Modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine

Abstract

The present invention relates to modified alkoxylated polyalkyleneimines and polyamines containing primary and secondary amino groups, where more than 50% of the primary and secondary amino groups have been reacted with lactones and / or hydroxycarbon acids to improve the biodegradability of the polymer, their preparation and their use, for example, in laundry and dishwashing.

Description

[Technical Field]

[0001] The present invention relates to modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine polymers (in this invention, abbreviated as "inventive polymer" or "inventive polymer" whenever an inventive polymer is intended), their preparation, their use, in particular for use in cleaning compositions such as laundry detergent compositions, and in particular for improving clay removal and / or oily / greasy soil removal in laundry care. [Background technology]

[0002] Detergent formulators continually face the challenge of developing improved products for the removal of various soils and stains from fabrics and hard surfaces. Soils and stains are chemically and physicochemically diverse, ranging from polar soils such as proteinaceous materials, clays, and inorganic soils to non-polar soils such as soot, carbon black, by-products of incomplete combustion of hydrocarbons, and organic soils such as sebum. Removal of greasy (i.e., oily / fatty) stains has been a particularly challenging challenge. Recently, these challenges have been accentuated by the growing interest and drive to reduce the amount of surfactants in cleaning detergents for environmental, sustainability, and cost reasons. It has generally been found that reducing the amount of surfactants, especially anionic surfactants such as linear alkylbenzene sulfonates (LAS), reduces the removal of oily / fatty stains. Furthermore, with a global trend toward lower wash temperatures, the grease-cleaning ability of typical detergents will be further reduced, as the performance of these stains, classified as oily and fatty, is most affected by lower temperatures. Clay soil stains, on the other hand, may have weaker contact with fabrics, but present a particular type of problem for soil removal because the clay itself carries a high charge. This high surface charge density can act to repel some laundry ingredients, so surfactants alone cannot remove the clay or carry it away into the wash liquor.

[0003] Another global trend is the compactification of laundry detergents with the aim of improving sustainability in terms of water usage and / or transportation costs, as well as improving convenience for the end consumer (e.g., individualized single mono dose products, tablets, sachets, etc.), which is driving market demand for new ingredients that are more efficient per weight and offer a greater range of performance properties.

[0004] Furthermore, there is a clear trend towards wanting to improve the "footprint" of every product, whether in terms of its origin, such as natural or renewable resources, or its production, in terms of its efficiency and therefore reduced energy use compared to conventional products, or its efficiency in use, in terms of obtaining the same performance with less or higher performance at the same dose, or its persistence in the natural environment after use, in particular its biodegradation, since reuse is technically very challenging and economically unattractive.

[0005] Therefore, one of the most important goals today in the detergent and cleaner (D&C) industry due to climate change is to significantly reduce CO2 emissions per wash by improving cold water conditions and increasing washing efficiency at temperatures below 30°C, as well as to reduce the amount of chemicals used per wash and improve the efficiency per weight of washing technology. Another important goal of the D&C industry is to obtain biodegradable polymers in order to improve the sustainability of detergent formulations and to avoid the accumulation of polymers or their degradation products resulting from incomplete biodegradation in ecosystems, thereby reducing the persistence of this material in nature after use.

[0006] These trends have created a strong demand for new biodegradable cleaning polymers that provide excellent primary (i.e., soil removal) and secondary (i.e., whiteness maintenance) cleaning benefits for both hydrophobic and hydrophilic stains, while also exhibiting improved biodegradability. These materials should also exhibit good soil removal for oily / greasy and particulate stains, while also improving whiteness maintenance by minimizing the amount of suspended and emulsified oily / greasy and particulate stains that redeposit on fabric or hard surfaces. It would also be desirable for the new ingredients to exhibit synergy with other cleaning technologies, such as other cleaning polymers, surfactants, and / or enzymes, that are known to improve oily / greasy or particulate stain removal alone and / or whiteness of fabrics and hard surfaces alone, thereby further improving detergent compositions.

[0007] Alkoxylated polyalkyleneimine and alkoxylated polyamine polymers, particularly those classified as alkoxylated hyperbranched polyethyleneimine (PEI) and alkoxylated linear polypropyleneimine (PPI) homo- and copolymers, are known from the literature to be effective in removing particulate or oily / greasy soils, especially with small amounts of surfactants and under cold water conditions (below 30°C). However, their performance is not satisfactory, both in terms of oily / greasy soil removal ability and in terms of broader performance characteristics. Furthermore, their biodegradation performance is generally poor and therefore does not meet current and future requirements. Ideally, the polymers are readily biodegradable, i.e., exhibit an oxygen consumption of 60% or more after 28 days in the OECD 301 F test, or at least 60% or more after 56 days in the OECD 301 F test. Alternatively, the polymers are inherently biodegradable, i.e., exhibit a dissolved organic carbon (DOC) concentration of 70% or more in the OECD 302 B test. Therefore, it was necessary to search for improved polymer structures with excellent performance properties, feasible preparation processes, and improved biodegradation behavior.

[0008] Below is an overview of the publications most relevant to the field of the present invention.

[0009] Alkoxylated polyalkyleneimines and polyamines are well known as additives for laundry detergents (e.g., EP 3301154, EP 3167034, EP 112593 and WO 2020 / 030469) or hard surface cleaners.

[0010] WO 2015 / 028191 relates to a water-soluble alkoxylated polyalkyleneimine having a polyethylene oxide inner block containing 5 to 18 polyethylene oxide units, a polyalkylene oxide middle block containing 1 to 5 polyalkylene oxide units, and polyethylene oxide outer blocks containing 2 to 14 polyethylene oxide units. The middle block is composed of polypropylene oxide units, polybutylene oxide units, and / or polypentene oxide units. WO 2015 / 028191 also relates to a water-soluble alkoxylated polyamine. However, this disclosure does not mention the biodegradability of the polymer, nor does it mention modifying the alkoxy chains with lactones or hydroxycarbon acids.

[0011] WO 2020 / 187648 relates to alkoxylated polyalkyleneimines or alkoxylated polyamines end-capped with short polybutylene oxide blocks. The compounds described therein can be used, for example, in cosmetic formulations and laundry detergent formulations. However, neither lactones nor hydroxycarbon acids are used to modify the alkoxy chains of the polymers to improve their biodegradability. The same is true of GB 2562172A and WO 95 / 32272.

[0012] U.S. Patent No. 4,960,540A describes alkoxylated modified diamines. Polyalkoxylates end-capped with alkyl groups are modified with, for example, acrylic acid or n-butyrolactone, and then coupled to diamines to form bis-amide structures. However, unlike the polymers of the present invention, these unmodified diamines do not contain secondary amino groups. Furthermore, no ester groups are introduced, and U.S. Patent No. 4,960,540A makes no mention of how the biodegradability of polymers based on polyalkyleneimines and polyamines containing primary and secondary amino groups can be enhanced.

[0013] WO2012030600A discloses a one-pot reaction resulting in a random structure in which caprolactone, propylene oxide, and ethylene oxide are bonded to polyethyleneimine. Therefore, WO201203600A does not describe a modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine in which more than 50% of the primary and / or secondary amino groups are reacted with lactones and / or hydroxycarbon acids to form amide bonds, thereby improving the biodegradability of the polymer. The only claim made about the resulting polymer is its use as an oilfield demulsifier.

[0014] WO 2021165468A describes modified (homo-)polyalkyleneimines and polyamines that exhibit higher biodegradation than known compounds. These alkoxylated polymers are further modified with lactones / hydroxycarbonates, resulting in the formation of amide groups between the amino-containing core molecule and the polyalkoxylate chains in the shell, as well as the formation of additional ester groups within the polyalkoxylate chains themselves. However, the document only discloses that amide groups are obtained by modifying less than 50% of the secondary amino groups of the polyalkyleneimine or polyamine with lactones / hydroxycarbonates, resulting in limited biodegradation of these compounds.

[0015] The unpublished patent applications EP 21192170.5 and EP 21192169.7 also describe lactone / hydroxycarbon acid modified (homo-)polyalkyleneimines and polyamines that exhibit superior biodegradation compared to known compounds. However, the polymers described in these applications are different from the present polymer and are therefore not relevant for assessing inventive step. Summary of the Invention [Problem to be solved by the invention]

[0016] Although the publications cited above have already described many alkoxylated polyalkyleneimines and polyamines, including their preparation processes and their use in detergents, there remains a need for polymers that exhibit improved performance, such as improved oily / greasy stain removal and clay removal from laundry, while at the same time exhibiting improved biodegradation behavior. Such polymer properties would allow the design of detergent formulations with multiple advantages, particularly at very high concentrations and sustainability.

[0017] More specifically, there remains a strong need for new cleaning polymers that provide both primary (i.e., soil removal) and secondary (i.e., whiteness maintenance) cleaning benefits, ideally for both hydrophobic and hydrophilic stains. Additionally, there is a need for convenient processes for the preparation of modified alkoxylated polyalkyleneimines and polyamines. [Means for solving the problem]

[0018] Surprisingly, the present inventors have found that the primary and secondary amino groups of a polyalkyleneimine or polyamine can be extensively modified by reacting the polyalkyleneimine or polyamine with at least 3 moles of lactone and / or hydroxycarbon acid per mole of NH functional groups. In particular, no polyalkyleneimine or polyamine with a large amount of secondary amino groups, more than 50% of which have been modified by reacting with lactone and / or hydroxycarbon acid, has been identified to date. By reacting lactone and / or hydroxycarbon acid with the primary and secondary amino groups of the polyalkyleneimine or polyamine, an amide bond is formed between the lactone and / or hydroxycarbon acid and the polyalkyleneimine or polyamine. Concurrently, the amino groups migrate toward the primary hydroxy groups. The more primary and secondary amino groups of the polyalkyleneimine or polyamine are modified, the more amide groups are produced. Subsequent addition of a lactone and / or hydroxycarbon acid results in the formation of one or more ester groups attached to the amide-modified polyalkyleneimine or polyamine core. All terminal functional groups are then alkoxylated. The formation of both amide and ester groups results in improved biodegradability compared to alkoxylated polyalkyleneimines or polyamines that are not modified with a lactone / hydroxycarbon acid.

[0019] Furthermore, it has been found that the modified alkoxylated polyalkyleneimines and polyamines of the present invention exhibit exceptional cleaning performance, thus combining the advantages of improved biodegradability with excellent behavior as cleaning formulation ingredients.

[0020] Additionally, the polymers include hyperbranched polyethyleneimines, prepared via ring-opening polymerization of ethyleneimine, and predominantly linear polypropyleneimines (PPIs), prepared, for example, via polycondensation of di- and oligoamines, which have significant advantages over structural alternatives, i.e., linear PEI and dendritic PPIs, such as ease of synthesis (single-step vs. multi-step synthesis) and cost-effectiveness of production.

[0021] Therefore, the object of the present invention is to provide a method for producing a method for manufacturing a semiconductor device comprising the steps of: a) reacting 1) at least one polyalkyleneimine or at least one polyamine containing a total of a plurality of primary and secondary amino groups with 2) at least one first lactone (LA1) and / or at least one first hydroxycarbon acid (HA1) to obtain a first intermediate (I1), wherein 3 to 10 mol of lactone (LA1) and / or hydroxycarbon acid (HA1) are used per mol of NH functional groups of the polyalkyleneimine or polyamine; b) reacting the first intermediate (I1) with (i) at least one first alkylene oxide (AO1) or (ii) with a mixture of 1) at least one first alkylene oxide (AO1) and 2) at least one second lactone (LA2) and / or at least one second hydroxycarbonic acid (HA2) to obtain a second intermediate (I2), wherein at least 5.0 mol of first alkylene oxide (AO1) and, in the case of a mixture, additionally at least 1.0 mol of second lactone (LA2) and / or second hydroxycarbonic acid (HA2) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); c) optionally reacting the second intermediate (I2) with (i) at least one second alkylene oxide (AO2) or (ii) with a mixture of 1) at least one second alkylene oxide (AO2) and 2) at least one third lactone (LA3) and / or at least one third hydroxycarbon acid (HA3) to obtain a third intermediate (I3), wherein at least 5.0 mol of second alkylene oxide (AO2) and, in the case of a mixture, additionally at least 1.0 mol of third lactone (LA3) and / or third hydroxycarbon acid (HA3) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); d) optionally reacting the second intermediate (I2) or the third intermediate (I3) with at least one quaternary lactone (LA4) and / or at least one quaternary hydroxycarboxylic acid (HA4) to obtain a fourth intermediate (I4), wherein at least 1.0 mol of the quaternary lactone (LA4) and / or the quaternary hydroxycarboxylic acid (HA4) is used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); e) optionally reacting the second intermediate (I2), the third intermediate (I3) or the fourth intermediate (I4) with at least one C1-C18 alkylating or esterifying reagent to obtain a modified alkoxylated polyalkyleneimine or a modified alkoxylated polyamine; The object of the present invention is to provide a novel modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine which can be obtained by a process comprising: However, the modified alkoxylated polyalkyleneimine is not PEI800-3CL / NH-20EO / NH-2CL / NH (PEI800 is polyethyleneimine with a weight-average molecular weight (Mw) of 800 g / mol, CL is caprolactone, and EO is ethylene oxide), which is described as compound P5 in Table 5 of PCT / EP2022 / 072996. DETAILED DESCRIPTION OF THE INVENTION

[0022] The polymers of the present invention may be quaternized to non-permanently or permanently quaternize the N groups of the core of the polymers of the present invention.

[0023] In the following, any alkylene oxide will be collectively referred to as "AO", and sometimes ethylene oxide will be referred to as "EO", propylene oxide as "PO", and butylene oxide as "BuO". "PEO" is sometimes used herein to represent a polyethylene oxide homopolymer or a PEO-block within a larger polymer structure; similarly, "PPO" represents a polypropylene oxide homopolymer or a polypropylene oxide polymer block within a larger polymer structure.

[0024] In order to specifically distinguish such polyalkyleneimines or polyamines having side chains from "unmodified polyalkyleneimines / unmodified polyamines" that do not have such side chains, they may also be referred to as "modified polyalkyleneimines / modified polyamines" in the present disclosure, while the term "polyalkyleneimines / polyamines" as used herein inclusively encompasses both such polyalkyleneimines or polyamines that have side chains and / or are quaternized, and such polyalkyleneimines or polyamines that have neither side chains nor are quaternized.

[0025] Processes for making the polymers of the present invention are also part of the present invention.

[0026] The use of such polymers of the invention in all kinds of applications in which known polyamines, polyethyleneimines, polypropyleneimines and their alkoxylated derivatives are used is likewise encompassed by the present invention.

[0027] As well as compositions in which known polyamines, polyethyleneimines, polypropyleneimines, and alkoxylated derivatives thereof are used, compositions containing such polyalkyleneimines or polyamines of the invention in place of or in combination with such known compounds also form part of the present invention.

[0028] As used herein, the terms "polymer," "polymer of the invention," or "polymer of the invention" refer to modified alkoxylated polyalkylenimines and modified alkoxylated polyamines prepared as described below and / or in the appended claims. The above terms should be understood broadly, i.e., they also encompass the intermediate described as the first intermediate (I1) as well as non-alkoxylated (unmodified) polyalkylenimines and polyamines, such as alkoxylated polyalkylenimines and polyamines.

[0029] The subject of the present invention is therefore the following embodiments 1 to 31, which are defined herein below, further explained by means of further embodiments and further exemplified in the experimental section:

[0030] Embodiment 1 Steps a) to e) shown below: a) reacting 1) at least one polyalkyleneimine or at least one polyamine containing a total of a plurality of primary and secondary amino groups with 2) at least one first lactone (LA1) and / or at least one first hydroxycarbon acid (HA1) to obtain a first intermediate (I1), wherein 3 to 10 mol of lactone (LA1) and / or hydroxycarbon acid (HA1) are used per mol of NH functional groups of the polyalkyleneimine or polyamine; b) reacting the first intermediate (I1) with (i) at least one first alkylene oxide (AO1) or (ii) with a mixture of 1) at least one first alkylene oxide (AO1) and 2) at least one second lactone (LA2) and / or at least one second hydroxycarbonic acid (HA2) to obtain a second intermediate (I2), wherein at least 5.0 mol of first alkylene oxide (AO1) and, in the case of a mixture, additionally at least 1.0 mol of second lactone (LA2) and / or second hydroxycarbonic acid (HA2) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); c) optionally reacting the second intermediate (I2) with (i) at least one second alkylene oxide (AO2) or (ii) with a mixture of 1) at least one second alkylene oxide (AO2) and 2) at least one third lactone (LA3) and / or at least one third hydroxycarbon acid (HA3) to obtain a third intermediate (I3), wherein at least 5.0 mol of second alkylene oxide (AO2) and, in the case of a mixture, additionally at least 1.0 mol of third lactone (LA3) and / or third hydroxycarbon acid (HA3) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); d) optionally reacting the second intermediate (I2) or the third intermediate (I3) with at least one quaternary lactone (LA4) and / or at least one quaternary hydroxycarboxylic acid (HA4) to obtain a fourth intermediate (I4), wherein at least 1.0 mol of the quaternary lactone (LA4) and / or the quaternary hydroxycarboxylic acid (HA4) is used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); e) optionally reacting the second intermediate (I2), the third intermediate (I3) or the fourth intermediate (I4) with at least one C1-C18 alkylating or esterifying reagent to obtain a modified alkoxylated polyalkyleneimine or a modified alkoxylated polyamine; 1. A modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine obtainable by a process comprising: However, the modified alkoxylated polyalkyleneimine is not PEI800-3CL / NH-20EO / NH-2CL / NH (PEI800 is polyethyleneimine having a weight-average molecular weight (Mw) of 800 g / mol, CL is caprolactone, and EO is ethylene oxide), which is described as compound P5 in Table 5 of PCT / EP2022 / 072996 specification, but is a modified alkoxylated polyalkyleneimine or a modified alkoxylated polyamine.

[0031] Polyalkyleneimines are linear or (hyper)branched polymers containing primary, secondary, and optionally tertiary amino groups. Hyperbranched polyethyleneimines are typically formed by polymerizing ethyleneimine in the presence of an amine, which typically contains several primary, secondary, and tertiary amino groups and serves as an initiator for polymer formation. Predominantly linear polypropyleneimines (PPIs) are typically formed via polycondensation (also referred to as "polytransamination") of di- and oligoamines and typically contain only two primary (chain-terminal) amino groups and multiple secondary amino groups, but no tertiary amino groups. The polyalkyleneimines of the present invention are linear or hyperbranched, preferably hyperbranched, and are formed by a ring-opening process of alkyleneimine monomers, preferably ethyleneimine. Alternatively, polyethyleneimines synthesized by hydrolysis of polyoxazolines and exhibiting a completely linear structure can also be used within the scope of the present invention. Also included within the scope of the present invention are linear polyalkyleneimines, more specifically polypropyleneimine homo- and copolymers prepared by the polycondensation of di- and oligoamines, preferably the (co)polymerization of 1,3-propylenediamine, to produce polypropyleneimine homo- and copolymers (e.g., WO2014131649A1 and WO2021254929A1). The term "hyperbranched" as used herein in connection with alkoxylated polyalkyleneimines refers to the definition known to those skilled in the art. Hyperbranched polymers include overall polydisperse branched macromolecules, preferably prepared in a single synthetic polymerization step that forms incomplete branches in a non-deterministic manner. Meanwhile, many preferred synthetic strategies for preparing hyperbranched polymers with low polydispersity are also known in the art. These are typically characterized by their degree of branching (DB). The imine-based hyperbranched polymers of the present invention contain tertiary, secondary, and primary amines prior to alkoxylation, where the primary amines can be converted, by way of example, to secondary and / or tertiary amines, and the secondary amines can be converted, for example, to tertiary amines, thereby producing the same imperfectly branched structure.The term "degree of branching (DB)" has the same meaning as known in the field of branched polymers and is used herein with the same meaning. A preferred definition is described, for example, in C.J. Hawker, R. Lee, and J.M.J. Frechet (1991), "The One-Step Synthesis of Hyperbranched Dendritic Polyesters," J.Am.Chem.Soc., 113:4583, which is incorporated herein by reference in its entirety.

[0032] The term "polyamine" as used herein includes any structure within the scope of formula (I) described below that is not included in the definition of polyalkyleneimine defined above. Thus, the term "polyamine" encompasses saturated and unsaturated, linear, cyclic, or branched organic compounds having a defined molecular weight, containing at least two terminal primary amino groups and at least one secondary amino group located between the terminal amino groups. Depending on the chain length, polyamines range in color from colorless to yellowish, and are either liquid or solid at room temperature. Preferably, the polyamine used in step a) does not contain tertiary amino groups. Representative examples of such polyamines include N-(2-aminoethyl)-1,3-propylenediamine (N3-amine), N,N'-bis-(3-aminopropyl)-ethylenediamine (N4-amine), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), diethylenetriamine (DETA), N-(3-aminopropyl)-diethylenetriamine (TETA), and N-(3-aminopropyl)-triethylenetetramine (TEPA).

[0033] The term "plurality," as used herein, is defined as three or more than three. When referring to the total amount of amino groups, this means that the polyalkyleneimines and polyamines used to prepare the polymers of the present invention contain at least 3, 4, 5, 6, 7, 8, 9, or more amino groups (i.e., the sum of all primary, secondary, and tertiary amino groups). Specifically, this means at least 2, 3, 4, 5, 6, 7, 8, 9, or more primary amino groups and at least 1, 2, 3, 4, 5, 6, 7, 8, 9, or more secondary amino groups.

[0034] The expression / term "modified" within the meaning of the present invention relates to the presence of (predominantly) hydrophobic oligoester or polyester blocks based on lactones and / or hydroxycarbon acids, such as caprolactone and / or lactic acid, or a combination of such lactones or hydroxycarbon acids with alkylene oxides, such as ethylene oxide and / or propylene oxide, attached to the inventive polymer, thereby forming a modified compound. The presence of alkylene oxides within or adjacent to the (predominantly) hydrophobic polyester blocks confers amphiphilic properties, which result in the inventive polymers exhibiting exceptional cleaning properties when used in detergent applications. Such modified inventive polymers are also referred to as "alkoxylated" and / or "modified and alkoxylated."

[0035] In the context of the present invention, the term "NH functionality" is defined as follows: a primary amino group (-NH) has an NH functionality of two, a secondary amino group has an NH functionality of only one, and therefore a tertiary amino group does not have a reactive NH functionality.

[0036] As used herein, "mixture" refers to a substantially uniform distribution of alkylene oxides (AO1, AO2, or AO3) and lactones (LA1, LA2, LA3, and LA4) and / or hydroxycarbon acids (HA1, HA2, HA3, and HA4), as further described below, while the material includes solid, liquid, or gaseous forms and even any mixtures thereof.

[0037] The term "3 to 10 moles of a first lactone (LA1) and / or at least one first hydroxycarboxylic acid (HA1)" means that preferably 3.5 to 8, more preferably 4 to 6, and even more preferably 4.5 to 5 moles of the above-mentioned substances can be used per mole of NH functional groups of the polyalkyleneimine or polyamine.

[0038] "At least 5 moles of primary / secondary alkylene oxide" means that at least 6, at least 7, at least 10, or at least 15 moles can be used. Similarly, the term "at least 1 mole of secondary, tertiary, or quaternary lactone and / or hydroxycarbon acid" as used herein means that at least 1.5, at least 2, at least 2.5, at least 3, at least 4, or at least 5 moles of the above-mentioned material can be used per mole of NH functionality of the polyalkyleneimine or polyamine.

[0039] As used herein, "C1-C18 alkylating or esterifying reagent" means that the alkylating reagent preferably has 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and most preferably 4 to 8 carbon atoms. Similarly, the esterifying reagent preferably has 2 to 15 carbon atoms, more preferably 3 to 10 carbon atoms, and most preferably 4 to 8 carbon atoms.

[0040] For the purposes of this invention, the definition of a "C1-C18 alkylating or esterifying agent" used to describe a hydrocarbon substituent on a nitrogen, carbon, or oxygen atom of the polymer of the invention means that the substituent (group) comprises an alkyl or alkylene group having 1 to 18 carbon atoms. This group may be either linear or branched, optionally cyclic, and saturated or unsaturated. Alkyl or alkylene groups containing both cyclic and linear components are also included in this definition. The same applies to other alkyl or alkylene groups, such as C1-C4 alkyl or alkylene groups. Examples of alkyl groups are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl. More specifically, the definition of C1-C18-alkylating or esterifying reagent includes typical alkylating reagents, such as alkyl halides and / or carbon acids and / or carbon acid derivatives, such as carbon acid anhydrides, carbon acid esters or carbon acid halides, which are unsubstituted or at least monosubstituted C1-C 18 -Alkyl, C7-C 18 -Aralkyl, -(CO)-C1-C 18 -Alkyl, -(CO)-C2-C 18 -alkenyl and / or -(CO)-C 18 -aralkyl, where the substituent is selected from -COOH or a salt thereof. Carbon anhydrides, specifically succinic anhydrides substituted with alkyl chains, are preferred, examples of which include C6 to C18-substituted succinic anhydrides. Commercially available examples include Pentasize 8 and Pentasize 68 (C18 alkenyl succinic anhydride or C16 / C18 alkenyl succinic anhydride, respectively, from Trigon Chemie GmbH).

[0041] Other typical abbreviations such as "C2-C12 alkylene oxide" have their usual meanings as used in the organic chemistry art.

[0042] Embodiment 2 2. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to embodiment 1, wherein at least one polyalkyleneimine or at least one polyamine comprises at least 2, 3, 4, 5, 6, 7, 8, 9 or more primary amino groups, and wherein more than 90%, preferably at least 95%, and more preferably at least 99%, of the primary amino groups in the modified alkoxylated polyalkyleneimine or alkoxylated polyamine have reacted with a first lactone (LA1) and / or a first hydroxycarbon acid (HA1) to form an amide bond.

[0043] Embodiment 3 3. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to embodiment 1 or 2, wherein at least one polyalkyleneimine or at least one polyamine comprises at least 1, 2, 3, 4, 5, 6, 7, 8, 9 or more secondary amino groups, and wherein more than 50%, preferably at least 75%, and more preferably at least 90%, of the secondary amino groups in the modified alkoxylated polyalkyleneimine or alkoxylated polyamine have reacted with a first lactone (LA1) and / or a first hydroxycarbon acid (HA1) to form an amide bond.

[0044] In principle, both the polyalkyleneimine and the polyamine may be entirely linear or branched. The polyalkyleneimines and polyamines used to prepare the polymers of the present invention contain a total of a plurality of primary and secondary amino groups.

[0045] As a result, the polymers of the present invention have a basic skeleton (backbone, before modification / alkoxylation) (designated R) comprising primary, secondary and optionally tertiary nitrogen atoms linked by i) alkylene groups or ii) ether alkyl units according to the general formula (III): - primary amino moieties are located in the main chain of the basic skeleton as well as at the end of the side chain, the hydrogen atoms of which can then be replaced by the side chain when modified with alkylene oxides and / or lactones / hydroxy acids: [ka] - the secondary amino moiety can be replaced by a side chain when its hydrogen atom is subsequently modified with alkylene oxides and / or lactones / hydroxy acids: [ka] - Tertiary amino moieties branch the main chain and side chains: [ka]

[0046] For completeness of description, variable B may be either i) a fragment that represents further branching of the polyalkyleneimine or polyamine backbone of the compound according to general formula (I) and includes at least one fragment containing at least one further amino moiety with a degree of branching of second order, third order or even higher, or ii) a fragment containing the same or different C1-C 18 - represents an alkyl unit. The degree of branching can be expressed, for example, as follows: 1 H-NMR or preferably 13 It can be determined by NMR spectroscopy such as C-NMR spectroscopy.

[0047] In a preferred embodiment, the polyalkyleneimine and / or polyamine of the present invention comprises a total of a plurality of primary, secondary and optionally tertiary amino groups, while the alkoxylated polyalkyleneimine / polyamine of the modified alkoxylated polyalkyleneimine / modified alkoxylated polyamine comprises only tertiary amino groups with amide groups formed by reaction with a lactone and / or hydroxycarbon acid in step (a).

[0048] The amine numbers of primary, secondary and tertiary amines are determined in accordance with the DIN EN ISO 9702 standard.

[0049] Embodiment 4 The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 3, wherein the alkylene oxides AO1 and AO2 are independently C2 to C 12 - Alkylene oxides, preferably alkoxylated polyalkyleneimines or alkoxylated polyamines, selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide.

[0050] In a preferred embodiment, the alkylene oxides AO1 and AO2 used successively in the synthesis of the modified alkoxylated polyalkyleneimine or polyamine are different from each other.

[0051] For the sake of clarity in this embodiment, this means that AO1 and AO2 may be the same as or different from each other.

[0052] AO1 is preferably ethylene oxide or a mixture of predominantly ethylene oxide with propylene oxide and / or butylene oxide.

[0053] AO2 is preferably propylene oxide or a mixture of predominantly propylene oxide with ethylene oxide and / or butylene oxide.

[0054] Embodiment 5 The polyalkyleneimine or polyamine of step a) is of formula (I): [ka] where the variables are defined as follows: R may be the same or different, i) linear or branched C2-C 12 an alkylene group or ii) a group of the following formula (III): [ka] where the variables are defined as follows: R 10 , R 11 , R 12 represent the same or different linear or branched C2-C6 alkylene groups, d is an integer ranging from 0 to 50. represents an ether alkyl unit of the formula: B is (i) the continuation of said polyalkyleneimine or polyamine by branching; and / or (ii) C1 to C, which may be the same or different 18 - alkyl; represents y is an integer with a value of at least 1, 5. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of embodiments 1 to 4, wherein z is an integer having a value from 0 to 150.

[0055] Embodiment 6 The modified alkoxylated polyalkyleneimine or alkoxylated polyamine may be represented by formula (Ia) and / or (Ib): [ka] (wherein the variables are defined as follows: The dotted line represents the bond to the remainder of the modified alkoxylated polyalkyleneimine or alkoxylated polyamine; R is as defined above; E1 and E2 are of formula (IIa): -[C(=O)-R1-O]m-[(C(=O)-R1-O)n-mix-(R2-O)o-mix-(R3-O)q]-R4 (IIa) where -mix- defines that the flanking units are randomly distributed with respect to one another; m is an integer having a value of 1 to 20, n is an integer having a value of 0 to 20, o is an integer having a value of 5 to 150, q is 0 or an integer having a value of 5 to 150, and the sum of m and n (m+n) is at least 3; R1 is a linear or branched C2-C 10 -alkylene group, more preferably a linear or branched C2-C5 alkylene group; R2 is a linear or branched C2-C 12 - an alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-ethylene; R3 is a linear or branched C2-C 12 - an alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-propylene and / or 1,2-butylene; R4 is hydrogen, unsubstituted or at least monosubstituted C1-C 18 -Alkyl, C7-C 18 -Aralkyl, -(CO)-C1-C 18 -Alkyl, -(CO)-C2-C 18 -alkenyl and / or -(CO)-C 18 -aralkyl, wherein the substituent is selected from -COOH or a salt thereof, more preferably hydrogen, methyl, ethyl or monosubstituted -(CO)-C-C 18 -alkenyl, most preferably hydrogen, R2 and R3 are not identical and represent residues according to The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 5.

[0056] Alternatively or additionally, the modified alkoxylated polyalkyleneimine or alkoxylated polyamine comprises structural elements according to formula (Ia) and / or (Ib) as set forth above, wherein R in formula (Ia) and (Ib) is as defined above; E1 and E2 are each a group represented by the formula (II): -[X]-[Y]-[Z] (II) (In the formula, X represents a segment according to formula (IIIa): -[C(=O)-R1-O]m- (IIIa) Y represents a segment according to formula (IIIb): -[(C(=O)-R1-O)n1-(R2-O)o1-(R3-O)p1]q1-[(C(=O)-R1-O)n2-(R3-O)p2-(R2-O)o2]q2-[(C(=O)-R1-O)n3-(R2-O)o3- ]q3-[(C(=O)-R1-O)n4-(R3-O)p3-]q4-[(R2-O)o4-(R3-O)p4]q5-[(C(=O)-R1-O)n5]q6-[(R2-O)o5]q7-[(R3-O)p5]q8- (IIIb) Z is hydrogen, unsubstituted or at least monosubstituted C1-C 18 -Alkyl, C7-C 18 -Aralkyl, -(CO)-C1-C 18 -Alkyl, -(CO)-C2-C 18 -alkenyl and / or -(CO)-C 18 -aralkyl, wherein the substituent is selected from -COOH or a salt thereof, more preferably hydrogen, methyl, ethyl or monosubstituted -(CO)-C-C 18 -alkenyl, most preferably hydrogen, m is an integer ranging from 1 to 20; n1 to n5 each independently represent an integer having a value ranging from 0 to 20, o1 to o5 each independently represent an integer having a value ranging from 0 to 150, p1 to p5 each independently represent an integer having a value in the range of 0 to 150, q1 to q8 each independently represent an integer having a value ranging from 0 to 150, The subunits q1 to q8 in segment Y are randomly distributed with respect to each other, the total number of repeat units -(C(=O)-R1-O)- in segments X and Y is on average at least 3 (m+n1×q1+n2×q2+n3×q3+n4×q4+n5×q6≧3); the total number of repeat units -(R2-O)- in segment Y is at least 5 (o1×q1+o2×q2+o3×q3+o4×q5+o5×q7≧5); R1 represents a linear or branched C2 to C10 alkylene group, more preferably a linear or branched C2 to C5 alkylene group; R2 represents a linear or branched C2-C12 alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-ethylene; R3 represents a linear or branched C2-C12 alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-propylene and / or 1,2-butylene; R2 and R3 are not identical).

[0057] Embodiment 7 The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 6, i) steps a) to e) are all carried out as a single-step reaction, optionally in the presence of a catalyst; and / or ii) A modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine, wherein the weight average molecular weight (Mw) of the polyalkyleneimine or polyamine used in step a) is in the range of 50 to 20,000 g / mol, preferably in the range of 150 to 10,000 g / mol, and more preferably in the range of 200 to 5,000 g / mol.

[0058] Those skilled in the art will recognize the respective weight average molecular weights (M W) can be determined / measured, for example, by size exclusion chromatography (such as GPC, e.g., in combination with light scattering). Preferably, M W The value of is determined according to the following method: OECD TG 118 (1996), i.e. in detail OECD (1996), Test No. 118: Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris, which is also available on the Internet, for example, at https: / / doi.org / 10.1787 / 9789264069848-en.

[0059] The molecular weight of the polyalkyleneimine or polyamine starting material can be determined by gel permeation chromatography (GPC). Measurements can be performed using a combination of three columns: HFIP-LG Guard, PL HFIP GEL, and PL HFIP GEL. Elution can be performed with hexafluoroisopropanol and 0.05 wt% potassium trifluoroacetate at a constant flow rate of 1 mL / min. The injected sample can be filtered through a Millipore Millex FG (0.2 μm) prefilter, and 50 μL can be injected at a concentration of 1.5 mg / mL (diluted with eluent). The effluent can be monitored at λ = 230 and 280 nm using a DRI Agilent 1100 UV detector. Calibration can be performed using PMMA standards (PSS, Mainz, Germany) with molecular weights ranging from 800 to 2,200,000 g / mol. Values ​​outside the calibration range can be extrapolated.

[0060] The molecular weight of the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine can be determined by gel permeation chromatography (GPC). Measurements can be performed using a combination of two columns (styrene-divinylbenzene and polyester copolymer, both 25 cm long and 4.6 mm in diameter) and 0.05 wt% potassium trifluoroacetate in hexafluoroisopropanol as the eluent. The molecular weight can be obtained using an RI detector and a PEO standard (Polymer Laboratories / Agilent, USA) for calibration. Furthermore, the absolute molecular weight can be determined by multi-angle light scattering (MALLS).

[0061] For completeness of explanation, when a single organic compound, such as N-(2-aminoethyl)-1,3-propylenediamine (N3-amine), N,N'-bis-(3-aminopropyl)-ethylenediamine (N4-amine), dipropylenetriamine (DPTA), tripropylenetetramine (TPTA), diethylenetriamine (DETA), N-(3-aminopropyl)-diethylenetriamine (TETA), and N-(3-aminopropyl)-triethylenetetramine (TEPA), is used as the polyamine in step a) of the inventive process, the weight average molecular weight (Mw) is equal to the number average molecular weight (Mn). Therefore, Mw and Mn are equal to the molar mass.

[0062] "Mw" is the weight average molecular weight, and "Mn" is the number average molecular weight. The values ​​of Mw and / or Mn can be determined as described later in the experimental section.

[0063] The molar mass distribution Mw / Mn obtained by GPC is equal to the polydispersity index (PDI), which is unitless ([g / mol / g / mol]).

[0064] Embodiment 8 8. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of embodiments 1 to 7, wherein the modified alkoxylated polyalkyleneimine or alkoxylated polyamine has a biodegradability according to OECD standard 301F of at least 20%, preferably at least 40%, more preferably at least 60% within 56 days, preferably within 28 days.

[0065] For the purposes of this invention, the aerobic biodegradability in wastewater according to OECD 301F is expressed as a percentage of the theoretical oxygen demand (ThOD, determined by elemental analysis of the target compound) required for the complete biodegradation of the polymer sample. This means that the amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for the amount taken up by a parallel blank inoculum) is expressed as a percentage of ThOD. The values ​​obtained are preferably measured in triplicate using the manometric respirometry method of OECD 301F. The oxygen consumption is determined by measuring the pressure change in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Details of the tests performed are given below in the experimental section.

[0066] The present invention provides modified polyalkyleneimines and modified polyamines that are alkoxylated, and in particular, the alkoxy chains, the amide and ester groups incorporated between the polyalkyleneimine or polyamine backbone and the alkoxy chain, and, when a mixture is applied in steps b) and / or c), the ester groups incorporated within the alkoxy chains, contribute significantly to the biodegradability value. Therefore, the composite core-shell products (i.e., modified alkoxylated polyakyleneimines and modified alkoxylated polyamines) exhibit high biodegradability. Furthermore, these inventive polymers also exhibit cleaning performance comparable to that of current products.

[0067] Embodiment 9 The modified alkoxylated polyalkyleneimine of any one of embodiments 5-7, wherein each variable is as defined below: R is ethylene and / or propylene, preferably ethylene; The sum of y+z is an integer having a value in the range of 4-200, preferably in the range of 10-150.

[0068] Preferably, the weight average molecular weight (Mn) of the polyalkyleneimine used in the process is in the range of 200 to 10000 g / mol, more preferably in the range of 400 to 6000 g / mol, most preferably in the range of 600 to 3000 g / mol.

[0069] Embodiment 10 The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 9, i) in step a), the first lactone (LA1) is caprolactone or lactide, and / or ii) in step a), the first hydroxycarboxylic acid (HA1) is lactic acid or glycolic acid, and / or iii) in steps b)(i) and (ii), the first alkylene oxide (AO1) is ethylene oxide or a mixture of ethylene oxide and propylene oxide or a mixture of ethylene oxide and butylene oxide, and / or in step b)(ii), the second lactone (LA2) is caprolactone or lactide, and / or the second hydroxycarboxylic acid (HA2) is lactic acid or glycolic acid, and / or iv) in steps c)(i) and (ii), the second alkylene oxide (AO2) is propylene oxide or a mixture of propylene oxide and ethylene oxide or a mixture of propylene oxide and butylene oxide, and / or in step c)(ii), the third lactone (LA3) is caprolactone or lactide, and / or the third hydroxycarboxylic acid (HA3) is lactic acid or glycolic acid, and / or v) in step d), the fourth lactone (LA4) is caprolactone or lactide, and / or vi) In step d), the quaternary hydroxycarboxylic acid (HA4) is lactic acid or glycolic acid; Modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines.

[0070] The polymers of the present invention contain side chains attached to nitrogen atoms of the polymer (modified alkoxy chains). These side chains are composed of lactones and / or hydroxycarbon acids and C2-C22 alkylene oxides. Typically, the side chains contain at least one lactone (LA) and / or at least one hydroxyacid (HA) and at least one alkylene oxide (AO). The reaction for preparing a side chain containing LA and / or HA and AO is typically carried out by reacting a polyalkyleneimine or polyamine with at least one LA and / or HA (at least 3 moles of LA and / or HA per mole of NH functional group), where LA1 or HA1 is first added to the polyalkyleneimine or polyamine. AO1 or a mixture of AO1 with LA2 and / or HA2 is then added. Optionally, AO2 or a mixture of AO2 with LA3 and / or HA3 is then added. In the next step, optionally, LA4 and / or HA4 are added, and in the final step, optionally, a C1-C18 alkylating reagent or an esterifying reagent is added.

[0071] According to steps a) through e) of the process of the present invention and as described above, the block structure is formed by the stepwise addition of monomers.

[0072] Furthermore, with regard to steps b) and c), if a mixture of AO with LA and / or HA is used and / or if these components are added at least immediately after each other, preferably with as short a time difference as possible, before the conversion of all monomers is complete, additional random copolymer sequences are formed within the block copolymer chains attached to the nitrogen atoms of the main chain.

[0073] Preferably, the side chains contain more than 5 AO units per NH functional group of the polymer of the invention, more preferably more than 10, and even more preferably more than 15. Furthermore, the side chains contain at least 3 LA and / or HA units per NH functional group. All such numbers are "average" numbers, i.e., they refer to the average number of such units per NH functional group, calculated based on the total number of NH functional groups in the polyalkyleneimine or polyamine.

[0074] It should be further noted that in connection with the process according to the present invention, each primary amino moiety of the main chain that is first reacted with at least one lactone and / or at least one hydroxyl carbon acid is converted to an amide moiety, with one of the two original hydrogen atoms of each primary amino moiety being replaced by a fragment derived from the respective lactone or hydroxyl carbon acid, while the second hydrogen atom of the main chain primary amino moiety is not replaced by this reaction. Furthermore, such second hydrogen atom of the main chain primary amino moiety is also not replaced in further reaction steps, e.g., further reactions with AO, LA, and / or HA.

[0075] The reactions that produce the polymers of the present invention are statistical reactions. That is, there is never a single, chemically defined compound; instead, the polymers of the present invention are always a mixture of slightly different structures, all resulting from the same reaction occurring within a single reaction space. These structural differences clearly result from the fact that not all functional units react in exactly the same way or at the same rate, particularly because the chemical reactivity of the functional units, primarily the NH functional group in this context, varies depending on its environment. That is, primary amino groups react differently than secondary amines (e.g., with lactones and / or hydroxycarboxylic acids, as discussed above), and the chemical environment of this group may differ depending on the monomer used. As a result, slightly different structures exist overall, and it should be emphasized that any polymer of the present invention as defined in the various embodiments, including numbered embodiments 1-31, and exemplified in the Examples, will never be a single compound, but will always be a mixture of slightly different compounds with a statistical distribution. Because there are no significant differences in the reactivities of these groups, the differences are relatively small. Therefore, defining the polymers of the present invention in terms of their monomers is a practical way of defining their structure. Likewise, defining the side chain composition in terms of average numbers (including, in this and subsequent embodiments, the variable defined based on the number of NH functional groups present in the polyalkyleneimine or polyamine; the number of such functional groups is itself an average number obtained from this actual mixture) is a useful way of defining the overall composition of any mixture defined herein as "a modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine of the present invention."

[0076] Therefore, unless otherwise specified, the values, ranges, and ratios described herein for NH functionality and molecular weight (Mn) refer to number-average values ​​in the case of a polymer mixture (polyalkyleneimine or polyamine), and not to the specified organic polyamine starting material used in step a) of the present invention. This is because the polymer of the present invention comprises several polymeric compounds, each with a slightly different chemical structure, and the "polyalkyleneimine or polyamine" defining this mixture is the result of its preparation method. As is known in polymer science, the weight-average molecular weight (Mw) is then a measure of the (heterogeneity) of the mixture of different chemical species in the "polyalkyleneimine or polyamine."

[0077] For completeness of explanation, when a defined (pure) organic polyamine is used in step a) of the process of the present invention, this implies that the weight average molecular weight (Mw) is equal to the number average molecular weight (Mn), and therefore Mw and Mn are then equal to their molar mass.

[0078] Suitable lactones and / or hydroxycarbon acids may be aliphatic, alicyclic or aromatic.

[0079] Particularly suitable aromatic hydroxycarbon acids are hydroxy-substituted benzoic and naphthalene carboxylic acids, such as p-hydroxyethylbenzoic acid and 2-hydroxynaphthalene-6-carboxylic acid. Aliphatic hydroxycarbon acids, particularly those with a hydroxyl group at the ω-position, and their lactones are preferred. Generally, aliphatic hydroxycarbon acids have 1 to 22 alkylene groups, preferably 2 to 10 alkylene groups, and more preferably 2 to 5 alkylene groups. The alkylene groups may be linear or branched. Examples include glycolic acid, lactic acid and its lactide, gamma-hydroxybutyric acid and gamma-butyrolactone, delta-hydroxyvaleric acid and gamma- and delta-valerolactone, epsilon-hydroxycaproic acid and epsilon-caprolactone, 12-hydroxystearic acid and ricinoleic acid, and mixtures, particularly mixtures containing naturally occurring acids. Preferably, glycolic acid, lactic acid, epsilon-caprolactone or lactide or mixtures thereof are used, more preferably epsilon-caprolactone.

[0080] For clarity of this embodiment, LA1, LA2, LA3 and LA4 may be the same or different from each other.

[0081] For clarity of this embodiment, HA1, HA2, HA3 and HA4 may be the same or different from each other.

[0082] Embodiment 11 The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 10, i) in steps b)(i), b)(ii), c)(i) and / or c)(ii) a total of 5 to 100 mol, preferably 10 to 80 mol, more preferably 12 to 60 mol, most preferably 15 to 40 mol of alkylene oxide (AO1 and / or AO2) is used per mole of NH functionality of the polyalkyleneimine or polyamine, and more than 70 mol %, preferably more than 90 mol % of the alkylene oxide is ethylene oxide; and / or ii) in steps a), b)(ii), c)(ii) and / or d), a total of 3 to 10 mol, preferably 3 to 7 mol, more preferably 3 to 6 mol of lactone (LA1, LA2, LA3 and / or LA4) and / or 3 to 20 mol, preferably 3 to 15 mol, more preferably 3 to 10 mol of hydroxycarbon acid (HA1, HA2, HA3 and / or HA4) is used per mol of NH functional group of the polyalkyleneimine or polyamine; Modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines.

[0083] It should be noted that the alkylene oxide used in preparing the polymers of the present invention may be derived from fossil or non-fossil carbon sources, or even a mixture of the above. Preferably, the amount of non-fossil carbon atoms in the alkoxy side chain is at least 10%, at least 20%, at least 40%, at least 70%, at least 95%, or contains only non-fossil carbon atoms. Those skilled in the art are familiar with commercially available alkylene oxide products made from non-fossil carbon sources (such products are often marketed as sustainable, renewable, or bio-based). For example, Croda International (Snaith, UK) markets bioethanol-based ethylene oxide and related products under the ECO Range. Furthermore, methods for preparing bio-based propylene oxide are also known (see Abraham, DS, "Production of propylene oxide from propylene glycol," Master's Thesis University of Missouri-Columbia (2007) (p. 75)).

[0084] Embodiment 12 12. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 11, i) in steps b)(i), b)(ii), c)(i) and / or c)(ii), a total of 25 to 120 mol, preferably 30 to 100 mol, more preferably 35 to 90 mol, most preferably 40 to 80 mol of alkylene oxide (AO1 and / or AO2) is used per mole of NH functional groups of the polyalkyleneimine or polyamine, and less than 70 mol %, preferably less than 60 mol % of the alkylene oxide is ethylene oxide; ii) in steps a), b)(ii), c)(ii) and / or d), a total of 3 to 10 mol, preferably 3 to 8 mol, more preferably 3 to 7 mol of lactone (LA1, LA2, LA3 and / or LA4) and / or 3 to 20 mol, preferably 3 to 15 mol, more preferably 3 to 10 mol of hydroxycarbon acid (HA1, HA2, HA3 and / or HA4) is used per mol of NH functional group of the polyalkyleneimine or polyamine, Modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines.

[0085] Embodiment 13 13. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 12, (1) in step a) the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 500 g / mol to 1000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; in step b)(i) 15 to 40 mol of ethylene oxide is used per mol of NH functional group of the polyalkyleneimine; or (2) in step a) the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 500 g / mol to 1000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; in step b)(ii) a mixture of 15 to 40 mol of ethylene oxide and 1 to 3 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; or (3) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 1500 g / mol to 2500 g / mol, and 3 to 5 mol of caprolactone are used per mol of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide are used per mol of NH functional group of the polyalkyleneimine; in step c)(i), 15 to 40 mol of propylene oxide are used per mol of NH functional group of the polyalkyleneimine; the molar ratio of EO:PO is in the range of 1.5:1 to 1:1.5; or (4) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 4000 g / mol to 6000 g / mol, and 3 to 5 moles of caprolactone are used per mole of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 moles of ethylene oxide are used per mole of NH functional group of the polyalkyleneimine; in step c)(i), 15 to 40 moles of propylene oxide are used per mole of NH functional group of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.5; or (5) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 1500 g / mol to 2500 g / mol, and 3 to 5 mol of caprolactone are used per mol of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide are used per mol of NH functional group of the polyalkyleneimine; in step c)(ii), a mixture of 15 to 40 mol of propylene oxide and 1 to 3 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.5; or (6) In step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 4000 g / mol to 6000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide is used per mol of NH functional group of the polyalkyleneimine; in step c)(ii), a mixture of 15 to 40 mol of propylene oxide and 1 to 3 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.5. Modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines.

[0086] Embodiment 14 14. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of embodiments 10 to 13, wherein at least 50%, preferably at least 60%, most preferably at least 80%, even more preferably at least 90, and most preferably at least 95% of all side chains attached to NH functional groups of one particular modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine have the same structural order, in the sense of the structural order determined by the order of a given alkylene oxide, lactone and / or hydroxycarbonate used in the stepwise synthesis of the polymer of the invention.

[0087] Although not wishing to be bound by the following explanation, there is evidence to explain the structure of the resulting modified alkoxylated polyalkylenimine or modified alkoxylated polyamine: In order to create such structural ordering of the side chains in the target reaction, and therefore to prepare a specific inventive polymer, the reaction of highly reactive chemical species is necessarily employed at each step of the inventive process, which, under suitable conditions, can lead to almost complete, or even "essentially complete," conversion rates of nearly 100%, if not 100%. Based on this, the statistical deviation in the composition of a mixture of the target "modified alkoxylated polyalkylenimine or modified alkoxylated polyamine" is not very large, i.e., the resulting structural ordering of the side chains is not very variable. In other words, the existence of such variation is generally accepted, and this is a reliable assumption that can, in principle, be proven by sophisticated, and therefore time-consuming and expensive, analytical means such as multidimensional NMR analysis. Therefore, it is clear that a "specific modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine" will not be a "single compound with a clearly defined chemical structure," but will consist of a) a mixture of compounds with slight differences. Such differences are due to b) slight variations that may already exist in the structures of the compounds constituting the "(unmodified) polyalkyleneimine or polyamine" used in the further modification steps described above, and d) c) slight variations in the structural order of the side chains resulting from bonding via multi-step reactions, which in turn are due to e) variations in the chemical reactivity of the NH functional groups and the subsequently formed OH functional groups, f) slight differences in reactivity resulting from the structures of the AO, LA, and HA used, and g) reactivity of the AO, LA, and HA to slight differences in the reactivity of the NH functional groups and the subsequently formed OH functional groups, and h) slight heterogeneity that occurs in commercial-scale processes.All of these factors a) through h), to name just a few important examples, result in a "particular modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine" that is not a single specific compound but is in fact a mixture of compounds having slight variations but a very similar overall chemical structure; therefore, such structure is best characterized by the average number of variables and the ratio of the amount of predominant structural order.

[0088] Furthermore, experimental evidence obtained by the present inventors, not included in the Examples section of this specification, suggests that transesterification of lactone and / or hydroxycarbon acid-derived moieties may occur within the alkoxy side chain. This reaction was observed only for lactones and / or hydroxycarbon acids that had reacted with each other and / or with AO to form ester bonds, but not for those directly attached to the NH functionality of the polyalkyleneimine to form amide bonds. This transesterification was observed when lactones and / or hydroxycarbon acids were first reacted with each other and / or with AO to form ester bonds, followed by reaction with alkylene oxides, such as ethylene oxide and / or propylene oxide. This observation appears consistent with the fact that the reaction with alkylene oxides occurs under high pressure, high temperature, and strongly alkaline conditions. Such transesterification may be another factor, in addition to the parameters mentioned above, that contributes to uncertainty regarding the final structure of the polymers of this invention.

[0089] Embodiment 15 15. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of embodiments 1 to 14, which is further modified by quaternization using standard means, such as protonation by pH adjustment or permanent quaternization by standard means, e.g., alkylation using standard reactants, which alkylation preferably alkylates all nitrogen atoms in the inventive polymer to a degree of 5 to 100, preferably 5 to 95, more preferably 50 to 95, and even more preferably 75 to 95 percent.

[0090] Generally, it is well known to those skilled in the art that the alkoxylated polyalkylenimines or alkoxylated polyamines can be quaternized using standard means, since the structure of the alkoxylated polyalkylenimines or alkoxylated polyamines is, in principle, chemically similar to known structures of this general type, and it is known that these known structures can be modified by quaternization.

[0091] It is apparent that the structures described herein as modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines can be quaternized as well.

[0092] The preferred degree of quaternization is up to 100%, in particular 5 to 95%. Quaternization is preferably carried out by introducing C1-C22 alkyl groups, C1-C4 alkyl groups and / or C7-C22 aralkyl groups, and the reaction can be carried out in a conventional manner using the corresponding alkyl halides and dialkyl sulfates.

[0093] Quaternization can be advantageous in tailoring the polymer of the present invention to the particular composition, such as the laundry composition, in which it is intended to be used, to enhance formulation compatibility and / or phase stability.

[0094] The quaternization of the polymers of the invention is preferably achieved by introducing C1-C22 alkylaryl groups, C1-C4 alkyl groups and / or C7-C22 aralkyl groups, aryl groups or alkylaryl groups, and can be carried out in a conventional manner by reaction with the corresponding alkyl halides, aralkyl halides and dialkyl sulfates, as described, for example, in WO 09 / 060059.

[0095] Quaternization can be achieved, for example, by reacting the polymer with an alkylating agent such as a C1-C4 alkyl halide, for example, methyl bromide, methyl chloride, ethyl chloride, methyl iodide, n-butyl bromide, isopropyl bromide, or an aralkyl halide, for example, benzyl chloride, benzyl bromide, or with a C1-C22 dialkyl sulfate, in particular dimethyl sulfate or diethyl sulfate, in the presence of a base. Suitable bases are, for example, sodium hydroxide and potassium hydroxide.

[0096] The amount of alkylating agent determines the amount of amino groups that are quaternized in the polymer, ie, the amount of quaternized moieties.

[0097] The amount of quaternized moieties can be calculated from the difference in amine number between the non-quaternized and quaternized amines. The amine number can be determined according to the method described in DIN 16945.

[0098] The quaternization can be carried out without using a solvent. However, a solvent or diluent such as water, acetonitrile, dimethyl sulfoxide, or N-methylpyrrolidone may be used. The reaction temperature is usually in the range of 10°C to 150°C, preferably in the range of 50°C to 100°C.

[0099] Quaternization can be advantageous in tailoring the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine to the particular composition, such as the laundry composition, in which it is intended to be used, to enhance formulation compatibility and / or phase stability.

[0100] Embodiment 16 16. A process for preparing a modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 15, comprising carrying out the process steps according to any one of embodiments 1 to 15.

[0101] In particular, the process involves the following steps: a) reacting 1) at least one polyalkyleneimine or at least one polyamine containing a total of a plurality of primary and secondary amino groups with 2) at least one first lactone (LA1) and / or at least one first hydroxycarbon acid (HA1) to obtain a first intermediate (I1), wherein 3 to 10 mol of lactone (LA1) and / or hydroxycarbon acid (HA1) are used per mol of NH functional groups of the polyalkyleneimine or polyamine; b) reacting the first intermediate (I1) with (i) at least one first alkylene oxide (AO1) or (ii) with a mixture of 1) at least one first alkylene oxide (AO1) and 2) at least one second lactone (LA2) and / or at least one second hydroxycarbonic acid (HA2) to obtain a second intermediate (I2), wherein at least 5.0 mol of first alkylene oxide (AO1) and, in the case of a mixture, additionally at least 1.0 mol of second lactone (LA2) and / or second hydroxycarbonic acid (HA2) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); c) optionally reacting the second intermediate (I2) with (i) at least one second alkylene oxide (AO2) or (ii) with a mixture of 1) at least one second alkylene oxide (AO2) and 2) at least one third lactone (LA3) and / or at least one third hydroxycarbon acid (HA3) to obtain a third intermediate (I3), wherein at least 5.0 mol of second alkylene oxide (AO2) and, in the case of a mixture, additionally at least 1.0 mol of third lactone (LA3) and / or third hydroxycarbon acid (HA3) are used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); d) optionally reacting the second intermediate (I2) or the third intermediate (I3) with at least one quaternary lactone (LA4) and / or at least one quaternary hydroxycarboxylic acid (HA4) to obtain a fourth intermediate (I4), wherein at least 1.0 mol of the quaternary lactone (LA4) and / or the quaternary hydroxycarboxylic acid (HA4) is used per mol of NH functional group of the polyalkyleneimine or polyamine used in step a); e) optionally reacting the second intermediate (I2), the third intermediate (I3) or the fourth intermediate (I4) with at least one C1-C18 alkylating or esterifying reagent to obtain a modified alkoxylated polyalkyleneimine or a modified alkoxylated polyamine; Including, However, the modified alkoxylated polyalkyleneimine is not PEI800-3CL / NH-20EO / NH-2CL / NH (PEI800 is polyethyleneimine with a weight-average molecular weight (Mw) of 800 g / mol, CL is caprolactone, and EO is ethylene oxide), which is described as compound P5 in Table 5 of PCT / EP2022 / 072996.

[0102] All terms used in embodiment 16 have already been defined and explained in detail in the previous descriptions of embodiments 1 to 15 in this specification, and it goes without saying that such terms and definitions also apply to embodiment 16.

[0103] The conversion of each reaction step may be monitored: only when the preceding reaction has proceeded to a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5% or more can the next reactant be added, and the next reaction, in turn, monitored to detect that it has also proceeded to a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5% or more, and then the next reactant is added, and so on, until all reactants have reacted and the reaction of the last reactant added has a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5% or more. With respect to side chains, not only all other structural sequences defined above, but also undefined structures resulting from uncontrollable parameters, are produced in this defined manner, resulting in a defined structural sequence, as a statistical average, that is directly attributable to the manner in which these stepwise reactions are carried out.

[0104] The conversion of each step can be determined according to methods known to those skilled in the art, such as NMR spectroscopy, for example 13C-NMR spectroscopy and / or 1H NMR spectroscopy.

[0105] With regard to reaction conditions such as catalyst, temperature, time, purification, etc. for producing side chain units of the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine of the present invention, the entire information contained in the disclosures of WO 2021 / 165468 and unpublished patent applications EP 21176904.7, EP 21176906.2, EP 21192170.5, and EP 21192169.7 is incorporated by reference as part of the present disclosure.

[0106] The reaction of polyalkyleneimines or polyamines or intermediates I1-I3 with LA or HA, and the reaction of any intermediate with AO, can be carried out without a catalyst or in the presence of any catalyst that aids in the deprotonation of amino or hydroxy groups, including, but not limited to, potassium hydroxide, potassium methoxide, or potassium tert-butyl hydroxide. Preferred catalysts for the reaction of polyalkyleneimines or polyamines or intermediates I1-I3 with LA or HA are selected from stannous octoate and alkali metal hydroxides or alkoxides, such as KOH, NaOH, KOMe, KOtBu, or NaOMe.

[0107] In this preferred embodiment, the alkoxylation is carried out in the presence of at least one catalyst. The catalyst in this one-step reaction of the alkoxylation step is preferably a basic catalyst. Examples of suitable catalysts include alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkali metal alkoxides, particularly sodium and potassium C1-C4 alkoxides, such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; alkali metal and alkaline earth metal hydrides, such as sodium hydride and calcium hydride; and alkali metal carbonates, such as sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, and potassium hydroxide and sodium hydroxide are particularly preferred. The amount of base typically used is 0.05 to 10% by weight, particularly 0.2 to 2% by weight, based on the total amount of polyalkyleneimine or polyamine, lactone and / or hydroxycarbon acid, and alkylene oxide.

[0108] Embodiment 17 17. The process according to embodiment 16, wherein the modified alkoxylated polyalkyleneimine or the modified alkoxylated polyamine is subjected to further process steps to obtain a purified (quaternized) polymer solution, a purified liquid (quaternized) polymer, a solid, such as a granulated or co-granulated (quaternized) polymer, or a purified solid (quaternized) polymer, respectively: a) a quaternization step such as protonation by pH adjustment or permanent quaternization by standard means, e.g., alkylation using standard reactants, which alkylation preferably results in alkylation of all nitrogen atoms in the polyalkyleneimine or polyamine to a degree of 5 to 100, preferably 5 to 95, more preferably 50 to 95, and even more preferably 75 to 95 percent; and / or b) purifying using standard means, such as steam distillation, high temperature distillation, vacuum evaporation including removal of all solvents, dialysis; and / or c) drying using standard drying means, for example spray drying, drum drying, paddle drying, vacuum drying means, including agglomeration methods such as fluidized bed drying; A process to be performed.

[0109] If, after carrying out the reaction to form the polymer of the present invention, residual monomers are present in undesirable amounts, the resulting product mixture containing the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine may be further purified by standard means to reduce the residual monomer content as well as the amount of potential by-products, reduce the amount of solvent used (i.e., concentrate) or replace the solvent with another solvent. Such processes are known to those skilled in the art.

[0110] Preferably, undesirable amounts of unreacted residual monomer are removed, preferably by a distillation process, more preferably by a heated distillation process, which may include the application of a reduced pressure to enhance the rate and / or effectiveness of removal.

[0111] In a preferred embodiment, only the additional process step b) is used.

[0112] Use of the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine of the present invention and compositions containing the same Part of the present invention is also the use of the modified alkoxylated polyalkylenimines or modified alkoxylated polyamines of the present invention in various applications, where they can replace similar structures currently known, but have an improved biodegradation rate compared to these previously known structures.

[0113] Embodiment 18 18. Use of at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 17 in cleaning compositions, in fabric care and home care products, in cosmetic formulations, as a crude oil emulsion breaker, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions, as a dispersant for agrochemical formulations.

[0114] Another subject of the present invention is the use of the above-mentioned modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines in fabric care and home care products, in cosmetic formulations, as emulsion breakers for crude oils, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions and / or as dispersants for agrochemical formulations, preferably in cleaning compositions and / or in fabric care and home care products, in particular in cleaning compositions for improving clay removal or oily and greasy stain removal, which cleaning compositions are preferably laundry detergent formulations and / or hand dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid hand dishwashing detergent formulations.

[0115] The modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines can be added to cosmetic formulations, as crude oil emulsion breakers, in pigment dispersions for ink-jet inks, in electroplating formulations, and in cementitious compositions, while the compounds of the present invention can also be added (used) in washing or cleaning compositions.

[0116] Another subject of the present invention is therefore cleaning compositions, fabric and home care products, institutional cleaning products, cosmetic formulations, crude oil emulsion breakers, pigment dispersions for inkjet inks, electroplating formulations, dispersants for cementitious compositions and / or agrochemical formulations, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as defined above.

[0117] Preferably, this is a cleaning composition and / or fabric care and home care product, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation, preferably for improving clay removal or oily and greasy stain removal, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as defined above.

[0118] In another preferred embodiment of the present invention, the cleaning composition can be used for soil removal of particulate stains and / or oily and greasy stains, as well as preferably for whiteness maintenance in laundry care.

[0119] In other embodiments, the cleaning compositions of the present invention are hard surface cleaning compositions that can be used to clean a variety of surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, glass, and the like.

[0120] In another embodiment, the cleaning composition of the present invention is a liquid or solid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition that can be used to clean dishes, such as dishes such as glasses, and the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine of the present invention improves glass stain removal.

[0121] In other embodiments, the cleaning compositions are designed for use in personal care and pet care compositions such as shampoo compositions, body wash formulations, liquid or bar soaps, etc.

[0122] In the present invention, the preferred application field for the use of the modified alkoxylated polyalkyleneimines or modified alkoxylated polyamines is in the field of fabric care and home care products and cleaning compositions, preferably cleaning compositions for institutional and consumer domestic use.

[0123] Embodiment 19 Use according to embodiment 18 in cleaning compositions and / or fabric care and home care products, preferably liquid and solid detergent compositions, wherein such detergent compositions preferably comprise: a) hand dishwashing and automatic dishwashing detergent compositions comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine and at least one chelating agent and / or at least one surfactant, more preferably comprising a chelating agent in the case of a liquid or solid automatic dishwashing composition and a surfactant system in the case of a liquid hand dishwashing detergent composition, respectively; and / or b) a laundry detergent composition comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine and at least one surfactant, preferably a surfactant system; That is, use.

[0124] In the preferred fields of application for such uses, typical tasks must be accomplished, all of which are encompassed under the general term "cleaning," but which in fact include different tasks, such as clay removal or removal of oily and fatty residues, solid residues, amphoteric residues, and hydrophilic residues. Another task is to protect the item to be cleaned from deterioration, such as protecting glass from corrosion, protecting silverware from oxidation, protecting against fading, etc. Another task is to improve the overall appearance of the item to be cleaned, such as enhancing or restoring color, whiteness, or imparting or increasing shine. In many of these applications, additional ingredients are typically added, important for cleaning applications being, for example, enzymes that aid in the biological breakdown of residues.

[0125] Embodiment 20: Use according to any one of embodiments 18 to 19, i) to remove clay, and / or ii) to improve the removal of oily / greasy stains, and / or iii) To remove particulate stains and / or iv) to disperse and / or emulsify dirt, and / or v) To modify the treated surface to improve removal of subsequent recontamination; and / or vi) to improve whiteness, and / or vii) additionally for improving oily / greasy stain removal, food stain removal and / or combination stain removal, in the case where at least one enzyme is present, selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, deoxyribonucleases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases and combinations of at least two of the above types, more preferably at least one enzyme being a protease; The use of Most preferably, in the cleaning composition: Use for improving i) clay removal and / or ii) oily / greasy stain removal, The above mentioned options i) to vii) each preferably relate to the use in laundry detergent formulations and / or hand dishwashing detergent compositions and / or formulations suitable for (pre-)treatment of textiles and / or bar soaps, more preferably in liquid laundry detergent formulations and / or liquid hand dishwashing detergent compositions.

[0126] Embodiment 21 Use according to embodiments 18 to 20 in cleaning compositions and / or in fabric care and home care products, preferably in cleaning compositions for fabric care and home care, wherein the cleaning composition is preferably a laundry detergent formulation or a liquid dishwashing detergent formulation, more preferably a liquid laundry detergent formulation or a liquid dishwashing detergent formulation.

[0127] Such ingredients are typically combined with other ingredients into formulations and compositions, which are sometimes called "products" (because such formulations are provided by suppliers to other customers as formulations to be used as is, such as for cleaning purposes, or to make other formulations which can in turn be sold to consumers as consumer "products").

[0128] Embodiment 22 18. A composition comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine, respectively, according to any one of embodiments 1 to 15 or obtained or obtainable by the process according to any one of embodiments 16 to 17, wherein the composition is a fabric care and home care product, a cleaning composition, an institutional cleaning product, a cosmetic or personal care product, an oil field formulation such as a crude oil emulsion breaker, a pigment dispersion for inks such as inkjet inks, an electroplating product, a cementitious composition, a lacquer, a paint, an agrochemical formulation, preferably a laundry detergent, a dishwashing composition, a cleaning composition and / or a fabric care and home care product.

[0129] Embodiment 23 23. The composition of embodiment 22, which is a solid or liquid laundry detergent composition or a solid or liquid hand dish detergent composition, preferably a liquid laundry detergent or hand dish detergent composition, more preferably a liquid laundry detergent composition, comprising the at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of embodiments 1 to 15 or obtained or obtainable by the process according to any one of embodiments 16 to 17; Optionally, the method further comprises at least one enzyme, preferably at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, deoxyribonucleases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and combinations of at least two of the above-mentioned types, preferably wherein the at least one enzyme is selected from proteases; optionally, at least one antimicrobial agent; the at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product; Such products or compositions further comprise from about 1% to about 70% by weight of a surfactant system comprising at least one surfactant, preferably an anionic surfactant, and more preferably at least one anionic surfactant, of the composition.

[0130] Embodiment 24 23. The composition of embodiment 22, which is a solid or liquid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as defined in any one of embodiments 1 to 15, or obtained or obtainable by the process as defined in any one of embodiments 16 to 17; Optionally, the method further comprises at least one enzyme, preferably at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, deoxyribonucleases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and combinations of at least two of the above-mentioned types, preferably the at least one enzyme selected from proteases and amylases; optionally, at least one antimicrobial agent; optionally comprising at least one compound selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates; optionally, at least one zinc salt; the at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine is present in a total amount ranging from about 0.001% to about 10%, preferably from about 0.005% to 5%, more preferably from about 0.01% to about 3%, and most preferably from about 0.1% to about 2%, and such products or compositions further comprise at least one chelating agent present in a total amount ranging from about 1% to about 70%, preferably from 10% to about 60%, and even more preferably from 30% to about 50%; optionally further comprising at least one surfactant, more preferably a surfactant system, in a total amount of from about 1% to about 70% by weight; All weight percentages are based on the total weight of such composition.

[0131] Embodiment 24a 25. The composition of embodiment 24, which is a solid automatic dishwashing detergent composition comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as defined in any one of embodiments 1 to 15, or obtained or obtainable by the process as defined in any one of embodiments 16 to 17, at least one chelating agent selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), citric acid, and salts thereof; At least one enzyme selected from proteases and / or amylases; at least one bleaching agent selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates, preferably alkali metal percarbonates; at least one nonionic surfactant; Optionally, at least one disintegrant, preferably a superdisintegrant, more preferably PVPP; optionally at least one zinc salt; The composition further comprising:

[0132] Superdisintegrants are known to those skilled in the art, for example from EP 1004661, EP 1263814 and EP 1036839, and are also described in Pharmaceutical Technology, Volume 2006 Supplement, Issue 5, "A Comparative Study of Current Superdisintegrants", October 1, 2006.

[0133] Embodiment 25 24. The composition of any one of embodiments 22 and 23, which is a detergent composition comprising at least one anionic surfactant as a surfactant.

[0134] Embodiment 26 24. The composition of any one of embodiments 22 and 23, which is a liquid detergent composition comprising at least one nonionic surfactant as a surfactant, and further comprising water.

[0135] Embodiment 27 27. The composition of any one of embodiments 22, 23, 25 and 26, which is a detergent composition comprising at least one further polymer selected from multifunctional alkoxylated polyethyleneimine, multifunctional alkoxylated diamine or terephthalic acid based soil release polyester, or mixtures thereof.

[0136] Embodiment 28 28. The composition of any one of embodiments 22, 23, and 25-27, which is a liquid detergent composition, comprising, as a surfactant, at least one 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation from 3 to 8.

[0137] Embodiment 29 29. The composition of any one of embodiments 22 to 28, further comprising an antibacterial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydiphenyl ether, preferably 2-phenoxyethanol in the range of 2 ppm to 5% by weight of the composition, more preferably 0.1 to 2% phenoxyethanol, or preferably 4,4'-dichloro 2-hydroxydiphenyl ether, each at a concentration of 0.001 to 3% by weight, more preferably 0.002 to 1% by weight, and even more preferably 0.01 to 0.6% by weight, based on the weight of the composition.

[0138] Embodiment 30 30. The composition according to any one of embodiments 22 to 29, further comprising at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, deoxyribonucleases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases and combinations of at least two of the aforementioned types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the aforementioned types, more preferably wherein the at least one enzyme is selected from proteases.

[0139] Embodiment 31 31. A method of protecting the aqueous composition of any one of embodiments 22-30 from microbial contamination or growth, comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether.

[0140] Also preferably, in accordance with the present invention, the cleaning composition additionally comprises (in addition to the at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as described above), preferably at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, deoxyribonucleases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, preferably at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the above types, more preferably at least one enzyme selected from proteases.

[0141] Preferably, such cleaning compositions of the present invention are fabric and home care products or institutional (I&I) cleaning products, preferably fabric and home care products, more preferably laundry detergents or hand dish detergents, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine of the present invention, and optionally further comprising at least one surfactant or surfactant system, for improved soil removal, dispersion and / or emulsification, and / or modifying and / or maintaining the whiteness of treated surfaces.

[0142] At least one inventive modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine described herein (such modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine as defined above, particularly as described in embodiments 1 to 15, will also be referred to in the following section as "inventive polymer") is present in said inventive cleaning compositions at a concentration of from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product; such cleaning compositions can further comprise, and preferably do comprise, from about 1% to about 70% by weight of a surfactant system.

[0143] More preferably, the cleaning compositions of the present invention comprising at least one inventive polymer and optionally further comprising at least one surfactant or surfactant system are intended for primary cleaning (i.e., stain removal) in laundry and hand dishwashing applications, more particularly for the removal of clay or oily and fatty stains, such as stains on fabrics and dishes, and may further comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, deoxyribonucleases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the above-mentioned types of enzymes, more preferably wherein the at least one enzyme is selected from the group consisting of proteases.

[0144] In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0145] In other preferred embodiments, the cleaning compositions of the present invention are liquid or solid (e.g., powder or tablet / unit dose) detergent compositions for hand dishwashing or automatic dishwashing, preferably either liquid hand dishwashing detergent compositions or solid automatic dishwashing compositions.

[0146] In one embodiment, the inventive polymers of the present invention can be utilized in cleaning compositions comprising a surfactant system comprising a C10-C15 alkyl benzene sulfonate (LAS) as the surfactant base and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants or mixtures thereof.

[0147] In a further embodiment, the polymers of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, comprising a C8 to C18 linear or branched alkyl ether sulfate salt containing 1 to 5 ethoxy units as the surfactant base, and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0148] In a further embodiment, the polymers of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, comprising a C12-C18 alkyl ethoxylate surfactant containing 5-10 ethoxy units as the surfactant base, and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0149] In a further embodiment, the polymers of the present invention can be utilized in cleaning compositions, such as any type of laundry detergent, that contain bio-derived surfactants, such as rhamnolipids and / or sophorolipids, as the surfactant base.

[0150] In one embodiment of the present invention, the inventive polymers are each a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or hand dishwashing detergent formulation, further comprising at least one surfactant, preferably at least one anionic surfactant.

[0151] The selection of the additional surfactant in these embodiments may depend on the application and the desired benefit.

[0152] As used herein, the articles "a" and "an," when used in a claim or an embodiment, are understood to mean one or more of the claimed or described subject matter. As used herein, the terms "include" and "including" are meant to be open-ended and thus encompass items beyond the specific items set forth after these words.

[0153] The compositions of the present disclosure can "comprise" (i.e., contain other ingredients), "consist essentially of" (contain primarily or almost only the recited ingredients, with only minor amounts of other ingredients, primarily limited to impurities), or "consist of" (i.e., contain only the recited ingredients, and, in addition, may contain only impurities unavoidable in the technical circumstances, preferably only the recited ingredients) the components of the present disclosure.

[0154] As used herein, the term "at least one" includes, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9 and more.

[0155] Similarly, the terms "substantially free of..." or "substantially free from..." or "containing / comprising essentially no..." can be used herein; this means that the specified substance is, at a minimum, not intentionally added to form part of the composition, and preferably is not present at analytically detectable levels. This is meant to encompass compositions in which the specified substance is present only as an impurity in one of the other intentionally included substances. The specified substance, if present at all, may be present at a level of less than 1% by weight of the composition, and may be less than 0.1%, less than 0.01%, or even 0%.

[0156] As used herein, the term "about," when used in a description such as "about X%," encompasses the exact numerical value "X" and small deviations from X, where small deviations from X include deviations of minus 5 to plus 5%, preferably minus 2 to plus 2%, more preferably minus 1 to plus 1%, and even more preferably minus 0.5 to plus 0.5% from X (in this calculation, X is set to 100%), and deviations even smaller than these. Needless to say, when the given numerical value X itself is already "100%" (e.g., purity), the term "about" can clearly only mean deviations smaller than "100," and therefore certainly only means deviations smaller than "100."

[0157] Unless otherwise specified, all component or composition levels refer to the active portion of that component or composition and exclude impurities, such as residual solvents or by-products, that may be present in commercial sources of such component or composition.

[0158] All temperatures herein are in degrees Celsius (°C) unless otherwise specified. All measurements herein are made at atmospheric pressure at 20°C unless otherwise specified. In all embodiments of the present disclosure, all percentages are by weight of the total composition unless otherwise specified. All ratios are by weight unless otherwise specified.

[0159] Description of cleaning compositions, formulations and their ingredients As used herein, the expression "cleaning composition" includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface.

[0160] "Institutional cleaning" compositions include those cleaning compositions designed for use in institutional cleaning, for example cleaning compositions for use in cleaning any type of soiled material or surface, such as hard surface cleaners for any type of surface, including tile, carpet, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces.

[0161] "Fabric care and home care compositions" include, but are not limited to, cleaning compositions and formulations such as laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry pre-wash detergents, laundry pre-treatments, laundry aids, spray products, dry cleaning agents or compositions, laundry rinse additives, rinse-off additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or within a porous substrate or nonwoven sheet, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein and that may be described in more detail later in the description of the compositions herein. Such compositions are further described hereinafter in the description of the uses and applications of the inventive polymers and compositions comprising such polymers, and may be used as laundry pre-treatments, post-laundry treatments, or added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation.

[0162] The cleaning compositions of the present invention can be in any form, i.e., liquid form; solids such as powders, granules, aggregates, pastes, tablets, sachets, bars, gels, etc.; emulsions; the type delivered in two- or multi-compartment containers; single- or multi-phase unit dose articles; spray or foam detergents; wet wipes (i.e., a cleaning composition combined with a nonwoven material such as those described in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes (i.e., a cleaning composition combined with a nonwoven material such as those described in U.S. Pat. No. 5,980,931 to Fowler et al.) that are activated by wetting with water by the user or consumer; or other homogeneous, heterogeneous, single-phase, or multi-phase cleaning products.

[0163] The liquid cleaning compositions of the present invention preferably have a viscosity of 50 to 10,000 mPa·s, the liquid manual dish wash cleaning compositions (also referred to as liquid manual "dish wash compositions") preferably have a viscosity of 100 to 10,000 mPa·s, more preferably 200 to 5,000 mPa·s, and most preferably 500 to 3,000 mPa·s at 20 1 / s and 20°C, and the liquid laundry cleaning compositions preferably have a viscosity of 50 to 3,000 mPa·s, more preferably 100 to 1,500 mPa·s, and most preferably 200 to 1,000 mPa·s at 20 1 / s and 20°C.

[0164] The liquid cleaning compositions of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4 to 14. More preferably, the pH of the composition is 6 to 13, even more preferably 6 to 10, and most preferably 7 to 9. The pH of the composition may be adjusted using pH adjusting ingredients known in the art, measured at a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used, although the actual weight percent of NaOH may vary to achieve a desired pH, such as pH 8.0. In one embodiment of the present invention, the pH may be adjusted to above 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0165] Detergent compositions, such as fabric care and home care products and institutional cleaning formulations, more particularly laundry and hand dish detergents, are known to those skilled in the art. Any compositions known to those skilled in the art and related to the respective application, particularly when such compositions are used in their field of use, can be used within the context of the present invention by including at least one inventive polymer, preferably at least one polymer in an amount suitable to develop specific properties in such compositions.

[0166] An aspect of the present invention is also the use of the polymers of the present invention as additives in detergent formulations, especially liquid detergent formulations, preferably concentrated liquid detergent formulations or laundry single dose formulations.

[0167] The cleaning compositions of the present invention may, and preferably do, contain cleaning adjuncts (sometimes abbreviated herein as "adjuncts"), such adjuncts preferably being in addition to the surfactant system defined above.

[0168] Suitable cleaning adjuncts include builders, co-builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersants, polymeric degreasers, solubilizers, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaches, bleach activators, bleach catalysts, optical brighteners, malodor control agents, pigments, dyes, opacifiers, color correctors, color transfer inhibitors, chelating agents, suds boosters, suds suppressors (defoamers), color speckles, silver care agents, anti-tarnish and / or corrosion inhibitors, alkalizing agents, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antimicrobial agents, antioxidants, softening agents, carriers, processing aids, perfume precursors, dye fixatives, and perfumes.

[0169] The liquid cleansing composition may additionally comprise, and preferably does comprise, at least one of a rheology control / regulator, an emollient, a humectant, a skin rejuvenating active, and a solvent.

[0170] The solid composition may additionally comprise, and preferably does comprise, at least one of a filler, a bleaching agent, a bleach activator, and a catalytic material.

[0171] Suitable examples of such cleaning adjuvants and amounts to be used are described in WO 99 / 05242, US Pat. No. 5,576,282, US Pat. No. 6,306,812 B1 and US Pat. No. 6,326,348 B1.

[0172] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that is useful in cleaning, stain removal, or laundering soiled materials.

[0173] Thus, cleaning compositions of the present invention, such as fabric care and home care products and institutional cleaning formulations, more particularly laundry and hand dish detergents, preferably additionally comprise a surfactant system as described above and in more detail below, and more preferably also further adjuvants.

[0174] The surfactant system can be composed of one surfactant or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those skilled in the art will understand that a detergent surfactant system includes any surfactant or mixture of surfactants that is beneficial for cleaning, stain removal, or laundering soiled materials.

[0175] The cleaning compositions of the present invention preferably contain a surfactant system in an amount sufficient to impart the desired cleaning properties. In some embodiments, the cleaning composition contains from about 1% to about 70% of the surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition contains from about 2% to about 60% of the surfactant system by weight of the composition. In further embodiments, the cleaning composition contains from about 5% to about 30% of the surfactant system by weight of the composition. The surfactant system may comprise a cleaning surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0176] (a) Laundry composition In laundry formulations, anionic surfactants usually make up the largest and by far the largest proportion of surfactants contained in such formulations. Preferably, therefore, the cleaning compositions of the present invention for use in laundry comprise at least one anionic surfactant and, optionally, a further surfactant selected from any of the surfactant classes described herein, preferably from nonionic surfactants and / or amphoteric surfactants and / or zwitterionic surfactants and / or cationic surfactants.

[0177] Non-limiting examples of anionic surfactants useful herein, which may also be used in combination of two or more surfactants, include C9-C20 linear alkyl benzene sulfonates (LAS), C10-C20 primary, branched and random alkyl sulfates (AS); C10-C18 Examples of suitable alkyl alkoxy sulfates include secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) (x is 1 to 30); C10-C18 alkyl alkoxy carboxylates containing 1 to 5 ethoxy units; internally branched alkyl sulfates as described in U.S. Pat. Nos. 6,020,303 and 6,060,443; internally branched alkyl alkoxy sulfates as described in U.S. Pat. Nos. 6,008,181 and 6,020,303; modified alkyl benzene sulfonates (MLAS) as described in WO 99 / 05243, WO 99 / 05242, and WO 99 / 05244; methyl ester sulfonates (MES); and α-olefin sulfonates (AOS).

[0178] Preferred examples of suitable anionic surfactants include alkali metal and ammonium salts of C8-C12 alkyl sulfates, C12-C18 fatty alcohol ether sulfates, C12-C18 fatty alcohol polyether sulfates, sulfate half esters of ethoxylated C4-C12 alkylphenols (ethoxylated with 3-50 mol / mol of ethylene oxide), C12-C18 alkyl sulfonic acids, C12-C18 sulfofatty acid alkyl esters, for example, C12-C18 sulfofatty acid methyl esters, C10-C18 alkylaryl sulfonic acids, preferably n-C10-C18 alkylbenzene sulfonic acids, C10-C18 alkylalkoxycarboxylic acid esters, and soaps, such as C8-C24 carboxylic acids. Alkali metal salts of the above-mentioned compounds are preferred, and sodium salts are particularly preferred.

[0179] In one embodiment of the present invention, the anionic surfactant is selected from n-C10 to C18 alkylbenzenesulfonic acids and from fatty alcohol polyether sulfates, which in the context of the present invention are in particular sulfate half esters of ethoxylated C12 to C18 alkanols (ethoxylation: 1 to 50 mol / mol ethylene oxide), preferably of n-C12 to C18 alkanols.

[0180] In one embodiment of the present invention, alcohol polyether sulfates derived from branched (ie, synthetic) C11-C18 alkanols (ethoxylated: 1-50 mol / mol ethylene oxide) can also be used.

[0181] Preferably, the alkoxylated groups of the alkoxylated alkyl sulfates based on C12-C18 fatty alcohols or based on branched (i.e. synthetic) C11-C18 alcohols are ethoxylated groups in both cases, and the average degree of ethoxylation of any alkoxylated alkyl sulfate is 1-5, preferably 1-3.

[0182] In a further embodiment of the invention, the anionic surfactant is selected from rhamnolipids and / or sophorolipids.

[0183] Preferably, the laundry detergent formulations of the present invention comprise one or more of the above-described anionic surfactants in an amount of at least 1% to 50% by weight, preferably in the range of from about 2% to about 30% by weight, more preferably in the range of from 3% to 25% by weight, and most preferably in the range of from 5% to 25% by weight, based on the total weight of the specific composition including other components and water and / or solvent.

[0184] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10 to C15 linear alkylbenzene sulfonates, C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units, and C10 to C18 alkyl sulfates.

[0185] Non-limiting examples of nonionic surfactants that may be used in combination with two or more other surfactants include: C8-C18 alkyl ethoxylates, such as NEODOL®, a nonionic surfactant from Shell; ethylene oxide / propylene oxide block alkoxylates, such as PLURONIC® from BASF; C14-C22 internally branched alkyl alkoxylates, such as those described in U.S. Pat. Nos. 6,153,577, 6,020,303, and 6,093,856; Coxylates BAEx (x is 1-30); alkyl polysaccharides as described in U.S. Patent No. 4,565,647 to Llenado, issued January 26, 1986; specifically, alkyl polyglycosides as described in U.S. Patent Nos. 4,483,780 and 4,483,779; polyhydroxy fatty acid amides as described in U.S. Patent No. 5,332,528; and ether-terminated poly(oxyalkylated) alcohol surfactants as described in U.S. Patent No. 6,482,994 and WO 01 / 42408.

[0186] Preferred examples of nonionic surfactants are, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, as well as alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides).

[0187] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (A): [ka] (The variables in the formula are defined as follows: R1 is selected from linear C1-C10 alkyl, preferably ethyl, particularly preferably methyl; R2 is selected from C8-C22 alkyl, for example n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33 or n-C18H37; R3 is selected from C1-C10-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; m and n range from zero to 300, and the sum of n and m is at least 1. Preferably, m is in the range of 1 to 100, and n is in the range of 0 to 30.

[0188] As used herein, the compound of general formula (A) can be a block copolymer or a random copolymer, with block copolymers being preferred.

[0189] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (B): [ka] (The variables in the formula are defined as follows: R1 are identical or different and are selected from linear C1-C4 alkyl, preferably identical in each case, ethyl, particularly preferably methyl; R4 is selected from C6-C20 alkyl, in particular n-C8H17, n-C10H21, n-C12H25, n-C14H29, n-C16H33, n-C18H37; a is a number ranging from 0 to 6, preferably from 1 to 6; b is a number ranging from 0 to 20, preferably from 4 to 20; and d is a number ranging from 4 to 25.

[0190] Preferably, at least one of a and b is greater than zero.

[0191] In this specification, the compound of general formula (B) can be a block copolymer or a random copolymer, with block copolymers being preferred.

[0192] Further suitable nonionic surfactants are selected from the di- and multi-block copolymers composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are also suitable. A summary of further suitable nonionic surfactants is given in EP 0851023 and DE 19819187.

[0193] Mixtures of two or more different nonionic surfactants may, of course, also be present.

[0194] In a preferred embodiment of the present invention, the nonionic surfactant is selected from C12 / 14 and C16 / 18 fatty alcohol alkoxylates, C13 / 15 oxoalcohol alkoxylates, C13 alcohol alkoxylates and 2-propylheptyl alcohol alkoxylates, each of which contains 3 to 15 ethoxy units, preferably 4 to 10 ethoxy units or 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0195] Non-limiting examples of amphoteric surfactants that can be used in combination with two or more other surfactants include water-soluble amine oxides containing one alkyl moiety having from about 8 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety having from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties having from about 1 to about 3 carbon atoms. See WO 01 / 32816, U.S. Pat. Nos. 4,681,704, and 4,133,779. Accordingly, suitable surfactants include so-called amine oxides, such as lauryldimethylamine oxide ("lauramine oxide").

[0196] A preferred example of an amphoteric surfactant is an amine oxide. Preferred amine oxides are alkyl dimethyl amine oxide or alkyl amidopropyl dimethyl amine oxide, more preferably alkyl dimethyl amine oxide, especially coconut oil alkyl dimethyl amine oxide. The amine oxide can have a linear or internally branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is represented by the formula: R1-N(R2)(R3)-O wherein R1 is a C8-18 alkyl, and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, and 3-hydroxypropyl. Linear amine oxide surfactants include, in particular, linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxyethyl dihydroxyethyl amine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides. As used herein, "mid-branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms, and on this alkyl moiety, has one alkyl branch with n2 carbon atoms. The alkyl branch is located on the alpha carbon to the nitrogen of the alkyl moiety. This type of branching of the amine oxide is also known in the art as an internal amine oxide. The sum of the carbon atoms in n1 and n2 is 10 to 24, preferably 12 to 20, and more preferably 10 to 16. The number of carbon atoms in one alkyl moiety (n1) must be approximately equal to the number of carbon atoms in one alkyl branch (n2) so that this one alkyl moiety and one alkyl branch are symmetrical. As used herein, "symmetrical" means that at least 50% by weight, more preferably at least 75% to 100% by weight of (n1-n2) of the internally branched amine oxide for use herein has 5 or less carbon atoms, preferably 4 or less, and most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from a C1-C3 alkyl group, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are selected from a C1-C3 alkyl group, and more preferably, both are selected as C1 alkyl groups.

[0197] In a preferred embodiment of the present invention, the amphoteric surfactant is selected from C8-C18 alkyl-dimethylamine oxide and C8-C18 alkyl-di(hydroxyethyl)amine oxide.

[0198] The cleaning composition may also include zwitterionic surfactants, which may be used in combination with two or more other surfactants.

[0199] Suitable zwitterionic surfactants include betaines, such as alkylbetaines, alkylamidobetaines, amidoazolinium betaines, sulfobetaines (INCI: Sultaine), as well as phosphobetaines. Examples of suitable betaines and sulfobetaines are as follows (listed according to INCI): Almond amidopropyl betaine, Apricotamidopropyl betaine, Avocadamidopropyl betaine, Babassuamidopropyl betaine, Behenamidopropyl betaine, Behenyl betaine, Canol amidopropyl betaine, Capryl / Capramidopropyl betaine, Carnitine, Cetyl betaine, Cocamidoethyl betaine, Cocamidopropyl betaine betaine, Cocamidopropyl Hydroxysultaine, Coco betaine, Coco Hydroxysultaine, Coco / Oleamidopropyl betaine, Coco Sultaine, Decyl betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl GlycineGlycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaine, Isostearamidopropyl betaine, Lauramidopropyl betaine, Lauryl betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milk Fatty Acid Amidopropyl Betaine, Mink Oil Fatty Acid Amidopropyl Betaine, Myristamidopropyl Betaine betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, olivanidopropyl betaine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernel amidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, Sesamidopropyl betaine, Soyamidopropyl betaine, Stearamidopropyl betaine, Stearyl betaine, Tallowamidopropyl betaine, Tallowamidopropyl Hydroxysultaine, Tallow betaine, Tallow dihydroxyethyl betaine, Undecylenamidopropyl betaine, and Wheat germ oil fatty acid amidopropyl betaine.

[0200] Preferred betaines are, for example, C12-C18 alkyl betaines and sulfobetaines. The zwitterionic surfactant is preferably a betaine surfactant, more preferably a cocamidopropyl betaine surfactant.

[0201] Non-limiting examples of cationic surfactants that may be used in combination with two or more other surfactants include: quaternary ammonium surfactants that may have up to 26 carbon atoms, such as the alkoxylated quaternary ammonium (AQA) surfactants described in U.S. Pat. No. 6,136,769; dimethylhydroxyethyl quaternary ammonium (DMHA) surfactants described in U.S. Pat. No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride; and the alkoxylated quaternary ammonium (DMHA) surfactants described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35006, WO 98 / 35008, WO 98 / 35009, WO 98 / 35010, WO 98 / 35011, WO 98 / 35012, WO 98 / 35013, WO 98 / 35014, WO 98 / 35015, WO 98 / 35016, WO 98 / 35017, WO 98 / 35018, WO 98 / 35019 ... Examples of suitable surfactants include polyamine cationic surfactants described in WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; cationic ester surfactants described in U.S. Pat. Nos. 4,228,042, 4,239,660, 4,260,529, and 6,022,844; and amino surfactants, specifically amidopropyldimethylamine (APA), described in U.S. Pat. No. 6,221,825 and WO 00 / 47708.

[0202] The composition according to the invention may contain at least one builder. In the context of the present invention, no distinction is made between builders and components otherwise referred to as "cobuilders." Examples of builders are complexing agents, ion exchange compounds, and precipitating agents, hereinafter also referred to as complexing agents. The builder is selected from citrates, phosphates, silicates, carbonates, phosphonates, amino carboxylates, and polycarboxylates.

[0203] The term citrate in the context of the present invention includes mono- and di-alkali metal salts of citric acid, especially monosodium salt and preferably trisodium salt, ammonium salt or substituted ammonium salt of citric acid, as well as citric acid. Citrate can be used as an anhydrous compound or as a hydrate, for example, sodium citrate dihydrate. The amount of citrate is calculated based on trisodium citrate anhydrous.

[0204] The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogen phosphate, sodium pyrophosphate, and polyphosphates, such as sodium tripolyphosphate. Preferably, however, the compositions according to the invention are free of phosphates and polyphosphates, including hydrogen phosphates, such as trisodium phosphate, pentasodium tripolyphosphate, and hexasodium metaphosphate ("phosphate-free"). "Free" in relation to phosphates and polyphosphates in the context of the present invention should be understood to mean that the total content of phosphates and polyphosphates, as determined by gravimetric analysis, is in the range of 10 ppm to 0.2% by weight of the respective composition.

[0205] The term carbonate includes alkali metal carbonates and alkali metal hydrogen carbonates, with sodium salts being preferred, Na2CO3 being particularly preferred.

[0206] Phosphonates include, for example, hydroxyalkane phosphonates and aminoalkane phosphonates. Among hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is particularly important as a builder. It is preferably used as the sodium salt; the disodium salt is neutral, and the tetrasodium salt is alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologs. These are preferably used in the form of neutral-reacting sodium salts, such as the hexasodium salt of EDTMP or the hepta- and octasodium salts of DTPMP.

[0207] Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, propylenediaminetetraacetic acid, ethanol-diglycine, methylglycinediacetate and glutaminediacetate. The terms aminocarboxylates and polycarboxylates also include their respective unsubstituted or substituted ammonium and alkali metal salts, e.g., sodium salts, and in particular their respective fully neutralized compounds.

[0208] Silicates relevant to the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as zeolites and layered silicates, in particular those having the formula α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5.

[0209] The compositions according to the invention may also contain one or more builders chosen from substances other than those mentioned above, such as alpha-hydroxypropionic acid and oxidized starch.

[0210] In one embodiment of the present invention, the builder is selected from polycarboxylates, the term "polycarboxylate" including non-polymeric polycarboxylic acids such as succinic acid, C2-C16 alkyldisuccinates, C2-C16 alkenyldisuccinates, ethylenediamine N,N'-disuccinate, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.

[0211] Oligomeric or polymeric polycarboxylates are, for example, the alkali metal salts of polyaspartic acid, especially of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

[0212] Suitable comonomers are monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are, in particular, polyacrylic acids, preferably having weight-average molecular weights Mw in the range of 2000 to 40000 g / mol, preferably 2000 to 10000 g / mol, in particular 3000 to 8000 g / mol. Further suitable polycarboxylate copolymers are, in particular, copolymers of acrylic acid with methacrylic acid and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

[0213] It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-C10 mono- or C4-C10 dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilically or hydrophobically modified comonomer, such as those listed below.

[0214] Suitable hydrophobic comonomers are, for example, isobutene, diisobutene, butene, pentene, hexane and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C22-α-olefins, mixtures of C20-C24-α-olefins with polyisobutenes having an average of 12 to 100 carbon atoms per molecule, etc.

[0215] Suitable hydrophilic comonomers include monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxyl or alkylene oxide groups. Examples include allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate, and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. In this case, the polyalkylene glycol may contain 3 to 50, particularly 5 to 40, and more particularly 10 to 30 alkylene oxide units per molecule.

[0216] Particularly preferred sulfonic acid group-containing monomers herein are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallyl sulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of the above acids, for example, their sodium, potassium, or ammonium salts.

[0217] Particularly preferred phosphonate group-containing monomers are vinylphosphonic acid and its salts.

[0218] Additionally, amphoteric polymers can also be used as builders.

[0219] The compositions according to the invention, in particular solid formulations, may contain builders in a total amount of, for example, 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight. Liquid formulations according to the invention preferably contain builders in an amount of 0.1 to 8% by weight.

[0220] The formulations according to the invention may contain one or more alkali carriers. The alkali carrier ensures, for example, a pH of at least 9 if an alkaline pH is desired. For example, in addition to the alkali metal carbonates, alkali metal bicarbonates, and alkali metal metasilicates mentioned above, alkali metal hydroxides are also suitable. In each case, the preferred alkali metal is potassium, with sodium being particularly preferred. In one embodiment of the invention, the pH is adjusted to above 7 using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0221] In one embodiment of the invention, the composition or laundry formulation according to the invention further comprises at least one enzyme.

[0222] In one embodiment, the composition according to the invention additionally comprises at least one enzyme.

[0223] Preferably, the at least one enzyme is a detergent enzyme.

[0224] In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), transferase (EC 2), hydrolase (EC 3), lyase (EC 4), isomerase (EC 5), or ligase (EC 6). This EC numbering is in accordance with the Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology, including addenda published in 1993-1999. Preferably, the enzyme is a hydrolase (EC 3).

[0225] In a preferred embodiment, the enzyme is: Protease, amylase, lipase, cellulase, mannanase, hemicellulase, phospholipase, esterase, pectinase, lactase, peroxidase, xylanase, cutinase, pectate lyase, keratinase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, beta-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, nuclease, deoxyribonuclease, phosphodiesterase, phytase, carbo The enzyme is selected from the group consisting of hydrolases, galactanases, xanthanases, xyloglucanases, oxidoreductases, perhydrolases, aminopeptidases, asparaginases, carbohydrases, carboxypeptidases, catalases, chitinases, cyclodextrin glycosyltransferases, alpha-galactosidases, beta-galactosidases, glucoamylases, alpha-glucosidases, beta-glucosidases, invertases, ribonucleases, transglutaminases, and dispersins, and combinations of at least two of the aforementioned types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, deoxyribonucleases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the aforementioned types. Most preferably, the enzyme is a protease, preferably a serine protease, more preferably a subtilisin protease.

[0226] Preferably, the protease is a protease that has at least 90% sequence identity with SEQ ID NO: 22 of EP1921147B1 and has the amino acid substitution R101E (according to BPN' numbering). Preferably, the amylase is an amylase that has at least 90% sequence identity with SEQ ID NO: 54 of WO2021032881A1.

[0227] The compositions of the present invention can contain one enzyme or two or more enzymes of different types, such as an amylase and a protease, or two or more enzymes of the same type, such as two or more different proteases, or a mixture thereof, such as an amylase and two different proteases.

[0228] The enzyme can be incorporated into the composition at a level sufficient to provide an effective amount to achieve a beneficial effect, preferably a primary cleaning effect and / or a secondary cleaning effect such as an anti-black stain or anti-pilling effect (e.g., in the case of cellulases). Preferably, the enzyme is present in the composition at a level such that the enzyme protein is from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, and even more preferably from about 0.001% to about 0.5% by weight of the composition.

[0229] Preferably, the enzyme-containing composition further comprises an enzyme stabilization system.

[0230] Preferably, the enzyme-containing compositions described herein comprise an enzyme stabilizing system in an amount of from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01% to about 6% by weight of the composition. The enzyme stabilizing system can be any stabilizing system compatible with the enzyme.

[0231] Preferably, the enzyme stabilization system comprises at least one compound selected from the group consisting of a polyol (preferably 1,3-propanediol, ethylene glycol, glycerol, 1,2-propanediol, or sorbitol), an inorganic salt (preferably CaCl, MgCl, or NaCl), a short-chain (preferably C1-C3) carboxylic acid or a salt thereof (preferably formic acid, a formate (preferably sodium formate), acetic acid, an acetate, or a lactate), a borate, boric acid, a boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), a peptide aldehyde (preferably Z-VAL-H or Z-GAY-H), a peptide acetal, and a peptide aldehyde bisulfite adduct. Preferably, the enzyme stabilization system comprises a combination of at least two compounds selected from the group consisting of salts, polyols, and short-chain carboxylic acids, preferably a combination of one or more compounds selected from the group consisting of borate, boric acid, boronic acid (preferably 4-formylphenylboronic acid (4-FPBA)), peptide aldehyde, peptide acetal, and peptide aldehyde hydrosulfite adduct. In particular, when a protease is present in the composition, a protease inhibitor preferably selected from borate, boric acid, boronic acid (preferably 4-FPBA), peptide aldehyde (preferably a peptide aldehyde such as Z-VAL-H or Z-GAY-H), peptide acetal, and peptide aldehyde hydrosulfite adduct can be added.

[0232] The compositions according to the invention may contain one or more bleaching agents.

[0233] Preferred bleaching agents are selected from sodium perborate, either anhydrous or, for example, as the monohydrate or as the tetrahydrate or as the so-called dihydrate, sodium percarbonate and sodium persulfate, either anhydrous or, for example, as the monohydrate, the term "persulfate" including in each case the salt of the peracid HSO as well as the peroxodisulfate.

[0234] In this connection, the alkali metal salts can also in each case be alkali metal hydrogen carbonates, alkali metal hydrogen perborates and alkali metal hydrogen persulfates, although in each case the dialkali metal salts are preferred.

[0235] The formulations according to the present invention contain one or more bleach catalysts, which may be selected from oxaziridinium bleach catalysts, bleach-boosting transition metal salts or complexes, such as manganese, iron, cobalt, ruthenium, or molybdenum salen complexes or carbonyl complexes. In addition to complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper with nitrogen-containing tripodal ligands, cobalt, iron, copper, and ruthenium amine complexes may also be used as bleach catalysts.

[0236] Formulations according to the invention may include one or more bleach activators, such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonate, (S)NOBS, LOBS, DOBA, PAP, N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quats (trimethylammonium acetonitrile salts).

[0237] As H2O2 precursors, peroxides, i.e. all compounds capable of generating hydrogen peroxide in aqueous solution, such as organic and inorganic peroxides known from the literature and commercially available, which bleach textile materials at conventional washing temperatures, e.g. 10-95°C, are also contemplated.

[0238] However, inorganic peroxides such as persulfates, perborates, percarbonates and / or persilicates are preferably used, typically in an amount of 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition.

[0239] Typically, the formula (1) is described in more detail below. [ka] The compound is present in the composition in an amount of 0.05 to 15% by weight, preferably 0.1 to 10% by weight, based on the weight of the entire composition.

[0240] Examples of suitable inorganic peroxides include sodium perborate tetrahydrate or sodium perborate monohydrate, sodium percarbonate, inorganic peroxy compounds such as potassium monopersulfate (MPS), etc. When an organic or inorganic peroxy compound is used as the peroxy compound, the amount will generally be in the range of about 2 to 80% by weight, preferably 4 to 30% by weight, based on the weight of the composition.

[0241] Organic peroxides are, for example, mono- or polyperoxides, urea peroxide, combinations of C1-C4 alkanol oxidases with C1-C4 alkanols (such as methanol oxidase and ethanol as described in WO 95 / 07972), alkyl hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide.

[0242] Peroxides can have various crystalline forms and may differ in the content of water of crystallization, and they can also be used together with other inorganic or organic compounds to improve their storage stability.

[0243] A peracid can also be used as the oxidizing agent. [ka] (In the formula, M represents hydrogen or a cation; R 19 is unsubstituted C1 to C 18 Alkyl; substituted C1-C 18 Examples of organic monoperacids include alkyl; unsubstituted aryl; substituted aryl; -(C1-C6 alkylene)-aryl (wherein the alkylene group and / or alkyl group may be substituted); and phthalimido C1-C8 alkylene (wherein the phthalimido group and / or alkylene group may be substituted).

[0244] Preferred organic monoperacids and salts thereof are represented by the formula [ka] (In the formula, M represents hydrogen or an alkali metal; R' 19 is unsubstituted C1-C4 alkyl; phenyl; C1-C2 alkylene-phenyl or phthalimide (representing C1-C8-alkylene).

[0245] CH3COOOH and its alkali metal salts are particularly preferred.

[0246] Also particularly preferred is ε-phthalimidoperoxyhexanoic acid and its alkali metal salts (PAP).

[0247] Also suitable are diperacids such as 1,12-diperoxydodecanedioic acid (DPDA), 1,9-diperoxyazelaic acid, diperoxybrassylic acid, diperoxysebasic acid, diperoxyisophthalic acid, 2-decyldiperoxybutane-1,4-diotic acid, and 4,4'-sulfonylbisperoxybenzoic acid.

[0248] In some cases, it may be advantageous to use additional bleach activators.

[0249] The term bleach activator is often used synonymously with peracid bleach precursor. All of the peroxy compounds mentioned above may be used alone or in combination with a peracid bleach precursor.

[0250] Such precursors are the corresponding carboxylic acids or the corresponding carboxylic anhydrides or the corresponding carbonyl chlorides or amides or esters, which can be perhydrolyzed to form peracids. Such reactions are generally known.

[0251] Peracid bleach precursors are known and have been described extensively in references such as British Patent Nos. 836988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent No. 3,337,921; European Patent Application Publication No. 0185522A; European Patent Application Publication No. 0174132A; European Patent Application Publication No. 0120591A; and U.S. Patents Nos. 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

[0252] Suitable bleach activators include bleach activators having O- and / or N-acyl groups and / or unsubstituted or substituted benzoyl groups. Polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED); acylated glycolurils, in particular tetraacetylglycol urea (TAGU), N,N-diacetyl-N,N-dimethylurea (DDU); sodium 4-benzoyloxybenzenesulfonate (SBOBS); sodium 1-methyl-2-benzoyloxybenzene-4-sulfonate; sodium 4-methyl-3-benzoloxybenzoate; trimethylammonium toluoyloxybenzenesulfonate; acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT); compounds of formula (10): [ka] (In the formula, R 22 is a sulfonate group, a carboxylic acid group, or a carboxylate group, and R 21 is a straight chain or branched (C7-C 15 Preferred are acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, and 2,5-diacetoxy-2,5-dihydrofuran; acetylated sorbitol and mannitol; and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetraacetylxylose, and octaacetyllactose, as well as acetylated, optionally N-alkylated glucamine and gluconolactone. It is also possible to use combinations of conventional bleach activators, as known from German Patent Application No. 4443177A. Nitrile compounds, which form perimine acids with peroxides, are also considered bleach activators.

[0253] Other useful peracid bleach precursors are those classified as cationic, i.e., quaternary ammonium-substituted peracid precursors, as disclosed in U.S. Patent Nos. 4,751,015 and 4,397,757, EP 0 284 292 A, and EP 331,229 A. Examples of this type of peracid bleach precursor are: 2-(N,N,N-trimethylammonium)ethyl sodium-4-sulfonephenylcarbonate chloride (SPCC), N-octyl-N,N-dimehyl-N10-carbophenoxydecylammonium chloride (ODC), 3-(N,N,N-trimethylammonium)propyl sodium-4-sulfophenylcarboxylate, and N,N,N-trimethylammonium toluyloxybenzenesulfonate.

[0254] It is also possible to use further bleach catalysts which are generally known, for example those disclosed in EP 1 194 514, EP 1 383 857 or WO 04 / 007657.

[0255] The formulations according to the invention may contain one or more corrosion inhibitors, which in the present specification are understood to include compounds that inhibit the corrosion of metals. Suitable corrosion inhibitors include, for example, triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and also phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyrogallol.

[0256] In one embodiment of the present invention, the formulation according to the present invention comprises corrosion inhibitors in a total amount in the range of 0.1 to 1.5 wt. %.

[0257] The formulations according to the invention may also comprise further detersive polymers and / or soil release polymers.

[0258] Additional detergent polymers include, but are not limited to, "multifunctional alkoxylated polyethyleneimines" (e.g., BASF's Sokalan® HP20), "multifunctional alkoxylated diamines" (e.g., BASF's Sokalan® HP96), BASF's Sokalan® SR400 A, as well as terephthalic acid-based polyesters such as Clariant's TexCare®, e.g., TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN260, TexCare® SRN 260 SG Terra, and TexCare® SRA 300, and different combinations of all the above-mentioned polymers.

[0259] Suitable polyfunctional alkoxylated polyethyleneimines are typically ethoxylated polyethyleneimines having a weight-average molecular weight Mw in the range of 3,000 to 250,000 g / mol, preferably 5,000 to 200,000 g / mol, more preferably 8,000 to 100,000 g / mol, more preferably 8,000 to 50,000 g / mol, more preferably 10,000 to 30,000 g / mol, and most preferably 10,000 to 20,000 g / mol. Suitable polyfunctional alkoxylated polyethyleneimines have 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, and most preferably 93% to 97% or 94% to 96% by weight of ethylene oxide side chains, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. A suitable polyethyleneimine core molecule is a polyethyleneimine having a weight-average molecular weight (Mw) in the range of 500 to 5,000 g / mol. Preferably, a molecular weight of 500 to 1,000 g / mol is used, and more preferably, Mw is 600 to 800 g / mol. In this case, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0260] Suitable polyfunctional alkoxylated diamines are typically ethoxylated C2-C12 alkylenediamines, preferably hexamethylenediamine, which are further quaternized and optionally sulfated. Typical polyfunctional alkoxylated diamines have a weight average molecular weight Mw in the range of 2,000 to 10,000 g / mol, more preferably 3,000 to 8,000 g / mol, and most preferably 4,000 to 6,000 g / mol. In a preferred embodiment of the present invention, a further quaternized and sulfated ethoxylated hexamethylenediamine is used, which contains an average of 10 to 50, preferably 15 to 40, and more preferably 20 to 30 ethylene oxide (EO) groups per NH group, and preferably has two cationic ammonium groups and two anionic sulfate groups.

[0261] In a preferred embodiment of the present invention, the cleaning composition may contain at least one polyfunctional alkoxylated polyethyleneimine and / or at least one polyfunctional alkoxylated diamine to improve the cleaning performance of the laundry detergent, for example, preferably to improve stain removal ability, particularly the primary cleaning power of particulate stains on polyester fabrics. The polyfunctional polyethyleneimine or polyfunctional diamine described above, or a mixture thereof, may be added to the laundry detergent and cleaning composition in a small amount of generally 0.05 to 15 wt %, preferably 0.1 to 10 wt %, more preferably 0.25 to 5 wt %, and even up to 2 wt %, based on the total specific composition including other components and water and / or solvent.

[0262] In another preferred embodiment of the present invention, the cleaning composition may comprise at least one terephthalic acid based polyester used as a soil release polymer to improve the whiteness of fabrics after washing, especially the whiteness of polyester fabrics.

[0263] Accordingly, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one inventive polymer and (ii) at least one compound selected from multifunctional alkoxylated polyethyleneimines, multifunctional alkoxylated diamines, and terephthalic acid-based polyesters, and mixtures thereof.

[0264] In one embodiment of the present invention, the ratio of the at least one polymer of the present invention to (ii) at least one compound selected from polyfunctional polyethyleneimines and polyfunctional diamines and mixtures thereof is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3.

[0265] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent (sometimes referred to as a "preservative").

[0266] The composition may include one or more antimicrobial agents and / or preservatives described on pages 35-39 of WO 2021 / 115912 A1.

[0267] Of particular note are the following antimicrobial and / or antiseptic agents: 4,4'-Dichloro-2-hydroxydiphenyl ether (CAS No. 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol, sold under the tradenames Diclosan, DCPP, and Tinosan® HP 100 (BASF) as a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propylene glycol; 2-phenoxyethanol (CAS No. 122-99-6, also known as phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE); 2-bromo-2-nitropropane-1,3-diol (CAS No. 52-51-7, also known as 2-bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® BN, and Myacide®). AS); glutaraldehyde (CAS No. 111-30-8, also known as 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA); glyoxal (CAS No. 107-22-2; synonyms: ethanedial, oxylaldehyde, 1,2-ethanedial, 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); 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, such as calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (potassium sorbate, CAS No. 24634-61-5); lactic acid and its salts; L-(+)-lactic acid (CAS No. 79-33-4); benzoic acid and its sodium salt (CAS No. 65-85-0, CAS No. 532-32-1) and salts of benzoic acid, such as ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate; salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate , TEA salicylate; benzalkonium chloride, bromide and saccharinate, such as benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS numbers 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 numbers 68424-95-3 and CAS number 7173-51-5); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine, CAS number 2372-82-9); peracetic acid (CAS number 79-21-0); hydrogen peroxide (CAS number 7722-84-1);

[0268] The antibacterial agent is added to the composition at a concentration of 0.001 to 10% by weight of the total composition.

[0269] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0270] Therefore, the present invention also includes a method for protecting an aqueous composition according to the present invention from bacterial contamination or growth, which method comprises adding 2-phenoxyethanol. Thus, the present invention also includes a method for imparting antimicrobial benefits to textiles after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, sticks, etc.), liquid laundry detergent, fabric softener, or post-rinse treatment agent containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0271] In a further embodiment, the present invention also encompasses a composition comprising an inventive polymer as described herein above, and further comprising an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2-phenoxyethanol, more preferably in an amount ranging from 2 ppm to 5% by weight of the composition, and even more preferably 0.1 to 2% phenoxyethanol.

[0272] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition from microbial contamination or growth, such composition comprising an inventive polymer as described hereinabove, such composition being preferably a detergent composition, such method comprising adding at least one antimicrobial agent selected from the antimicrobial agents of the present disclosure as disclosed hereinafter, such antimicrobial agent being preferably 2-phenoxyethanol.

[0273] In a further embodiment, the present invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid laundry softener composition, each of which comprises an inventive polymer as described herein above, and each of which further comprises 4,4'-dichoro-2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, by weight of the composition.

[0274] In a further embodiment, the present invention also encompasses a method of laundering fabrics or cleaning hard surfaces, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwashing composition, even more preferably a liquid laundry detergent composition or a liquid laundry softener composition, such composition comprising an inventive polymer as described herein above, such composition further comprising 4,4'-dichoro 2-hydroxydiphenyl ether.

[0275] As used herein, the term "dye fixing agent" refers to a compound that reduces or even eliminates color bleeding during the washing process of colored fabrics. Dye fixing agents include, but are not limited to, cationic dye fixing agents, crosslinking fixation agents, and formaldehyde-based fixing agents. Those skilled in the art are familiar with these compounds, and they can be purchased commercially from BASF SE, Huntsman, Archroma, Fineotex, Biotex Malaysia, or Dystar. Non-limiting examples of dye fixing agents include Basilen Fixing Agent F-RP, Albafix ECO, Finofix NF, poly DADMAC, and polyamines (such as DCDA-DETA, Epichloro-DMA, and Epichloro-DETA).

[0276] Formulations according to the invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0277] Further optional ingredients can be, but are not limited to, viscosity modifiers, cationic surfactants, suds boosters or suppressors, fragrances, dyes, optical brighteners and dye transfer inhibitors.

[0278] (b) General cleaning compositions and formulations The liquid formulations disclosed in this section may contain 0-2%, preferably about 1%, of 2-phenoxyethanol in addition to all other ingredients mentioned.

[0279] The liquid formulations disclosed above and below can contain 0-0.2%, preferably about 0.15%, of 4,4'-dichoro 2-hydroxydiphenyl ether in addition to all other ingredients described above. The bleach-free solid laundry compositions can contain 0-0.2%, preferably about 0.15%, of 4,4'-dichoro 2-hydroxydiphenyl ether in addition to all other ingredients described above.

[0280] The formulations disclosed in this chapter may comprise, in addition to all other ingredients mentioned above, one or more enzymes selected from those disclosed herein above, more preferably a protease and / or amylase, and even more preferably the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN' numbering), and the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881A1, and such enzymes are preferably present in the formulation at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, and even more preferably from about 0.001% to about 0.5% of the enzyme protein by weight of the composition.

[0281] The compositions set forth below, including those set forth in the following tables, disclose certain types of general cleaning compositions, which represent typical compositions corresponding to typical cleaning conditions commonly employed in various regions and countries of the world. At least one inventive polymer can be added to such formulations in an appropriate amount as outlined herein.

[0282] Compositions shown here that do not contain a polymer of the present invention are comparative compositions, and when the polymer of the present invention is contained in an amount, particularly in a preferred range, more preferred range, etc., as described herein, such compositions are also considered to be within the scope of the present invention.

[0283] In a preferred embodiment, at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine (as defined in any of the embodiments herein, particularly embodiments 1-15; in this section, the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine is also referred to as the "polymer of the invention") is used in a laundry detergent.

[0284] The liquid laundry detergent according to the present invention comprises: 0.05 to 20% of at least one polymer of the present invention; 1 to 50% surfactant, 0.1 to 40% of a builder, cobuilder and / or chelating agent; With 0.1 to 50% of other adjuvants, Water that adds up to 100% It consists of:

[0285] Preferred liquid laundry detergents according to the present invention include: 0.2 to 6% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15 LAS and C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units; 1.5 to 10% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 2-20% of a soluble organic builder / cobuilder selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids; an enzyme system comprising 0.05 to 5% of at least one enzyme suitable for detergent applications, preferably further comprising an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1 to 20% of other adjuvants, Water that adds up to 100% It consists of:

[0286] The solid laundry detergent (e.g., powder, granule, or tablet) according to the present invention comprises: 0.05 to 20% of at least one polymer of the present invention; 1 to 50% surfactant, 0.1 to 80% of a builder, cobuilder and / or chelating agent; 0-50% bulking agent and 0-40% bleaching active substance and 0.1 to 30% of other adjuvants and / or water, It consists of The ingredients add up to 100%.

[0287] A preferred laundry detergent bar according to the invention comprises: 0.2 to 6% of at least one polymer of the present invention; 5 to 30% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl sulfates, and C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units; 1.5 to 7.5% of a nonionic surfactant selected from C10 to C18 alkyl ethoxylates containing 3 to 10 ethoxy units; 5-50% of an inorganic builder selected from sodium carbonate, sodium bicarbonate, zeolite, soluble silicates, and sodium sulfate; 0.5 to 15% of a cobuilder selected from C10 to C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids and polycarboxylic acids; an enzyme system comprising 0.1 to 5% of at least one enzyme suitable for detergent applications, preferably further comprising an enzyme stabilizing system; With 0.1 to 20% of other adjuvants, Water that adds up to 100% It consists of:

[0288] In a preferred embodiment, the polymers according to the present invention are used in hand dish detergents.

[0289] The liquid hand dish detergent according to the present invention comprises: 0.05 to 10% of at least one polymer of the present invention; 1 to 50% surfactant, With 0.1 to 50% of other adjuvants, Water that adds up to 100% It consists of:

[0290] Preferred liquid hand dish detergents according to the present invention include: 0.2 to 5% of at least one polymer of the present invention; 5 to 40% of an anionic surfactant selected from C10 to C15-LAS, C10 to C18 alkyl ether sulfates containing 1 to 5 ethoxy units, and C10 to C18 alkyl sulfates; 0-10% cocamidopropyl betaine and 0-10% lauramine oxide, 0-2% of a nonionic surfactant, preferably a C10 Guerbet alcohol alkoxylate; 0-5% of an enzyme, preferably an amylase, and preferably also an enzyme stabilizing system; 0.5 to 20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol; With 0.1 to 20% of other adjuvants, Water that adds up to 100% It consists of:

[0291] The polyalkyleneimine or polyamine polymers of the present invention are biodegradable, and cleaning formulations, in particular, typically have a pH of about 7 or higher and often also contain enzymes to break down biodegradable substances, such as grease, proteins, and polysaccharides, present in stains and soils and that need to be removed by the cleaning composition. Therefore, some consideration must be given when formulating such biodegradable polymers of the present invention. Suitable formulations are known in principle and include solid, liquid, and semi-liquid formulations. In the case of solids, the enzyme and polymer can be separated by a coating or can be added as separate particles. In the case of liquids and semi-liquids, the polymer and enzyme can be separately formulated in different compartments, such as a multi-compartment sachet or a multi-compartment bottle, with predetermined amounts of liquid dispensed simultaneously to ensure that each component is applied in the correct amount for each individual application. Such multi-compartment sachets and bottles are also known to those skilled in the art.

[0292] The following tables show certain types of common cleaning compositions, which correspond to typical compositions associated with typical cleaning conditions commonly employed in different regions and countries of the world. To such formulations, at least one inventive polymer can be added in an appropriate amount as outlined herein.

[0293] [Table 1]

[0294] [Table 2]

[0295] [Table 3]

[0296] [Table 4]

[0297] [Table 5]

[0298] [Table 6]

[0299] [Table 7]

[0300] [Table 8]

[0301] [Table 9]

[0302] [Table 10]

[0303] The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.

[0304] The specific embodiments described throughout this disclosure are included herein as part of the present invention; various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" (or "preferably," etc.) options for a particular embodiment can be selected individually and independently (unless such independent selection is impossible due to the nature of the feature or unless such independent selection is expressly excluded) and can be combined within any other embodiment (provided that other such options and preferences can also be selected individually and independently, unless such independent selection is impossible due to the nature of the feature or unless such independent selection is expressly excluded), and each and every such possible combination is included as an individual embodiment as part of the present invention. [Example]

[0305] Hereinafter, "CL / NH" means caprolactone (CL) repeat units per NH function of the polyalkyleneimine or polyamine used in step a), "EO / NH" means ethylene oxide (EO) repeat units per NH function of the polyalkyleneimine or polyamine used in step a), and "PO / NH" means propylene oxide (PO) repeat units per NH function of the polyalkyleneimine or polyamine used in step a).

[0306] The amounts of ε-caprolactone, ethylene oxide, and propylene oxide added in the reactions described below are calculated based on the determined OH number of the precursor polymer. In the table below, the amounts of ε-caprolactone, ethylene oxide, and propylene oxide have been recalculated to ensure that the equivalent amounts of ε-caprolactone, ethylene oxide, and propylene oxide per NH functionality of the polyalkyleneimine or polyamine used in step a) are consistent with the definitions chosen in the claims and throughout this patent application.

[0307] Abbreviations used in particular in the tables: PDI = polydispersity index; MW = molecular weight determined by multi-angle light scattering (MALLS or LS); hbPEI = hyperbranched poly(ethyleneimine); CL = ε-caprolactone; EO = ethylene oxide; PO = propylene oxide; LOM = launderometer; HP20 = Sokalan® HP20 = ethoxylated PEI.

[0308] 1) Synthesis Examples a) Example Synthesis for Removing Clay Stains A summary of the examples prepared is shown in Table 5.

[0309] [Table 11]

[0310] i) Synthesis of polymers 1.1-1.3 and Ref2 Polymers 1.1-1.3 and Ref2 were prepared by a two-step process.

[0311] 1) Addition of caprolactone to poly(ethyleneimine) Typically, 100 g of poly(ethyleneimine) MW 800 (Lupasol® FG, commercially available from BASF SE, Germany) is placed in a four-necked round-bottom flask equipped with a condenser and a dropping funnel under a nitrogen atmosphere. The product is heated to 80°C, and the respective amount of caprolactone per NH functional group of the poly(ethyleneimine) is slowly added at 80°C. After the caprolactone addition, the temperature is slowly increased to 160°C, and the mixture is reacted at 160°C for 16 hours to ensure that no residual caprolactone remains. Typically, a light brown, highly viscous liquid is obtained with a yield of >90%.

[0312] 2) Ethoxylation of hbPEI800-XCL / NH (X = 2, 3, 4 or 5) Typically, 100 g of the hbPEI800-XCL / NH (X = 2, 3, 4, or 5) obtained above is charged into a steel pressure reactor, and 0.2 wt. % potassium methoxide (32.5 wt. % in methanol) based on the total weight of the final product is added. Methanol is removed at 80 °C and 20 mbar. Air is removed from the reactor by purging with nitrogen, and the nitrogen pressure is set to 2 bar. The reactor is heated to 120 °C, and the respective amount of ethylene oxide is added to the reactor within 8 hours. The amount of ethylene oxide added is calculated based on the calculated OH value of the hbPEI800-XCL / NH (X = 3, 4, or 5) reactant. The amount of ethylene oxide in Table 5 is recalculated to obtain the equivalent amount of ethylene oxide added per NH functional group of poly(ethyleneimine). The mixture is post-reacted at 120 °C for 6 hours to eliminate residual ethylene oxide. Typically, a light brown, highly viscous liquid is obtained in a yield of >90%.

[0313] The notation "polymer hbPEI800-3CL / NH-20EO / NH" is synonymous with the notation "polymer hbPEI800-3CL / NH-25EO / OH."

[0314] The notation "polymer hbPEI800-4CL / NH-26EO / NH" is synonymous with the notation "polymer hbPEI800-4CL / NH-35EO / OH."

[0315] The notation "polymer hbPEI800-5CL / NH-27EO / NH" is synonymous with the notation "polymer hbPEI800-5CL / NH-35EO / OH."

[0316] The first expression is the amount of EO recalculated relative to the NH functional groups of the polyalkyleneimine, and the second expression shows the actual molar amount of EO used per OH functional group determined for the precursor.

[0317] ii) Comparative example Ref1 Sokalan® HP20 (Ref 1) is commercially available from BASF SE (Ludwigshafen, Germany) and was used without modification.

[0318] iii) Test results for all examples on clay stain removal All of the polymers 1.1 to 1.3 of the present invention are readily biodegradable, ie, the biodegradation rate after 28 days in OECD301F is ≧60%, whereas neither of the comparative examples (Ref1 and Ref2) are readily biodegradable.

[0319] b) Synthesis of Examples for Removing Oily / Greasy Stains A summary of the examples prepared is shown in Table 6.

[0320] [Table 12]

[0321] i) Synthesis of polymers 2.1-2.5 and Ref4 Polymers 2.1-2.5 and Ref4 were prepared by a three-step process.

[0322] 1) Addition of caprolactone to poly(ethyleneimine) Typically, 100 g of poly(ethyleneimine) with a molecular weight of 800 (Lupasol® FG, commercially available from BASF SE, Germany), 2000 (Lupasol® PR8515, commercially available from BASF SE, Germany), or 5000 (Lupasol® G100, commercially available from BASF SE, Germany) is placed in a four-neck round-bottom flask equipped with a condenser and a dropping funnel under a nitrogen atmosphere. The product is heated to 80°C, and the respective amount of caprolactone per NH functional group of the poly(ethyleneimine) is slowly added at 80°C. After the caprolactone addition, the temperature is slowly increased to 160°C, and the mixture is reacted at 160°C for 16 hours to ensure that no residual caprolactone remains. Typically, a light brown, highly viscous liquid product is obtained in a yield of >90%.

[0323] 2) First alkoxylation of hbPEI(MW)-XCL / NH (X=2, 3, 4, or 5) Typically, 100 g of the hbPEI(MW)-XCL / NH (X = 2, 3, 4, or 5) obtained above is charged into a steel pressure reactor, and 0.2 wt. % potassium methoxide (32.5 wt. % in methanol) based on the total weight of the final product is added. Methanol is removed at 80°C and 20 mbar. Air is removed from the reactor by purging with nitrogen, and the nitrogen pressure is set to 2 bar. The reactor is heated to 130°C, and the respective amount of ethylene oxide is introduced into the reactor within 8 hours. The amount of ethylene oxide added is calculated based on the determined OH value of the hbPEI800-XCL / NH (X = 2, 3, 4, or 5) reactant. The amount of ethylene oxide in Table 6 is recalculated to obtain the equivalent amount of ethylene oxide added per NH functional group of poly(ethyleneimine). The mixture is post-reacted at 130°C for 3 hours to remove residual ethylene oxide.

[0324] 3) Second Alkoxylation of hbPEI(MW)-XCL / NH (X=2, 3, 4, or 5) Subsequently, within 6 hours, the product from step (2) is charged with the respective amount of propylene oxide in the reactor. The amount of propylene oxide added is calculated based on the OH value determined for the initial hbPEI800-XCL / NH (X = 2, 3, 4, or 5) reactant. The amount of propylene oxide in Table 6 is recalculated to obtain the equivalent amount of propylene oxide added per NH functionality of poly(ethyleneimine). The mixture is post-reacted at 130°C for 6 hours to eliminate residual propylene oxide. A light brown, highly viscous liquid product is typically obtained in a yield of >90%.

[0325] The notation "polymer hbPEI2000-2CL / NH-22EO / NH-15PO / NH" is synonymous with the notation "polymer hbPEI2000-2CL / NH-30EO / OH-20PO / OH."

[0326] The notation "polymer hbPEI800-3CL / NH-21EO / NH-14PO / NH" is synonymous with the notation "polymer hbPEI800-3CL / NH-30EO / OH-20PO / OH."

[0327] The notation "polymer hbPEI2000-3CL / NH-21EO / NH-21PO / NH" is synonymous with the notation "polymer hbPEI2000-3CL / NH-30EO / OH-30PO / OH."

[0328] The notation "polymer hbPEI2000-4CL / NH-27EO / NH-27PO / NH" is synonymous with the notation "polymer hbPEI2000-4CL / NH-40EO / OH-40PO / OH."

[0329] The notation "polymer hbPEI2000-5CL / NH-33EO / NH-35PO / NH" is synonymous with the notation "polymer hbPEI2000-5CL / NH-50EO / OH-50PO / OH."

[0330] The notation "polymer hbPEI5000-3CL / NH-20EO / NH-20PO / NH" is synonymous with the notation "polymer hbPEI5000-3CL / NH-30EO / OH-30PO / OH."

[0331] The first expression is the amount of EO and PO recalculated relative to the NH functionality of the polyalkyleneimine, and the second expression is the actual molar amount of EO used per OH value calculated for the precursor.

[0332] ii) Comparative example Ref3 Ref3 is prepared in a three-step process.

[0333] 1) hbPEI800+0.9EO / NH 400 g of hbPEI800 (Lupasol® FG, commercially available from BASF SE, Ludwigshafen, Germany) and 40 g of distilled water are charged into a steel pressure reactor. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is then heated to 100°C, and 369 g of ethylene oxide are charged within 4 hours. The reaction mixture is then maintained at 100°C for post-reaction. Volatile compounds are removed under vacuum, and 766 g of a yellowish solid product (99% yield) is removed from the reactor.

[0334] 2) hbPEI800+24EO / NH 100 g of hbPEI800+0.9EO / NH obtained in step 1) are charged into a steel pressure reactor and 9.9 g of potassium hydroxide (50% by weight) are added. Water is removed at 80°C and 20 mbar. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is heated to 120°C and 1232 g of ethylene oxide are charged within 12 hours. The mixture is post-reacted at 120°C for 4 hours to eliminate any residual ethylene oxide. 1335 g of a dark orange, viscous liquid product are obtained (yield 100%).

[0335] 3) hbPEI800+24EO / NH+16PO / NH 700 g of hbPEI800+24EO / NH obtained in step 2) are charged into a steel pressure reactor and 2.6 g of potassium hydroxide (50% by weight) are added. Water is removed at 80°C and 20 mbar. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is heated to 130°C and 592 g of propylene oxide are added within 10 hours. The mixture is post-reacted at 130°C for 4 hours to eliminate any residual propylene oxide. 1274 g of a dark orange, viscous liquid product (98% yield) are obtained.

[0336] iii) Synthesis of polymer 2.6 The polymer was prepared in a three-step process.

[0337] 1) hbPEI2000-4CL / NH 120 g of poly(ethyleneimine) MW 2000 (Lupasol® PR8515, commercially available from BASF SE, Germany) is placed in a four-necked round-bottom flask equipped with a condenser and a dropping funnel under a nitrogen atmosphere. The product is heated to 80°C, and 1285 g of ε-caprolactone per NH functional group of poly(ethyleneimine) is slowly added at 80°C. After the addition of ε-caprolactone, the temperature is slowly increased to 160°C, and the mixture is reacted at 160°C for 16 hours to eliminate any residual caprolactone. 1422 g of a dark, viscous liquid product are obtained with a yield of 94%.

[0338] 2) hbPEI2000-4CL / NH-22EO / NH 200 g of hbPEI2000-4CL / NH obtained in step 1) is charged into a pressure reactor and 3.6 g of potassium methoxide (32.5 wt. % in methanol) is added. Methanol is removed at 80°C and 20 mbar. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is heated to 120°C and 382 g of ethylene oxide is charged within 7 hours. The mixture is post-reacted at 120°C for 6 hours to remove any residual ethylene oxide. The amount of ethylene oxide added is calculated based on the determined OH number of the hbPEI2000-4CL / NH reactant. The mixture is post-reacted at 120°C for 6 hours to remove any residual ethylene oxide. 582 g of a dark orange, viscous liquid product is obtained with a yield of 99%.

[0339] The notation "polymer hbPEI2000-4CL / NH-22EO / NH" is synonymous with the notation "polymer hbPEI2000-4CL / NH-30EO / OH."

[0340] 3)hbPEI2000-4CL / NH-22EO / NH-(3CL-mix-16PO) / NH 250 g of hbPEI2000-4CL / NH-22EO / NH was charged into a steel pressure reactor, and 3.8 g of potassium methoxide (32.5 wt. % in methanol) was added. Methanol was removed at 80 °C and 20 mbar. The reactor was purged with nitrogen to remove air, and the nitrogen pressure was set at 2 bar. The reactor was heated to 130 °C, and a mixture of 286 g of propylene oxide and 74 g of caprolactone was charged into the reactor within 10 hours. The amounts of propylene oxide and caprolactone added were calculated based on the determined OH number of the hbPEI2000-4CL / NH-22EO / NH reactant. The mixture was post-reacted at 130 °C for 6 hours to remove residual propylene oxide and caprolactone. 585 g of a brown, viscous liquid product was obtained (96% yield).

[0341] The notation "polymer hbPEI2000-4CL / NH-22EO / NH-(3CL-mix-16PO) / NH" is synonymous with the notation "polymer hbPEI2000-4CL / NH-30EO / OH-(3CL-mix-23PO) / OH."

[0342] iv) Synthesis of polymer 2.7 The polymer was prepared in a three-step process.

[0343] 1) hbPEI2000-4CL / NH hbPEI2000-4CL / NH was prepared as described in section iv) step 1) for polymer 2.6.

[0344] 2)hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH 200 g of hbPEI2000-4CL / NH obtained in step 1) is charged into a pressure reactor, and 4.0 g of potassium methoxide (32.5 wt. % in methanol) is added. Methanol is removed at 80 °C and 20 mbar. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is heated to 120 °C, and a mixture of 363 g of ethylene oxide and 94 g of caprolactone is charged into the reactor within 8 hours. The amounts of ethylene oxide and caprolactone added are calculated based on the determined OH number of the hbPEI2000-4CL / NH reactant. The mixture is post-reacted at 120 °C for 6 hours to remove residual ethylene oxide and caprolactone. 642 g of a dark orange solid product (yield 98%) is obtained.

[0345] The notation "polymer hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH" is synonymous with the notation "polymer hbPEI2000-4CL / NH-(3CL-mix-30EO) / OH."

[0346] 3)hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH-22PO / NH 250 g of hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH obtained in step 2) is charged into a steel pressure reactor and 2.3 g of potassium methoxide (32.5 wt. % in methanol) is added. Methanol is removed at 80 °C and 20 mbar. The reactor is purged with nitrogen to remove air, and the nitrogen pressure is set to 2 bar. The reactor is heated to 130 °C, and within 8 hours, 373 g of a mixture of propylene oxide is charged into the reactor. The amount of propylene oxide added is calculated based on the determined OH number of the hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH reactant. The mixture is post-reacted at 130 °C for 6 hours to eliminate residual propylene oxide. 620 g of a dark orange solid product (98% yield) is obtained.

[0347] The notation "polymer hbPEI2000-4CL / NH-(3CL-mix-21EO) / NH-22PO / NH" is synonymous with the notation "polymer hbPEI2000-4CL / NH-(3CL-mix-30EO) / OH-30PO / OH."

[0348] v) Results for removal of all oily / greasy stains with polymers 2.1-2.7 The biodegradability of the polymers 2.1 to 2.7 of the present invention was significantly improved compared to both Ref3 and Ref4.

[0349] 2) Characterization of the polymer of the present invention and comparative examples The identity of the resulting polymers of the present invention was confirmed by H- and C-NMR spectroscopy in deuterated methanol. H-NMR spectra were recorded at room temperature on a Bruker AV-401 instrument. C-NMR spectra were recorded at room temperature on a Bruker AV-401 instrument.

[0350] The molecular weights of the polymers of the present invention and comparative examples can be determined by gel permeation chromatography (GPC). Measurements can be performed using a combination of two columns (styrene-divinylbenzene and polyester copolymers, both 25 cm long and 4.6 mm in diameter) and 0.05 wt. % potassium trifluoroacetate in hexafluoroisopropanol as the eluent. Molecular weights can be obtained using an RI detector and PEO calibration standards (Polymer Laboratories / Agilent, USA). Additionally, absolute molecular weights can be determined by multi-angle light scattering (MALLS).

[0351] The OH numbers of the inventive polymers and their intermediates were determined according to the respective ISO standards and in accordance with BASF's in-house procedures.

[0352] The amine number was determined according to the method described in DIN 16945.

[0353] 3) Biodegradation data Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures sample biodegradation by measuring oxygen consumption. A measured volume of medium was added with 100 mg / L of the test substance, nominally the sole carbon source, along with an inoculum (30 mg / L, aerated sludge taken from the Mannheim municipal wastewater treatment plant). This was stirred in a sealed flask at a constant temperature (20°C or 25°C) for 28 or 56 days, respectively. Oxygen consumption was determined by measuring the pressure change in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). The released carbon dioxide was absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent oxygen from being used by nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for the amount taken up by a parallel blank inoculum) is expressed as a percentage of ThOD (theoretical oxygen demand as determined by elemental analysis of the compound). For each cabinet, test samples are tested along with the positive controls glucose / glutamic acid.

[0354] 4) Application experiment Table 7 shows the base liquid laundry detergent without polymer (LLD.1) used in application testing to determine the effect of the inventive polymer on primary wash performance.

[0355] [Table 13]

[0356] Primary cleaning performance for particle stains To determine primary detergency, cleaning performance against four different particle stains on polyester fabric (CFT, Vlaardingen, The Netherlands) was measured using a reflectometer (Mach5 plus, a multi-area color measurement device from ColourConsult) to determine the color difference (Delta E) between the washed stain and an unstained white fabric. Experiments involving four different particle circular stains (ground clay, standard clay, red china clay, and tennis court clay; all four stains on the same polyester fabric) were repeated three times, using two such fabrics per wash, and the resulting data were used to calculate an average Delta E.

[0357] These Delta E values ​​were used to calculate for each stain what is called a "normalized cleaning performance" (Delta Delta E), which is the difference in performance between a laundry detergent containing a modified alkoxylated polyalkyleneimine of the present invention or a comparative polymer, respectively, compared to a laundry detergent containing neither the modified alkoxylated polyalkyleneimine nor the comparative polymer, respectively.

[0358] Table 8 shows the wash test conditions, and Table 9 summarizes the resulting normalized wash performance. The normalized wash performance shown in Table 9 is the sum of the normalized wash performances for all four stains. The higher the sum of the ΔΔE values, the greater the positive contribution of the modified alkoxylated polyalkyleneimine of the present invention or the comparative polymer compared to the wash performance of a laundry detergent that does not contain the modified alkoxylated polyalkyleneimine or the comparative polymer, respectively.

[0359] [Table 14]

[0360] [Table 15]

[0361] Test results: The measurement error is ±2 ΔΔE units. Thus, any value above 2 (sum of ΔΔE) means that the respective polymer makes a directional, visible contribution to the overall cleaning performance of each detergent formulation; any value above 4 (sum of ΔΔE) means that the respective polymer makes even a significant contribution to the overall cleaning performance, i.e., the respective polymer significantly improves the formulation. All polymers (inventive and comparative) show high cleaning effectiveness against particle stains.

[0362] The cleaning performance of the modified alkoxylated poly(ethyleneimine) samples 1.1 to 1.3 of the present invention was equivalent to that of Sokalan® HP20 (Ref 1), even taking into account measurement error.

[0363] Primary cleaning performance for oily / greasy stains To determine primary detergency, cleaning performance against 16 different oily / greasy stains on cotton, polycotton, and polyester fabrics (CFT, Vlaardingen, The Netherlands) was measured using a reflectometer (Mach5 plus, a multi-area color measurement device from ColourConsult) to determine the color difference (ΔE) between the stains after cleaning and unstained white fabric. Experiments involving 16 different oily / greasy circular stains (lipstick, makeup, beef tallow, frying oil, burnt butter, palm oil, sebum BEY, sebum Tefo, collar soil; all on separate fabrics) were each repeated six times, and the resulting data were used to calculate the average ΔE.

[0364] These ΔE values ​​were used to calculate the so-called "normalized cleaning performance" (ΔΔE) for each stain, which is the difference in performance between a laundry detergent containing a modified alkoxylated polyalkyleneimine of the present invention or a comparative polymer, respectively, compared to a laundry detergent containing neither the modified alkoxylated polyalkyleneimine nor the comparative polymer, respectively.

[0365] Table 10 shows the wash test conditions, and Table 11 summarizes the resulting normalized wash performance. The normalized wash performance shown in Table 11 is the sum of the normalized wash performances for all 16 stains. The higher the sum of the ΔΔE values, the greater the positive contribution of the modified alkoxylated polyalkyleneimine of the present invention or the comparative polymer compared to the wash performance of a laundry detergent that does not contain the modified alkoxylated polyalkyleneimine or the comparative polymer, respectively.

[0366] [Table 16]

[0367] [Table 17]

[0368] Test results: The measurement error is ±10 ΔΔE units. Thus, any value above 10 (sum of ΔΔE) means that the respective polymer makes a directional, visible contribution to the overall cleaning performance of each detergent formulation; any value above 20 (sum of ΔΔE) means that the respective polymer makes even a significant contribution to the overall cleaning performance, i.e., the respective polymer significantly improves the formulation. All polymers (inventive and comparative) show high cleaning effectiveness against oily / greasy stains.

[0369] The cleaning performance of the modified alkoxylated poly(ethyleneimine) samples 2.1 to 2.7 of the present invention was equivalent to that of reference sample Ref.3 even taking into account measurement errors, and was significantly superior to that of reference sample Ref.4.

Claims

1. Steps a) to e) shown below: a) reacting 1) at least one polyalkyleneimine or at least one polyamine containing in total a plurality of primary and secondary amino groups with 2) at least one first lactone (LA1) and / or at least one first hydroxycarbon acid (HA1) to obtain a first intermediate (I1), wherein 3 to 10 mol of lactone (LA1) and / or hydroxycarbon acid (HA1) are used per mol of NH functional groups of the polyalkyleneimine or polyamine; b) reacting said first intermediate (I1) with (i) at least one first alkylene oxide (AO1) or (ii) with a mixture of 1) at least one first alkylene oxide (AO1) and 2) at least one second lactone (LA2) and / or at least one second hydroxycarbon acid (HA2) to obtain a second intermediate (I2), wherein at least 5.0 mol of first alkylene oxide (AO1) and, in the case of said mixture, additionally at least 1.0 mol of second lactone (LA2) and / or second hydroxycarbon acid (HA2) are used per mol of NH functional groups of the polyalkyleneimine or polyamine used in step a); c) optionally reacting said second intermediate (I2) with (i) at least one second alkylene oxide (AO2) or (ii) with a mixture of 1) at least one second alkylene oxide (AO2) and 2) at least one tertiary lactone (LA3) and / or at least one tertiary hydroxycarbon acid (HA3) to obtain a third intermediate (I3), wherein at least 5.0 mol of second alkylene oxide (AO2) and, in the case of said mixture, additionally at least 1.0 mol of tertiary lactone (LA3) and / or tertiary hydroxycarbon acid (HA3) are used per mol of NH functional groups of the polyalkyleneimine or polyamine used in step a); d) optionally, reacting the second intermediate (I2) or the third intermediate (I3) with at least one quaternary lactone (LA4) and / or at least one quaternary hydroxycarboxylic acid (HA4) to obtain a fourth intermediate (I4), wherein at least 1.0 mol of the quaternary lactone (LA4) and / or the quaternary hydroxycarboxylic acid (HA4) is used per mol of NH functional groups of the polyalkyleneimine or polyamine used in step a); e) optionally reacting said second intermediate (I2), third intermediate (I3) or fourth intermediate (I4) with at least one C1-C18 alkylating or esterifying reagent to obtain said modified alkoxylated polyalkyleneimine or said modified alkoxylated polyamine; A modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine obtainable by a process comprising: However, the modified alkoxylated polyalkyleneimine is not PEI800-3CL / NH-20EO / NH-2CL / NH (PEI800 is polyethyleneimine having a weight-average molecular weight (Mw) of 800 g / mol, CL is caprolactone, and EO is ethylene oxide), which is described as compound P5 in Table 5 of PCT / EP2022 / 072996 specification, but is a modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine.

2. 2. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to claim 1, wherein the at least one polyalkyleneimine or the at least one polyamine comprises at least two primary amino groups, and in the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine, more than 90%, preferably at least 95%, and more preferably at least 99% of the primary amino groups have reacted with the first lactone (LA1) and / or the first hydroxycarbon acid (HA1) to form amide bonds.

3. 3. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to claim 1 or 2, wherein the at least one polyalkyleneimine or the at least one polyamine comprises at least one secondary amino group, and in the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine, more than 50%, preferably at least 75%, and more preferably at least 90% of the secondary amino groups have reacted with the first lactone (LA1) and / or the first hydroxycarbon acid (HA1) to form an amide bond.

4. The polyalkyleneimine or polyamine of step a) has formula (I): 【Chemistry 1】 where the variables are defined as follows: R may be the same or different, i) linear or branched C ２ ~C １２ - an alkylene group or ii) a group represented by the following formula (III): 【Chemistry 2】 where the variables are defined as follows: R １０ , R １１ , R １２ are the same or different, linear or branched C ２ ~C ６ represents an alkylene group, d is an integer ranging from 0 to 50. represents an ether alkyl unit of the formula: B is, (i) the continuation of said polyalkyleneimine or polyamine by branching; and / or (ii) the same or different C １ ~C １８ - alkyl; represents y is an integer having a value of at least 1; z is an integer ranging from 0 to 150. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of claims 1 to 3, defined according to

5. Formula (Ia) and / or (Ib): 【Transformation 3】 (In both formulas, the variables are defined as follows: The dotted line represents the bond to the remainder of the modified alkoxylated polyalkyleneimine or alkoxylated polyamine; R is as defined above; E1 and E2 are of formula (IIa): -[C(=O)-R1-O]m-[(C(=O)-R1-O)n-mix-(R2-O)o-mix-(R3-O)q]-R4 (IIa) where -mix- defines that adjacent units are randomly distributed with respect to one another; m is an integer having a value of 1 to 20, n is an integer having a value of 0 to 20, o is an integer having a value of 5 to 150, q is 0 or an integer having a value of 5 to 150, and the sum of m and n (m+n) is at least 3; R1 is a linear or branched C ２ ~C １０ - an alkylene group, more preferably a linear or branched C ２ ~C ５ represents an alkylene group; R2 represents a linear or branched C2-C12-alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-ethylene; R3 represents a linear or branched C2-C12-alkylene group, more preferably 1,2-ethylene, 1,2-propylene and / or 1,2-butylene, most preferably 1,2-propylene and / or 1,2-butylene; R4 is hydrogen, unsubstituted or at least monosubstituted C １ ~C １８ -Alkyl, C ７ ~C １８ -aralkyl, -(CO)-C １ ~C １８ -alkyl, -(CO)-C ２ ~C １８ -alkenyl and / or -(CO)-C ７ ~C １８ -aralkyl, wherein the substituents are selected from -COOH or salts thereof, more preferably hydrogen, methyl, ethyl or monosubstituted -(CO)-C ２ ~C １８ -alkenyl, most preferably hydrogen, R2 and R3 are not identical) 5. The modified alkoxylated polyalkyleneimine or alkoxylated polyamine according to claim 1, comprising a structural element according to

6. i) steps a) to e) are all carried out as a single-step reaction, optionally in the presence of a catalyst; and / or ii) The weight average molecular weight (Mw) of the polyalkyleneimine or polyamine used in step a) is in the range of 50 to 20,000 g / mol, preferably in the range of 150 to 10,000 g / mol, more preferably in the range of 200 to 5,000 g / mol.

7. 7. The modified alkoxylated polyalkyleneimine of any one of claims 4 to 6, wherein the variables are each as defined below: R is ethylene and / or propylene, preferably ethylene; The sum of y+z is an integer having a value in the range of 4-200, preferably in the range of 10-150.

8. 8. The modified alkoxylated polyalkyleneimine or polyamine according to any one of claims 1 to 7, wherein up to 100% of the nitrogen atoms present in the modified alkoxylated polyalkyleneimine or polyamine are further quaternized, preferably the degree of quaternization of the nitrogen atoms present in the modified alkoxylated polyalkyleneimine or polyamine is in the range of 5% to 95%.

9. i) in step a), said first lactone (LA1) is caprolactone or lactide, and / or ii) in step a), the first hydroxycarboxylic acid (HA1) is lactic acid or glycolic acid; and / or iii) in steps b)(i) and (ii), the first alkylene oxide (AO1) is ethylene oxide or a mixture of ethylene oxide and propylene oxide or a mixture of ethylene oxide and butylene oxide, and / or in step b)(ii), the second lactone (LA2) is caprolactone or lactide, and / or the second hydroxycarbon acid (HA2) is lactic acid or glycolic acid, and / or iv) in steps c)(i) and (ii), the second alkylene oxide (AO2) is propylene oxide or a mixture of propylene oxide and ethylene oxide or a mixture of propylene oxide and butylene oxide, and / or in step c)(ii), the third lactone (LA3) is caprolactone or lactide, and / or the third hydroxycarbon acid (HA3) is lactic acid or glycolic acid; and / or v) in step d), said fourth lactone (LA4) is caprolactone or lactide, and / or vi) in step d), the quaternary hydroxycarboxylic acid (HA4) is lactic acid or glycolic acid; The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 8.

10. i) in steps b)(i), b)(ii), c)(i) and / or c)(ii) a total of 5 to 100 mol, preferably 10 to 80 mol, more preferably 12 to 60 mol, most preferably 15 to 40 mol of alkylene oxide (AO1 and / or AO2) is used per mol of NH functional groups of the polyalkyleneimine or polyamine, and more than 70 mol %, preferably more than 90 mol % of said alkylene oxide is ethylene oxide; and / or ii) in steps a), b)(ii), c)(ii) and / or d), a total of 3 to 10 mol, preferably 3 to 7 mol, more preferably 3 to 6 mol of lactone (LA1, LA2, LA3 and / or LA4) and / or 3 to 20 mol, preferably 3 to 15 mol, more preferably 3 to 10 mol of hydroxycarbon acid (HA1, HA2, HA3 and / or HA4) is used per mol of NH functional groups of the polyalkyleneimine or polyamine, The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 9.

11. i) in steps b)(i), b)(ii), c)(i) and / or c)(ii) a total of 25 to 120 mol, preferably 30 to 100 mol, more preferably 35 to 90 mol, most preferably 40 to 80 mol of alkylene oxide (AO1 and / or AO2) is used per mol of NH functional groups of the polyalkyleneimine or polyamine, and less than 70 mol %, preferably less than 60 mol %, of said alkylene oxide is ethylene oxide; ii) in steps a), b)(ii), c)(ii) and / or d), a total of 3 to 10 mol, preferably 3 to 8 mol, more preferably 3 to 7 mol of lactone (LA1, LA2, LA3 and / or LA4) and / or 3 to 20 mol, preferably 3 to 15 mol, more preferably 3 to 10 mol of hydroxycarbon acid (HA1, HA2, HA3 and / or HA4) is used per mol of NH functional groups of the polyalkyleneimine or polyamine, The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 9.

12. (1) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 500 g / mol to 1000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional groups of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide is used per mol of NH functional groups of the polyalkyleneimine; or (2) in step a) the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 500 g / mol to 1000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional groups of the polyalkyleneimine; in step b)(ii) a mixture of 15 to 40 mol of ethylene oxide and 1 to 3 mol of caprolactone is used per mol of NH functional groups of the polyalkyleneimine; or (3) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 1500 g / mol to 2500 g / mol, and 3 to 5 mol of caprolactone are used per mol of NH functional groups of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide are used per mol of NH functional groups of the polyalkyleneimine; in step c)(i), 15 to 40 mol of propylene oxide are used per mol of NH functional groups of the polyalkyleneimine; the molar ratio of EO:PO is in the range of 1.5:1 to 1:1.5; or (4) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 4000 g / mol to 6000 g / mol, and 3 to 5 mol of caprolactone are used per mol of NH functional groups of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide are used per mol of NH functional groups of the polyalkyleneimine; in step c)(i), 15 to 40 mol of propylene oxide are used per mol of NH functional groups of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.5; or (5) in step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 1500 g / mol to 2500 g / mol, and 3 to 5 mol of caprolactone are used per mol of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide are used per mol of NH functional group of the polyalkyleneimine; in step c)(ii), a mixture of 15 to 40 mol of propylene oxide and 1 to 3 mol of caprolactone are used per mol of NH functional group of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.5; or (6) In step a), the at least one polyalkyleneimine is a polyethyleneimine having a weight average molecular weight (Mw) in the range of 4000 g / mol to 6000 g / mol, and 3 to 5 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; in step b)(i), 15 to 40 mol of ethylene oxide is used per mol of NH functional group of the polyalkyleneimine; in step c)(ii), a mixture of 15 to 40 mol of propylene oxide and 1 to 3 mol of caprolactone is used per mol of NH functional group of the polyalkyleneimine; the molar ratio of ethylene oxide to propylene oxide is in the range of 1.5:1 to 1:1.

5. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 11.

13. 13. The modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 12, wherein the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine has a biodegradability according to OECD standard 301F of at least 20%, preferably at least 40%, more preferably at least 60% after at least 56 days, preferably after 28 days.

14. 14. A process for preparing a modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 13, comprising carrying out the process steps according to any one of claims 1 to 13.

15. 14. Use of the modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 13 in cleaning compositions, in fabric care and home care products, in cosmetic formulations, as crude oil emulsion breakers, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions, as dispersants for agrochemical formulations.

16. 16. Use according to claim 15 in a cleaning composition and / or in a fabric care and home care product, preferably in a cleaning composition, comprising i) to remove clay, and / or ii) to improve the removal of oily / greasy stains, and / or iii) to remove particulate stains, and / or iv) to disperse and / or emulsify dirt, and / or v) to modify the treated surface to improve removal of subsequent recontamination; and / or vi) to improve whiteness, and / or vii) selected from the list consisting of lipases, hydrolases, amylases, deoxyribonucleases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases and combinations of at least two of the aforementioned types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the aforementioned types, more preferably wherein at least one enzyme is a protease, when at least one enzyme is present, additionally for improving oily / greasy stain removal, food stain removal and / or combination stain removal, The use of Most preferably, in the cleaning composition: i) clay removal and / or ii) oily / greasy stain removal It is used to improve The above mentioned options i) to vii) each preferably relate to the use in laundry detergent formulations and / or hand dishwashing detergent compositions, and / or formulations suitable for the (pre)treatment of textiles, and / or bar soaps, more preferably in liquid laundry detergent formulations and / or liquid hand dishwashing detergent compositions.

17. 14. Cleaning compositions, fabric and home care products, institutional cleaning products, cosmetic formulations, crude oil emulsion breakers, pigment dispersions for inkjet inks, electroplating formulations, cementitious compositions, dispersants for agrochemical formulations, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 13, preferably cleaning compositions and / or fabric and home care products and / or institutional cleaning products comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 13.

18. 18. A cleaning composition according to claim 17, comprising at least one modified alkoxylated polyalkyleneimine or modified alkoxylated polyamine according to any one of claims 1 to 13, at least one anionic surfactant and water.

19. (a) further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichloro 2-hydroxydiphenyl ether; preferably 2-phenoxyethanol in an amount of 2 ppm to 5% by weight of the composition; more preferably phenoxyethanol in an amount of 0.1 to 2% or preferably 4,4'-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 to 3%, more preferably 0.002 to 1%, even more preferably 0.01 to 0.6%, each by weight of the composition; and / or (b) selected from the list consisting of lipases, hydrolases, amylases, deoxyribonucleases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the aforementioned types, preferably further comprising at least one enzyme selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the aforementioned types, more preferably wherein the at least one enzyme is selected from proteases; 19. The composition of claim 17 or 18.

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