (567 g). Total amine value: 22 mg KOH/g, OH value: 65 mg KOH/g.

II.5 Ethoxylation (A6.1)

A 2-liter steel autoclave was charged with 200 g backbone (a1 .6). An amount of 6.4 g of KOH (50%) was added and the mixture was heated to 130°C under stirring (100 rpm). Then, 50 g of ethylene oxide were fed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 1341 g of ethylene oxide were fed into the autoclave over a period of 33 hours. The reaction mixture was stirred at 130 °C for further 6 hours. After that, the mixture was removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 1581 g of an ethoxylate was obtained as a brown wax, total amine value: 43.0 mg KOH/g, OH value: 137 mg KOH/g.

III. Tests

111.1 Laundering experiments

The laundering experiments were performed with respect to the secondary detergency, mixed stains

To determine the secondary detergency, the whiteness of 8 different test fabrics was measured by determining the color difference (delta E) between the test fabrics after wash and the unsoiled (white) test fabric before wash, using a reflectometer (Datacolor SF600 plus). The stains cover the dispersing power of clays and soiled clays, (anti-redeposition benefit) and another set has a focus on stains that would correlate with a benefit for the removal of clay stains.

The following stained fabrics were tested: (from Center of Test Materials CFT Vlaardingen) P- H108: Clay, Ground soil, P-H115: Standard Clay; P-H144: Red Pottery Clay; P-H145: tennis Court Clay) and 5g of commercially available soil ballast sheet wfk SBL 2004 (from wfk Test- gewebe GmbH Brueggen).

By using delta E values, the so-called “standardized cleaning performance” (delta delta E) has been calculated for each individual fabric. The “standardized cleaning performance” (delta delta E) is the difference of the performance of the laundry detergent including the inventive polymers with an appropriate PO capping propylene imine copolymer or comparative homoethoxylates.

A good performance correlates with > 12 delta delta E is assigned with ++ in Table 1. A range of 8 to 12 units correlates with +, a range of 6 to 8 units correlates with 0 and below 6 is rated as -. An even negative impact is assigned

Table 2 shows the composition of the laundry detergent of the respective inventive amphiphilic alkoxylated polyethyleneApropylene imine copolymer or comparative polymer, respectively, on the secondary cleaning performance.

Table 1: Inventive polymers (A) and test results

1 ) Weight average molecular weight of backbone

2) EOx refers to the molar amount of ethylene oxide per 1 mol of the total amount of reactive groups in the backbone capable of being ethoxylated. 3) Mole of PO based on mole of EO chains

Table 2: Ingredients of a test liquid detergent formulation

Laundering conditions: Launder-Ometer commercially available from SDL Atlas Modell M228AA 250 ml, 20 balls

30°C, 60 minutes, water hardness (Ca:Mg:HC03) 1 mmol/L (4:1 :8) (14 °dH)

Fabric to liquor ratio: 1 :10

111.2 Biodegradation tests

General: the tests were carried out in accordance with the OECD Guidelines. According to the

OECD guidelines a test is valid if:

1. The reference reaches 60% within 14 days.

2. The difference of the extremes of the test replicates by the end of the test is less than 20%. 3. Oxygen uptake of inoculum blank is 20 to 30 mg O2/I and must not be greater than 60 mg O2/I.

4. The pH value measured at the end of the test must be between 6 and 8.5.

Description of the test method used in the context of the present invention: Biodegradation in sewage was tested in triplicate using the OECD 301 F manometric respirometry method. OECD 301 F is an aerobic test that measures biodegradation of a sewage sample by measuring the consumption of oxygen. To a measured volume of sewage, 100 mg/L test substance, which is the nominal sole source of carbon, was added along with the inoculum (aerated sludge taken from the municipal sewage treatment plant, Mannheim, Germany). This sludge was stirred in a closed flask at a constant temperature (25°C) for 28 days. The consumption of oxygen is determined by measuring the change in pressure in the closed flask using an Oxi TopC. Carbon dioxide evolved was absorbed in a solution of sodium hydroxide. Nitrification inhibitors were added to the flask to prevent consumption of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control glucose/glutamic acid is run along with the test samples for each cabinet as reference.

Calculations:

Theoretical oxygen demand: Amount of O2 required to oxidize a compound to its final oxidation products. This is calculated using the elemental analysis data. % Biodegradation

Experimental O2 uptake x 100 and divided by the theoretical oxygen demand

Claims

Patent claims

1 . Aqueous composition comprising at least one compound

(A) that comprises at least one alkoxylated aliphatic or cycloaliphatic mono- or polyamine comprising

(a) a backbone that is derived from a compound bearing at least one primary amino group per molecule,

(b) polyalkylenoxide chains comprising a

(b1) polyethylene oxide chains with 15 to 50 ethylene oxide groups attached directly or indirectly to each nitrogen atom,

2. Composition according to claim 1 wherein said backbone (a) is derived from a compound bearing at least 2 primary amino groups per molecule or at least one primary and at least one secondary amino group per molecule.

3. Composition according to claim 2 wherein said compound bearing at least 2 primary amino groups per molecule or at least one primary and at least one secondary amino group per molecule is selected from methylcyclohexane-2,4-diamine, N,N'-bis-(3-ami- nopropyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-ethylenediamine, N,N'-bis-(2-ami- noethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethyla- mino]ethyl]ethane-1 ,2-diamine, arginine, lysine and polylysine.

4. Composition according to any of the preceding claims wherein said backbone (a) comprises at least one carboxylic ester group and/or at least one carboxamide group.

5. Composition according to any of the preceding claims wherein at least a part of the polyethylene oxide chains (b1) are attached indirectly to a nitrogen atom through a propylene oxide group.

6. Composition according to any of the preceding claims wherein backbone (a) is selected from condensates formed from at least one of polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3- aminopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-aminoethyl)- ethylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethyla- mino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine, arginine, lysine or polylysine or a combination of at least two of the foregoing or a combination of one of the foregoing with at least one aliphatic di- or polyol, such as pentaerythrol or triethanolamine, where the polyamine compound is optionally converted with 0.01 to 1 moles of ethylene oxide per N-H group, and condensed with at least one di- or tricarboxylic acid, such as adipic acid, se- bacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid, or with an organic carbonate. Composition according to any one of the preceding claims wherein backbone (a) is selected from

(a.1) condensates formed from (i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 1 moles of C2-C4- alkylene oxide per N-H group, and (ii) at least one di- or tricarboxylic acid or a C1-C2- alkyl ester of said di- or tricarboxylic acid and (iii) optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a.2) condensates formed from (i¹) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule and (ii) at least one di- or tricarboxylic acid, or a Ci-C2-al- kyl ester of said di- or tricarboxylic acid and (iii) optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a.3) condensates formed from lysine, arginine or polylysine and at least one aliphatic polyol having at least 3 OH groups and optionally an aliphatic dicarboxylic acid and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a.4) condensates formed from (i”) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 1 moles of C2-C4- alkylene oxide per N-H group, followed by self-condensation of the converted product, and (ii) at least one di- or tricarboxylic acidor a Ci-C2-alkyl ester of said di- or tricarboxylic acid, and (iii) optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups. Composition according to any of the preceding claims wherein said composition additionally comprises

(B) at least one hydrolase, where the hydrolyse (B) is in particular a lipase (B) that is selected from selected from triacylglycerol lipases according to EC 3.1.1.3.. Compound (A) which is an alkoxylated aliphatic or cycloaliphatic mono- or polyamine comprising

(b) polyalkylenoxide chains comprising

(b2) capped with a polypropylene oxide or polybutylene oxide chain comprising from 0.5 to 4 PO or BuO groups, respectively, and amounting to 2.5 to 20 % by weight of the respective polyethylene oxide chain. Compound (A) according to claim 9 having an average molecular weight M_w in the range of from 750 to 350,000 g/mol. Compound (A) according to claim 9 or 10 wherein said backbone (a) is derived from a compound bearing at least 2 primary amino groups per molecule or at least one primary and at least one secondary amino group per molecule. Compound (A) according to any of claims 9 to 11 wherein said compound bearing at least 2 primary amino groups per molecule or at least one primary and at least one secondary amino group per molecule is selected from methylcyclohexane-2,4-diamine, N,N'-bis-(3- aminopropyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-ethylenediamine, N,N'-bis-(2-ami- noethyl)-diethylenetriamine, N'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethyla- mino]ethyl]ethane-1 ,2-diamine, arginine, lysine and polylysine. Compound (A) according to any of claims 9 to 12 wherein said backbone (a) comprises at least one carboxylic ester group and/or at least one carboxamide group.

14. Compound (A) according to any of the claims 9 to 13 wherein at least a part of the polyethylene oxide chains (b1) are attached indirectly to each of the nitrogen atoms through a propylene oxide group.

15. Compound (A) according to any of the claims 9 to 14 wherein backbone (a) is selected from polycondensates formed from at least one of polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3- aminopropyl)-ethylenediamine, methylcyclohexane, 2,4-diamine, N,N'-bis-(2-ami- noethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)-diethylenetriamine, N'-[2-[2-[2-(2-ami- noethylamino)ethylamino]ethylamino]ethyl]ethane-1 ,2-diamine, arginine, lysine or polylysine or a combination of at least two of the foregoing or a combination of one of the foregoing with an aliphatic di- or polyol, such as pentaerythrol or triethanolamine, where the polyamine compound is optionally converted with 0.01 to 1 moles of C2-C4-alkylene oxide per 1 mole of N-H groups, and subsequently condensed with at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a C1-C2- alkyl ester of said di- or tricarboxylic acid, or with an organic carbonate.

16. Compound (A) according to claim 15 wherein backbone (a) is selected from

(a.1) condensates formed from (i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 1 moles of C2-C4- alkylene oxide per 1 mole of N-H groups, and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a.2) condensates formed from (i¹) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups; (a.3) condensates formed from lysine, arginine or polylysine and at least one aliphatic polyol having at least 3 OH groups and optionally an aliphatic dicarboxylic acid and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a.4) condensates formed from (i”) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 1 moles of C2-C4- alkylene oxide per 1 mole of N-H groups, followed by self-condensation of the converted product, and (ii) at least one di- or tricarboxylic acid, such as adipic acid, se- bacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups.

17. Use of a composition or a compound (A) according to any of the preceding claims for laundry care.

18. Process for making polymers according to any of claims 9 to 16 comprising the steps of (a) providing a backbone molecule that is derived from a compound bearing at least one primary amino group per molecule,

(P) reacting said backbone molecule with ethylene oxide and then with either of propylene oxide and butylene oxide.

19. Compound (A’) which is an ethoxylated aliphatic or cycloaliphatic mono- or polyamine comprising

(a’) a backbone which is selected from condensates of

(i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, such as N,N'-bis-(3-aminopropyl)-ethylenediamine, methylcyclohexane, 2,4- diamine, N,N'-bis-(2-aminoethyl)-ethylenediamine, N,N'-bis-(2-aminoethyl)- diethylenetriamine, N'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethyla- mino]ethyl]ethane-1,2-diamine, arginine, lysine or polylysine or a combination of at least two of the foregoing, where the polyamine compound is optionally converted with 0.01 to 0.3 moles of C2-C4-alkylene oxide per 1 mole of N-H groups,

(ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid; (iii) optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(b1) uncapped polyethylene oxide chains with 15 to 50 ethylene oxide groups attached directly or indirectly to each nitrogen atom. Compound (A’) according to claim 19 wherein backbone (a’) is selected from

(a'.1) condensates formed from (i) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule, which has been converted with 0.01 to 0.3 moles of a C2- C4-alkylene oxide per 1 mol of N-H groups, and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid, and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a¹.2) condensates formed from (i¹) at least one polyamine compound bearing at least 2 primary amino groups or at least one primary and at least one secondary amino group per molecule and (ii) at least one di- or tricarboxylic acid, such as adipic acid, sebacic acid, glutamic acid or citric acid, or a Ci-C2-alkyl ester of said di- or tricarboxylic acid, and optionally at least one of aliphatic diols and aliphatic polyols having at least 3 OH groups;

(a¹.3) condensates formed from lysine, arginine or polylysine and at least one aliphatic polyol having at least 3 OH groups and optionally an aliphatic dicarboxylic acid. Aqueous composition comprising at least one compound (a’) according to one of claims

19 or 20. Use of a composition of claim 21 or a compound (A’) according to any one of claims 19 or

20 for laundry care.