Polypropyleneimine polymers (PPIs), their preparation, uses and compositions containing such PPIs

Abstract

The present invention deals with polypropyleneimine polymers (PPIs) bearing side chains resulting from polycondensation or polyaddition reactions with alkylene oxides and lactones and / or hydroxycarbon acids and their derivatives, their preparation and use, for example in laundry or dishwashing.

Description

[Technical field]

[0001] The present invention deals with polypropyleneimine homopolymers and copolymers (abbreviated in the present invention as "PPI" or "inventive polymer" or "polymer of the invention" whenever referring to an inventive polymer), their manufacture, their use in particular for use in cleaning compositions such as laundry detergent and dishwashing detergent compositions, in particular for improved oily / greasy soil removal in laundry care and for preventing or reducing glass corrosion in dishwashing, for improved degreasing properties in dishwashing, and many others.

[0002] Additionally, hereinafter, all alkylene oxides may be referred to collectively as "AO," ethylene oxide as "EO," propylene oxide as "PO," and butylene oxide as "BuO." "PEO" is used in some parts of this specification to describe polyethylene oxide homopolymers or PEO blocks in larger polymer structures, and similarly, "PPO" describes polypropylene oxide homopolymers or polymer blocks in larger polymer structures. [Background technology]

[0003] Detergent formulators are continually challenged to develop improved products for the removal of various soils and stains from fabrics and hard surfaces. Chemically and physicochemically, the various soils and stains range from polar soils such as proteinaceous, clay, 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. The removal of greasy (i.e. oily / fatty) stains has been a particularly challenging challenge. This challenge has become prominent due to the recent high interest and drive to reduce the concentration of surfactants in cleaning detergents for environmental, sustainability, and cost reasons. It has been found that the reduction in the concentration of surfactants, especially oil-derived surfactants such as linear alkyl benzene sulfonates (LAS), generally leads to weakened oily / fatty stain removal. Moreover, this class of oily and fatty stains shows a significant decrease in performance when the temperature is reduced, so the trend to use lower temperature washing conditions worldwide further reduces the grease cleaning ability of common detergents. Also, the challenge of reducing or avoiding glass corrosion during cleaning of any kind of glass surface during dishwashing in particular, and even more particularly, automatic dishwashing (the latter sometimes referred to as "ADW"), poses another problem.

[0004] Another global trend is the compaction of laundry and dishwashing detergents (e.g., single, single-dose products, tablets, pouches, etc.) to improve sustainability in terms of water usage and / or transportation costs and to improve convenience for the end consumer, which creates high market demand for new raw materials that are weight-efficient and have significantly broader performance profiles.

[0005] A further trend that has recently and rapidly emerged is the desire to improve the "footprint" of any product, whether that be with regard to its origin, such as being derived from natural or renewable resources, or with regard to its production, in terms of production efficiency and thus reduced energy use, all compared to past products, with regard to its efficiency of use, such as the same performance at reduced quantities or improved performance at the same usage level, or with regard to its permanence in the natural environment during and / or after its use, such as biodegradation.

[0006] Therefore, due to climate change, one of the most important goals of the detergent and cleaning agent (D&C) industry today, for example, is to improve the washing efficiency at low temperatures of 40, 30, or 20 or even lower, improving cold water conditions to significantly reduce CO2 emissions per wash, as well as increasing the weight efficiency of the washing technology to reduce the amount of chemicals used per wash. Another technological hurdle is the reduction of glass corrosion in automatic dishwashing (ADW), in order to generally prolong the useful life of dishware, thereby contributing to improving overall sustainability. Another important goal of the D&C industry is the need for biodegradable polymers to improve the sustainability of detergent formulations and avoid the accumulation of polymer blocks (persistent blocks) resulting from non-degradable polymers or incomplete biodegradation of polymers in ecosystems, reducing the persistence in nature after material use.

[0007] As a result of these trends, there is a strong need for new biodegradable cleaning polymers that provide both excellent primary (i.e., soil removal) and secondary (i.e., whiteness maintenance) cleaning benefits for both hydrophobic and hydrophilic stains, and do not contain any persistent blocks in their polymeric structure. The materials should exhibit good soil removal for oily / greasy and particulate stains, and should also provide improved whiteness maintenance, minimizing the amount of suspended and emulsified oily / greasy and particulate soils redeposited on the surface of fabrics or hard surfaces. Preferably, the novel ingredients also exhibit synergistic effects with other cleaning polymers known to improve only the removal of oily / greasy or particulate stains and / or the whiteness of fabrics and hard surfaces, resulting in further improved detergent compositions.

[0008] As a result of these trends, a need has arisen for new biodegradable polymers that reduce glass corrosion in ADW to extend the useful life of tableware, especially glass tableware, and that do not contain any persistent blocks in their polymeric structure.

[0009] It is known in the literature that the class of alkoxylated polyalkyleneimine polymers, especially alkoxylated branched PEI and alkoxylated linear polypropyleneimine homo- and copolymers, can contribute to the removal of particulate or oily / greasy soils, especially at low surfactant levels and in cold water conditions (below 30°C). However, their performance is not sufficient, both in terms of oily / greasy soil removal ability and in terms of broad performance profile. Moreover, polypropyleneimine homo- and copolymers known in the state of the art are difficult to synthesize and further process on an industrial scale. Moreover, their biodegradation performance is generally low or even poor, especially in that they do not contain persistent blocks, and therefore not suitable for current new and future requirements. For this reason, there was a need to find an improved polymer structure with a good performance profile, a viable preparation process, and a completely biodegradable (i.e. all starting materials, components in aqueous environment that may be hydrolyzed, and final molecule) backbone.

[0010] The following provides a summary of the most relevant publications in the technical field of the present invention.

[0011] Alkoxylated polyalkyleneimines are well known as additives for laundry detergents (e.g. EP 3301154, EP 3167034, EP 112593 and WO 2020 / 030469) or as additives for hard surface cleaners.

[0012] EP 2209837B1 describes amphiphilic water-soluble alkoxylated polyalkyleneimines for improving the removal of oily / greasy stains in detergents. In general, various polyalkyleneimines based on various radicals A1 interconnecting nitrogen atoms can be used as core materials. Radicals A1 can be the same or different, linear or branched C2-C6 alkylene radicals, such as 1,2-alkylene. Preferably, 1,2-ethylene, 1,2-propylene and 1,6-hexamethylene are used. There is no mention of the use of 1,3-propylene. The focus of this patent is on linear oligoamines such as 1,6-hexamethylenediamine and branched polyethyleneimines, as disclosed in the present examples. There is no mention of linear polypropyleneimines. The polymers contain modifications of PEO / PPO blocks with 24-50 EO units and 30-50 PO units, so that the alkoxylate chains are longer than those described in WO2006108856A2. The longer PEO / PPO chains improve their oily / greasy soil removal performance. No mention is made of the biodegradability of the polyamine itself, and of the alkoxylated derivatives.

[0013] More specifically, polypropyleneimines and alkoxylated polypropyleneimines for cleaning applications are described in EP 2 961 819 B1, which discloses such polymers whose main chain number average molecular weight Mn ranges from 300 to 4,000 g / mol, preferably from 400 to 2,000 g / mol, as determined by size exclusion chromatography. In a preferred embodiment, the molar mass distribution Mw / Mn of the main chain of the alkoxylates is defined to be in the range of 1.2 to 20, preferably from 1.5 to 7.5. However, these alkoxylated polymers are not biodegradable.

[0014] Even more specifically, polyethylene / propyleneimine copolymers are described in the yet unpublished International Patent Application PCT / EP2021 / 065279, which discloses as claim 7: "A polyethylene / propyleneimine copolymer, before alkoxylation, comprising repeat units of monomer (A) and monomer (B) and monomer (C) according to any one of claims 1 to 7 in condensed form". Monomer A in this unpublished patent application is similar to monomer A of the present invention when the variables n and l are each 1 (see embodiment 1 below), and monomer B in this unpublished patent application is similar to monomer B of the present invention (only when the variable m is 1). Monomer C in this unpublished patent application is different from monomer C of the present invention, and monomer C in this unpublished patent application is not used in the present invention, since monomer C in this unpublished patent application leads to a polyamine with very poor biodegradability due to the tertiary amino group in its backbone. However, the copolymer disclosed in claim 7 of this unpublished patent application contains monomer C. The patent application further discloses "an alkoxylated polyethylene / propyleneimine copolymer according to any one of claims 1 to 4, comprising a backbone made only from monomers A and B and containing no monomer C, wherein the weight-average molecular weight Mw of the polyethylene / propyleneimine backbone without alkoxy chains is at least 300 g / mol, preferably at least 500 g / mol." In contrast, the experimental section describes only a polymer with a weight-average molecular weight of 767 g / mol based on a backbone A.2 comprising monomer A (1,3-propylenediamine, i.e. equal to monomer A of the invention) and monomer B of the invention (in the structure of monomer B of the invention, n, l=1).

[0015] However, this polyamine A.2 with Mw of 767 g / mol is not biodegradable. Furthermore, none of the alkoxylated polymers in this unpublished patent application are biodegradable.

[0016] WO 2021 / 165468 and unpublished European Patent Applications 21176904.7, 21176906.2, 21192170.5, and 21192169.7 describe modified polyalkyleneimines and amines that exhibit better biodegradability than known compounds due to modifications in the side chains made from alkylene oxides and lactones / hydroxycarbon acids resulting in ester and / or amide functional groups in the side chains. However, the core of the modified polyalkyleneimines is still not biodegradable. WO 2021 / 165468 discloses that the molecular weight (Mw) of the polyalkyleneimine backbone or polyamine backbone is in the range of 50 to 10,000 g / mol, preferably in the range of 500 to 5,000 g / mol, more preferably in the range of 600 to 2,000 g / mol. Besides one low molecular weight oligoamine (N4 amine with MW of 174 g / mol), the only polyamine described in the experimental section is a branched polyethyleneimine, which has a different structure and a different (i.e., higher) molecular weight than the polyamines of the present invention and is therefore not biodegradable.

[0017] Unmodified polyalkyleneimines are well known as additives for automatic dishwashing detergents to prevent glass corrosion of tableware. EP 2768935B1, EP 2981600B1, and EP 2768937B1 describe ADW compositions based on chelating agents such as methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), citric acid, and their salts, and linear or branched polyethyleneimine. Optionally, at least one zinc salt is added to the composition to further reduce glass corrosion. The linear or branched polyethyleneimines described are not biodegradable. Polypropyleneimine is not described at all. Summary of the Invention

[0018] Although already many different polyalkyleneimines and alkoxylated polyalkyleneimines have been described in the publications cited above, including their preparation processes and their use in detergents, there remains a need for more weight-efficient polymers, i.e. polymers that show further improved benefits such as for the removal of oily / greasy stains in laundry and / or improved degreasing at lower working concentrations in manual dishwashing, in combination with a significantly broader performance profile (two-in-one solutions) and / or improved glass corrosion protection in ADW, in particular novel polymers with improved biodegradability within 28 or 56 days under controlled conditions as defined by OECD 301B and / or F, which among other things allows the design of concentrated and sustainable (i.e. fully degradable and non-permanent) multi-benefit detergent formulations.

[0019] More specifically, there is a strong need for new cleaning polymers that provide both excellent primary (i.e., soil removal) and secondary (i.e., whiteness maintenance) cleaning benefits, ideally for both hydrophobic and hydrophilic stains. Additionally, simplified processes for making polyamine backbones and backbones with polymer melting points at or below room temperature (25° C.+ / -2) are highly desirable, as are facile formulations, to prevent clogging of reaction tubes and piping, and to improve handling when filling or pumping either the polymers themselves or the polymers in the formulations into or out of containers, allowing for a safe and viable industrial-scale transamination process.

[0020] In the context of the present invention, non-biodegradable or permanent means less than 10% biodegradation after 28 days and / or 56 days according to the test conditions of OECD 301B and / or F. Weakly biodegradable means less than 20% biodegradation after 28 days according to the test conditions of OECD 301B and / or F and / or less than 40% biodegradation after 56 days according to the test conditions of OECD 301B and / or F.

[0021] Certain homopolymers of PPI based on monomers A, B and / or C, preferably A and / or B, as well as certain copolymers of PPI (e.g. derived from monomers A and B) having an Mn of 200-400 and an Mw of less than 700 g / mol, have been found to be biodegradable, i.e. at least 20% biodegradable after 28 days according to the test conditions of OECD 301B and / or F and / or at least 40% biodegradable after 56 days according to the test conditions of OECD 301B and / or F. It has also been found that modifications using structural elements, reactions and reaction procedures for modifying the backbone with alkylene oxides and lactones / hydroxycarbon acids, and thus side chains comprising ester and / or amide functional groups, as disclosed in WO 2021 / 165468, and in particular those of the unpublished patent applications European Patent Applications Nos. 21176904.7, 21176906.2, 21192170.5 and 21192169.7, result in "modified PPIs" (defined below in this disclosure) that combine the advantages of a biodegradable core (the PPI of the present invention) and shell (similar to the side chains) with the advantage of a final molecule that is biodegradable due to various ester and / or amide functional groups between the core and shell, which improve the biodegradation rate of the entire molecule (i.e. of the "modified PPI"). As a result, these modified PPIs have a structure that is more favorable for biodegradation compared to conventional structures.

[0022] The object of the present invention is to provide a process for the preparation of polycondensed polysaccharides comprising the steps of: Formula (A) [ka] where m is selected from an integer from 1 up to 5, Formula (B) [ka] wherein n is selected from the integers 1, 3, 4, and 5; Monomer (B), wherein l is selected from 0 or 1; and (C) formula [ka] where k is selected from an integer from 1 up to 7, The present invention provides a novel polypropyleneimine polymer (abbreviated as "PPI" in the present invention) comprising at least one repeating unit selected from the monomer units above.

[0023] The PPI may be further modified by reaction with an alkylene oxide and a lactone and / or a hydroxy acid to provide a PPI bearing at least one side chain attached to its NH group, the side chain comprising at least one AO ​​and at least one lactone and / or hydroxy acid per side chain, and / or may be quaternized to introduce a non-permanent or permanent quaternization of at least one N group of the PPI structure.

[0024] PPIs with such side chains are sometimes referred to within the present disclosure as "modified PPIs" to clearly distinguish them from "unmodified" PPIs that do not bear such side chains, while the term "PPI" as used herein generally includes any such PPI, whether it bears side chains and / or is quaternized, or whether it bears no side chains and is not quaternized.

[0025] Processes for producing such PPIs are also part of the present invention.

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

[0027] Similar to these compositions in which known polyamines, polyethyleneimines, polypropyleneimines, and their alkoxylated derivatives are used, compositions comprising such PPIs of the present invention, either in place of such known compounds or in combination with such known compounds, are also part of the present invention.

[0028] As used herein, the terms "polymer", "polymer of the invention" or "inventive polymer" refer to a polypropyleneimine polymer comprising at least one of Monomer A, Monomer B, and / or Monomer C, or combinations thereof, as described below and / or in the appended claims.

[0029] The subject of the present invention is therefore the following embodiments 1 to 35, which are defined and further explained below together with further embodiments and are further exemplified in the experimental section. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] EMBODIMENT 1 In polycondensation form, Formula (A) [ka] The monomer (A) is represented by Monomer (A), wherein m is selected from an integer from 1 up to 5, Formula (B) [ka] The monomer (B) is represented by wherein n is selected from the integers 1, 3, 4, and 5; Monomer (B), wherein l is selected from 0 or 1; and (C) formula [ka] The monomer (C) is represented by where k is selected from an integer from 1 up to 7, A polypropyleneimine polymer (PPI) comprising at least one repeating unit selected from the monomer units: Preferably, i) at least one repeat unit derived from monomer A, and / or ii) at least one repeat unit derived from monomer B, and / or iii) at least one repeat unit derived from monomer C, and / or More preferably, i) at least one repeat unit derived from monomer A, and / or ii) at least one repeat unit derived from monomer B, and Optionally, at least one repeat unit derived from monomer C is selected,PPI.

[0031] EMBODIMENT 2 The PPI according to embodiment 1, comprising at least one monomer selected from i) A, ii) B, iii) A and B, iv) A and C, v) B and C, or vi) A and B and C, preferably i) A, ii) B, iii) A and B, iv) A and C, more preferably i) A, and iii) A and B, and most preferably iii) A and B.

[0032] EMBODIMENT 3 The PPI according to embodiment 1 or 2, having a weight average molecular weight Mw of less than 700 g / mol, and preferably of at least 300 g / mol.

[0033] EMBODIMENT 4 4. The PPI according to any one of the preceding embodiments, having a number-average molecular weight Mn of 200 to 400 g / mol and a weight-average molecular weight Mw of from 300 g / mol to less than 700 g / mol.

[0034] EMBODIMENT 5 The PPI according to any one of embodiments 1 to 4, having a polydispersity index (PDI) of 1.3 to 2.5, preferably 1.5 to 2.0.

[0035] The molecular weight of the PPIs can be determined by gel permeation chromatography (GPC). Measurements were performed on a column combination of three columns: HFIP-LG Guard, PL HFIPGEL, and PL HFIPGel. Further details are disclosed in the experimental section.

[0036] The molecular weights of the side-chain modified PPIs (both inventive and comparative examples) were obtained by theoretical calculations using the determined weight average molecular weights of the unmodified PPIs and assuming complete conversion during the modification process. Further details are also disclosed in the experimental section.

[0037] "Mw" is the weight average molecular weight and "Mn" is the number average molecular weight. The respective values ​​of Mw and / or Mn can be determined as described in the experimental section below.

[0038] The molar mass distribution Mw / Mn is equal to the polydispersity index (PDI), where PDI does not contain the units (g / mole / g / mole).

[0039] EMBODIMENT 6 The PPI of any one of embodiments 1 to 5, comprising an average of at least 6 and at most 12 nitrogen atoms.

[0040] The number of nitrogen atoms is defined by the amount of monomers, their ratio, and reaction conditions. It has been unexpectedly found that low molecular weight PPIs, and therefore PPIs with a relatively low number of nitrogen atoms, such as 6 to a maximum of 12, provide useful properties, such as lower melting points and better biodegradation, while still providing at least comparable performance, as described in detail herein below.

[0041] EMBODIMENT 7 The PPI according to any one of embodiments 1 to 6, which is essentially linear, more preferably at least 95% linear, and more preferably completely linear.

[0042] EMBODIMENT 8 The PPI of embodiment 7, which does not contain a tertiary amino group.

[0043] In principle, polypropyleneimine polymers may generally be linear or branched in which the branches form tertiary amino groups, and the branches may be (i) relatively short intact alkyleneamino groups (e.g. -(CH2)3-NH2 groups) up to very long side chains which may contain further amino groups branched in turn, resulting in more highly branched structures such as the common highly branched polyethyleneimines (PEIs) known to date, or (ii) hydrocarbon units which do not carry further amino groups.

[0044] Consequently, the PPIs of the present invention have a backbone (main chain) that includes primary and secondary nitrogen atoms connected by alkylene radicals R (where "R" is a generic representation of each of the alkyl units of monomers A, B, and C for the purposes of the following description only) in a random arrangement (such arrangement in actual PPIs based on actual monomer structures A, B, and C) and in the form of the following moieties: - a primary amino moiety which terminates the backbone of the base skeleton and, where applicable, also the side chains, the hydrogen atom of which can be replaced by the side chain when subsequently modified with alkylene oxides and lactones / hydroxy acids. [ka] - A secondary amino moiety, the hydrogen atom of which can be subsequently replaced by a side chain when modified with alkylene oxides and lactones / hydroxy acids. [ka]

[0045] For the purposes of the present invention, a definition such as C1-C18 alkyl to denote a hydrocarbon substituent on a nitrogen atom of a PPI means that this substituent (radical) is an alkyl radical having 1 to 18 carbon atoms, in the case of "C1-C18 alkyl". The alkyl radical may be either linear or branched or optionally cyclic. Alkyl radicals having both cyclic and linear components are also within the scope of this definition. The same applies to other alkyl radicals such as C1-C4-alkyl radicals. Examples of alkyl radicals 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, or dodecyl.

[0046] Other such common abbreviations, such as "C2-C22 alkylene oxide," have their common meaning as used in the organic chemical art.

[0047] In the present invention, preferred PPIs are predominantly linear, more preferably at least 95% linear, more preferably essentially linear (herein "essentially linear" is defined as containing less than 1%, preferably less than 0.5% tertiary nitrogen atoms), e.g. completely linear (herein "completely linear" is defined as containing no detectable amounts of tertiary amines). If tertiary nitrogen atoms are present, these nitrogen atoms are preferably substituted only with hydrocarbon units, more preferably with C1-C4 alkyl groups, most preferably with C1 and / or C2 alkyls, most preferably with C1 alkyls only. Most preferably, such tertiary nitrogen atoms are essentially absent, and thus the PPI is essentially linear.

[0048] The degree of branching can be determined, for example, by NMR spectroscopy, such as 1H-NMR or, preferably, 13C-NMR.

[0049] The amine numbers of primary and secondary and tertiary amines are determined in accordance with standard DIN EN ISO 9702.

[0050] EMBODIMENT 9 The PPI according to any one of embodiments 1 to 8, a) in the case of monomer A: m is 1, 2 or 3, preferably 1; and / or b) in the case of monomer B: n is 1, and / or c) in the case of monomer B: l is 1, and / or d) For monomer C: k is 1; When such monomers A, B, and / or C, or groups with such variables, are present, Preferably, all of options a) to d) are required features of the PPI.

[0051] EMBODIMENT 10 The PPI according to any one of embodiments 1 to 9, which is at least 20% by weight, preferably at least 25% by weight, more preferably at least 30, even more preferably at least 35, most preferably at least 40%, and any value greater, biodegradable within 56 days, preferably within 28 days according to OECD 301 F.

[0052] For the purposes of the present invention, biodegradation in wastewater is preferably expressed as a weight percentage based on the solid content, measured in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures the biodegradation of a sample by measuring the oxygen consumption. Oxygen consumption is determined by measuring the change in pressure inside the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH&Co KG). The amount of oxygen taken up by the microbial population during the biodegradation of the test material is expressed as a percentage of ThOD (theoretical oxygen demand, measured by elemental analysis of the compound). Details of the tests carried out are described in the experimental section below.

[0053] A major advantage of the present invention in terms of biodegradation is that not only the "shell" (i.e., the side chains in the modified PPI attached to the (unmodified) PPI) but also the "core" (i.e., the unmodified PPI) exhibit a useful degree of biodegradability. Currently known polyalkyleneimines and their alkoxylated derivatives (including those with lactones, etc. in addition to AO) are not biodegradable per se, since the core (i.e., the polyalkyleneimine) is not biodegradable to a significant degree. On the other hand, low molecular weight cores such as the PPIs of the present invention and their modified derivatives that are biodegradable and also exhibit significant and therefore commercially useful performance are not known to date.

[0054] Thus, the present invention provides PPIs that themselves exhibit a significant biodegradation rate, and modification of these PPIs (as the core) with side chains that also exhibit a significant biodegradation rate, such that the core-shell combination product (i.e., the modified PPI) inherits this significant biodegradation rate and exhibits only fragments that should not be essentially permanent after hydrolysis in an aqueous environment.

[0055] EMBODIMENT 11 The PPI according to any one of embodiments 1 to 10, having a melting point of at most 25°C, preferably below 20°C, even more preferably below 15°C.

[0056] Due to the low molecular weight and therefore low nitrogen valence, as well as the structure of the monomers used, the resulting PPI exhibits a low melting point around room temperature (defined herein as 25° C.) or preferably below room temperature, such as below 20° C., below 15° C., below 10° C., below 5° C., or even lower. Such a low melting point allows for a more simplified production process, since the resulting PPI can be handled as a liquid at relatively moderately high temperatures or even already at room temperature, thus easily preventing clogging of reaction tubes, vessels, and piping, and improving the handling when filling or pumping either the neat PPI or the PPI in the formulation into or out of a container or vessel. Thus, such a low melting point allows for a safe and feasible production process on an industrial scale, any process that requires transporting and storing the PPI, easy formulation development, and generally easy handling.

[0057] EMBODIMENT 12 The PPI may be further modified by additionally including at least one side chain attached to at least one NH functional group of the PPI, such chain comprising an additional monomer: (D) at least one lactone and / or at least one hydroxyl carbon acid (E) at least one alkylene oxide (AO) selected from C2 to C22 alkylene oxides, preferably C2 to C6, more preferably C2, C3, and / or C4 and The order of D and E in the side chain may be in any order, such as random, block, or statistical distribution, although block order is preferred; The amount of D is 0.5 to 15 based on molar equivalents per NH functional group; The PPI according to any one of the preceding embodiments, wherein the amount of E is 10-100 based on molar equivalents per NH functional group.

[0058] EMBODIMENT 13 The PPI of embodiment 12, wherein the sum of the total amounts of monomer (A), monomer (B), and monomer (C) in the PPI is at least 1% by weight and at most 10% by weight, with the remainder to make up 100% by weight being side chains.

[0059] The PPI may include a side chain attached to a nitrogen atom of the PPI. The side chain may be attached by, and is preferably attached by, a polycondensation or polyaddition reaction. The side chain comprises a C2-C22 alkylene oxide, lactone, and / or hydroxycarbon acid. Typically, the side chain comprises at least one alkylene oxide (AO), and at least one lactone (LA) and / or at least one hydroxyacid (HA). The (poly)condensation or (poly)addition reaction for preparing the side chains containing AO, LA and HA, as an example of a general side chain preparation, is typically carried out by reacting PPI with at least one AO ​​and at least one LA and / or HA either i) in a mixture in which all the components used are added simultaneously or at least immediately after each other, preferably with as short a time difference as possible, ii) by first adding either AO or LA or HA, then the second component, then the third component, to obtain a block of AO, LA and HA, or iii) by adding one or two components as previously defined for method i) and then adding the remaining two or one component according to method ii) as previously defined.Of course, it is also possible to generate block structures by repeating the reaction at a later time with additional amounts of the same component types AO, LA and / or HA.

[0060] Preferably, the side chain comprises more than 1 unit per NH function of the PPI derived from AO, more preferably more than 2, even more preferably more than 3 units, and at least 0.5 units per NH function. All these figures are "average" figures, that is, they refer to the average number of such units per NH function calculated based on all NH functions of the PPI.

[0061] Furthermore, in the context of the process of the present invention, it should be noted that these primary amino moieties of the respective backbones, which react with at least one lactone and / or at least one hydroxyl carbon acid, are transferred to amide moieties, in which one of the originally two hydrogen atoms of each primary amino moiety is replaced by a fragment derived from the respective lactone or hydroxyl carbon acid, but the second hydrogen atom of the primary amino moiety of the backbone is not replaced by this reaction. Moreover, such second hydrogen atom of the primary amino moiety of the backbone is also not replaced in further reaction steps, such as further reactions with AO, LA, and / or HA.

[0062] The reaction that results in the PPI is a statistical reaction, which means that there is never only one type of chemically strictly defined compound, but the PPI of the present invention is always a mixture of slightly deviating structures, all originating from the same reaction in one reaction space; these structural differences clearly stem from the fact that no reaction proceeds exactly the same way and at the same rate on all functional units, in particular because the chemical reactivity of the functional units (here mainly that of the NH functional groups) differs depending on their environment, i.e. primary amino groups react differently from secondary amines and react differently compared to tertiary amino groups (especially in terms of reaction with lactones and / or hydroxycarbon acids as mentioned above), and furthermore, the chemical environment of these three main groups may differ from the monomers used; this should be emphasized that there are slightly deviating structures, and thus leads to the overall insight that any of the PPIs of the present invention defined as in the various embodiments, including the numbered embodiments 1 to 35, and as illustrated in the examples, are never only one type of chemical compound, but always a mixture of slightly deviating structures with a statistical distribution. The deviations are relatively small, since the reactivity of these groups does not vary significantly. Thus, defining PPIs by their monomers is a viable way to define the structure, and defining the composition of side chains by average number (including variables defined in embodiment 14 below) based on the number of NH functional groups present in the PPI (which is itself an average number for this factual mixture) is a useful means to define the overall composition of any mixture defined herein as a "PPI."

[0063] Thus, unless otherwise indicated, the values, ranges and ratios given herein for a, b, c, d and e, the number of NH functional groups, and the molecular weight (Mn) refer to the number-average values ​​of a mixture of several PPI compounds, each containing individual, slightly different chemical structures from each other, resulting in a PPI, where "PPI" defines this mixture resulting from the preparation process. As is well known in polymer science, the weight-average molecular weight (Mw) is then an indicator of the homogeneity (or heterogeneity) within the mixture of different species in the "PPI".

[0064] Suitable lactones and / or hydroxycarbon acids can be aliphatic, alicyclic, or aromatic.

[0065] Particularly suitable aromatic hydroxycarbon acids are hydroxy-substituted benzoic acids and naphthalene carboxylic acids, such as p-hydroxyethylbenzoic acid and 2-hydroxynaphthalene-6-carboxylic acid. Aliphatic hydroxycarbon acids, especially those with a hydroxyl group in the ω-position, and their lactones are preferred. In general, the aliphatic hydroxycarbon acids have 1 to 22 alkylene radicals, preferably 2 to 10 alkylene radicals, more preferably 2 to 5 alkylene radicals. The alkylene radicals may be linear or branched. Examples which may be mentioned are glycolic acid, lactic acid and its lactides, γ-hydroxybutyric acid and γ-butyrolactone, δ-hydroxyvaleric acid and γ- and δ-valerolactone, ε-hydroxycaproic acid and ε-caprolactone, 12-hydroxystearic acid and ricinoleic acid, as well as mixtures, especially including the naturally occurring acids. Preferably, glycolic acid, lactic acid, ε-caprolactone, or lactide, or a mixture thereof, is used, and even more preferably, ε-caprolactone is used.

[0066] EMBODIMENT 14 The order of D and E within the side chain is preferably block order, and the side chain has the following structural order: i)[PPI]-N-(E1)a-(D1)d-(E2)b-(E3)c ii) [PPI]-N-(D1)d-(E2)b-(E3)c iii) [PPI]-N-(E1)a-(D1)d-(E2)b iv) [PPI]-N-(D1)d-(E2)b v)[PPI]-N-(E1)a-(D1)d-(E2)b-(D2)e vi) [PPI]-N-(D1)d-(E2)b-(D2)e At least one of (E1), (E2), (E3) each independently represent a subunit composed of a monomer which is at least one alkylene oxide, preferably a single alkylene oxide; (D1) and (D2) each represent, independently of the other, a subunit composed of at least one lactone and / or hydroxyl carbon acid monomer, preferably a single lactone and / or hydroxyl carbon acid monomer; a, b, c, d, and e define the total average number of individual repeat units within each subunit (E1), (E2, (E3), (D1), and (D2); Preferably, the side chain is selected from i), ii), iii), and iv), more preferably from i) and ii), most preferably i); The variables are the average molar equivalents per NH functional group of the following PPIs: a 0.5 to 2, preferably 0.8 to 1.5, and / or b 10 to 40, preferably 15 to 35, and / or c 5 to 40, preferably 10 to 35, and / or d 0.5 to 5, preferably 1.0 to 3.0, and / or e based on 2 to 10, preferably 2 to 6; Preferably, D1 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid and / or glycolic acid, in one preferred embodiment D1 is caprolactone; D2 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid and / or glycolic acid, in one preferred embodiment D2 is caprolactone; E1 is preferably C2-C5-AO, most preferably PO and / or BuO; E2 is a C2-C5-AO containing more than 50 wt% EO, preferably more than 90 wt% EO, most preferably 100 wt% EO; E3 is a C2-C5-AO containing more than 50 wt.% PO and / or BuO, preferably more than 90 wt.% PO and / or BuO, most preferably 100 wt.% PO and / or BuO, in one preferred embodiment E3 is 100 wt.% PO; A PPI according to embodiment 12 or 13.

[0067] It should be emphasized that the stepwise use of the various AOs, shown as E1, E2, and E3 in this above embodiment 14, and the lactone / hydroxycarbon acids, shown as D1 and D2 in this above embodiment 14, in a stepwise manner is a preferred embodiment. Such a stepwise method is to be understood as follows.

[0068] For example, using the structural order "i) [PPI]-N-(E1)a-(D1)d-(E2)b-(E3)c", in order to obtain such structural order, a reaction sequence is used in which the PPI defined in the present invention is first reacted with an AO represented by E1, followed by reacting in a second reaction with a lactone / hydroxy acid represented by D1, followed by reacting in a third reaction with an AO represented by E2, and then reacting in a fourth reaction with an AO represented by E3.

[0069] The conversion of each reaction is monitored. Only when the previous reaction (in this example, E1 as the first reactant reacts with PPI) has proceeded to or even exceeded a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5%, is the next reactant (in this example, D1 as the second reactant) added, and its conversion is also monitored to detect when this next reaction has proceeded to or even exceeded a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5%, and then the next reactant (in this example, E2 as the third reactant) is added, and so on until all reactants are reacted and the reaction of the last reactant added has proceeded to or even exceeded a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, and even more preferably at least 99.5%, and so on. All other structural orders defined in embodiment 14, as well as the undefined structures resulting from embodiment 13, are carried out in this defined manner, resulting, on statistical average, in defined structural orders that derive directly from the manner in which such reactions are carried out.

[0070] The conversion of each corresponding step can be determined according to methods known to those skilled in the art, such as NMR spectroscopy, such as 13C-NMR spectroscopy and / or 1H-NMR spectroscopy.

[0071] EMBODIMENT 15 The subunits are i) E1 is PO and / or BuO; and / or ii) E2 is EO; and / or iii) E3 is PO; and / or iv) D1 is caprolactone; and / or v) D2 is caprolactone; A PPI described in any one of embodiments 12 to 14, wherein preferably at least two, more preferably at least three, even more preferably at least four, and most preferably all of options i) to v) are linked with "and" and are therefore required features.

[0072] EMBODIMENT 16 The subunits are, on average, i) E1 is PO and / or BuO in the range of 0.8 to 1.5; and / or ii) E2 is 15 to 35 EO, and / or iii) E3 is 10-35 PO; and / or iv) D1 is 1.0 to 3.0 caprolactone, and / or v) D2 is configured as 2-6 caprolactone; All numbers are moles per NH functionality of PPI. A PPI described in any one of embodiments 12 to 15, wherein preferably at least two, more preferably at least three, even more preferably at least four, and most preferably all of options i) to v) are linked with "and" and are therefore required features.

[0073] EMBODIMENT 17 A PPI described in any one of embodiments 12 to 16, 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 PPI have the same structural order, which structural order is as defined as "structural order" in embodiment 14 as i), ii), iii), iv), v), or vi).

[0074] Without being bound by the following explanation, there is a theoretical basis for explaining the obtained structure of PPI and modified PPI. Due to the fact that the reaction in question, which is necessarily used to prepare these structural orders of side chains and thus to prepare certain modified PPIs, is a reaction of highly reactive species, which can bring about almost complete, if not 100%, almost 100% and even "substantially complete" conversion under suitable conditions, the statistical deviation of the composition of the mixture of the "PPI" in question is not very high, which means that the structural order of side chains does not show a large deviation. Therefore, this is a reliable assumption that can be proved in principle by sophisticated and therefore time-consuming and expensive analytical methods such as multi-dimensional NMR analysis, and therefore it is generally accepted that such deviations exist. Thus, a "specific modified PPI" will not be "just one chemical compound with a well-defined chemical structure", but will clearly be composed of a) a mixture of slightly different compounds, with these differences being due to b) slight deviations already present in the structure of the compound constituting the "(unmodified) PPI" used for further modification steps, and c) slight deviations in the structural order of the side chains, which are attached by d) multi-step condensation reactions, which are due to e) variations in the chemical reactivity of the NH functional groups, f) slight variations in the reactivity of the AO, LA, and HA used due to their structures, and g) their reactivity towards NH functional groups of slightly different reactivity, and h) slight heterogeneity that occurs in industrial-scale processes. All of these factors a)-h) (to name a few important ones) result in a "specific modified PPI" that is not one specific chemical compound, but in fact a mixture of slightly different compounds with a very similar overall chemical structure. Such a structure is therefore best described by the average number of variables and the percentage of the amount of dominant structural order.

[0075] EMBODIMENT 18 The PPI according to any one of the preceding embodiments, which is further modified by permanent quaternization, preferably by alkylation, to the extent of 5 to 100, preferably up to 95, more preferably up to 70, and even more preferably up to 50 percent of all nitrogen atoms in the PPI, by standard techniques including protonation by pH adjustment, or alkylation using standard reactants.

[0076] It is well known to those skilled in the art that such PPI structures and such modified PPI structures can be quaternized using standard techniques due to their fundamental chemical similarity to known structures of this general type, and the known ability to modify these known structures by quaternization.

[0077] Obviously, the structures of the invention described herein as PPIs and modified PPIs may be quaternized as well.

[0078] The preferred degree of quaternization is up to 100%, specifically 5-95%. The quaternization is preferably carried out by introducing C1-C22 alkyl groups, C1-C4 alkyl groups, and / or C7-C22 aralkyl groups, and may also be carried out in a conventional manner by reaction with the corresponding alkyl halides and dialkyl sulfates.

[0079] Quaternization can be advantageous to tailor the PPIs of the present invention to the particular compositions in which they are used, such as laundry compositions, and to achieve better compatibility and / or phase stability of the formulation.

[0080] Quaternization of the PPIs of the present invention is preferably achieved by introducing C1-C22 alkyl, C1-C4 alkyl, and / or C7-C22 aralkyl, aryl, or alkylaryl groups, as described, for example, in WO 09 / 060059, and may be carried out in conventional manner by reaction with the corresponding alkyl halides, aralkyl halides, and dialkyl sulfates.

[0081] Quaternization can be achieved, for example, by reacting the PPI of the present invention with an alkylating agent, such as a C1-C4 alkyl halide, such as methyl bromide, methyl chloride, ethyl chloride, methyl iodide, n-butyl bromide, isopropyl bromide, or an aralkyl halide, such as benzyl chloride, benzyl bromide, or a di-C1-C22 alkyl sulfate in the presence of a base, in particular dimethyl sulfate or diethyl sulfate. Suitable bases are, for example, sodium hydroxide and potassium hydroxide.

[0082] The amount of alkylating agent determines the amount of amino groups that are quaternized in the polymer, ie, the amount of quaternized moieties.

[0083] The amount of quaternized moieties can be calculated from the difference in amine value between the non-quaternized and quaternized amines. The amine value can be determined according to the method described in DIN 16945.

[0084] The quaternization can be carried out without any solvent. However, solvents or diluents such as water, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, etc. may be used. The reaction temperature is usually within the range of 10°C to 150°C, preferably 50°C to 100°C.

[0085] Quaternization can be advantageous to tailor modified or unmodified PPIs to the particular compositions in which they are used, such as laundry compositions, to achieve better compatibility and / or phase stability of the formulation.

[0086] EMBODIMENT 19 A step a) of reacting at least one monomer (A) and / or at least one monomer (B) and / or at least one monomer (C) in a polycondensation reaction, preferably at least one monomer (A) and / or at least one monomer (B) and optionally at least one monomer (C), to obtain a PPI, Monomer (A) has the formula [ka] is represented by wherein m is selected from an integer from 1 up to 5; Monomer (B) has the formula [ka] is represented by wherein n is selected from the integers 1, 3, 4, and 5; l is selected from 0 or 1; Monomer (C) has the formula [ka] is represented by wherein k is selected from an integer from 1 up to 7; The following characteristics: i) comprising at least one monomer selected from i) A, ii) B, iii) A and B, iv) A and C, v) B and C, vi) A and B and C, or vii) C, preferably i) A, ii) B, iii) A and B, iv) A and C, more preferably i) A, and iii) A and B, most preferably iii) A and B; ii) having a weight average molecular weight Mw of less than 700 g / mol, and preferably at least 300 g / mol; iii) having a number average molecular weight Mn of 200 to 400 g / mol and a weight average molecular weight Mw of 300 g / mol to less than 700 g / mol; iv) having a polydispersity index (PDI) of 1.3 to 2.5, preferably 1.5 to 2.0; v) containing an average of at least 6 and at most 12 nitrogen atoms; vi) being predominantly linear, more preferably at least 90% linear, more preferably essentially linear, e.g. completely linear; and / or vii) does not contain any tertiary amino groups (prior to further modifications as defined in the embodiments below). Step a) obtaining a PPI having at least one of A process for producing a PPI described in any one of embodiments 1 to 18, comprising:

[0087] All terms in embodiment 19 have already been defined and explained in detail within the description of embodiments 1-18 herein above, and it is understood that such terms and definitions apply equally to embodiment 19 as well as the following embodiments 20-22, 22a, and 22b.

[0088] EMBODIMENT 20 The process further comprises step b) in which the PPI obtained in step (a) is further modified in a further polycondensation or polyaddition reaction to produce a modified PPI comprising at least one side chain attached to at least one NH functional group of the PPI, said chain being linked to a further monomer: (D) at least one lactone and / or at least one hydroxyl carbon acid, and / or (E) a moiety derived from polycondensation or polyaddition of at least one alkylene oxide selected from C2 to C22 alkylene oxides, preferably C2 to C6, and more preferably C2, C3, and / or C4 alkylene oxides; It consists of: a further polycondensation or polyaddition reaction is by reacting the PPI with D and E by using components D and E as a mixture after alternating or overlapping addition, preferably alternating as stepwise addition, when the reaction with the first added reactant has proceeded to a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, even more preferably at least 99.5%, or even more than that is achieved, such as when the reaction has substantially stopped; As a result, preferably, an order is obtained, which is defined below as "structural order" i) to vi), and which is represented by the following groups i) to vi): i)[PPI]-N-(E1)a-(D1)e-(E2)b-(E3)c ii) [PPI]-N-(D1)e-(E2)b-(E3)c iii) [PPI]-N-(E1)a-(D1)e-(E2)b iv) [PPI]-N(D1)e-(E2)b v)[PPI]-N-(E1)a-(D1)e-(E2)b-(D2)f vi) [PPI]-N-(D1)e-(E2)b-(D2)f and forming at least one side chain having a block structure selected from In the formula, (E1), (E2), and (E3) each independently represent a single or multiple alkylene oxides, preferably a single alkylene oxide; In the formula, (D1) and (D2) each independently represent a single or multiple lactones and / or hydroxyl carbon acids, preferably a single lactone and / or hydroxyl carbon acid; wherein (E1)a, (E2)b, (E3)c, and (D1)e, (D2)f each represent a block made from such starting materials, each block can be made from a plurality of alkylene oxides or lactones and / or hydroxy carbon acids, respectively, and thus within the block containing a plurality of alkylene oxides or lactones and / or hydroxy carbon acids, the order is random; Preferably, the side chain structure has a structural order selected from i), ii), iii) and iv), more preferably selected from i) and ii), most preferably i), 20. The process of embodiment 19, comprising:

[0089] It should be noted in the context of the process of the present invention that these primary amino moieties of the respective backbones, which react with at least one lactone and / or at least one hydroxyl carbon acid in the first reaction step of the modification step (b), are transferred to amide moieties, one of the original two hydrogen atoms of each primary amino moiety being replaced by a fragment derived from the respective lactone or hydroxyl carbon acid, but the second hydrogen atom of the primary amino moiety of the backbone is not replaced by this reaction. In addition to this, such second hydrogen atom of the primary amino moiety of the backbone is also replaced by a fragment derived from the respective intermediate backbone, for example, at least one C2-C 22 When alkoxylated with an epoxide, it does not become substituted in a further reaction step in step (b) of the process of the present invention.

[0090] Embodiment 20a In a preferred embodiment of embodiment 20, the PPI comprises side chains having a structural order that is similar or preferably essentially identical to 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 PPI, such structural order being as defined as "structural order" in embodiment 20 as i), ii), iii), iv), v), or vi).

[0091] EMBODIMENT 21 Monomers D and E are as follows: D=at least one lactone and / or at least one hydroxycarbon acid, and E=C2-C22 alkylene oxide, preferably C2-C6, more preferably at least one alkylene oxide selected from C2, C3, and / or C4 It is defined as Preferably, D1 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid and / or glycolic acid, in one preferred embodiment D1 is caprolactone, and / or D2 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid and / or glycolic acid, in one preferred embodiment D2 is caprolactone, and / or E1 is preferably C2-C5-AO, most preferably PO and / or BuO; and / or E2 is a C2-C5-AO containing more than 50 wt.% EO, preferably more than 90 wt.% EO, most preferably 100 wt.% EO; and / or E3 is defined as a C2-C5-AO containing more than 50 wt.% PO and / or BuO, preferably more than 90 wt.% PO and / or BuO, most preferably 100 wt.% PO and / or BuO, in one preferred embodiment E3 is 100 wt.% PO, The process according to embodiment 20 or its preferred embodiment 20a, wherein preferably at least two, more preferably at least three, even more preferably at least four, and most preferably all of the options E1, E2, E3, D1, and D2 are linked with "and" and are therefore required features.

[0092] EMBODIMENT 22 The variables defined in embodiment 20 are the molar equivalents per NH functionality of the PPI as follows: a 0.5 to 2, preferably 0.8 to 1.5, and / or b 10 to 40, preferably 15 to 35, and / or c 5 to 40, preferably 10 to 35, and / or d 0.5 to 5, preferably 1.0 to 3.0, and / or e is an average number based on 2 to 10, preferably 2 to 6; The process of embodiment 20, 20a, or 21.

[0093] Embodiment 22a The subunits are i) E1 is PO and / or BuO; and / or ii) E2 is EO; and / or iii) E3 is PO; and / or iv) D1 is caprolactone, and / or v) D2 is caprolactone; A PPI described in any one of embodiments 20 to 22 (including embodiment 20a), wherein preferably at least two, more preferably at least three, even more preferably at least four, and most preferably all of options i) to v) are linked with "and" and are therefore required features.

[0094] Embodiment 22b The subunits are, on average, i) E1 is 0.8 to 1.5 PO and / or BuO; and / or ii) E2 is 15-35 EO; and / or iii) E3 is 10-35 PO; and / or iv) D1 is 1.0 to 3.0 caprolactone, and / or v) D2 is configured as 2-6 caprolactone; All numbers are moles per NH functional group of PPI. A PPI according to any one of embodiments 20 to 22 (including embodiments 20a and 22a), wherein preferably at least two, more preferably at least three, even more preferably at least four, and most preferably all of options i) to v) are linked with "and" and are therefore required features.

[0095] With regard to reaction conditions such as catalyst, temperature, duration, purification, etc. of the condensation reaction to produce E1, E3, E3, D1, and D2 units as part of the side chain of the PPI, the respective information within the disclosures of WO 2021 / 165468 and unpublished patent applications European Patent Applications Nos. 21176904.7, 21176906.2, 21192170.5, and 21192169.7 are all incorporated by reference into this recent disclosure.

[0096] EMBODIMENT 23 The catalyst used in the reaction with hydrogen in step a) is a) containing cobalt and / or manganese; and / or b) is a fixed bed catalyst; and / or c) the reaction temperature during the reaction with hydrogen is in the range of 50 to 200 ° C; and / or d) the pressure during the reaction with hydrogen is 30-100 bar; Preferably, the catalyst used contains at least one additional metal, in particular additionally contains aluminium, the catalyst being a Raney type catalyst, more preferably a Raney-nickel or Raney-cobalt catalyst (preferably containing aluminium), The process according to any one of embodiments 19 to 22b (including 20a and 22a), wherein preferably at least two, more preferably at least three, and most preferably all of options a) to d) are linked with "and" and are therefore required features.

[0097] In principle, any suitable catalyst can be used, not only those explicitly mentioned as preferred features in embodiment 23 above. In principle, catalysts for the preparation of PPIs are well known. Further suitable catalysts and their preparation, suitable preconditioning, confectioning in a specific form, etc., as well as methods of using such catalysts in polycondensation reactions similar to those of the present invention are disclosed in WO2014131649, from page 11, line 24 to page 20, line 29. All of these can also be used in principle for the present invention, and therefore in further embodiments, any one of the catalysts disclosed and referenced in this mentioned publication, as well as any method of preparing the catalyst, preconditioning the catalyst, confectioning the catalyst in a specific form, etc., can be used. However, as a preferred embodiment, embodiment 23 defines such preferred features.

[0098] EMBODIMENT 24 PPIs, a) permanent quaternization of 5 to 100, preferably up to 95, more preferably up to 70, even more preferably up to 50 percent of all nitrogen atoms in the PPI by standard techniques, including protonation by pH adjustment, or by alkylation using standard reactants, preferably by alkylation; and / or b) Purification using standard means such as steam distillation, thermal distillation, vacuum evaporation, etc., including removal of all solvent; and / or c) further subjected to a process step of drying using standard drying means such as spray drying, drum drying, paddle vacuum drying means, including agglomeration methods such as fluidized bed drying; The process of any one of embodiments 19 to 23 (including all further embodiments marked "a" and "b"), wherein a purified (quaternized) polymer solution, a purified liquid (quaternized) polymer, a solid (quaternized) polymer, or a purified solid (quaternized) polymer is obtained, respectively.

[0099] If residual monomers are present in undesirable amounts after the reaction resulting in the PPI, the resulting PPI-containing product mixture may be further purified by standard means to reduce the residual monomer content, as well as to reduce the amount of possible by-products, to reduce the amount of solvent used (i.e., to concentrate) or to replace the solvent with another solvent. Such processes are known to those skilled in the art.

[0100] Preferably, undesirable amounts of residual unreacted monomer are removed, preferably by a distillation process, more preferably by a thermal distillation process, which may additionally include the application of reduced pressure to increase the rate and / or efficiency of removal.

[0101] In a preferred embodiment of embodiment 24, only the additional process step b) of embodiment 24 is used.

[0102] Uses of PPIs and compositions containing PPIs The use of the PPIs of the present invention for various fields of application, in which the PPIs of the present invention can replace similar structures currently known, but which result in an improved biodegradation rate compared to these known structures, is also part of the present invention.

[0103] EMBODIMENT 25 a) in a cleaning composition, preferably as an additive for a liquid, solid or semi-solid detergent formulation, in particular a liquid detergent formulation, preferably a concentrated liquid detergent formulation, or a single unit dose laundry detergent formulation, or a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation, b) In fabric care and home care products, c) in electroplating formulations, d) in a cementitious composition, e) preferably as a dispersant in pesticide formulations, f) as an adhesion promoter for printing inks, for example on laminate films; g) as an aid (adhesion) for the compatibilization of, for example, different polymer layers as well as metal foils to produce multilayer composite films; h) as adhesion promoters for adhesives, for example in combination with polyvinyl alcohol, butyrate, and acetate, and styrene copolymers, or as cohesion promoters for label adhesives; i) as a primer in coating applications to improve adhesion to substrates such as glass, wood, plastics, and metals; j) to improve the wet adhesion, e.g. in standard emulsion paints, and to improve the immediate rain resistance, e.g. of paints for road markings, k) as a complexing agent with high binding capacity, especially for heavy metals such as Hg, Pb, Cu, Ni, etc. l) as a flocculant, e.g. in water treatment / water processing; m) as a penetration aid for active metal salt formulations, for example in wood protection; n) as corrosion inhibitors, for example for ferrous and non-ferrous metals and in the oil production and secondary oil production sectors; o) as a support for immobilizing microorganisms or enzymes and microorganisms for the immobilization of proteins and enzymes, p) Barring and sealing, e.g. for the mineral oil and natural gas industries; q) as fixing agents, for example in the textile industry, in particular as formaldehyde-free fixing solutions, r) as additives in cosmetic formulations, for example for hair setting compositions and hair rinses, s) as an auxiliary in the paper industry, for example as a multipurpose auxiliary for accelerating dewatering, removing contraries, neutralizing charges, and for paper processing; t) for oil-water separation, e.g. in the metal processing industry, u) As an additive for landfill sealants v) as a flocculant, w) as an algaecide for swimming pools, x) for producing bitumen chemicals by reacting with fatty acids; y) as an anti-swelling agent to retard the absorption of water by clays; z) as an emulsifier or demulsifier, aa) As surfactants in the industrial cleaning (IC) sector, bb) as a wood preservative, cc) for preparing complexing agents (polycarboxylates), dd) for the production of auxiliary materials for mineral extraction and mineral processing; ee) as dispersants for pigments, ceramics, carbon black, carbon, carbon fibres, metal powders, e.g. as emulsifiers or dispersants for inkjet printing inks, ff) as an absorbent for CO2, NOX, SOX, Cl2 and aldehydes, for gas cleaning and for neutralizing acidic components; gg) for softening hard water, hh) as crystallization inhibitors, for example in pesticide formulations for oil field applications; ii) as a rheology modifier (thickener); jj) as an auxiliary or component for the extraction and processing of oil, coal, and natural gas; kk) for the production of synthetic rubber and rubber chemicals; ll) as additives in coolants, lubricants and cooling lubricants; mm) As an auxiliary in the construction chemicals sector, nn) As a component of a zinc plating bath, or oo) Use of at least one PPI as described in any one of embodiments 1 to 18 or as producible or produced by a process as described in any one of embodiments 19 to 24 for producing a non-viral genetic vector.

[0104] A subject of the present invention is the use of the above-mentioned PPIs (including modified PPIs) in fabric care and home care products, in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions and / or as dispersants for pesticide formulations, preferably in cleaning compositions and / or in fabric care and home care products, in particular cleaning compositions for improving the removal of oily and greasy stains, where the cleaning compositions are preferably laundry detergent formulations and / or manual dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid manual dishwashing detergent formulations.

[0105] The PPIs of the present invention can be added in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cement-based compositions, etc. However, the compounds of the present invention can also be added (used) in water washing or cleaning compositions.

[0106] Another subject of the present invention is therefore cleaning compositions, fabric and home care products, institutional cleaning products, cosmetic formulations, crude oil demulsifiers, pigment dispersions for inkjet inks, formulations for electroplating, cement-based compositions and / or dispersants for pesticide formulations, which comprise at least one PPI as defined above.

[0107] Preferably, this is a cleaning composition and / or a fabric care and home care product comprising at least one PPI as defined above, preferably for improving the removal of oily and greasy stains, preferably a laundry detergent formulation and / or a manual dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid manual dishwashing detergent formulation.

[0108] In another preferred embodiment of the present invention the cleaning composition may be used for stain removal of particulate stains and / or oily and greasy stains and more preferably for whiteness maintenance in laundry care.

[0109] In another embodiment, 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.

[0110] In another embodiment, the cleaning compositions of the invention are liquid or solid automatic dishwashing detergent compositions, preferably solid automatic dishwashing detergent compositions, that may be used to clean dishes, such as glass dishes, where the PPIs of the invention prevent corrosion of glass surfaces.

[0111] In another embodiment, the cleaning compositions are designed for use in personal care and pet care compositions such as shampoo compositions, body wash formulations, liquid or solid soaps, etc.

[0112] In the present invention, the preferred application areas for the use of PPIs are in the field of fabric care and home care products and cleaning compositions, preferably institutional cleaning compositions, and consumer household use.

[0113] EMBODIMENT 26 The use according to embodiment 25 in cleaning compositions and / or fabric care and home care products, preferably liquid and solid detergent compositions, which preferably comprise a) manual and automatic dishwashing detergent compositions comprising at least one PPI and at least one chelating agent and / or at least one surfactant, or more preferably a chelating agent in the case of liquid or solid automatic dishwashing compositions and a surfactant system in the case of liquid manual dishwashing detergent compositions, respectively; and / or b) A laundry detergent composition comprising at least one PPI and at least one surfactant, or more preferably a surfactant system.

[0114] Within the application field of these preferred uses, typical roles must be performed, all of which are usually encompassed by the term "cleaning", but which in reality include various roles such as removing oily and fatty residues, solid residues, amphiphilic residues, and hydrophilic residues. Other roles are to protect the item to be cleaned from deterioration, such as protecting glass from corrosion, protecting silverware from oxidation, protecting dyes from fading, etc. Other roles are to improve the overall appearance of the item to be cleaned, such as improving or restoring color, whiteness, imparting or increasing luster. For many such applications, additional ingredients are generally added, important in cleaning applications, such as enzymes, which help to biologically decompose the residues.

[0115] EMBODIMENT 27 i) improved removal of oily / greasy stains, and / or ii) Removal of clay; and / or iii) Removal of particulate stains; and / or iv) Dispersion and / or emulsification of dirt; and / or v) modification of the treated surface to improve removal upon subsequent recontamination; and / or vi) prevention or reduction, preferably prevention, of glass corrosion; and / or vii) improving whiteness; and / or viii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, 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 selected from proteases, if present, additionally for improved removal of oily / greasy stains, food stains and / or combination stains, Most preferred is the use according to embodiment 25 or 26 for i) improving the removal of oily / greasy stains in a cleaning composition, The use, wherein each of the above options i) to viii) is preferably for use in a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a preferably solid, automatic dishwashing detergent or a liquid manual dishwashing detergent formulation.

[0116] EMBODIMENT 28 Use according to any one of embodiments 25 to 27 in a cleaning composition and / or in a fabric care and home care product, preferably in a cleaning composition for fabric care and home care, wherein the cleaning composition is preferably a laundry detergent formulation or a dishwashing detergent formulation.

[0117] Such ingredients are typically blended with other ingredients in formulations and compositions that may also be referred to as "products" (which are provided as formulations by suppliers to other customers who either use the formulation as is, such as for cleaning purposes, or who use the formulation to produce other formulations that may then be sold to consumers as "products" for their own use).

[0118] EMBODIMENT 29 A composition which 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 demulsifier, 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, comprising at least one PPI according to any one of embodiments 1 to 18, or at least one PPI obtained or obtainable by the process according to any one of embodiments 19 to 24, respectively.

[0119] EMBODIMENT 30 As claimed in any one of claims 5 to 7 and comprising at least one PPI, preferably at least one (modified) PPI, as claimed in claim 9, Optionally, at least one enzyme, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases, and peroxidases, and combinations of at least two of the above classes, preferably at least one enzyme selected from proteases; Optionally containing at least one antimicrobial agent; The at least one PPI is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to about 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 the composition or product; The composition of embodiment 29, wherein the product or composition is a solid or liquid laundry detergent composition or a solid or liquid manual dishwashing detergent composition, preferably a liquid laundry detergent or manual dishwashing detergent composition, more preferably a liquid laundry detergent composition, further comprising from about 1% to about 70% by weight of at least one surfactant, preferably an anionic surfactant, or even more preferably a surfactant system comprising at least one anionic surfactant.

[0120] EMBODIMENT 31 10. A composition comprising at least one (unmodified) PPI as claimed in claim 1, Optionally, at least one enzyme is preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases, and peroxidases, and combinations of at least two of the above types, preferably at least one enzyme selected from proteases and amylases, Optionally containing at least one antimicrobial agent; Optionally, at least one compound selected from an alkali metal percarbonate, an alkali metal perborate, and an alkali metal persulfate; Optionally containing at least one zinc salt; at least one (unmodified) PPI 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 product or composition further comprises at least one chelating agent present in a total amount of from about 1% to about 70%, preferably from 10% to about 60%, and even more preferably from 30% to about 50%, A solid or liquid automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition, optionally further comprising at least one surfactant, or more preferably a surfactant system, in a total amount of from about 1% to about 70% by weight, The composition of embodiment 29, wherein all weight percentages are based on the total weight of such composition.

[0121] Embodiment 31a comprising at least one (unmodified) PPI according to any one of claims 1 to 4 and claim 8, Additionally, 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 non-ionic surfactant, Optionally, at least one disintegrant, preferably a super-disintegrant, more preferably PVPP; The composition of embodiment 31, which is a solid automatic dishwashing detergent composition, optionally containing at least one zinc salt.

[0122] Superdisintegrants are known to the skilled artisan from, for example, 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.

[0123] EMBODIMENT 32 The composition of embodiments 31 and 31a, which is a detergent composition in which a PPI is used to prevent or reduce glass corrosion.

[0124] EMBODIMENT 33 33. The composition of any one of embodiments 29, 30, 31, and 32, which is a detergent composition comprising at least one anionic surfactant as a surfactant and further comprising water.

[0125] Embodiment 33a The composition of any one of embodiments 29, 31, 31a, and 32, which is a detergent composition comprising at least one nonionic surfactant as a surfactant and further comprising water.

[0126] EMBODIMENT 34 The composition of any one of embodiments 29-33 and 33a, which is a detergent composition comprising at least one further polymer selected from a multifunctional polyethyleneimine or a multifunctional diamine, or a mixture thereof.

[0127] EMBODIMENT 35 The composition of any one of embodiments 29-34, 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 5.

[0128] EMBODIMENT 36 36. The composition of any one of embodiments 29 to 35, further comprising an antibacterial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydiphenyl ether, preferably comprising 2-phenoxyethanol in the range of 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% phenoxyethanol, or preferably comprising 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.

[0129] EMBODIMENT 37 A method for protecting the aqueous composition according to any one of embodiments 29 to 35 from microbial contamination or growth, comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dicolo-2-hydroxydiphenyl ether.

[0130] It is also preferred in the present invention that the cleaning composition additionally comprises (besides at least one PPI as defined above) at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the above types, more preferably selected from proteases.

[0131] 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 manual dishwashing detergents comprising at least one PPI of the present invention and optionally further comprising at least one surfactant or surfactant system to provide improved soil removal, dispersion and / or emulsification, and / or modification of treated surfaces and / or whiteness maintenance of treated surfaces.

[0132] At least one PPI of the invention as described herein (the PPIs defined above, particularly in embodiments 1-18, are also referred to in this following section as "polymers of the invention") is present in the above-described cleaning compositions of the invention at a concentration of 0.001 to 10, preferably about 0.005% to 5%, more preferably about 0.01% to about 5%, and most preferably about 0.1% to about 3%, based on the total weight of such composition, and such cleaning compositions may further comprise, and preferably further comprise, about 1% to about 70% by weight of a surfactant system.

[0133] Even more preferably, the cleaning compositions of the present invention comprising at least one polymer of the present invention and optionally further comprising at least one surfactant or surfactant system are intended for primary cleaning (i.e. stain removal) in laundry and manual dishwashing applications, even more particularly for the removal of oily and fatty stains such as on fabrics and dishes, and may additionally comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the abovementioned types of enzymes, more preferably at least one enzyme selected from the list consisting of proteases.

[0134] In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

[0135] In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g. powder or tablet / unit dose) detergent composition for manual or automatic dishwashing, preferably a liquid manual dishwashing detergent composition or a solid automatic dishwashing composition.

[0136] In one embodiment, the polymers of the present invention can be used in cleaning compositions comprising a surfactant system comprising a C10-C15 alkyl benzene sulfonate (LAS) as a primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic, or other anionic surfactants, or mixtures thereof.

[0137] In a further embodiment, the polymers of the present invention may be utilized in cleaning compositions, such as any type of laundry detergent, that include a C8 to C18 linear or branched alkyl ether sulfate having 1-5 ethoxy units as the primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0138] In a further embodiment, the polymers of the present invention may be utilized in cleaning compositions, such as any type of laundry detergent, that include a C12-C18 alkyl ethoxylate surfactant having 5-10 ethoxy units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

[0139] In one embodiment of the present invention, the polymer of the present invention is a component of a cleaning composition, preferably a laundry or dishwashing formulation, more preferably a liquid laundry or manual dishwashing formulation, each additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0140] The selection of the additional surfactant in these embodiments can depend on the application and the desired benefit.

[0141] As used herein, the articles "a" and "an" when used in a claim or an embodiment are understood to mean one or more of what is claimed or described. As used herein, the terms "comprises" and "including" are meant to be open-ended and thus encompass more than the specific items referenced following the word.

[0142] The compositions of the present disclosure can "comprise" (i.e., contain other ingredients), "consist essentially of" (contain primarily or almost exclusively the mentioned ingredients, with only very small amounts of other ingredients primarily as impurities), or "consist" (i.e., contain only the mentioned ingredients, plus possibly only impurities that are unavoidable in the technical environment, and preferably contain only those ingredients).

[0143] Similarly, the terms "substantially free of..." or "substantially free of..." or "essentially free of..." may be used herein to mean that the specified material is present in very minimal amounts that are not intentionally added to the composition to form part of the composition, or preferably is not present at levels detectable by analysis. It is thereby intended to encompass compositions in which the specified material is present only as an impurity in one of the other materials that is intentionally included. The specified material, if present, may be present at a level of less than 1%, or even less than 0.1%, or even less than 0.01%, or even 0% by weight of the composition.

[0144] The term "about" as used herein encompasses the exact number "X" referred to, such as, for example, "about X%", as well as small variations of X, including deviations of ±5%, preferably ±2%, more preferably ±1%, even more preferably ±0.5% and smaller variations from X (wherein, in this calculation, X is taken as 100%). Of course, in cases where the given value X is itself already "100%" (e.g., with respect to purity, etc.), the term "about" can and therefore only refers to deviations that are clearly smaller than "100".

[0145] Unless otherwise stated, all component or composition concentrations are in terms of the active portion of that component or composition and are exclusive of impurities, such as residual solvents or by-products, that may be present in commercial sources of such component or composition.

[0146] 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.

[0147] Description of cleaning compositions, formulations and their ingredients The phrase "cleaning composition" as used herein includes compositions and formulations designed for cleaning soiled materials, including those designed to clean any type of soiled material or surface.

[0148] "Industrial cleaning" compositions include cleaning compositions designed for use in industrial cleaning, such as hard surface cleaners for any type of surface including tiles, carpets, PVC surfaces, wood surfaces, metal surfaces, lacquered surfaces, and the like, for use in cleaning any type of soiled material or surface.

[0149] "Fabric care and home care compositions" include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric improving compositions, fabric freshening compositions, laundry pre-wash agents, laundry pre-treatment agents, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, water wash additives, post-rinse fabric treatment agents, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that will be apparent to those skilled in the art in view of the teachings herein and are detailed herein below when describing the compositions. Such compositions can be used as laundry pre-treatment agents, laundry post-treatment agents, or can be added during the rinse or wash cycle of a laundry operation, preferably during the wash cycle of a laundry or dishwashing operation, as described in more detail herein below when describing the use and application of the polymers of the present invention and compositions comprising such polymers.

[0150] The cleaning compositions of the present invention can be in any form, i.e., liquids; solids such as powders, granules, agglomerates, pastes, tablets, pouches, bars, gels, etc.; emulsions; types delivered in two-compartment or multi-compartment containers; single-phase or multi-phase unit doses; spray or foam detergents; wet wipes (i.e., cleaning compositions combined with nonwoven materials such as those described in U.S. Pat. No. 6,121,165 to Mackey et al.); dry wipes that are activated by the user or consumer with water (i.e., cleaning compositions combined with nonwoven materials such as those described in U.S. Pat. No. 5,980,931 to Fowler et al.); and other homogeneous, heterogeneous, or single-phase or multi-phase cleaning products.

[0151] The liquid cleaning compositions of the present invention preferably have a viscosity of 50-10000 mPa*s, the liquid manual dishwashing cleaning compositions (also liquid manual "dishwashing compositions") preferably have a viscosity of 100-10000 mPa*s, more preferably 200-5000 mPa*s, most preferably 500-3000 mPa*s at 20 1 / s and 20°C, and the liquid laundry cleaning compositions preferably have a viscosity of 50-3000 mPa*s, more preferably 100-1500 mPa*s, most preferably 200-1000 mPa*s at 20 1 / s and 20°C.

[0152] The liquid cleaning composition of the present invention may have any suitable pH value. Preferably, the pH of the composition is adjusted to 4-14. More preferably, the composition has a pH of 6-13, even more preferably 6-10, and most preferably 7-9. The pH of the composition may be adjusted using pH adjusting ingredients known in the art, measured at 25°C, at a concentration of 10% by weight of the product in demineralized water. For example, NaOH may be used, and the actual weight % of NaOH may be varied to adjust to the desired pH, for example pH 8.0. In one embodiment of the present invention, the pH is adjusted to >7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0153] Detergent compositions, such as fabric care and home care products and commercial cleaning formulations, more specifically laundry and manual dishwashing detergents, are known to those skilled in the art. Any compositions known to those skilled in the art related to the respective application can be used in the context of the present invention by including at least one of the polymers of the present invention, preferably at least one polymer in an amount suitable for developing specific properties in such compositions, especially when such compositions are used in their field of use.

[0154] The use of the polymers of the present invention as additives in detergent formulations, in particular liquid detergent formulations, preferably concentrated liquid detergent formulations, or for single unit doses for laundry, is also an aspect of the present invention.

[0155] The cleaning compositions of the present invention may, and preferably do, contain auxiliary cleaning additives (also abbreviated herein as "auxiliaries"), which are preferably in addition to the surfactant system defined above.

[0156] Suitable auxiliary cleaning additives 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, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, color toning agents, dye transfer inhibitors, chelating agents, foam boosters, foam suppressors (defoamers), color speckle, silver care, anti-tarnish and / or anti-corrosion agents, alkalinity sources, pH adjusters, pH buffers, hydrotropes, scrubbing particles, antimicrobial agents, antioxidants, softeners, carriers, processing aids, pro-fragrances and fragrances.

[0157] The liquid cleaning composition may additionally comprise, and preferably does comprise, at least one of a rheology adjusting / modifying agent, an emollient, a moisturizer, a skin rejuvenating active, and a solvent.

[0158] The solid composition may additionally comprise, and preferably does comprise, at least one of a filler, a bleach, a bleach activator, and a catalytic material.

[0159] Suitable examples of such cleaning adjuncts and usage levels can be found in WO 99 / 05242, U.S. Pat. Nos. 5,576,282, 6,306,812 B1, and 6,326,348 B1.

[0160] Those skilled in the art will appreciate that a detersive surfactant includes any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0161] Thus, cleaning compositions of the present invention, such as fabric care and home care products and institutional cleaning formulations, more particularly laundry and manual dishwashing detergents, preferably additionally comprise a surfactant system, and more preferably further adjuvants, as described above and in more detail below.

[0162] The surfactant system may be comprised of one or a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof. Those skilled in the art will appreciate that a surfactant system for a detergent encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0163] The cleaning compositions of the present invention preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of the surfactant system, by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of the surfactant system, by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of the surfactant system, by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and combinations thereof.

[0164] (a) Laundry composition In laundry formulations, anionic surfactants usually contribute by far the largest proportion of surfactants in such formulations. Therefore, preferably, the cleaning composition of the present invention for use in laundry comprises 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.

[0165] Non-limiting examples of anionic surfactants useful herein, which may also be used in combinations of two or more surfactants, include C9-C20 linear alkylbenzene sulfonates (LAS), C10-C20 primary, branched and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) (where x is 1-30); C10-C18 alkyl alkoxy carboxylates containing 1-5 ethoxy units; and those disclosed in U.S. Pat. No. 6,020,303. and 6,060,443; mid-chain branched alkyl alkoxy sulfates, as discussed in U.S. Pat. Nos. 6,008,181 and 6,020,303; modified alkylbenzene sulfonates (MLAS), as discussed in WO 99 / 05243, WO 99 / 05242, and WO 99 / 05244; methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS).

[0166] Preferred examples of suitable anionic surfactants are 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: 3-50 moles of ethylene oxide / mol), C12-C18 alkyl sulfonic acids, C12-C18 sulfofatty acid alkyl esters, such as C12-C18 sulfofatty acid methyl esters, C10-C18 alkylaryl sulfonic acids, preferably n-C10-C18 alkylbenzene sulfonic acids, C10-C18 alkyl alkoxy carboxylic acids and alkali metal and ammonium salts of soaps such as C8-C24 carboxylic acids. Alkali metal salts of the abovementioned compounds are preferred, and sodium salts are particularly preferred.

[0167] In one embodiment of the invention, the anionic surfactants are chosen from n-C10 to C18 alkylbenzene sulfonic acids and, in the context of the present invention, particularly from fatty alcohol polyether sulfates which are the sulfuric acid half esters of ethoxylated C12 to C18 alkanols (ethoxylated: 1 to 50 moles of ethylene oxide / mol), preferably n-C12 to C18 alkanols.

[0168] In one embodiment of the present invention, alcohol polyether sulfates derived from branched (ie, synthetic) C11-C18 alkanols (ethoxylated: 1-50 moles of ethylene oxide / mole) may also be used.

[0169] Preferably, the alkoxylated groups of both types of alkoxylated alkyl sulfates, based on C12-C18 fatty alcohols or based on branched (i.e. synthetic) C11-C18 alcohols, are ethoxylated groups, and the average degree of ethoxylation of any of the alkoxylated alkyl sulfates is between 1 and 5, preferably between 1 and 3.

[0170] Preferably, the laundry detergent formulations of the present invention comprise at least 1% to 50% by weight of one or more anionic surfactants as defined above, 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 particular composition including other ingredients and water and / or solvent.

[0171] In a preferred embodiment of the present invention, the anionic surfactant is selected from C10-C15 linear alkylbenzene sulfonates, C10-C18 alkyl ether sulfates containing 1-5 ethoxy units, and C10-C18 alkyl sulfates.

[0172] 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® nonionic surfactants from Shell; ethylene oxide / propylene oxide block alkoxylates, such as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx (where x is 1-30), as discussed in U.S. Pat. Nos. 6,153,577, 6,020,303, and 6,093,856. alkyl polysaccharides, such as those discussed in U.S. Pat. No. 4,565,647, issued Jan. 26, 1986 to Llenado; alkyl polyglycosides, particularly those discussed in U.S. Pat. Nos. 4,483,780 and 4,483,779; polyhydroxy fatty acid amides, such as those discussed in U.S. Pat. No. 5,332,528; and ether-capped poly(oxyalkylated) alcohol surfactants, such as those discussed in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0173] Preferred examples of nonionic surfactants are, in particular, alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are the so-called amine oxides.

[0174] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (A) [ka] where the variables are defined as follows: R1 is selected from linear C1-C10 alkyl, preferably ethyl, particularly preferably methyl; R2 is selected from C8 to C22 alkyl, such as 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 are in the range of 0 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.

[0175] Here, the compound of general formula (A) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0176] Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (B): [ka] where the variables 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.

[0177] Preferably, at least one of a and b is greater than zero.

[0178] Here, the compound of general formula (B) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0179] Further suitable nonionic surfactants are selected from diblock and multiblock 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. Overviews of suitable further nonionic surfactants can be found in EP-A0851023 and DE-A19819187.

[0180] Of course, mixtures of two or more different nonionic surfactants may also be present.

[0181] In a preferred embodiment of the invention, the nonionic surfactants are 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 has 3 to 15 ethoxy units, preferably 5 to 10 ethoxy units or has 1 to 3 propoxy units and 2 to 15 ethoxy units.

[0182] Non-limiting examples of amphoteric surfactants that may also be used in combination with two or more other surfactants include water-soluble amine oxides containing one alkyl moiety of about 8 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of about 1 to about 3 carbon atoms. See WO 01 / 32816, U.S. Pat. Nos. 4,681,704, and 4,133,779. Suitable surfactants thus include so-called amine oxides, such as lauryl dimethylamine oxide ("lauramine oxide").

[0183] A preferred example of an amphoteric surfactant is an amine oxide. A preferred amine oxide is an alkyl dimethyl amine oxide or an alkyl amidopropyl dimethyl amine oxide, more preferably an alkyl dimethyl amine oxide, especially coconut dimethyl amine oxide. The amine oxide may have a linear or mid-branched alkyl moiety. Exemplary 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 of 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 may include, inter alia, linear C10-C18 alkyl dimethylamine oxides and linear C8-C12 alkoxyethyl dihydroxyethylamine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethylamine oxides. As used herein, "mid-branched" means that the amine oxide has one alkyl moiety with n1 carbon atoms and has one alkyl branch on the alkyl moiety with n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching for amine oxides is also known in the art as internal amine oxides. The sum of n1 and n2 is 10-24 carbon atoms, preferably 12-20, more preferably 10-16. The number of carbon atoms (n1) for one alkyl moiety should be approximately the same as the number of carbon atoms (n2) for one alkyl branch, so that this one alkyl moiety and one alkyl branch are symmetric. As used herein, "symmetric" means that at least 50% by weight, more preferably at least 75% to 100% by weight of the medium-branched amine oxide used herein has 5 or less carbon atoms (n1-n2), preferably 4 or less carbon atoms, most preferably 0 to 4 carbon atoms. The amine oxide further comprises two moieties independently selected from C1-C3 alkyl, C1-C3 hydroxyalkyl, or polyethylene oxide group containing an average of about 1 to about 3 ethylene oxide groups. Preferably, the two moieties are selected from C1-C3 alkyl, more preferably both are selected as C1 alkyl.

[0184] 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.

[0185] The cleaning compositions may also contain zwitterionic surfactants, which may also be used in combination with two or more other surfactants.

[0186] Suitable zwitterionic surfactants include betaines such as alkyl betaines, alkyl amido betaines, amido azolinium betaines, sulfo betaines (INCI: Sultaine), and phospho betaines. Examples of suitable betaines and sulfo betaines are as follows (listed according to INCI): almond amidopropyl betaine, apricot amidopropyl betaine, avocado amidopropyl betaine, babassu amidopropyl betaine, behenamidopropyl betaine, behenyl betaine, canola amidopropyl betaine, capryl / capramidopropyl betaine, carnitine, cetyl betaine, cocamidoethyl betaine, cocamidopropyl betaine, cocamidopropyl Hydroxysultaine, Coco Betaine, Coco Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG-Betaine, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl betaine, lauryl betaine, lauryl hydroxysultaine, lauryl sultaine, milkamidopropyl betaine, minkamidopropyl betaine, myristamidopropyl betaine, myristyl betaine, oleamidopropyl betaine, oleamidopropyl hydroxysultaine, oleyl betaine, oliamidopropyl betaine, coconutamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, coconut kernel fatty acid 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 germamidopropyl betaine.

[0187] 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.

[0188] Non-limiting examples of cationic surfactants that may be used in combination with two or more other surfactants include quaternary ammonium surfactants that can have up to 26 carbon atoms, including alkoxylated quaternary ammonium (AQA) surfactants as discussed in U.S. Pat. No. 6,136,769; dimethylhydroxyethyl quaternary ammonium as discussed in U.S. Pat. No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride; WO 98 / 35002; WO 98 / 35003; Polyamine cationic surfactants such as those discussed in US 98 / 35004, US 98 / 35005, and US 98 / 35006; cationic ester surfactants such as those discussed in US 4,228,042, US 4,239,660, US 4,260,529, and US 6,022,844; and amino surfactants, particularly amidopropyldimethylamines (APAs), such as those discussed in US 6,221,825 and WO 00 / 47708.

[0189] 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 elsewhere called "cobuilders". Examples of builders are complexing agents, also called complexing agents hereinafter, ion exchange compounds, and precipitating agents. The builders are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates.

[0190] In the context of the present invention, the term citrate includes mono- and di-alkali metal salts of citric acid, in particular monosodium salt and preferably trisodium salt, ammonium or substituted ammonium salts of citric acid, and citric acid. Citrate can be used as anhydrous compound or as a hydrate, for example as sodium citrate dihydrate. The amount of citrate is calculated based on anhydrous trisodium citrate.

[0191] The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogen phosphate, sodium pyrophosphate, and polyphosphates, such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free of phosphates and polyphosphates, such as free of trisodium phosphate, pentasodium tripolyphosphate, and hexasodium metaphosphate, with hydrogen phosphates being included ("phosphate-free"). In relation to phosphates and polyphosphates, "free" should be understood in the context of the present invention as meaning that the content of phosphates and polyphosphates is, in total, within the range of 10 ppm to 0.2% by weight of the respective composition, as determined by gravimetry.

[0192] The term carbonate includes alkali metal carbonates and alkali metal hydrogen carbonates, with the sodium salts being preferred, Na2CO3 being particularly preferred.

[0193] Examples of phosphonates are hydroxyalkane phosphonates and aminoalkane phosphonates. Among the 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 being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkane phosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues. These are preferably used in the form of the sodium salts that react neutrally, for example as the hexasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP.

[0194] Examples of aminocarboxylates and polycarboxylates are nitrilotriacetate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, triethylenetetraaminehexaacetate, propylenediaminetetraacetate, ethanol-diglycine, methylglycinediacetate, and glutaminediacetate. The term aminocarboxylates and polycarboxylates also includes their corresponding unsubstituted or substituted ammonium salts and alkali metal salts, such as the sodium salts, in particular of the corresponding fully neutralized compounds.

[0195] In the context of the present invention, silicates include in particular sodium disilicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, in particular those of the formulae α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.

[0196] The compositions according to the invention may contain one or more builders selected from materials not mentioned above. Examples of builders are alpha-hydroxypropionic acid and oxidized starch.

[0197] In one embodiment of the invention, the builder is selected from polycarboxylates, the term "polycarboxylate" including non-polymeric polycarboxylates such as succinic acid, C2-C16 alkyl disuccinates, C2-C16 alkenyl disuccinates, ethylenediamine N,N'-disuccinate, tartrate diacetate, alkali metal malonates, tartrate monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid, and cyclopentanetetracarboxylic acid.

[0198] Oligomeric or polymeric polycarboxylates are, for example, the alkali metal salts of polyaspartic acid or, in particular, of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

[0199] 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 a weight-average molecular weight Mw in the range from 2000 to 40000 g / mol, preferably from 2000 to 10000 g / mol, in particular from 3000 to 8000 g / mol. Further suitable copolymeric polycarboxylates are in particular those of acrylic acid and methacrylic acid, as well as those of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

[0200] 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 anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid, and citraconic acid, with at least one hydrophilic or hydrophobic modifying comonomer as listed below.

[0201] Suitable hydrophobic comonomers are, for example, isobutene, diisobutene, butene, pentene, hexene 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 on average 12 to 100 carbon atoms per molecule.

[0202] Suitable hydrophilic comonomers are monomers with sulfonate or phosphonate groups, and non-ionic monomers with hydroxyl functionality or alkylene oxide groups. Examples may 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 specification, the polyalkylene glycol may contain 3 to 50, particularly 5 to 40, and especially 10 to 30 alkylene oxide units per molecule.

[0203] 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 the salts of the above acids, such as the sodium, potassium or ammonium salts thereof.

[0204] Particularly preferred phosphonic acid group-containing monomers are vinylphosphonic acid and its salts.

[0205] Additionally, amphoteric polymers can also be used as builders.

[0206] The compositions according to the invention, in particular in the case of solid formulations, may for example comprise in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder. Liquid formulations according to the invention preferably comprise in the range 0.1 to 8% by weight of builder.

[0207] The formulation according to the invention may contain one or more alkaline carriers. The alkaline carriers ensure, for example, a pH of at least 9 when an alkaline pH is desired. For example, the above-mentioned alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates and additionally alkali metal hydroxides are suitable. The preferred alkali metal is in each case potassium, with sodium being particularly preferred. In one embodiment of the invention, the pH is adjusted to >7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0208] In one embodiment of the invention, the laundry formulation according to the invention additionally comprises at least one enzyme.

[0209] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, and peroxidases, as well as combinations of at least two of the above classes, more preferably at least one enzyme selected from proteases.

[0210] Such enzymes can be incorporated at a level sufficient to provide an effective amount for cleaning. A preferred amount is in the range of 0.001% to 5% active enzyme by weight of the detergent composition of the present invention. Enzyme stabilizing systems may also be used in conjunction with the enzymes, such as calcium ions, boric acid, boronic acid, propylene glycol, and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids containing 1 to 3 carbon atoms per molecule, and dicarboxylic acids containing 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH2)3COOH, adipic acid, and mixtures of at least two of the above, as well as the sodium and potassium salts of each.

[0211] The compositions according to the invention may contain one or more bleaching agents.

[0212] Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or the so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, in each case the term "persulfate" including the salts of the peracid HSO and peroxodisulfate.

[0213] In this connection, the alkali metal salts can in each case also be alkali metal hydrogen carbonates, alkali metal hydrogen perborates and alkali metal hydrogen persulfates, although the dialkali metal salts are preferred in each case.

[0214] The formulation according to the invention may contain one or more bleach catalysts. The bleach catalysts may be selected from oxaziridinium bleach catalysts, bleach-promoting transition metal salts or transition metal complexes, such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts.

[0215] The formulations of the present invention may include one or more bleach activators, such as tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetylglycoluril, tetraacetylhexylenediamine, acylated phenolsulfonates such as n-nonanoyl- or isononanoyloxybenzenesulfonates, 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).

[0216] The formulation according to the invention can contain one or more corrosion inhibitors.In the present case, this is understood to include compounds that inhibit the corrosion of metals.Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and also phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0217] In one embodiment of the invention, the formulation according to the invention comprises in total in the range of 0.1-1.5 wt. % of corrosion inhibitors.

[0218] The formulations of the present invention may also contain additional cleaning polymers and / or soil release polymers.

[0219] Additional cleaning polymers may include, but are not limited to, "multifunctional polyethyleneimines" (e.g., Sokalan® HP20 from BASF) and / or "multifunctional diamines" (e.g., Sokalan® HP96 from BASF). Such multifunctional polyethyleneimines are typically ethoxylated polyethyleneimines having a weight average molecular weight Mw in the range of 3000 to 250000 g / mol, preferably 5000 to 200000 g / mol, more preferably 8000 to 100000 g / mol, more preferably 8000 to 50000 g / mol, more preferably 10000 to 30000 g / mol, and most preferably 10000 to 20000 g / mol. Suitable polyfunctional polyethyleneimines have 80% to 99% by weight of ethylene oxide side chains, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, most preferably 93% to 97% by weight or 94% to 96% by weight, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core and a polyethylene oxide shell. Suitable polyethyleneimine core molecules are polyethyleneimines with a weight average molecular weight Mw in the range of 500 to 5000 g / mol. Preferably, molecular weights of 500 to 1000 g / mol are used, with Mw of 600 to 800 g / mol being even more preferred. Thus, the ethoxylated polymer has an average of 5 to 50, preferably 10 to 35, even more preferably 20 to 35 ethylene oxide (EO) units per NH functionality.

[0220] Suitable polyfunctional diamines are typically ethoxylated C2-C12 alkylenediamines, preferably hexamethylene diamines, which are further quaternized and optionally sulfated. Typical polyfunctional diamines have a weight average molecular weight Mw in the range of 2000-10000 g / mol, more preferably 3000-8000 g / mol, most preferably 4000-6000 g / mol. In a preferred embodiment of the present invention, a further quaternized and sulfated ethoxylated hexamethylene diamine may be used, which contains an average of 10-50, preferably 15-40, even more preferably 20-30 ethylene oxide (EO) groups per NH functionality, which preferably has two cationic ammonium groups and two anionic sulfate groups.

[0221] In a preferred embodiment of the present invention, the cleaning composition may contain at least one multifunctional polyethyleneimine and / or at least one multifunctional diamine to improve the cleaning performance of the laundry detergent, preferably the soil removal ability, especially the primary cleaning power of particulate soils on polyester fabrics, etc. The multifunctional polyethyleneimine or multifunctional diamine or mixtures thereof according to the above description may be added to the laundry detergent and cleaning composition in low amounts, generally 0.05 to 15% by weight, preferably 0.1 to 10% by weight, more preferably 0.25 to 5% by weight, even up to 2% by weight, based on the total of the particular composition including other components and water and / or solvent.

[0222] Thus, 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 polyethyleneimines and multifunctional diamines, and mixtures thereof.

[0223] In one embodiment of the present invention, the ratio of at least one polymer of the present invention to (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof, is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3.

[0224] Laundry formulations containing the polymers of the present invention may also contain at least one antimicrobial agent (often also referred to as a "preservative").

[0225] The composition may contain one or more antimicrobial agents and / or preservatives listed on pages 35-39 of WO 2021 / 115912 A1.

[0226] Of particular interest are the following antimicrobial and / or antiseptic agents: 4,4'-Dichloro-2-hydroxydiphenyl ether (CAS number 3380-30-1), also known as 5-chloro-2-(4-chlorophenoxy)phenol (Diclosan, DCPP) (commercially available as a 30% by weight solution of 4,4'-dichloro-2-hydroxydiphenyl ether in 1,2-propylene glycol under the trade name Tinosan® HP100 (BASF)); 2-phenoxyethanol (CAS number 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 number 52-51-7, also known as 2-bromo-2-nitro-1,3-propanediol, Bronopol®, Protectol® BN, Myacide AS); glutaraldehyde (CAS No. 111-30-8; synonyms: 1-5-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde, Protectol® GA, Protectol® GA50, Myacide® GA); glyoxal (CAS No. 107-22-2; synonyms: ethanedial, oxylaldehyde 1,2-ethanedial, Protectol® GL); 2-butanol 2-methyl-2H-isothiazol-3-one (MIT, CAS number 2682-20-4); 2-octyl-2H-isothiazol-3-one (OIT, CAS number 26530-20-1); 5-chloro-2-methyl-2H-isothiazol-3-one (CIT, CMIT, CAS number 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 number 110-44-1) and its salts, such as calcium sorbate, sodium sorbate, potassium (E,E)-hexa-2,4-dienoate (potassium sorbate, CAS number 24634-61-5); lactic acid and its salts; L-(+)-lactic acid (CAS number 79-33-4); benzoic acid and its sodium salts (CAS number 65-85-0, CAS number 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, benzalkonium bromide, and benzalkonium saccharinate, such as benzalkonium chloride, benzalkonium bromide, and 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 number 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).

[0227] The antibacterial agent is added to the composition at a concentration of 0.001 to 10% based on the total weight of the composition.

[0228] Preferably, the composition contains 2-phenoxyethanol at a concentration of 0.1-2% or 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005-0.6%.

[0229] Thus, the present invention further includes a method of protecting the aqueous compositions of the present invention from microbial contamination or growth, the method comprising the addition of 2-phenoxyethanol.Thus, the present invention further includes a method of imparting antimicrobial benefit to fabrics after treatment with a solid laundry detergent (e.g., powder, granules, capsules, tablets, bars, etc.), liquid laundry detergent, fabric softener, or after-rinse containing 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP).

[0230] In a further embodiment, the present invention also encompasses a composition comprising the polymer of the present invention as described herein above, further comprising an antimicrobial agent as disclosed herein below, 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.

[0231] In a further embodiment, the present invention also encompasses a method of protecting an aqueous composition from microbial contamination or growth, said composition comprising the polymer of the present invention as described herein above, said composition being preferably a detergent composition, said method comprising adding at least one antimicrobial agent selected from the antimicrobial agents of the present disclosure disclosed herein below, said antimicrobial agent being preferably 2-phenoxyethanol.

[0232] 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 dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use on laundry, such composition comprising a polymer of the present invention as described herein above, such composition further comprising 4,4'-dichoro 2-hydroxydiphenyl ether, each at a concentration of from 0.001 to 3%, preferably from 0.002 to 1%, more preferably from 0.01 to 0.6% by weight of the composition.

[0233] In a further embodiment, the present invention also encompasses a method of laundering a fabric or a method of cleaning a hard surface, the method comprising treating the fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition or a liquid softener composition for use on laundry, such composition comprising a polymer of the present invention as described herein above, such composition further comprising 4,4'-dichoro 2-hydroxydiphenyl ether.

[0234] The formulations of the present invention may also contain water and / or additional organic solvents, such as ethanol or propylene glycol.

[0235] Further optional ingredients can be, but are not limited to, viscosity modifiers, cationic surfactants, foam boosters or reducers, fragrances, dyes, optical brighteners, and dye transfer inhibitors.

[0236] (b) Dishwashing compositions Another aspect of the invention is also a dishwashing composition comprising at least one PPI as described above (as defined in any one of the embodiments herein, in particular in any one of the embodiments 1 to 18 (the PPI in this section is also referred to as the "polymer of the invention").

[0237] Therefore, an aspect of the present invention is also the use of the above inventive polymers in dishwashing applications, such as manual or automatic dishwashing applications.

[0238] The dishwashing composition of the present invention may be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, with solid embodiments including, for example, powders and tablets.Liquid compositions are typically suitable for manual dishwashing applications, while solid and pouch formulations (pouches may contain solids in addition to liquid components) are typically suitable for automatic dishwashing compositions, although in some parts of the world, liquid automatic dishwashing compositions are also used, and therefore are of course also encompassed by the term "dishwashing composition".

[0239] Dishwashing compositions are intended for direct or indirect application onto tableware and metal and glass surfaces, including drinking and other glasses, beakers, dishes, and cookware such as pots and pans, and cutlery such as forks, spoons, knives, and the like.

[0240] The method of the present invention for cleaning dishware, metal, and / or glass surfaces preferably comprises the step of applying a liquid dishwashing detergent composition to the surface, either directly or with a cleaning implement (i.e., in neat form). The composition is applied directly to the surface to be treated and / or to a cleaning implement or implement, such as a cloth, sponge, or dish brush, without extensive dilution (immediately) prior to application. The cleaning implement or implement is preferably moistened before or after the composition is delivered. In the method of the present invention, the composition may be applied in diluted form.

[0241] Both neat and diluted application provide excellent cleaning performance. That is, the formulations of the present invention containing at least one polymer of the present invention show excellent degreasing properties. Due to the presence of the polymer of the present invention, the effort of removing greasy and / or oily soils from dishware, metal and / or glass surfaces is reduced even when the level of surfactant used is lower than in conventional compositions.

[0242] Preferably, the compositions are formulated to provide superior grease cleaning (degreasing) performance, long lasting foam, and / or improved viscosity control when exposed to low temperatures, preferably at least two, more preferably all three, are present in the dishwashing compositions of the present invention. Optional (and preferably present) additional benefits of the manual dishwashing compositions of the present invention include stain removal, shine, and / or hand protection, more preferably at least two, most preferably all three, are present in the manual dishwashing compositions of the present invention.

[0243] In a preferred embodiment of the present invention, the polymer of the present invention is a component of an automatic dishwashing formulation, preferably a solid automatic dishwashing formulation. Formulations containing the polymer of the present invention significantly reduce glass corrosion.

[0244] In another preferred embodiment of the present invention, the polymer of the present invention is a component of a manual dishwashing formulation additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0245] In another embodiment of the present invention, the polymer of the present invention is a component of a manual dishwashing formulation additionally comprising at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric and / or zwitterionic surfactants. In a preferred embodiment of the present invention, the manual dishwashing formulation contains at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or a mixture thereof, to promote foaming, detergency, and / or mildness of the detergent composition.

[0246] Examples of suitable anionic surfactants have already been described above in relation to the laundry compositions.

[0247] Preferred anionic surfactants for manual dishwashing compositions are selected from C10-C15 linear alkyl benzene sulfonates, C10-C18 alkyl ether sulfates having 1-5 ethoxy units, and C10-C18 alkyl sulfates.

[0248] Preferably, the manual dishwashing detergent formulations of the present invention comprise one or more anionic surfactants as described above in an amount of at least 1% to 50% by weight, preferably in the range of from about 3% to about 35% by weight, more preferably in the range of from 5% to 30% by weight, and most preferably in the range of from 5% to 20% by weight, based on the total specific composition including other ingredients and water and / or solvent.

[0249] The dishwashing compositions, preferably manual dishwashing compositions, of the present invention may comprise at least one amphoteric surfactant.

[0250] Examples of amphoteric surfactants suitable for dishwashing compositions have already been described above in relation to laundry compositions.

[0251] Preferred amphoteric surfactants for dishwashing compositions are selected from C8-C18 alkyl-dimethylamine oxides and C8-C18 alkyl-di(hydroxyethyl)amine oxides.

[0252] The manual dishwashing detergent composition of the present invention preferably comprises an amphoteric surfactant, preferably an amine oxide surfactant, in an amount of from 1% to 15%, preferably from 2% to 12%, more preferably from 3% to 10%, by weight of the composition. Preferably, the composition of the present invention comprises a mixture of an anionic surfactant and an alkyldimethylamine oxide in a weight ratio of less than about 10:1, more preferably less than about 8:1, more preferably from about 5:1 to about 2:1.

[0253] The addition of amphoteric surfactants provides good foaming properties in dishwashing compositions.

[0254] The dishwashing compositions, preferably manual dishwashing compositions, of the present invention may comprise at least one zwitterionic surfactant.

[0255] Examples of zwitterionic surfactants suitable for dishwashing compositions have already been described above in relation to laundry compositions.

[0256] Preferred zwitterionic surfactants for dishwashing compositions are selected from the betaine surfactants, more preferably from the cocamidopropyl betaine surfactants.

[0257] In a preferred embodiment of the present invention, the zwitterionic surfactant is cocamidopropyl betaine.

[0258] The manual dishwashing detergent compositions of the present invention optionally comprise from 1% to 15%, preferably from 2% to 12%, more preferably from 3% to 10% by weight of the composition of a zwitterionic surfactant, preferably a betaine surfactant.

[0259] The dishwashing compositions, preferably manual dishwashing compositions, of the present invention may comprise at least one cationic surfactant.

[0260] Examples of cationic surfactants suitable for dishwashing compositions have already been described above in relation to laundry compositions.

[0261] When a cationic surfactant is present in the composition, it is present in an effective amount, more preferably from 0.1% to 5%, preferably from 0.2% to 2% by weight of the composition.

[0262] The dishwashing compositions of the present invention, preferably both manual and automatic dishwashing compositions, may contain at least one non-ionic surfactant.

[0263] Examples of non-ionic surfactants suitable for dishwashing compositions have already been described above with respect to laundry compositions. Non-ionic surfactants typically improve the rinsing properties of automatic dishwashing formulations.

[0264] Suitable nonionic surfactants for automatic dishwashing compositions are C8 to C18 alkyl ethoxylate and ether-capped poly(oxyalkylated) alcohol surfactants, such as those described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0265] Examples of non-ionic surfactants suitable for dishwashing compositions have already been described above with respect to laundry compositions. Non-ionic surfactants typically improve the foaming properties of manual dishwashing formulations.

[0266] Preferred nonionic surfactants for manual dishwashing formulations are the condensation products of Guerbet alcohols with 2 to 18 moles, preferably 2 to 15 moles, more preferably 5 to 12 moles of ethylene oxide per mole of alcohol. Other preferred nonionic surfactants suitable for use herein include fatty alcohol polyglycol ethers, alkyl polyglucosides, and fatty acid glucamides.

[0267] The manual dishwashing detergent composition of the present invention may comprise 0.1% to 10%, preferably 0.3% to 5%, more preferably 0.4% to 2% by weight of the composition of a linear or branched C10 alkoxylated nonionic surfactant having an average degree of alkoxylation of 2 to 6, preferably 3 to 5. Preferably, the linear or branched C10 alkoxylated nonionic surfactant is a branched C10 ethoxylated nonionic surfactant having an average degree of ethoxylation of 2 to 6, preferably 3 to 5. Preferably, the composition comprises 60% to 100%, preferably 80% to 100%, more preferably 100% by weight of the branched C10 ethoxylated nonionic surfactant of the total linear or branched C10 alkoxylated nonionic surfactant. The linear or branched C10 alkoxylated nonionic surfactant is preferably a 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 3 to 5. A suitable 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, available from BASF SE, Ludwigshafen, Germany. The use of 2-propylheptyl ethoxylated nonionic surfactants having an average degree of ethoxylation of 3 to 5 improves foaming levels and foam retention.

[0268] Thus, one aspect of the present invention is a manual dishwashing detergent composition, in particular a liquid manual dishwashing detergent composition, comprising (i) at least one inventive polymer and (ii) at least one further 2-propylheptyl ethoxylated nonionic surfactant having an average degree of ethoxylation from 3 to 5.

[0269] In one embodiment of the present invention, the polymer of the present invention is a component of a dishwashing formulation, preferably an automatic dishwashing formulation, additionally comprising at least one builder, preferably at least one chelating agent.

[0270] Examples of suitable builders have already been described above in relation to the laundry compositions.

[0271] Preferred builders for dishwashing compositions are selected from citrates, phosphates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates. Even more preferred are builders selected from citrates, silicates, carbonates, phosphonates, aminocarboxylates, and polycarboxylates (i.e., phosphate-free compositions).

[0272] Particularly preferred are Na2CO3 and sodium citrate. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a builder. Preferred aminocarboxylates are methylglycine diacetate (MGDA) and glutamine diacetate (GLDA). The terms aminocarboxylates and polycarboxylates also include their corresponding unsubstituted or substituted ammonium salts and alkali metal salts, such as sodium salts, in particular the alkali metal salts of the respective fully neutralized compounds. Preferred polycarboxylates are, for example, polyaspartic acid or, in particular, the alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers. Suitable polymers are, in particular, polyacrylic acids, preferably having a weight-average molecular weight Mw in the range of 2000 to 40000 g / mol, preferably 2000 to 10000 g / mol, in particular 3000 to 8000 g / mol.

[0273] In the context of the present invention, silicates include in particular sodium disilicate and sodium metasilicate, aluminosilicates such as zeolites and layered silicates, in particular those of the formulae α-Na2Si2O5, β-Na2Si2O5, and δ-Na2Si2O5.

[0274] The compositions according to the invention, in particular in the case of solid formulations, may for example comprise in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder. Liquid formulations according to the invention preferably comprise in the range 0.1 to 8% by weight of builder.

[0275] The dishwashing compositions, preferably automatic dishwashing compositions, of the present invention comprise one or more bleaching agents.

[0276] Examples of suitable bleaching agents have already been described above in relation to the laundry compositions.

[0277] A preferred bleaching agent for dishwashing compositions is sodium percarbonate, either anhydrous or, for example, as the monohydrate.

[0278] In one embodiment of the present invention, the polymer of the present invention is a component of an automatic dishwashing formulation that additionally contains one or more bleach catalysts.

[0279] Examples of suitable bleach catalysts have already been described above with respect to the laundry compositions.

[0280] The dishwashing compositions of the present invention, particularly automatic dishwashing compositions, comprise one or more bleach activators.

[0281] Examples of suitable bleach activators have already been described above in relation to the laundry compositions.

[0282] A preferred bleach activator for dishwashing compositions is tetraacetylethylenediamine.

[0283] The dishwashing formulation of the present invention may contain one or more corrosion inhibitors. In the present case, this is understood to include compounds that inhibit corrosion of metals and / or glass. Examples of preferred corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, but also phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol, or zinc salts, in particular zinc benzoate, zinc gluconate, zinc lactate, zinc formicate, ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2, zinc gallate, zinc oxide, zinc hydroxide, and zinc carbonate.

[0284] In one embodiment of the invention, the dishwashing formulation of the present invention additionally comprises at least one enzyme.

[0285] Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, and peroxidases, as well as combinations of at least two of the above classes, preferably at least one protease and one amylase.

[0286] Such enzymes can be incorporated at a level sufficient to provide an effective amount for cleaning. A preferred amount is in the range of 0.001% to 5% active enzyme by weight of the detergent composition of the present invention. Enzyme stabilizing systems may also be used in conjunction with the enzymes, such as calcium ions, boric acid, boronic acid, propylene glycol, and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids containing 1 to 3 carbon atoms per molecule, and dicarboxylic acids containing 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, HOOC(CH2)3COOH, adipic acid, and mixtures of at least two of the above, as well as the sodium and potassium salts of each.

[0287] The dishwashing formulation of the present invention may contain one or more alkaline carriers. The alkaline carriers ensure, for example, a pH of at least 9 when an alkaline pH is desired. For example, the above-mentioned alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal metasilicates and additionally alkali metal hydroxides are suitable. The preferred alkali metal is in each case potassium, with sodium being particularly preferred. In one embodiment of the present invention, the pH is adjusted to >7 by using an amine, preferably an alkanolamine, more preferably triethanolamine.

[0288] The dishwashing compositions of the present invention may contain an effective amount of at least one hydrotrope to ensure compatibility of the liquid dishwashing detergent composition with water.

[0289] Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium, and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof and related compounds, as disclosed in U.S. Pat. No. 3,915,903.

[0290] The liquid dishwashing detergent compositions of the present invention typically comprise from 0.1% to 15% by weight of the total liquid detergent composition of a hydrotrope or mixtures thereof, preferably from 1% to 10% by weight of the total liquid manual dishwashing composition, most preferably from 2% to 5% by weight.

[0291] The dishwashing compositions of the present invention may include at least one organic solvent.

[0292] Examples of organic solvents are C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6-C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear C1-C5 alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.

[0293] When present, the liquid dishwashing composition contains from 0.01% to 20%, preferably from 0.5% to 15%, more preferably from 1% to 10%, and most preferably from 1% to 5% of the solvent by weight of the liquid detergent composition. These solvents may be used in combination with an aqueous liquid carrier such as water, or they may be used without any aqueous liquid carrier present. With higher solvent systems, the absolute viscosity may decrease, but there is a local maximum in the viscosity profile.

[0294] The dishwashing composition herein may further comprise 30% to 90% by weight of an aqueous liquid carrier comprising water in which other essential and optional ingredients are dissolved, dispersed or suspended. More preferably, the composition of the present invention comprises 45% to 85% by weight, more preferably 60% to 80% by weight of an aqueous liquid carrier. However, the aqueous liquid carrier may comprise other materials that are liquid at room temperature (25°C) or that dissolve in the liquid carrier and that may also perform some function other than that of an inert filler.

[0295] The dishwashing compositions of the present invention may include at least one electrolyte.

[0296] Suitable electrolytes are preferably selected from inorganic salts, even more preferably from monovalent salts, most preferably sodium chloride.

[0297] The dishwashing composition of the present invention may contain from 0.1% to 5% by weight of the composition, preferably from 0.2% to 2% by weight of electrolyte.

[0298] Liquid dishwashing formulations containing the polymers of the present invention may also contain at least one antimicrobial agent.

[0299] Examples of antimicrobial agents suitable for dishwashing compositions have already been described above in relation to laundry compositions.

[0300] The antimicrobial agent may be added to the liquid dishwashing composition of the invention in a concentration of 0.0001% to 10% by weight relative to the total weight of the composition. Preferably, the formulation comprises 2-phenoxyethanol in a concentration of 0.01% to 5% by weight, more preferably 0.1% to 2% by weight, and / or 4,4'-dichloro-2-hydroxydiphenyl ether in a concentration of 0.001% to 1% by weight, more preferably 0.002% to 0.6% by weight (in all cases relative to the total weight of the composition).

[0301] Further additional ingredients include, but are not limited to, conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, cyclic diamines, structurants, emollients, moisturizers, skin rejuvenation actives, carboxylic acids, scrubbing particles, fragrances, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, disintegrants, pH adjusters including NaOH, and alkanolamines such as monoethanolamine, and buffering means.

[0302] (c) 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.

[0303] The liquid formulations disclosed above and below may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichoro 2-hydroxydiphenyl ether. The no-bleach solid laundry compositions may contain, in addition to all other ingredients mentioned, 0-0.2%, preferably about 0.15%, of 4,4'-dichoro 2-hydroxydiphenyl ether.

[0304] The formulations disclosed in this chapter may comprise, in addition to all other ingredients mentioned, one or more enzymes selected from those disclosed herein above, more preferably a protease and / or an amylase, and even more preferably, the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP 1921147 B1 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 WO 2021032881 A1, and such enzymes are preferably present in the formulation at a level of about 0.00001% to about 5% by weight, preferably about 0.00001% to about 2% by weight, more preferably about 0.0001% to about 1% by weight, or even more preferably about 0.001% to about 0.5% by weight of enzyme protein, based on the weight of the composition.

[0305] The compositions set forth below, including those in the table, disclose certain types of general cleaning compositions that correspond to typical compositions associated with typical cleaning conditions typically employed in various regions and countries of the world. At least one inventive polymer may be added to such formulations in suitable amounts as outlined herein.

[0306] Where a given composition does not include a polymer of the present invention, such composition is a comparative example composition. Where a given composition includes a polymer of the present invention, particularly in an amount described herein as a preferred range, more preferred range, etc., such composition is considered to fall within the scope of the present invention.

[0307] In a preferred embodiment, at least one PPI (as defined in any one of the embodiments herein, in particular any one of embodiments 1 to 18 (the PPI in this section is also referred to as the "polymer of the invention")) is used in the laundry detergent.

[0308] The liquid laundry detergent of the present invention comprises: 0.05 to 20% of at least one polymer of the invention, 1-50% surfactant, 0.1 to 40% of builders, cobuilders, and / or chelating agents; 0.1~50% of other auxiliary substances, Water to make the total 100% It consists of:

[0309] The preferred liquid laundry detergents of the present invention include 0.2 to 6% of at least one polymer of the invention, 5-40% of anionic surfactants selected from C10-C15-LAS and C10-C18-alkyl ether sulfates containing 1-5 ethoxy units, 1.5 to 10% of non-ionic surfactants selected from C10-C18-alkyl ethoxylates containing 3 to 10 ethoxy units, 2-20% of soluble organic builders / cobuilders selected from C10-C18 fatty acids, di- and tri-tricarboxylic acids, hydroxy-di- and hydroxy-tricarboxylic acids, and polycarboxylic acids, 0.05-5% of an enzyme system containing at least one enzyme suitable for detergent applications and preferably also an enzyme stabilizing system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol, 0.1~20% of other auxiliary substances, Water to make the total 100% It consists of:

[0310] The solid laundry detergent of the present invention (e.g., powder, granule, or tablet) may include: 0.05 to 20% of at least one polymer of the invention, 1-50% surfactant, 0.1 to 80% of builders, cobuilders, and / or chelating agents, 0-50% filler, 0-40% bleach actives, Consists of 0.1 to 30% of other auxiliary substances and / or water; The sum of the ingredients equals 100%.

[0311] A preferred solid laundry detergent of the present invention comprises: 0.2 to 6% of at least one polymer of the invention, 5-30% of an anionic surfactant selected from C10-C15-LAS, C10-C18 alkyl sulfates, and C10-C18 alkyl ether sulfates containing 1-5 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, zeolites, soluble silicates, and sodium sulfate; 0.5 to 15% of a cobuilder selected from C10 to C18 fatty acids, di- and tri-tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, and polycarboxylic acids, 0.1-5% of an enzyme system containing at least one enzyme suitable for detergent applications and preferably further an enzyme stabilizing system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol, 0.1~20% of other auxiliary substances, Water to make the total 100% It consists of:

[0312] In a preferred embodiment, the polymers of the present invention are used in manual dishwashing detergents.

[0313] The liquid manual dishwashing detergent of the present invention comprises: 0.05 to 10% of at least one polymer of the invention, 1-50% surfactant, 0.1~50% of other auxiliary substances, Water to make the total 100% It consists of:

[0314] The preferred liquid manual dishwashing detergent of the present invention comprises: 0.2 to 5% of at least one polymer of the invention, 5-40% of anionic surfactants selected from C10-C15-LAS, C10-C18 alkyl ether sulfates and C10-C18 alkyl sulfates containing 1-5 ethoxy units; 2-10% cocamidopropyl betaine, 0-10% lauramine oxide, 0-2% of a non-ionic surfactant, preferably a C10 Guerbet alcohol alkoxylate; 0-5% of an enzyme, preferably an amylase and preferably also an enzyme stabilizing system, 0.5-20% of a mono- or diol selected from ethanol, isopropanol, ethylene glycol or propylene glycol, 0.1~20% of other auxiliary substances, Water to make the total 100% It consists of:

[0315] Some consideration is required to formulate the biodegradable polypropyleneimine polymers of the present invention, especially since cleaning formulations typically have a pH of about 7 or higher and additionally often contain enzymes that are included in such cleaning formulations to degrade biodegradable substances such as grease, proteins, polysaccharides, etc., present in stains and dirt and removed by the cleaning composition. Such suitable formulations are known in principle, and include solid formulations (where the enzymes and polymers can be separated by coating or adding them in separate particles mixed together) and liquid and semi-liquid formulations (where the polymers and enzymes can be separated by combining them in different compartments, such as a multi-chamber pouch or various compartments of a bottle with various chambers, from which the liquids are poured in predetermined amounts at the same time to ensure that the correct amount is applied at each separate use point of each component in each chamber). Such multi-compartment pouches and bottles are also known to those skilled in the art.

[0316] The following table shows certain types of typical cleaning compositions corresponding to typical compositions associated with typical cleaning conditions typically employed in various regions and countries of the world. At least one inventive polymer may be added to such formulations in suitable amounts as outlined herein.

[0317] [Table 1]

[0318] [Table 2]

[0319] [Table 3]

[0320] [Table 4]

[0321] [Table 5]

[0322] [Table 6]

[0323] The following examples illustrate the invention in more detail without limiting its scope.

[0324] The specific embodiments described throughout this disclosure are included herein as part of the present invention, and the various additional options disclosed herein as "optional," "preferred," "more preferred," "even more preferred," or "most preferred" (or "preferably," etc.) options for a particular embodiment may be individually and independently selected (provided that such independent selection is possible due to the nature of the feature or such independent selection is not expressly excluded) and then combined in any of the other embodiments (where such other options and preferences may also be individually and independently selected, but only if such independent selection is not possible due to the nature of the feature or such independent selection is expressly excluded), with all such possible combinations being included as part of the present invention as separate embodiments. EXAMPLES

[0325] 1) Synthesis Examples General remarks: in all examples, step b) starts after step a) is complete and step c) starts after step b) is complete (monomer conversion >95%).

[0326] a) Synthesis of the Compounds of the Invention i) Synthesis of (unmodified) PPIs Hereinafter, "N,N'-bis-(3-aminopropyl)ethylenediamine" will be abbreviated as "N4-amine" or "N4", "1,3-propylenediamine" will be abbreviated as "1,3-PDA" or simply "PDA", and "hexamethylenediamine" will be abbreviated as "HMDA".

[0327] Example 1: Synthesis of PPI homopolymer (poly(PDA)) with Mn=230 g / mol, Mw=380 g / mol (A.1) In a tubular reactor with an internal diameter of 10 mm, equipped with an internal thermowell of 3.17 mm, 1,3-PDA ​​was continuously introduced with 15 NI / h hydrogen gas over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar and the temperature was 164° C. 1,3-PDA ​​was fed into the reactor at 0.68 kg / Lcat*h. After 1 h of monomer removal under vacuum (10 mbar, 80° C.), the desired product was obtained as a colorless, transparent liquid.

[0328] Example 2: Synthesis of PPI copolymer (poly(PDA-co-N4)) with Mn=280 g / mol, Mw=520 g / mol (A.2) In a tubular reactor with an internal diameter of 10 mm and equipped with an internal thermowell of 3.17 mm, 1,3-PDA ​​and N4-amine in a ratio of 3:1 wt.% were continuously introduced with 15 NI / h hydrogen gas onto a fixed-bed catalyst consisting of Co as active metal. The pressure was 50 bar and the temperature was 160°C. The mixture of 1,3-PDA ​​and N4-amine was fed into the reactor at 0.32 kg / Lcat*h. After 1 h of monomer removal under vacuum (10 mbar, 80°C), the desired product was obtained as a colorless, transparent liquid.

[0329] Example 3: Synthesis of PPI copolymer (poly(PDA-co-HMDA)) with Mn=340 g / mol, Mw=690 g / mol (A.3) In a tubular reactor with an internal diameter of 10 mm and an internal thermowell of 3.17 mm, 1,3-PDA ​​and HMDA in a ratio of 3:1 wt.% were continuously introduced with 15 NI / h hydrogen gas onto a fixed-bed catalyst consisting of Co as the active metal. The pressure was 50 bar and the temperature was 163°C. The mixture of 1,3-PDA ​​and HMDA was fed into the reactor at 0.44 kg / Lcat*h. The desired product was immediately obtained as a colorless, transparent liquid without any intermediate purification steps.

[0330] ii) Synthesis of modified PPIs Example 1: Synthesis of Poly(PDA-co-N4) (Mw 520 g / mol; A.2) + 2CL / NH + 24EO / NH + 16PO / NH (P.1) Example 1a: Poly(PDA-co-N4) (Mw 520 g / mol; A.2)+2CL / NH 80 g of the previously obtained product is placed in a 4-neck round-bottom flask equipped with a condenser and a dropping funnel under a nitrogen atmosphere. The product is heated to 80° C. and 463 g of caprolactone are slowly added at 80° C. After the addition of caprolactone, the temperature is slowly increased to 160° C. and the mixture is post-reacted at 160° C. for 16 hours to remove any remaining caprolactone. 492 g of a light brown highly viscous liquid is obtained.

[0331] Example 1b: Poly(PDA-co-N4) (Mw 520 g / mol; A.2) + 2CL / NH + 24EO / NH 100 g of the previously obtained product (Example 1a) are charged into a steel pressure reactor and 1.3 g of potassium methanolate (32.5% by weight in methanol) are 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 at 2 bar. The reactor is heated to 130° C. and 287 g of ethylene oxide are dosed into the reactor within 4 hours. The mixture is post-reacted at 130° C. for 6 hours to remove any remaining ethylene oxide.

[0332] Example 1c: Poly(PDA-co-N4) (Mw 520 g / mol; A.2) + 2CL / NH + 24EO / NH + 16PO / NH (P.1) In the reaction vessel, 252 g of propylene oxide are dosed to the already obtained product (Example 1b) within 5 hours. The mixture is post-reacted at 130° C. for 6 hours to remove any residual propylene oxide. Finally, 652 g of an orange-yellow, highly viscous liquid is obtained as product P.1.

[0333] b) Comparative Examples i) Synthesis of polypropyleneimine Comparative Example 1: Synthesis of polypropyleneimine homopolymer (poly(PDA)) with Mn=570 g / mol, Mw=1400 g / mol (CA.1) In a tubular reactor with an internal diameter of 10 mm and equipped with an internal thermowell of 3.17 mm, 1,3-PDA ​​was continuously introduced with 15 NI / h hydrogen gas over a fixed bed catalyst consisting of Co as the active metal. The pressure was 50 bar and the temperature was 170°C. 1,3-PDA ​​was fed into the reactor at 0.29 kg / Lcat*h. The desired product was immediately obtained as a white solid without any intermediate purification steps.

[0334] Comparative Example 2: Synthesis of polypropyleneimine copolymer (poly(PDA-co-N4)) with Mn=410 g / mol, Mw=820 g / mol (CA.2) In a tubular reactor with an internal diameter of 10 mm and an internal thermowell of 3.17 mm, 1,3-PDA ​​and N4-amine in a ratio of 3:1 wt.% were continuously introduced with 15 NI / h hydrogen gas onto a fixed-bed catalyst consisting of Co as the active metal. The pressure was 50 bar and the temperature was 167°C. 1,3-PDA ​​was fed into the reactor at 0.3 kg / Lcat*h. The desired product was immediately obtained as a highly viscous material without any intermediate purification steps.

[0335] Comparative Example 3: PEI600 (CA.3) PEI600 was purchased as Lugalvan® from BASF SE (Ludwigshafen, Germany).

[0336] ii) Synthesis of Modified PPIs and Comparative Examples Comparative Example 1: Synthesis of PEI600+2CL+23EO / NH+15PO / NH (CP.1) Example 1a: PEI600+2CL / NH 280 g of polyethyleneimine (Mw=600 g / mol) is charged into a 4-neck round bottom flask equipped with a condenser and a dropping funnel under nitrogen atmosphere. The product is heated to 80° C. and 1499 g of caprolactone is slowly added at 80° C. After the caprolactone is added, the temperature is slowly increased to 160° C. and the mixture is post-reacted at 160° C. for 16 hours to remove any remaining caprolactone. 1725 g of an orange-yellow highly viscous liquid is obtained.

[0337] Example 1b: PEI600+2CL / NH+23EO / NH 100 g of the previously obtained product (Example 1a) are charged into a steel pressure reactor and 4.8 g of potassium methanolate (32.5% by weight in methanol) are 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 at 2 bar. The reactor is heated to 130° C. and 360 g of ethylene oxide are dosed into the reactor within 6 hours. The mixture is post-reacted at 130° C. for 3 hours to remove any remaining ethylene oxide.

[0338] Example 1c: PEI600+2CL / NH+23EO / NH+15PO / NH In the reaction vessel, 317 g of propylene oxide are dosed to the already obtained product (Example 1b) within 6 hours. The mixture is post-reacted at 130° C. for 5 hours to remove any remaining propylene oxide. Finally, 767 g of a dark red liquid is obtained as product CP.1.

[0339] Comparative Example 2: Ethoxylated and Propoxylated PEI600 (24EO-16PO) (CP.2) This example is prepared by a two-step alkoxylation method as described in WO 95 / 32272.

[0340] 2) Polymer characterization The molecular weights of the (unmodified) PPI and the comparative polymers were determined by gel permeation chromatography (GPC). Measurements were performed on three column combinations: HFIP-LG Guard, PL HFIPGEL, and PL HFIPGel. Elution was performed with hexafluoroisopropanol and 0.05 wt% potassium trifluororoacetate at a constant flow rate of 1 mL / min. The ejected samples were prefiltered with Millipore Millex FG (0.2 μm) and 50 μL was ejected at a concentration of 1.5 mg / mL (diluted in the eluent). The effluent was monitored at λ=230 and 280 nm by an ultraviolet detector DRI Agilent 1100. Calibration was performed with PMMA standards (PSS, Mainz, Germany) with molecular weights between 800 and 2,200,000 g / mol. Values ​​outside the calibration range were extrapolated.

[0341] The molecular weight of the modified alkoxylated polyalkyleneimine can be measured by gel permeation chromatography (GPC). The measurement can be carried out on a combination of two columns (styrene-divinylbenzene and polyester copolymer, both 25 cm long) using 0.05% by weight potassium trifluoroacetate in hexafluoroisopropanol as the eluent. The molecular weight can be obtained by using an RI detector and PEO standard (Polymer Laboratories / Agilent, USA) for calibration. In addition, the absolute molar mass can be measured by multi-angle light scattering (MALLS).

[0342] The molecular weights of the modified PPI and modified comparative polymers were obtained by theoretical calculations using the determined weight average molecular weights of the polyamine starting materials and assuming complete conversion during the modification step (b). The calculations were performed as follows:

[0343] In the case of copolymer backbones, the molar ratio of the monomers in the polymer backbone was first calculated based on the composition weight percent of the material. Then, based on the weight average molecular weight of the polyamine starting material (from GPC data (see above)), the known molecular weight of the monomers used, and their molar ratios, the average number of monomer repeat units in the backbone was calculated. Based on the known structural information of the monomers used, and the number of their individual NH functionalities, the total number of NH functionalities of the polyamine starting material was obtained, which represents the sum of the NH functionalities of all primary and secondary amino groups in the polymer backbone. In the second step, the molar amounts of hydroxycarbon acid, EO, and PO used per NH functional group were used to calculate the average theoretical molecular weight of one combined linear chain, assuming complete conversion in all individual modification reactions in step (b). In the third step, the overall molecular weights of the modified polypropyleneimine homo- and copolymers of the present invention and the comparative polymers were calculated by (i) multiplying the number of NH functionalities of the polyamine backbone by the average molecular weight of one coupled linear chain, assuming that on average one linear chain was coupled to one available NH functional group of the backbone in the case of the first alkoxylation reaction in step (b) and one primary NH2 functional group and one secondary NH functional group of the backbone in the case of the first amidation reaction in step (b), and (ii) adding the molecular weight of the polyamine backbone (from GPC data (see above)) itself, respectively.

[0344] The compositions and analytical data of the modified PPIs of the present invention and comparative polymers are summarized in Table 1.

[0345] "CL / NH" means caprolactone (CL) repeat units per NH group of the core amine, "EO / NH" means ethylene oxide (EO) repeat units per NH group of the core amine, and "PO / NH" means propylene oxide (PO) repeat units per NH group of the core amine. The caprolactone, EO, and PO units are linked in a block structure, in which the caprolactone is directly linked to the polyamine core.

[0346] [Table 7]

[0347] 3) Application experiment Primary cleaning performance for oily / greasy stains To determine the primary cleaning power, cleaning performance on 16 different oily / greasy stains on cotton, polycotton and polyester fabrics (CFT, Vlaardingen, The Netherlands) was measured by determining the color difference (ΔE) between the stains after cleaning and unsoiled white fabric using a reflectometer (Datacolor SF600 plus). Each experiment involving 16 different circular oily / greasy stains (lipstick, makeup, beef tallow, frying grease, burnt butter, palm oil, sebum BEY, sebum Tefo, collar stain; all on different fabrics) was replicated six times and the data obtained was used to calculate the average ΔE value.

[0348] These ΔE values ​​were used to calculate the so-called "normalized cleaning performance" (ΔΔE) for each individual stain, which is the difference in performance between a laundry detergent containing a modified polyalkyleneimine (inventive or comparative, respectively) and a laundry detergent that does not contain any modified polyalkyleneimine (inventive or comparative, respectively).

[0349] Table 2 shows the laundry detergent compositions, Table 3 shows the wash test conditions, and Table 4 summarizes the standardized wash performances obtained. The standardized wash performances shown in Table 4 are the sum of the standardized wash performances for all 16 stains. The higher the sum of the ΔΔE values, the greater the positive contribution of the modified polyalkyleneimine (inventive or comparative, respectively) to wash performance.

[0350] [Table 8]

[0351] [Table 9]

[0352] [Table 10]

[0353] Test results: The error of the measurement is + / -10 ΔΔE units.Therefore, any value (ΔΔE total) greater than 10 means that the corresponding polymer shows a directional and visible contribution to the overall cleaning performance of the corresponding detergent formulation, and any value (ΔΔE total) greater than 20 means that the corresponding polymer even shows a significant contribution to the overall cleaning performance, i.e., the corresponding polymer brings about a significant improvement of the formulation.All polymers (inventive and comparative) show significant cleaning effect on oily / greasy stains.

[0354] 4) Biodegradation data Biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. OECD 301F is an aerobic test that measures the biodegradation of samples by measuring oxygen consumption. 100 mg / L of the test substance, nominally the only source of carbon, is added to a measured volume of medium together with an inoculum (30 mg / L, aerated sludge taken from the wastewater treatment plant in Mannheim). This is stirred in a closed flask at constant temperature (20°C or 25°C) for 28 or 56 days, respectively. Oxygen consumption is determined by measuring the change in pressure inside the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH&Co KG). The released carbon dioxide is absorbed in a sodium hydroxide solution. Nitrification inhibitors are added to the flask to prevent the use of oxygen by nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substances (corrected for uptake by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand, measured by elemental analysis of the compounds). A positive control glucose / glucosamine is run alongside the test samples in each cabinet.

[0355] [Table 11]

[0356] Comments on biodegradation test results Only the polyamine materials of the invention (A.1-A.3) show good biodegradability in the OECD 301F test (>20% after 28 days, >40% after 56 days). It can also be clearly seen that polyamine A.2 shows significantly better biodegradability compared to polyamine CA.2, which has the same molecular composition and structure but a significantly lower molecular weight. Thus, only the inventive modified substance P.1 (based on polyamine A.2) shows a good combination of cleaning performance (i.e. a clear improvement of the formulation) and biodegradability, both of the starting material and of the final product. In comparison with P.1, polymer CP.1 also shows good cleaning performance and biodegradability of the final product, whereas polyamine CA.3, which forms the core of polymer CP.1, must be considered as non-biodegradable or at least permanent (see also table 6 below).

[0357] 5) Melting point of the amine starting material The melting points of the amine starting materials were determined according to DIN EN 11357-3 on a TA Instruments Q2000 apparatus.

[0358] [Table 12]

[0359] The analytical data demonstrate that due to their low molecular weight and predominantly linear structure, and regardless of their composition (homopolymer / copolymer), the polyamine backbones of the inventive polymers (A.1-A.3) have significantly lower melting points compared to the polyamine backbones of the comparative polymers (CA.1 and CA.2). Due to the lower melting points, they are much easier to manufacture.

[0360] 6) Summary of all examples

[0361] [Table 13]

[0362] Test results: The experimental examples show that only the inventive polymer P.1 shows very good biodegradability both in terms of the final macromolecule and in parallel with the synthesis process (all starting materials and hydrolyzed fractions). In addition, P.1, like the non-degradable or partially degradable comparative polymers CP.1 and CP.2, shows a significant cleaning effect in the primary cleaning of oily / greasy stains. Furthermore, the inventive polymer P.1 is based on the inventive polyamine backbone A.2, which has a significantly lower melting point compared to other high molecular weight polypropyleneimines, especially compared to high molecular weight polypropyleneimine homopolymers, and therefore allows for better handling in the production process. The inventive polymers are therefore ideally suited for the preparation of fully biodegradable multi-benefit detergent formulations and in particular for improving the removal of oily soils in laundry care and for improving degreasing in manual dishwashing.

[0363] 7) Formulations containing the polymer of the present invention and a biocide Inventive and comparative liquid laundry detergent formulations are prepared with or without (comparative) 2.8% by weight of the inventive polymer P.1 (100% active ingredient) and either 0.2% of the biocide Tinosan® HP100 (from BASF SE) or 1% of 2-phenoxyethanol (Protectol® PE, BASF SE). The formulations are prepared by first preparing a premix containing the AEO and AES surfactants, the solvents 1,2-propanediol and ethanol, and, where appropriate, Tinosan® HP100 or 2-phenoxyethanol. The premix is ​​stirred at room temperature until a homogenous mixture is obtained. Then, LAS, fatty acids, and citric acid are added as shown in Table 7, as well as water up to 90%. Then, the pH is set to 8.5 using NaOH. The final formulation is then prepared by mixing 90% of this resulting mixture with the appropriate concentration of the inventive polymer and water up to 100% at room temperature.

[0364] The compositions and results are shown in Table 8.

[0365] [Table 14]

[0366] AEO: C13 / C15 oxo-alcohols (7EO) Lutensol® AO7 (BASF SE) (CAS 68002-97-1) AES: C12 / C14 fatty alcohol ether sulfate (2EO), sodium salt: Texapon® N70 (BASF SE) (CAS 68891-38-3) LAS: Linear alkylbenzene sulfonic acid Maranil® DBS / LC (BASF SE) (CAS 85536-14-7) Coco fatty acid: Edenor® K12-18 (Emery Oleochemicals) (CAS 90990-15-1) 1,2-Propanediol: Racemic mixture (CAS 57-55-6) Tinosan® HP100 is a commercial product manufactured by BASF SE that contains 30% antibacterial active 4,4′-dichloro-2-hydroxydiphenyl ether (CAS 3380-30-1) in 1,2-propylene glycol. 2-Phenoxyethanol (CAS 122-99-6) is available as Protectol® PE from BASF SE. In the above table, concentrations of surfactant trade products are given.

[0367] From the above table it is evident that in liquid laundry formulations it is possible to combine the polymer P.1 of the invention with Tinosan HP100 or with 2-phenoxyethanol.

Claims

1. In polycondensation form, (A) Formula 【Chemistry 1】 The monomer (A) is represented by Monomer (A), wherein m is selected from an integer from 1 up to 5; (B) Formula 【Chemistry 2】 The monomer (B) is represented by wherein n is selected from the integers 1, 3, 4, and 5; Monomer (B), wherein l is selected from 0 or 1; and (C) Formula 【Chemistry 3】 The monomer (C) is represented by where k is selected from an integer from 1 to a maximum of 7, A polypropyleneimine polymer (PPI) comprising at least one repeating unit selected from the monomer units: i) at least one repeat unit derived from monomer A, and / or ii) at least one repeat unit derived from monomer B, and / or iii) at least one repeat unit derived from monomer C; More preferably, i) at least one repeat unit derived from monomer A, and / or ii) at least one repeat unit derived from monomer B, and Optionally, at least one repeat unit derived from monomer C is selected, Even more preferably, the PPI contains only at least one monomer selected from i) A, ii) B, iii) A and B, iv) A and C, v) B and C, or vi) A, B and C.

2. and / or has a weight average molecular weight Mw of less than 700 g / mol, and preferably of at least 300 g / mol; and / or having a number average molecular weight Mn of 200 to 400 g / mol and a weight average molecular weight Mw of 300 to less than 700 g / mol; and / or 2. The PPI of claim 1, which contains an average of at least 6 and at most 12 nitrogen atoms.

3. 3. The PPI of claim 1 or 2, which is essentially linear.

4. The PPI according to any one of claims 1 to 3, having a melting point of at most 25°C, preferably below 20°C, even more preferably below 15°C.

5. The PPI may be further modified by additionally including at least one side chain attached to at least one NH functional group of the PPI, such chain comprising an additional monomer: (D) at least one lactone and / or at least one hydroxyl carbon acid (E) at least one alkylene oxide (AO) selected from C2 to C22 alkylene oxides, preferably C2 to C6, more preferably C2, C3, and / or C4 and The order of D and E in the side chain may be in any order, such as random, block, or statistical distribution, although block ordering is preferred; the amount of D is 0.5 to 15 based on molar equivalents per NH functional group; The amount of E is 10-100 based on molar equivalents per NH functional group; A PPI according to any one of claims 1 to 4.

6. The order of D and E in the side chain is block order, and the side chain has the following structural order: i) [PPI]-N-(E1)a-(D1)d-(E2)b-(E3)c ii) [PPI]-N-(D1)d-(E2)b-(E3)c iii) [PPI]-N-(E1)a-(D1)d-(E2)b iv) [PPI]-N-(D1)d-(E2)b v) [PPI]-N-(E1)a-(D1)d-(E2)b-(D2)e vi) [PPI]-N-(D1)d-(E2)b-(D2)e and (E1), (E2), (E3) each independently represent a subunit composed of a monomer which is at least one alkylene oxide, preferably a single alkylene oxide; (D1) and (D2) each represent, independently of one another, a subunit composed of at least one lactone and / or hydroxyl carbon acid monomer, preferably a single lactone and / or hydroxyl carbon acid monomer; a, b, c, d, and e define the total average number of individual repeat units within each subunit (E1), (E2, (E3), (D1), and (D2); Preferably, the side chain is selected from i), ii), iii), and iv), more preferably from i) and ii), most preferably i); The variables are the average molar equivalents per NH functionality of the PPI: a 0.5 to 2, preferably 0.8 to 1.5, and / or b 10 to 40, preferably 15 to 35, and / or c 5 to 40, preferably 10 to 35, and / or d 0.5 to 5, preferably 1.0 to 3.0, and / or e 2 to 10, preferably 2 to 6 It is based on Preferably, D1 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid, and / or glycolic acid, in one preferred embodiment D1 is caprolactone; D2 is a linear or branched C3-C11 aliphatic lactone, most preferably caprolactone, and / or a hydroxycarbon acid, most preferably lactic acid, and / or glycolic acid, in one preferred embodiment D2 is caprolactone; E1 is preferably C2-C5-AO, most preferably PO and / or BuO; E2 is C2-C5-AO containing more than 50 wt% EO, preferably more than 90 wt% EO, most preferably 100 wt% EO; E3 is a C2-C5-AO containing more than 50 wt.% PO and / or BuO, preferably more than 90 wt.% PO and / or BuO, most preferably 100 wt.% PO and / or BuO, in one preferred embodiment E3 is 100 wt.% PO. The PPI according to claim 5.

7. 7. The PPI according to claim 5 or 6, wherein at least 50%, preferably at least 60%, and most preferably at least 80% of all side chains attached to NH functional groups of one particular modified PPI have the same order within all side chains.

8. A method for producing a PPI according to any one of claims 1 to 7, comprising the steps of: In step a) at least one monomer (A) and / or at least one monomer (B) and / or at least one monomer (C) are reacted in a polycondensation reaction, preferably at least one monomer (A) and / or at least one monomer (B) and optionally at least one monomer (C) to obtain said PPI, Monomer (A) has the formula 【Chemistry 4】 is represented by wherein m is selected from an integer from 1 up to 5; Monomer (B) has the formula 【Chemistry 5】 is represented by wherein n is selected from the integers 1, 3, 4, and 5; l is selected from 0 or 1; Monomer (C) has the formula 【Chemistry 6】 is represented by wherein k is selected from an integer from 1 up to 7; The following characteristics: i) comprising at least one monomer selected from i) A, ii) B, iii) A and B, iv) A and C, v) B and C, vi) A and B and C, or vii) C, preferably i) A, ii) B, iii) A and B, iv) A and C, more preferably i) A, and iii) A and B, most preferably iii) A and B; ii) having a weight average molecular weight Mw of less than 700 g / mol, and preferably at least 300 g / mol; iii) having a number average molecular weight Mn of 200 to 400 g / mol and a weight average molecular weight Mw of from 300 g / mol to less than 700 g / mol; iv) having a polydispersity index (PDI) of 1.3 to 2.5, preferably 1.5 to 2.0; v) containing an average of at least 6 and at most 12 nitrogen atoms; vi) being predominantly linear, more preferably at least 90% linear, more preferably essentially linear, e.g. completely linear; and / or vii) does not contain any tertiary amino groups (prior to further modifications as defined in the claims below); Step a) obtaining a PPI having at least one of The method includes:

9. The method comprises a further step b) in which the PPI obtained in step (a) is further modified in a further polycondensation reaction to produce a modified PPI comprising at least one side chain attached to at least one NH functional group of the PPI, said chain being linked to a further monomer of: (D) at least one lactone and / or at least one hydroxyl carbon acid, and / or (E) at least one alkylene oxide selected from C2 to C22 alkylene oxides, preferably C2 to C6, more preferably C2, C3, and / or C4 at least one polycondensation-derived moiety of It consists of: said further polycondensation or polyaddition reaction is by reacting said PPI with D and E by using components D and E as a mixture after alternating or overlapping addition, preferably alternating as stepwise addition, when the reaction with the first added reactant has proceeded to a conversion of at least 90%, preferably at least 95%, more preferably at least 99%, even more preferably at least 99.5%, or even more than that is achieved, such as when the reaction has substantially stopped and the next reactant is added; As a result, preferably, the order defined below as i) to vi) is obtained, and the following groups i) to vi) i) [PPI]-N-(E1)a-(D1)e-(E2)b-(E3)c ii) [PPI]-N-(D1)e-(E2)b-(E3)c iii) [PPI]-N-(E1)a-(D1)e-(E2)b iv) [PPI]-N(D1)e-(E2)b v) [PPI]-N-(E1)a-(D1)e-(E2)b-(D2)f vi) [PPI]-N-(D1)e-(E2)b-(D2)f and forming at least one side chain having a block structure selected from In the formula, (E1), (E2), and (E3) each independently represent a single or multiple alkylene oxides, preferably a single alkylene oxide; In the formula, (D1) and (D2) each independently represent a single or multiple lactones and / or hydroxyl carbon acids, preferably a single lactone and / or hydroxyl carbon acid; wherein (E1)a, (E2)b, (E3)c, and (D1)e, (D2)f each represent a block made from such starting materials, each block can be made from a plurality of alkylene oxides or lactones and / or hydroxy carbon acids, respectively, and thus within a block containing a plurality of alkylene oxides or lactones and / or hydroxy carbon acids, the order is random; Preferably, said side chain structure is selected from i), ii), iii), and iv), more preferably selected from i) and ii), most preferably i), The method of claim 8 , comprising:

10. a) in a cleaning composition, preferably as an additive for a liquid, solid or semi-solid detergent formulation, in particular a liquid detergent formulation, preferably a concentrated liquid detergent formulation, or a single unit dose laundry detergent formulation, or a liquid manual dishwashing detergent formulation, or a solid automatic dishwashing formulation, b) in fabric care and home care products, c) in an electroplating formulation: d) in a cement-based composition, e) preferably as dispersants in pesticide formulations, f) as an adhesion promoter for printing inks, for example on laminate films; g) as an aid (adhesion) for example for adapting different polymer layers as well as metal foils to produce multilayer composite films; h) as adhesion promoters for adhesives, for example in combination with polyvinyl alcohol, butyrate and acetate, and styrene copolymers, or as cohesion promoters for label adhesives; i) as a primer in coating applications to improve adhesion to substrates such as glass, wood, plastics, and metals; j) to improve the wet adhesion, e.g. in standard emulsion paints, and to improve the immediate rain resistance, e.g. of paints for road markings, k) as a complexing agent with a high binding capacity, especially for heavy metals such as Hg, Pb, Cu, Ni, l) as flocculants, for example in water treatment / water treatment; m) as penetration assistants for active metal salt formulations, e.g. in wood protection, n) as corrosion inhibitors, for example for ferrous and non-ferrous metals and in the oil production and secondary oil production sectors; o) as a support for immobilizing microorganisms or enzymes and microorganisms for the immobilization of proteins and enzymes; p) Barriers and seals, e.g. for the mineral oil and natural gas industries; q) as fixing agents, for example in the textile industry, in particular as formaldehyde-free fixing fluids, r) as additives in cosmetic formulations, for example for hair setting compositions and hair rinses; s) as an auxiliary in the paper industry, for example as a multipurpose auxiliary for accelerating dewatering, removing contaminants, neutralizing charges, and for paper processing; t) for oil-water separation, e.g. in the metal processing industry; u) As an additive for landfill sealants v) as a flocculant, w) as an algaecide for swimming pools, x) for producing bitumen chemicals by reacting with fatty acids; y) as an anti-swelling agent to retard the absorption of water by clays; z) as emulsifiers or demulsifiers, aa) as surfactants in the industrial cleaning (IC) sector, bb) as wood preservatives, cc) for preparing the complexing agent (polycarboxylate), dd) for producing auxiliary agents for mineral mining and mineral processing; ee) as dispersants for pigments, ceramics, carbon black, carbon, carbon fibres, metal powders, e.g. as emulsifiers or dispersants for inkjet printing inks; ff) as an absorbent for CO2, NOX, SOX, Cl2 and aldehydes, for gas scrubbing and for neutralizing acidic components; gg) for softening hard water; hh) as crystallization inhibitors of pesticide formulations, e.g. for oil field applications, ii) as rheology modifiers (thickeners), jj) as an auxiliary or component for the extraction and processing of oil, coal, and natural gas; kk) for producing synthetic rubber and rubber chemicals; ll) as additives in coolants, lubricants and cooling lubricants; mm) as an auxiliary in the construction chemicals sector, nn) as a component of a zinc plating bath, or oo) for generating non-viral gene vectors, Use of at least one PPI according to any one of claims 1 to 7, or producible or produced by the process according to claims 8 or 9.

11. Use according to claim 10 in cleaning compositions and / or fabric care and home care products, preferably liquid and solid detergent compositions, said detergent compositions preferably comprising a) manual and automatic dishwashing detergent compositions comprising at least one PPI and at least one chelating agent and / or at least one surfactant, or more preferably a surfactant system; and / or b) said at least one PPI, at least one surfactant, or more preferably a surfactant system; The use of a laundry detergent composition comprising:

12. i) improved removal of oily / greasy stains, and / or ii) removal of clay; and / or iii) removing particulate stains; and / or iv) dispersing and / or emulsifying dirt; and / or v) modification of the treated surface to improve removal upon subsequent recontamination; and / or vi) prevention or reduction, preferably prevention, of glass corrosion; and / or vii) improving whiteness; and / or viii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, and peroxidases, and combinations of at least two of the above classes, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the above classes, more preferably proteases, additionally for improved oily / greasy stain removal, food stain removal, and / or combination stain removal, Most preferably, in the cleaning composition: i) For improved removal of oily / greasy stains, 12. The use according to claim 10 or 11, The use, wherein each of the above options i) to viii) is preferably for use in a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a preferably solid, automatic dishwashing detergent, or a liquid manual dishwashing detergent formulation.

13. 10. Compositions which are fabric and home care products, cleaning compositions, institutional cleaning products, cosmetics or personal care products, oil field formulations such as crude oil demulsifiers, pigment dispersions for inks such as inkjet inks, electroplating products, cementitious compositions, lacquers, paints, agrochemical formulations, preferably laundry detergents, dishwashing compositions, cleaning compositions and / or fabric and home care products, comprising at least one PPI according to any one of claims 1 to 7 or at least one PPI producible or produced by the process according to claims 8 or 9, respectively.

14. 10. A detergent composition, in particular a laundry detergent composition or a manual dishwashing detergent composition, comprising (i) at least one PPI according to any one of claims 5 to 7 or 9 and (ii) at least one surfactant, preferably at least one anionic surfactant, said composition being liquid, solid or semi-solid, more preferably liquid, and optionally further comprising (iii) water.

15. (i) at least one PPI according to any one of claims 1 to 4 or 8; and (ii) at least one chelating agent selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), citric acid, and salts thereof.

1. A detergent composition, particularly a solid automatic dishwashing detergent composition, comprising:

16. 1. A laundry detergent composition or a manual dishwashing detergent composition, preferably a liquid laundry detergent composition, comprising: Optionally, at least one enzyme is preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases, and peroxidases, preferably selected from one or more of lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the above types, more preferably selected from proteases, Optionally containing at least one antimicrobial agent; the at least one PPI 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 the composition or product; The product or composition further comprises from about 1% to about 70% by weight of at least one surfactant, preferably a surfactant system. The composition according to any one of claims 13 to 15.

17. at least one PPI according to any one of claims 1 to 4 or 8 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%, most preferably from about 0.1% to about 2%, 1. An automatic dishwashing detergent composition, preferably a solid automatic dishwashing detergent composition, further comprising at least one chelating agent in a total amount of from about 1% to about 70%, preferably from 10% to about 60%, even more preferably from 30% to about 50%, and 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, The composition of any one of claims 13 to 16, wherein all weight percentages are based on the total weight of the composition.

18. 18. The composition of any one of claims 13 to 17, further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dicolo 2-hydroxydiphenyl ether, preferably comprising 2-phenoxyethanol in the range of 2 ppm to 5% by weight of the composition, more preferably comprising 0.1 to 2% phenoxyethanol, or preferably comprising 4,4'-dichloro 2-hydroxydiphenyl ether at a concentration of 0.001 to 3%, more preferably 0.002 to 1%, even more preferably 0.01 to 0.6% by weight, each based on the weight of the composition.

19. A method for protecting an aqueous composition according to any one of claims 13 to 17 from microbial contamination or growth, comprising adding an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dicolo-2-hydroxydiphenyl ether.

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