Amphiphilic alkoxylated polyamines and their uses

Abstract

The present invention relates to novel alkoxylated polyamines having amphiphilic properties, obtainable by a process comprising steps a) to d). In step a), a polyamine containing up to 10 amine groups is reacted with a first alkylene oxide (AO1) to obtain a first intermediate (I1). In step b), the first intermediate (I1) is reacted with a lactone and / or a hydroxycarbon acid to obtain a second intermediate (I2). In step c), the second intermediate (I2) is then optionally reacted with an alkylene oxide to obtain a third intermediate (I3). In optional step d), the third intermediate (I3) is then reacted with a second alkylene oxide (AO2) to obtain the novel alkoxylated polyamine according to the invention. A process for preparing such alkoxylated polyamines is also disclosed. The invention also relates to the use of such compounds, for example, in cleaning compositions and / or in fabric care and home care products, and to such compositions or products.

Description

[Technical field]

[0001] The present invention relates to novel alkoxylated polyamines having amphiphilic properties, obtainable by a process comprising steps a) to d). According to step a), the polyamine itself is reacted with a first alkylene oxide (AO1) to obtain a first intermediate (I1). The first intermediate (I1) is reacted in step b) with a lactone and / or a hydroxycarbon acid to obtain a second intermediate (I2), which is then reacted in step c) with ethylene oxide to obtain a third intermediate (I3). The third intermediate (I3) is then optionally reacted in step d) with a second alkylene oxide (AO2) to obtain a novel alkoxylated polyamine according to the invention. The present invention further relates to the process for preparing such alkoxylated polyamines as such, as well as to the use of such compounds, for example in cleaning compositions and / or in fabric and home care products. Furthermore, the present invention also relates to those compositions or products as such. [Background technology]

[0002] Due to climate change, one of the most important goals of the D&C industry today is to significantly reduce CO2 emissions per wash by improving cold water conditions. Another important goal of the D&C industry is the need for biodegradable polymers to improve the sustainability of laundry formulations and avoid the accumulation of non-degradable polymers in the ecosystem. Although the technical hurdles to improve cold water washing performance are very high, especially for oily and greasy soil classes, it is already known in the literature that amphiphilic alkoxylated polyamines, especially those based on polyalkyleneimines such as polyethyleneimines (PEI), can contribute to oily / greasy soil removal in such conditions. However, these structures are not biodegradable.

[0003] WO 2020 / 187648 also relates to polyalkoxylated polyalkyleneimines or alkoxylated polyamines according to general formula (I). The compounds described herein may be utilized, for example, in cosmetic formulations. However, the specific compounds disclosed in WO 2020 / 187648 are different from the respective compounds of the present invention, since the substituents in WO 2020 / 187648 do not include fragments based on lactones and / or hydroxycarbon acids.

[0004] WO 95 / 32272 describes ethoxylated and / or propoxylated polyalkyleneamine polymers for enhancing soil dispersion performance, the polymers having an average ethoxylation / propoxylation per nitrogen of 0.5 to 10. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020 / 187648 [Patent Document 2] WO 95 / 32272 Summary of the Invention [Means for solving the problem]

[0006] The object of the present invention is to provide new compounds based on a polyamine backbone, which, moreover, should possess the beneficial properties of biodegradability when utilized in compositions.

[0007] The purpose is to carry out the following steps a) to c) and optional step d): a) the reaction of i) at least one polyamine containing up to 10, preferably up to 8, more preferably up to 6, most preferably up to 5 amine groups with ii) at least one first alkylene oxide (AO1) to obtain a first intermediate (I1), wherein 0.25 to 7.0 mol of alkylene oxide (AO1) are used per mol of NH functional groups of the polyamine, b) reaction of the first intermediate (I1) with at least one lactone and / or at least one hydroxyl carbon acid to obtain the second intermediate (I2), wherein 0.25 to 10 mol of lactone and / or hydroxyl carbon acid are used per mol of NH functional group of the polyamine (used in step a)), c) reaction of the second intermediate (I2) with at least one second alkylene oxide (AO2) to obtain the alkoxylated polyamine or, if optional step d) is used, the third intermediate (I3), in which at least one mole of alkylene oxide (AO2) is used per mole of NH functional group of the polyamine (used in step a)), d) optional reaction of the third intermediate (I3) with at least one second alkylene oxide (AO2) to obtain an alkoxylated polyamine, in which at least one mole of alkylene oxide (AO2) is used per mole of NH functional group of the polyamine (used in step a)) and in case where only one second alkylene oxide (AO2) is used in step d), the second alkylene oxide (AO2) in this step is achieved by an alkoxylated polyamine containing up to 10, preferably up to 8, more preferably up to 6, most preferably up to 5, for example 4, 3 or 2 amine groups, which can be obtained by a process comprising a reaction different from that with ethylene oxide, the alkylene oxides AO1 and / or AO2 are selected such that at least 10, preferably at least 20, more preferably at least 30, more preferably at least 40, and most preferably at least 50 weight percent of the total amount of moieties in the alkoxylated polyamine derived from alkylene oxides (i.e. from AO1 and AO2) are derived from C3 and / or C4-alkylene oxides; The total amount of alkylene oxide used is from 0.5, preferably from 1 to up to 25, more preferably up to 20, even more preferably up to 17, most preferably up to 15 mol per mol of NH functional groups of the polyamine (i.e. the polyamine used in step a).

[0008] The alkoxylated compounds according to the present invention may be used in cleaning compositions.They can provide the cleaning performance of said compositions, for example, in terms of removing fat and / or oil, at least equivalent, and preferably even improved, when compared with the corresponding alkoxylated compounds according to the prior art.In addition, the alkoxylated compounds according to the present invention can improve biodegradability when used in compositions, for example, cleaning compositions.

[0009] The advantage of the alkoxylated compounds according to the invention, especially due to the use of higher alkylene oxides than ethylene oxide in step d) of the inventive process, can be seen in their amphiphilic properties. The compounds of the invention combine good biodegradable properties with amphiphilic properties.

[0010] Another advantage can be realized within each detergent formulation containing the compound of the invention, for example in liquid and solid (powder) formulations containing at least one surfactant and the compound of the invention, by focusing preferably on laundry formulations and hand dishwashing formulations, primarily on liquid laundry and liquid hand dishwashing formulations, and very specifically on liquid laundry formulations and single doses for washing containing at least one anionic surfactant, water and the compound of the invention.

[0011] For the purposes of the present invention, for example, R 2 For the group, C1 to C as defined below 22 Definitions such as alkyl mean that the substituent (group) is an alkyl group having 1 to 22 carbon atoms. The alkyl group may be either linear or branched or optionally cyclic. Alkyl groups having both cyclic and linear components are likewise within the scope of this definition. The same applies to other alkyl groups such as C1-C4 alkyl groups. Examples of alkyl groups include 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.

[0012] As used herein, the term “C2-C 22 The term "alkylene" refers to a saturated divalent straight or branched hydrocarbon chain of 2, 3, 4, 5, 6, 10, 12 or up to 22 carbon atoms, such as, for example, ethane-1,2-diyl ("ethylene"), propane-1,3-diyl, propane-1,2-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl (=1-methyl-propane-1,3-diyl). ), butane-1,2-diyl ("1,2-butylene"), butane-2,3-diyl, 2-methyl-butane-1,3-diyl, 3-methyl-butane-1,3-diyl (=1,1-dimethylpropane-1,3-diyl), pentane-1,4-diyl, pentane-1,5-diyl, pentane-2,5-diyl, 2-methylpentane-2,5-diyl (=1,1-dimethylbutane-1,3-diyl) and hexane-1,6-diyl.

[0013] As used herein, "C5-C 10The term "cycloalkylene" refers to a saturated divalent hydrocarbon of 5, 6, 7, 8, 9, or 10 carbon atoms, where all or at least a portion of the respective number of carbon atoms form a ring. When not all of the respective number of carbon atoms form a ring, such remaining carbon atoms (i.e., the carbon atoms that do not form a ring) are each a C5 to C6 carbon atom. 10 -cycloalkylene groups, forming a methane-1,1-diyl ("methylene") or ethane-1,2-diyl ("ethylene") fragment. One of the two valencies of each of the methylene or ethylene fragments is attached to the adjacent nitrogen atom in general formula (I), while the second valency of the fragment is attached to the C5-C 10 - is attached to a cyclic fragment of a cycloalkylene group.

[0014] In other words, C5~C 10 -Cycloalkylene group, in addition to its cyclic fragment, in general formula (I) has a C5-C bond to the adjacent nitrogen atom. 10 -Cycloalkylene groups may also contain several acyclic fragments that bridge or link the cyclic fragments of the cycloalkylene group. The number of such carbon linker atoms is usually not more than 3, preferably 1 or 2. For example, a C7-cycloalkylene group may contain one C6-ring and one C1-linker.

[0015] Each hydrocarbon ring itself can be unsubstituted or at least monosubstituted by C1-C3-alkyl. The carbon atoms of each C1-C3-alkyl substituent can be C5-C6-alkyl. 10 It should be noted that the C5-C cycloalkylene group is not taken into account in determining the number of carbon atoms. 10 The number of carbon atoms in a cycloalkylene group is determined alone without any substituents, but only by the number of carbon atoms in the cyclic fragment and, optionally, the carbon linker atom (methylene or ethylene fragment).

[0016] C5~C 10Examples of -cycloalkylene include cyclopentane-1,2-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl, cycloheptane-1,3-diyl or cyclooctane-1,4-diyl, each of the aforementioned groups may be at least monosubstituted with C1-C3-alkyl.

[0017] Each C5~C 10 -Cycloalkylene groups are preferably used as a mixture of two or more individual cycloalkylene groups having the same ring size. It is particularly preferred to use a mixture of cyclohexane-1,3-diyls monosubstituted with methyl at the 2- or 4-position of the ring, respectively. The ratio of the two compounds is preferably in the range of 95:5 to 75:25, most preferably about 85:15 (4-methyl to 2-methyl).

[0018] 3-(Methane-1,1-diyl)-cyclohexane-1,3-diyl is a C5-C cyclic cyclohexane derivative that has a non-cyclic fragment in addition to its cyclic fragment. 10 -cyclo-alkylene group is a preferred example. In this particular case, the acyclic fragment is a C1-linker and the cyclic fragment is a C6-ring, resulting in a C7-cycloalkylene group. 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl can also be substituted with at least one C1-C3-alkyl, preferably three methyl groups, in particular 3,5,5-trimethyl. The latter is a fragment of isophoronediamine and can be used as a scaffold with the general formula (I).

[0019] For the purposes of the present invention, for example, R 2The term "aralkyl", as defined below for the formula of the group, means that the substituent (group) is an aromatic ("ar") in combination with an alkyl substituent ("alkyl"). The aromatic "ar" moiety may be monocyclic, bicyclic, or optionally polycyclic aromatic. In the case of polycyclic aromatics, the individual rings may optionally be fully or partially saturated. Preferred examples of aryl are phenyl, naphthyl, or anthracyl, especially phenyl.

[0020] Polyamines in the context of the present invention are (mainly, and preferably only) linear compounds (with respect to their main chain, without taking into account any alkoxylation) which contain within their backbone primary and / or secondary amino moieties, but no tertiary amino moieties.

[0021] Within the context of the present invention, the term "polyamine backbone" refers to a fragment of the alkoxylated polyamine of the invention that is not alkoxylated. The polyamine backbone is used in the present invention as an educt in step a) which is reacted with at least one first alkylene oxide (AO1), followed by reaction with at least one lactone or hydroxycarbon acid (in step b), followed by ethoxylation in step c) and then realkoxylation with at least one second alkylene oxide (AO2) in step d) to obtain the alkoxylated polyamine of the invention ("alkoxylated compound"). In step d), the at least one second alkylene oxide (AO2) in this step must be different from the ethylene oxide used in step c). The polyamines themselves (backbone or non-alkoxylated compound) are known to those skilled in the art.

[0022] Within the context of the present invention, the term "NH functionality" is defined as follows: in the case of (mainly) linear amines, the structure itself gives information about the content of primary, secondary and tertiary amines, for example N4 amines or diamines and oligoamines such as hexamethylenediamine. Primary amino groups (-NH2) have two NH functional groups, secondary amino groups have only one NH functional group, and tertiary amino groups consequently have no reactive NH functional groups. The exact distribution of primary and secondary (and tertiary) amino groups can be determined as explained in Lukovkin GM, Pshezhetsky VS, Murtazaeva GA: Europ. Polymer Journal 1973, 9, 559-565, and St. Pierre T., Geckle M.: ACS Polym. Prep. 1981, 22, 128-129. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] The present invention is specified in more detail as follows. The present invention relates to the following steps a) to c) and optional step d): a) the reaction of i) at least one polyamine containing up to 10, preferably up to 8, more preferably up to 6, most preferably up to 5 amine groups with ii) at least one first alkylene oxide (AO1) to obtain a first intermediate (I1), wherein 0.25 to 7.0 mol of alkylene oxide (AO1) are used per mol of NH functional groups of the polyamine, b) reaction of the first intermediate (I1) with at least one lactone and / or at least one hydroxyl carbon acid to obtain the second intermediate (I2), wherein 0.25 to 10 mol of lactone and / or hydroxyl carbon acid are used per mol of NH functional group of the polyamine (used in step a)), c) reaction of the second intermediate (I2) with at least one second alkylene oxide (AO2) to obtain the alkoxylated polyamine or, if optional step d) is used, the third intermediate (I3), in which at least one mole of alkylene oxide (AO2) is used per mole of NH functional group of the polyamine (used in step a)), d) optional reaction of the third intermediate (I3) with at least one second alkylene oxide (AO2) to obtain an alkoxylated polyamine, in which at least one mole of alkylene oxide (AO2) is used per mole of NH functional group of the polyamine (used in step a)), and in which, if only one second alkylene oxide (AO2) is used in step d), the second alkylene oxide (AO2) in this step is different from ethylene oxide, the alkylene oxides AO1 and / or AO2 are selected such that at least 10, preferably at least 20, more preferably at least 30, more preferably at least 40, and most preferably at least 50 weight percent of the total amount of moieties in the alkoxylated polyamine derived from alkylene oxides (i.e. from AO1 and AO2) are derived from C3 and / or C4-alkylene oxides; The total amount of alkylene oxide used is from 0.5, preferably from 1 to up to 25, more preferably up to 20, even more preferably up to 17, and most preferably up to 15 mol per mol of NH functional groups of the polyamine (i.e. the polyamine used in step a).

[0024] The polyamine used in step a) can be any compound known to those skilled in the art. The at least one polyamine used in step a) has the general formula (I)

[0025] [ka] wherein the variables are defined as follows: R is the same or different i) Linear or branched C2-C 12 an alkylene group, or ii) a compound of formula (III):

[0026] [ka] wherein the variables are defined as follows: R 10 , R 11 , R 12 represents the same or different linear or branched C2 to C6 alkylene groups, and d is an integer having a value ranging from 0 to 50. iii) C5-C optionally substituted with at least one C1-C3 alkyl 10 a cycloalkylene group, y is an integer having a value in the range of 0 to 8, preferably up to 6, more preferably up to 4, even more preferably up to 3, and most preferably up to 2; Preferably, R is the same or different. ia) a C2-C6-alkylene group selected from ethylene, propylene and hexamethylene, or iib) C5-C optionally substituted with at least one C1-C3-alkyl 10 -cycloalkylene group, more preferably R is at least one C6-C7-cycloalkylene group substituted with at least one methyl or ethyl, More preferably, R is selected only from the previous group ia), even more preferably R is selected from ethylene and / or propylene, most preferably ethylene).

[0027] In a preferred embodiment thereof, the alkoxylated polyamine comprises up to 5 amino groups, for example 4, 3 or 2 amino groups.

[0028] In a preferred embodiment of the present invention, the alkoxylated polyamine has the general formula (IIa)

[0029] [ka] wherein the variables are defined as follows: R 1 But, C2~C 22 represents a -(1,2-alkylene) group, R 2 is hydrogen and / or C1-C 22 -Alkyl and / or C7-C 22 represents aralkyl, R 3 is a linear or branched C1-C 22 represents an alkylene group, R 4 is C2~C 22 represents a -(1,2-alkylene) group, R 5 represents 1,2-ethylene, m is an integer having a value of at least 1 and at most 10; n is an integer having a value of at least 1 and at most 25, more preferably at most 20, even more preferably at most 15, for example, from 5 to 15; o is an integer having a value from 0 up to 25, more preferably up to 20, even more preferably up to 15, and most preferably 0; p is an integer having a value of at least 1 and at most 5; with the proviso that the sum of n+o+p is at most 25, preferably at most 20, even more preferably at most 17, and most preferably at most 15; Residue R in the alkoxylated polyamine 1 , R 4 at least 50 weight percent of the total amount of moieties is derived from C3 and / or C4-alkylene oxide; If o is not 0, R 1 and R 5 is R 1 and R 5The moieties containing R 1 and R 5 and the selected alkylene oxide is selected for R 1 and R 5 and (b) are selected so that the arrangement of said alkylene oxides is different when the alkyl groups are the same for both.

[0030] "Residue" in the present invention means a substituent of defined chemical nature as defined by structures IIa, IIb and IIc, present on a nitrogen atom of a polyamine, i.e., chemically bonded via an addition reaction of a first unit, which is either a first alkylene oxide (as in structures IIa and IIc) or a first carbonyl group (as in IIb) derived from a lactone or a hydroxy acid.

[0031] In addition to the presence of at least one residue according to general formula (IIa) above, the alkoxylated polyamine may also have the general formula (IIb):

[0032] [ka] wherein the variables are defined as follows: R 1 But, C2~C 22 represents a -(1,2-alkylene) group, R 2 is hydrogen and / or C1-C 22 -Alkyl and / or C7-C 22 represents aralkyl, R 3 is a linear or branched C1-C 22 represents an alkylene group, R 5 represents 1,2-ethylene, m is an integer having a value of at least 1 and at most 10; n is an integer having a value of at least 1 and at most 25, preferably at most 20, more preferably at most 15, for example, from 5 to 15; o is an integer having a value from 0 up to 25, preferably up to 20, more preferably up to 15, preferably 0; Residue R in the alkoxylated polyamine 1 and, if a residue of formula IIa is also present, R 4 at least 50 weight percent of the total amount of moieties is derived from C3 and / or C4-alkylene oxide; R 1 and R 5 is R 1 and R 5 The moieties containing R 1 and R 5 and the selected alkylene oxide is selected for R 1 and R 5 When the alkylene oxides are the same for both, the arrangement of the alkylene oxides is different. However, it is preferred that the sum of n+o is at most 25, preferably at most 20, even more preferably at most 17, most preferably at most 15).

[0033] In another embodiment of the present invention, the alkoxylated polyamine has the general formula (IIc):

[0034] [ka] wherein the variables are defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group, R 2 is hydrogen and / or C1-C 22 -alkyl, R 5 represents 1,2-ethylene, n is an integer having a value of at least 5 and at most 100, preferably at most 25, more preferably at most 20, even more preferably at most 15; o is an integer having a value of at least 0 to 100, preferably at most 25, more preferably at most 20, even more preferably at most 15; at least 50 weight percent of the total amount of moieties in the alkoxylated polyamine derived from alkylene oxides (i.e., residues R1 and, if residues of formula IIa are also present, R4) are derived from C3 and / or C4-alkylene oxides; However, it is preferred that the sum of n+o is at most 25, preferably at most 20, even more preferably at most 17, most preferably at most 15).

[0035] In another embodiment of the present invention, i) step a) is carried out in the presence of water and / or in the presence of a base catalyst, and / or ii) the weight average molecular weight (Mw) of the polyamine used in step a) is in the range of 50 to 2000 g / mol, preferably in the range up to 1000 g / mol, more preferably in the range up to 500 g / mol, and / or iv) at least two different alkylene oxides are used in consecutive order as the second alkylene oxide (AO2) in step d), preferably ethylene oxide followed by propylene oxide are used in consecutive order as the second alkylene oxide (AO2) in step d), and / or v) in step d), the second alkylene oxide (AO2) comprises >80% by weight, preferably >90% by weight, of propylene oxide and / or 1,2-butylene oxide, and / or vi) It is preferred that residues according to general formula (IIc) do not account for >50% of all residues on the alkoxylated polyalkyleneimine or alkoxylated polyamine.

[0036] Those skilled in the art will appreciate that the weight average molecular weight (M W) can be determined / measured. This can be done, for example, by size exclusion chromatography (e.g., GPC). Preferably, M W The values ​​are determined according to the following method: OECD TG 118 (1996), which is described in detail in OECD(1996), Test No. 118: Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris, also available on the Internet under, for example, https: / / doi.org / 10.1787 / 9789264069848-en.

[0037] Another embodiment of the present invention relates only to the above alkoxylated polyamines (per se), in which y is an integer having a value ranging from 0 to 3; R is the same or different linear or branched C2-C 12 represents an alkylene group or an ether alkyl unit according to formula (III), d is 1 to 10; R 10 , R 11 , R 12 are preferably independently selected from linear or branched C3-C4 alkylene groups.

[0038] In another embodiment, residue (IIa) represents at least 80, more preferably at least 90, even more preferably at least 95% by weight of all residues (IIa), (IIb) and (IIc) bonded to amino groups of the polyamine used in step a).

[0039] In another embodiment of the present invention, i) in step b), the lactone is caprolactone, and / or ii) in step b), the hydroxycarbon acid is lactic acid or glycolic acid, and / or iii) In step a), the first alkylene oxide (AO1) comprises at least one C2-C 22 epoxides, preferably ethylene oxide and / or propylene oxide, and / or iv) In step c), the second alkylene oxide (AO2) has at least one C2-C 22 -epoxides, preferably propylene oxide or a mixture of ethylene oxide and propylene oxide.

[0040] In another embodiment of the present invention, i) in step a) 0.5 to 2 mol of alkylene oxide (AO1) are used per mol of NH functional group of the polyamine, and / or ii) in step b) 0.5 to 3 mol of lactone and / or hydroxycarbon acid are used per mol of NH functional group of the polyamine (used in step a)), and / or iii) In step c), it is preferred that 5 to 14.5 mol of alkylene oxide (AO2) are used per mol of NH functional groups of the polyamine (used in step a)).

[0041] In one embodiment, the alkoxylated polyamines of the invention are quaternized. The preferred degree of quaternization is up to 100%, in particular 10 to 95%. The quaternization is carried out by using C1 to C 22 Alkyl group, C1-C4 alkyl group, and / or C7-C 22 Introduction of an aralkyl group is preferably carried out, which may be carried out in the conventional manner by reacting the corresponding alkyl halide and dialkyl sulfate.

[0042] Quaternization can be advantageous to tailor the alkoxylated polyamines to the particular composition, such as the cosmetic composition in which they are used, to achieve better compatibility and / or phase stability of the formulation; for example, hydrophilicity is increased by the cationic charge, thus increasing interaction with anionic surfaces.

[0043] The quaternization of alkoxylated polyamines is carried out from C1 to C 22 Alkyl, C1-C4 alkyl group, and / or C7-C 22 This may preferably be achieved by introducing an aralkyl group, an aryl group or an alkylaryl group, and may be carried out in a conventional manner by reacting the corresponding alkyl halides, aralkyl halides and dialkyl sulfates, as described, for example, in WO 09 / 060059.

[0044] The quaternization can be carried out by, for example, combining an alkoxylated polyalkyleneimine with an alkylating agent such as a C1-C4-alkyl halide, for example methyl bromide, methyl chloride, ethyl chloride, methyl iodide, n-butyl bromide, isopropyl bromide, or an aralkyl halide, for example benzyl chloride, benzyl bromide, and a di-C1-C 22 -alkyl sulfates, in particular dimethyl sulfate or diethyl sulfate, in the presence of a base. Suitable bases are, for example, sodium hydroxide and potassium hydroxide.

[0045] The amount of alkylating agent determines the amount of quaternization of amino groups in the polymer, ie, the amount of quaternized moieties.

[0046] The amount of quaternized moieties can be calculated from the difference in amine numbers in the non-quaternized and quaternized amines.

[0047] The amine number can be determined according to the method described in DIN 16945.

[0048] The quaternization can be carried out without a solvent. However, a solvent or diluent such as water, acetonitrile, dimethylsulfoxide, N-methylpyrrolidone, etc. may be used. The reaction temperature is usually in the range of 10°C to 150°C, preferably 50°C to 100°C.

[0049] The alkoxylated polyamines as described above can be, and preferably are, prepared by the process as described below. In the following, steps a) to d) (as described above for the alkoxylated polyamines) are described in more detail. The following information also applies to the aforementioned polymers themselves as they can be obtained by the respective processes. Within this process, the polyamine (itself) is first reacted with a first alkylene oxide (AO1) according to step a), followed by reaction of the respective intermediate (I1) with at least one lactone and / or at least one hydroxycarbon acid in step b), followed by ethoxylation in step c), followed by reaction (in step d)) of at least one second alkylene oxide (AO2) with at least one alkylene oxide different from ethylene oxide (in step c) to obtain the respective alkoxylated compound.

[0050] It should be noted that the alkoxylation process by which polyamines are reacted with alkylene oxides such as ethylene oxide or propylene oxide according to step a) is known per se to those skilled in the art. The same method can be applied to the present invention in step c) or in step d), respectively, where the respective intermediate (I2) obtained by reaction with a first alkylene oxide and then with a lactone or a hydroxyl carbon acid is first subjected to an ethoxylation process (step c)) followed by a second alkoxylation process in step d).

[0051] The conversion of each step can be determined by methods known to those skilled in the art, such as NMR spectroscopy. For example, both the first reaction step, the second reaction step and / or the third reaction step can be carried out by: 13 C-NMR spectroscopy and / or1 This can be monitored by 1 H-NMR spectroscopy.

[0052] In relation to the second step b) of the process for preparing alkoxylated polyamines, the respective intermediate (I1) obtained in step a) is reacted with at least one lactone and / or at least one hydroxycarbon acid, this second reaction step per se being known to the person skilled in the art.

[0053] However, within this second reaction step b), it is preferred that the reaction temperature is in the range of 50-200°C, more preferably in the range of 70-180°C, most preferably in the range of 100-160°C.

[0054] This second reaction step b) may be carried out in the presence of at least one solvent and / or at least one catalyst. However, within the second reaction step b), each step is preferably carried out without solvent and / or catalyst. Suitable solvents are preferably selected from xylene, toluene, tetrahydrofuran (THF), methyl-tert-butyl ether or diethyl ether. Preferred catalysts are selected from alkali metal hydroxides or alkali metal alkoxides, such as KOMe or NaOMe.

[0055] As mentioned above, the first, third and / or fourth reaction steps (steps a), c) and d)) of the process itself (alkoxylation, in particular ethoxylation) are known to the person skilled in the art. The alkoxylation itself (first, third and fourth reaction steps of the process according to the invention) may be carried out independently of one another as a one-step reaction or the alkoxylation itself may be divided into two or more individual steps.

[0056] Each step (alkoxylation) is preferably carried out in conjunction with steps a), c) and / or d) as a single step reaction.

[0057] In a preferred embodiment, the alkoxylation step (a) is carried out as a single step reaction in the absence of any catalyst but in the presence of water.

[0058] In another embodiment, the alkoxylation step (a) is carried out in at least two steps, the first step being carried out in the absence of any catalyst but in the presence of water and the second (and optionally further steps) step being carried out in the presence of a catalyst but in the absence of water.

[0059] The absence of water is defined according to the present invention as a residual water level of <1% water by weight, preferably <0.5% water by weight, more preferably <0.25% water by weight.

[0060] Within this preferred embodiment, the alkoxylation steps (c) and (d) are carried out in the presence of at least one catalyst and / or in the absence of water.

[0061] In this at least two-step reaction variant of the alkoxylation step (a), as well as in these single-step reactions of the alkoxylation steps ((c) and (d)), the catalyst is preferably a basic catalyst. Examples of suitable catalysts are hydroxides of alkali metals and alkaline earth metals, such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular C1-C4-alkoxides of sodium and potassium, such as sodium methoxide, potassium methoxide, sodium ethoxide and potassium tert-butoxide, hydrides of alkali metals and alkaline earth metals, such as sodium hydride and calcium hydride, and alkali metal carbonates, such as sodium carbonate and potassium carbonate. Alkali metal hydroxides and alkali metal alkoxides are preferred, with potassium hydroxide, potassium methoxide and potassium tert-butoxide being particularly preferred. Typical amounts of base used are from 0.05 to 10% by weight, especially from 0.5 to 2% by weight, based on the total amount of polyalkyleneimine or polyamine, hydroxycarbon acid and alkylene oxide.

[0062] If the alkoxylation step (a) is carried out in at least two steps, the first step is carried out in the absence of a catalyst but in the presence of water. In this procedure, an initial initial alkoxylation of the polyamine is carried out. In this first part of step a), the polyamine is reacted with only a part of the total amount of alkylene oxide used, corresponding to about 1 mol of alkylene oxide per mole of NH moiety or per mole of NH function, respectively. This reaction (first part of step a)) is generally carried out in an aqueous solution at 70-200°C, preferably 80-160°C, in the absence of a catalyst, under a pressure of up to 10 bar, in particular up to 8 bar. The water content in this first part of step a) is >1% by weight, preferably >5% by weight, more preferably >10% by weight.

[0063] This second part of the alkoxylation reaction (step a) of the alternative process according to the invention) is typically carried out in the presence of the same type of catalyst as described above for the single-step alkoxylation reaction (steps (c) and (d)).

[0064] All catalysis steps of the alkoxylation in the absence of water can be carried out in water (variant a)) or in organic solvents (variant b)). The process conditions specified below can be used for both steps of the alkoxylation reaction.

[0065] In variant a), the aqueous solution of the initially alkoxylated polyamine obtained in the first step is first dehydrated after the addition of the catalyst. This can be carried out in a simple manner by heating to 80-150° C. and distilling off the water under reduced pressure of less than 30 mbar. The subsequent reaction with alkylene oxide is typically carried out at 70-200° C., preferably 100-180° C., and at pressures of up to 10 bar, in particular up to 8 bar, in each case subject to temperatures of about 100-160° C., continuous stirring times of about 0.5-4 hours and constant pressure.

[0066] Suitable reaction media for variant b) are especially non-polar and polar aprotic organic solvents. Examples of particularly suitable non-polar aprotic solvents include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. Examples of particularly suitable polar aprotic solvents are ethers, especially cyclic ethers such as tetrahydrofuran and dioxane, N,N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyllactams such as N-methylpyrrolidone. Of course, it is also possible to use mixtures of these aprotic solvents. Preferred solvents are xylene and toluene.

[0067] Also in variant b), the solution obtained in the first step, after addition of catalyst and solvent, is first dehydrated, advantageously carried out by separating off the water at a temperature between 120 and 180° C., preferably supported by a gentle nitrogen stream. The subsequent reaction with alkylene oxide may be carried out analogously to variant a).

[0068] In variant a), the alkoxylated polyamine is obtained directly in the material and may be converted into an aqueous solution, if desired. In variant b), the organic solvent is typically removed and replaced with water. Of course, the product may be isolated in the material.

[0069] For example, the amount of residues according to formula (IIa), formula (IIb) and / or formula (IIc) can be controlled by several factors such as the stoichiometry of the extractant employed, the reaction temperature within the individual steps, the amount and / or type of catalyst employed and / or solvent selected, etc. In a preferred embodiment of the invention, residues according to general formula (IIc) do not account for >50% of the total residues on the alkoxylated polyamine.

[0070] Another subject of the present invention, and therefore an embodiment of the present invention, is the use of the above alkoxylated polyamines in fabric care and home care products, in particular cleaning compositions for improved oily and greasy stain removal, which cleaning compositions are preferably laundry detergent formulations and / or hand dishwashing detergent formulations, more preferably liquid laundry detergent formulations and / or liquid hand dishwashing detergent formulations.

[0071] Another subject of the present invention, and therefore an embodiment of the present invention, are cleaning compositions, fabric care products and home care products, preferably cleaning compositions and / or fabric care products and home care products, more preferably laundry formulations, comprising at least one alkoxylated polyamine as defined above.

[0072] In particular, it is a cleaning composition for improved oily and greasy soil removal, preferably a laundry detergent formulation and / or a hand dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid hand dishwashing detergent formulation.

[0073] Thus, in one embodiment, the alkoxylated polyamines are preferably used in cleaning compositions and / or in fabric and home care products. i) clay removal; and / or ii) soil removal of particulate stains; and / or iii) dispersing and / or emulsifying the dirt; and / or iv) modification of the treated surface to improve removal upon subsequent recontamination; and / or v) improving whiteness, Each of the above options i) to v) is preferably for use in a laundry care composition, more preferably in a laundry detergent composition.

[0074] Further encompassed by the present invention is the use of a cleaning composition as defined hereinbefore, i) clay removal; and / or ii) soil removal of particulate stains; and / or iii) dispersing and / or emulsifying the dirt; and / or iv) modification of the treated surface to improve removal upon subsequent recontamination; and / or v) Use of the cleaning composition for improving whiteness.

[0075] At least one alkoxylated polyamine described herein (hereinafter also referred to as "polymer of the invention" or "polymer of the invention") is present in the cleaning compositions of the invention at a concentration of from 0.1 to 10, preferably from about 0.25% to 5%, more preferably from about 0.5% to about 3%, and most preferably from about 1% to about 3%, based on the total weight of such compositions, and such cleaning compositions may further comprise, and preferably do comprise, from about 1% to about 70% by weight of a surfactant system.

[0076] Similarly, the cleaning compositions and / or fabric care and home care products detailed in the previous embodiments comprise at least one inventive polymer at a concentration of 0.1 to 10, preferably about 0.25% to 5%, more preferably about 0.5% to about 3%, and most preferably about 1% to about 3%, based on the total weight of such composition.

[0077] Preferably, the inventive cleaning compositions are fabric and home care products, preferably fabric and home care products, more preferably laundry detergents or hand dishwashing detergents, comprising at least one inventive polymer, and optionally further comprising at least one surfactant or surfactant system, providing improved removal of soils, dispersion and / or emulsification of soils, and / or modification of treated surfaces, and / or maintenance of whiteness of treated surfaces.

[0078] Further subject of the present invention are fabric and home care products comprising grafted polymers comprising the polymers of the present invention as described above. The products can be laundry detergents, dishwashing detergents, cleaning compositions and / or fabric and home care products containing at least one polymer as described above.

[0079] Such laundry detergents, cleaning compositions, and / or fabric care and home care products are known to those skilled in the art. Any compositions etc. known to those skilled in the art in connection with the respective uses can be used in the context of the present invention.

[0080] In preferred laundry detergents, cleaning compositions, and / or fabric care and home care products according to the present invention, the at least one polymer is present in an amount ranging from about 0.01% to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1% to about 10%, and most preferably from about 0.5% to about 5%, based on the total weight of such composition or product.

[0081] Laundry Detergent Compositions: Suitable laundry detergent compositions include laundry detergent powder compositions, laundry detergent liquid compositions, laundry detergent gel compositions, and aqueous laundry detergent compositions.

[0082] Dishwashing Detergent Compositions: Suitable dishwashing detergent compositions include hand dishwashing detergent compositions and automatic dishwashing detergent compositions.

[0083] Surfactant System: The composition comprises a surfactant system in an amount sufficient to impart the desired cleaning characteristics. In some embodiments, the composition comprises from about 1% to about 70% of a surfactant system, by weight of the composition. In other embodiments, the liquid composition comprises from about 2% to about 60% of a surfactant system, by weight of the composition. In further embodiments, the composition comprises from about 5% to about 30% of a 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, ampholytic surfactants, and mixtures thereof. One skilled in the art will appreciate that a detersive surfactant encompasses any surfactant or mixture of surfactants that provides a cleaning, stain removal, or laundering benefit to soiled materials.

[0084] Anionic Surfactants: In some examples, the surfactant system of the composition may comprise from about 1% to about 70% by weight of the surfactant system of one or more anionic surfactants. In other examples, the surfactant system of the composition may comprise from about 2% to about 60% by weight of the surfactant system of one or more anionic surfactants. In further examples, the surfactant system of the composition may comprise from about 5% to about 30% by weight of the surfactant system of one or more anionic surfactants. In further examples, the surfactant system may consist essentially of one or more anionic surfactants, or may even consist of one or more anionic surfactants.

[0085] Specific non-limiting examples of suitable anionic surfactants include any conventional anionic surfactant, which may include, for example, sulfate detersive surfactants for alkoxylated and / or non-alkoxylated alkyl sulfate materials, and / or sulfonic acid-based detersive surfactants, such as alkyl benzene sulfonates.

[0086] Other useful anionic surfactants can include the alkali metal salts of alkylbenzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms in a linear (straight chain) or branched configuration.

[0087] Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LABs). Suitable LABs include low 2-phenyl LABs such as those supplied by Sasol under the trade name Isochem® or those supplied by Petresa under the trade name Petrelab®, and other suitable LABs include high 2-phenyl LABs such as those supplied by Sasol under the trade name Hyblene®. Suitable anionic detersive surfactants are alkylbenzene sulfonates obtained by the DETAL catalyzed process, although other synthetic routes such as HF may be suitable. In one embodiment, magnesium salts of LAS are used.

[0088] The detersive surfactant may be a mid-chain branched detersive surfactant, in one aspect a mid-chain branched anionic detersive surfactant, in one aspect a mid-chain branched alkyl sulfate and / or a mid-chain branched alkyl benzene sulfonate, such as a mid-chain branched alkyl sulfate. In one aspect, the mid-chain branching is 1~4 The alkyl groups are usually methyl and / or ethyl groups.

[0089] Other anionic surfactants useful herein are the water-soluble salts of paraffin sulfonates and secondary alkane sulfonates containing from about 8 to about 24 (and in some examples from about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially C 8~18 Ethers of alcohols (e.g., derived from tallow and coconut oil). Mixtures of alkylbenzene sulfonates with the above-mentioned paraffin sulfonates, secondary alkane sulfonates, and alkyl glyceryl ether sulfonates are also useful. Further suitable anionic surfactants include methyl ester sulfonates and alkyl ether carboxylates.

[0090] Anionic surfactants may be present in acid form, and the acid form may be neutralized to form surfactant salts. Typical neutralizing agents include metal counterion bases such as hydroxides, e.g., NaOH or KOH. Further suitable neutralizing agents for neutralizing these acid form anionic surfactants include ammonia, amines, or alkanolamines. Non-limiting examples of alkanolamines include monoethanolamine, diethanolamine, triethanolamine, and other linear or branched alkanolamines known in the art. Suitable alkanolamines include 2-amino-1-propanol, 1-aminopropanol, monoisopropanolamine, or 1-amino-3-propanol. Amine neutralization may be complete or partial, for example, a portion of the anionic surfactant mixture may be neutralized with sodium or potassium, and a portion of the anionic surfactant mixture may be neutralized with amines or alkanolamines.

[0091] Nonionic surfactants: The surfactant system of the composition may include a nonionic surfactant. In some examples, the surfactant system includes up to about 25% by weight of the surfactant system of one or more nonionic surfactants, e.g., as a co-surfactant. In some examples, the composition includes from about 0.1% to about 15% by weight of the surfactant system of one or more nonionic surfactants. In further examples, the composition includes from about 0.3% to about 10% by weight of the surfactant system of one or more nonionic surfactants.

[0092] Suitable nonionic surfactants useful herein can include any conventional nonionic surfactant, which can include, for example, alkoxylated fatty alcohols, and amine oxide surfactants.

[0093] Other non-limiting examples of nonionic surfactants useful herein include C8-C 18 Alkyl ethoxylates (NEODOL® nonionic surfactants (Shell), etc.); C6-C 12 Alkylphenol alkoxylates (the alkoxylate units can be ethyleneoxy units, propyleneoxy units, or combinations thereof); C 12 ~C 18 C6-C with alcohol and ethylene oxide / propylene oxide block polymer 12 Alkylphenol condensates (such as Pluronic® (BASF)); C 14 ~C 22 Medium-chain branched alcohol (BA); C 14 ~C 22 Medium Chain Branched Alkyl Alkoxylate, BAE x (wherein x is 1 to 30); alkyl polysaccharides; specifically, alkyl polyglycosides; polyhydroxy fatty acid amides; and ether-terminated poly(oxyalkylated) alcohol surfactants.

[0094] Suitable nonionic detersive surfactants also include alkyl polyglucosides and alkyl alkoxylated alcohols. Suitable nonionic surfactants also include those sold by BASF under the trade name Lutensol®.

[0095] Anionic and Nonionic Combinations: The surfactant system may include a combination of anionic and nonionic surfactant materials. In some examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 2:1. In other examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 5:1. In further examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 10:1.

[0096] Cationic surfactants: The surfactant system may include a cationic surfactant. In some embodiments, the surfactant system includes from about 0% to about 7%, from about 0.1% to about 5%, or from about 1% to about 4% by weight of the surfactant system of a cationic surfactant, e.g., as a co-surfactant. In some embodiments, the compositions of the present invention are substantially free of cationic surfactants and surfactants that become cationic at a pH below 7 or below 6. Non-limiting examples of cationic surfactants include quaternary ammonium surfactants, which may have 26 or fewer carbon atoms, including alkoxylate quaternary ammonium (AQA) surfactants; dimethylhydroxyethyl quaternary ammonium; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants; cationic ester surfactants; and amino surfactants, e.g., amidopropyl dimethylamine (APA).

[0097] Suitable cationic detersive surfactants also include alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphonium compounds, alkyl tertiary sulfonium compounds, and mixtures thereof.

[0098] Zwitterionic surfactants: Examples of zwitterionic surfactants include secondary and tertiary amine derivatives, heterocyclic secondary and tertiary amine derivatives, or derivatives of quaternary ammonium compounds, quaternary phosphonium compounds, or tertiary sulfonium compounds. Betaines, including alkyl dimethyl betaines and cocodimethylamidopropyl betaine, C8-C 18 (For example, C 12 ~C 18 ) amine oxides, and sulfo and hydroxy betaines such as N-alkyl-N,N-dimethylamino-1-propanesulfonates (wherein the alkyl group is C8 to C 18 In a specific embodiment, C 10 ~C 14 (It can be said that.)

[0099] Amphoteric Surfactants: Examples of amphoteric surfactants include aliphatic derivatives of secondary or tertiary amines, or heterocyclic secondary and tertiary amines, where the aliphatic group may be linear or branched and one of the aliphatic substituents contains at least about 8 carbon atoms, or from about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate. Examples of compounds falling within this definition are sodium 3-(dodecylamino)propionate, sodium 3-(dodecylamino)propane-1-sulfonate, sodium 2-(dodecylamino)ethyl sulfate, sodium 2-(dimethylamino)octadecanoate, disodium 3-(N-carboxymethyldodecylamino)propane-1-sulfonate, disodium octadecyl-iminodiacetate, sodium 1-carboxymethyl-2-undecylimidazole, and sodium N,N-bis(2-hydroxyethyl)-2-sulfato-3-dodecoxypropylamine.Suitable amphoteric surfactants also include sarcosinates, glycinates, taurinates, and mixtures thereof.

[0100] Branched Detersive Surfactants: Suitable branched detersive surfactants include branched sulfate or sulfonate surfactants, such as branched alkyl sulfates, branched alkyl alkoxylated sulfates, and branched alkyl benzene sulfonates, which may include one or more random alkyl branches, such as C 1~4 Included are anionic branched surfactants containing alkyl groups, typically methyl and / or ethyl groups.

[0101] The branched detersive surfactant may be a mid-chain branched detersive surfactant, typically a mid-chain branched anionic detersive surfactant, such as a mid-chain branched alkyl sulfate and / or a mid-chain branched alkyl benzene sulfonate. In some embodiments, the detersive surfactant is a mid-chain branched alkyl sulfate. In some embodiments, the mid-chain branching is 1~4 The alkyl groups are usually methyl and / or ethyl groups.

[0102] Further suitable branched anionic detersive surfactants include those derived from alcohols branched at the 2-alkyl position, which are sold under the trade names Isalchem® 123, Isalchem® 125, Isalchem® 145, Isalchem® 167, etc., and are derived from the oxo process. Due to the oxo process, the branch is located at the 2-alkyl position. These 2-alkyl branched alcohols typically have a length of C 11 ~C 14 / C 15 and all include structural isomers branched at the 2-alkyl position.

[0103] Auxiliary cleaning additives: The compositions of the present invention may also contain auxiliary cleaning additives. Suitable auxiliary cleaning additives include builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, tinting agents, dye transfer inhibitors, chelating agents, suds suppressors, softeners and fragrances.

[0104] enzyme: Proteases: The compositions of the present invention may include a protease in addition to the protease of the present invention. A mixture of two or more proteases can contribute to enhanced cleaning over a broader temperature, cycle duration and / or substrate range, particularly when used with an anti-redeposition agent and / or a sulfonated polymer, and can provide superior shine benefits.

[0105] Suitable proteases for use in combination with the variant proteases of the present invention include metalloproteases and serine proteases, including neutral or alkaline microbial serine proteases, such as subtilisin (EC 3.4.21.62). Suitable proteases include those of animal, vegetable or microbial origin. In one aspect, such suitable proteases may be of microbial origin. Suitable proteases include chemically or genetically modified variants of the aforementioned suitable proteases. In one aspect, suitable proteases may be serine proteases, such as alkaline microbial proteases or / and trypsin-type proteases. Examples of suitable neutral or alkaline proteases include: (a) Subtilisins (EC 3.4.21.62), in particular those described in WO 2004 / 067737, WO 2007 / 131656, WO 2015 / 091990, WO 2015 / 024739, WO 2015 / 143360, U.S. Pat. Nos. 6,312,936(B1), 5,679,630, 4,760,025 ... Patent Publication Nos. 102006022216(A1), 102006022224(A1), International Publication Nos. 2015 / 089447, 2015 / 089441, 2016 / 066756, 2016 / 066757, 2016 / 069557, 2016 / 069563, and 201 Bacillus species, such as Bacillus spp., B. lentus, B. alkalophilus, B. subtilis, B. amyloliquefaciens, B. pumilus, B. gibsonii, and B. akibaii, as described in US Pat. Nos. 6 / 069569, 2016 / 174234, 2017 / 215925, 2020 / 207944, and 2020 / 114968. Specifically, the mutations S9R, A15T, V66A, A188P, V199I, Q239R, and N255D (savinase numbering system). (b) trypsin- or chymotrypsin-type proteases, such as trypsin (e.g., of porcine or bovine origin), including the Fusarium protease described in WO 89 / 06270, and the chymotrypsin protease derived from Cellumonas, described in WO 05 / 052161 and WO 05 / 052146. (c) metalloproteases, in particular those from Bacillus amyloliquefaciens as described in WO 07 / 044993(A2); those from species of the genera Bacillus, Brevibacillus, Thermoactinomyces, Geobacillus, Paenibacillus, Lysinibacillus or Streptomyces as described in WO 2014 / 194032, WO 2014 / 194054 and WO 2014 / 194117; those from Kribella aluminosa as described in WO 2015 / 193488; alluminosa, and those derived from Streptomyces and Lysobacter as described in WO 2016 / 075078. (d) a protease having at least 90% identity to the subtilase from Bacillus sp. TY145, NCIMB 40339, described in WO 92 / 17577 (Novozymes A / S), including variants of this Bacillus sp. TY145 subtilase described in WO 2015 / 024739 and WO 2016 / 066757.

[0106] Particularly preferred additional proteases for the detergent of the present invention show at least 90%, preferably at least 95%, more preferably at least 98%, even more preferably at least 99%, especially 100% identity to the wild-type enzyme from Bacillus lentus and are expressed at the following positions: S9R, A15T, V68A, N76D, N87S, S99D, S99SD, S99A, S101G, S101M, S103A, V104N / I, G118V, G118R, S128L, P ... and / or M222S (using the BPN' numbering system and amino acid abbreviations as exemplified in WO 00 / 37627, incorporated herein by reference).

[0107] Most preferably, the additional protease is selected from the group of proteases that comprise the following mutations (BPN numbering system) relative to either the PB92 wild type (SEQ ID NO: 2 of WO 08 / 010925) or the subtilisin 309 wild type (sequence according to the PB92 backbone but containing the naturally occurring mutation N87S): (i) G118V+S128L+P129Q+S130A (ii)S101M+G118V+S128L+P129Q+S130A (iii)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+N248R (iv)N76D+N87R+G118R+S128L+P129Q+S130A+S188D+V244R (v)N76D+N87R+G118R+S128L+P129Q+S130A (vi) V68A+N87S+S101G+V104N (vii) S99AD (viii)S9R+A15T+V68A+N218D+Q245R

[0108] Suitable commercially available additional protease enzymes include those sold under the trade names Alcalase®, Savinase®, Primase®, Durazym®, Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®, Ovozyme®, Neutrase®, Everlase®, Coronase®, Blaze®, Blaze Ultra® and Esperase® by Novozymes A / S (Denmark), those sold under the trade names Maxatase®, Maxacal®, Maxapem®, Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®, Excellase®, Ultimase® and Purafect those sold by Dupont under the trade names Opticlean® and Optimase® by Solvay Enzymes, and those available from Henkel / Kemira, namely, BLAP (whose sequence is shown in FIG. 29 of U.S. Pat. No. 5,352,604 and has the mutations S99D+S101R+S103A+V104I+G159S, hereinafter referred to as BLAP), BLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP with S3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D), and KAP from Kao (Bacillus alkalophilus subtilisin with the mutations A230V+S256G+S259N).

[0109] Commercially available proteases selected from the group consisting of Properase®, Blaze®, Ultimase®, Everlase®, Savinase®, Excellase®, Blaze Ultra®, BLAP and BLAP variants are particularly preferred for use herein in combination with the variant proteases of the invention.

[0110] Preferred concentrations of protease in the products of the present invention include from about 0.05 to about 10 mg, more preferably from about 0.5 to about 7 mg, and especially from about 1 to about 6 mg of active protease per gram of composition.

[0111] Lipase: The enzyme system preferably further comprises a lipase. The presence of oils and / or fats may further increase the recovery of stains containing mannans and other polysaccharides. Thus, the presence of lipase in the enzyme package may further improve the removal of such stains. Suitable lipases include those of bacterial, fungal or synthetic origin and variants thereof. Chemically modified or protein engineered variants are also suitable. Examples of suitable lipases include lipases from Humicola (synonym Thermomyces), e.g., from H. lanuginosa (T. lanuginosus).

[0112] The lipase may be a "first cycle lipase" such as, for example, those described in WO 06 / 090335 and WO 13 / 116261. In one aspect, the lipase is a first wash lipase, preferably a variant of the wild-type lipase from Thermomyces lanuginosus, including the T231R and / or N233R mutations.

[0113] Preferred lipases include those sold under the trade names Lipex®, Lipolex®, and Lipoclean® by Novozymes (Bagsvaerd, Denmark).

[0114] Other suitable lipases include, for example, Liprl 139 as described in WO 2013 / 171241, TfuLip2 as described in, for example, WO 2011 / 084412 and WO 2013 / 033318, Pseudomonas stutzeri lipase as described in, for example, WO 2018 / 228880, Microbulbifer thermotolerans lipase as described in, for example, WO 2018 / 228881, Sulfobacillus acidocaldarius lipase as described in, for example, EP 3299457, acidocaldarius lipases, e.g., LIP062 lipase as described in WO 2018 / 209026, PinLip lipase as described in WO 2017 / 036901, and Absidia species lipases as described in WO 2017 / 005798.

[0115] Suitable lipases are (a) Substitution T231R and (b) Substitution N233R or N233C and (c) a variant of SEQ ID NO: 1 comprising at least three additional substitutions selected from E1C, D27R, N33Q, G38A, F51V, G91Q, D96E, K98L, K98I, D111A, G163K, H198S, E210Q, Y220F, D254S, I255A, and P256T; The positions correspond to those of SEQ ID NO:1, and the lipase variant has at least 90% but less than 100% sequence identity to a polypeptide having the amino acid sequence of SEQ ID NO:1, and the variant has lipase activity.

[0116] One preferred lipase is a variant of SEQ ID NO:1 that includes the following substitutions: T231R, N233R, D27R, G38A, D96E, D111A, G163K, D254S, and P256T.

[0117] One preferred lipase is a variant of SEQ ID NO:1 that includes the following substitutions: T231R, N233R, N33Q, G91Q, E210Q, I255A.

[0118] Suitable lipases are commercially available from Novozymes, for example as Lipex Evity 100L, Lipex Evity 200L (both liquid ingredients) and Lipex Evity 105T (granules), which have a different structure to the products Lipex 100L, Lipex 100T and Lipex Evity 100T, which are outside the scope of the present invention.

[0119] Cellulase: Suitable cellulases include cellulases of bacterial or fungal origin. These include chemically modified or genetically engineered variants of proteins. Suitable cellulases include cellulases from the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia, and Acremonium, such as the fungal cellulases produced from Humicola insolens, Myceliophthora thermophila, and Fusarium oxysporum, as disclosed in U.S. Patent Nos. 4,435,307, 5,648,263, 5,691,178, 5,776,757, and 5,691,178.

[0120] In one aspect, preferred enzymes include endoglucanases from microorganisms exhibiting endo-beta-1,4-glucanase activity (EC 3.2.1.4), preferably selected from the group comprising: (a) a bacterial polypeptide endogenous to a member of the genus Bacillus having a sequence at least 90%, 94%, 97% or even 99% identical to the amino acid sequence of SEQ ID NO:2 in U.S. Pat. No. 7,141,403(B2), wherein preferred substitutions include one or more positions corresponding to positions 292, 274, 266, 265, 255, 246, 237, 224 and 221 of the mature polypeptide of SEQ ID NO:2, wherein the variant has cellulase activity; (b) a glycosyl hydrolase having enzymatic activity on both xyloglucan and amorphous cellulose substrates, the glycosyl hydrolase being selected from GH family 5, 7, 12, 16, 44 or 74; (c) glycosyl hydrolases having a sequence that is at least 90%, 94%, 97%, and even 99% identical to the amino acid sequence of SEQ ID NO: 3 of WO 09 / 148983; (d) a variant exhibiting at least 70% identity to SEQ ID NO: 5 in WO 2017 / 106676. Preferred substitutions include one or more positions corresponding to positions 4, 20, 23, 29, 32, 36, 44, 51, 77, 80, 87, 90, 97, 98, 99, 102, 112, 116, 135, 136, 142, 153, 154, 157, 161, 163, 192, 194, 204, 208, 210, 212, 216, 217, 221, 222, 225, 227, and 232; (e) and mixtures thereof.

[0121] Suitable endoglucanases are sold under the trade names Celluclean® and Whitezyme® (Novozymes A / S, Bagsvaerd, Denmark). Examples include Celluclean® 5000L, Celluclean® Classic 400L, Celluclean® Classic 700T, Celluclean® 4500T, Whitezyme® 1.5T, Whitezyme® 2.0L.

[0122] Other commercially available cellulases include Celluzyme®, Carezyme®, Carezyme® Premium (Novozymes A / S), Clazinase®, Puradax HA®, Revitalenz® 1000, Revitalenz® 2000 (Genencor International Inc.), KAC-500(B)® (Kao Corporation), Biotouch® FCL, Biotouch® DCL, Biotouch® DCC, Biotouch® NCD, Biotouch® FCC, Biotouch® FLX1 (AB Enzymes).

[0123] Suitable glucanases include endo-β-1,3-glucanases, preferably from EC class 3.2.1.39, obtained from Paenibacillus sp., Zobellia galactanivorans, Thermotoga petrophila, or Trichoderma sp. microorganisms, preferably Paenibacillus sp. or Zobellia galactanivorans, most preferably Paenibacillus sp.

[0124] Amylase: Preferably, the composition of the present invention comprises an amylase. Suitable alpha-amylases include those of bacterial or fungal origin. Chemically or genetically modified variants are included. Preferred alkaline alpha-amylases are derived from Bacillus species, such as Bacillus licheniformis, Bacillus amyloliquefaciens, Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus species, such as Bacillus species NCBI12289, NCBI12512, NCBI12513, DSM9375 (U.S. Pat. No. 7,153,818), DSM12368, DSMZ No. 12649, KSM AP1378 (WO 97 / 00324), KSM K36, or KSM K38 (EP 1,022,334). Preferred amylases include the following: (a) variants described in U.S. Pat. No. 5,856,164, and in WO 99 / 23211, WO 96 / 23873, WO 00 / 60060, WO 06 / 002643, and WO 2017 / 192657, in particular those at the following positions relative to the AA560 enzyme described as SEQ ID NO: 12 in WO 06 / 002643: 26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186, 193, 202, 214, 231, 246, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298, 299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383, 419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484, preferably D183 * and G184 * Variants that also contain deletions. (b) variants exhibiting at least 85%, preferably 90% identity with SEQ ID NO: 4 in WO 06 / 002643, the wild-type enzyme from Bacillus sp. SP722, in particular variants in which positions 183 and 184 are deleted, as well as variants described in WO 00 / 60060, WO 2011 / 100410 and WO 2013 / 003659, in particular the following positions relative to SEQ ID NO: 4 in WO 06 / 002643, which is incorporated herein by reference: Those having one or more substitutions at 51, 52, 54, 109, 304, 140, 189, 134, 195, 206, 243, 260, 262, 284, 347, 439, 469, 476, and 477. (c) variants exhibiting at least 90% identity with the wild-type enzyme from Bacillus sp. 707 (SEQ ID NO: 7 in U.S. Pat. No. 6,093,562), in particular those comprising one or more of the following mutations: M202, M208, S255, R172, and / or M261. Preferably, the amylase comprises one or more of M202L, M202V, M202S, M202T, M202I, M202Q, M202W, S255N and / or R172Q. Particularly preferred are those comprising the M202L or M202T mutations. Additional associated mutations / deletions based on the SP707 backbone are W48, A51, V103, V104, A113, R118, N125, V131, T132, E134, T136, E138, R142, S154, V165, R182, G182, H183, E190, D192, T193, I206, M208, D209, E212, V213, V214, N214, L217, R218, N21 Includes 9, V222, T225, T227, G229, I235, K242, Y243, S244, F245, T246, I250, S255, A256, H286, V291, T316, V317, V318, N417, T418, A419, H420, P421, I428, M429, F440, R443, N444, K445, Q448, S451, A465, N470, S472. (d) a variant described in WO 09 / 149130, preferably SEQ ID NO: 1 or SEQ ID NO: 2 in WO 09 / 149130, which shows at least 90% identity to the wild-type enzyme from Geobacillus Stearophermophilus, or a truncated version thereof. (e) a variant described in WO 10 / 115021, in particular SEQ ID NO: 2 in WO 10 / 115021, which exhibits at least 75%, or at least 85%, or at least 90%, or at least 95% identity with the alpha-amylase from Bacillus sp. TS-23. (f) a variant exhibiting at least 89% identity to SEQ ID NO: 1 in WO 2016 / 091688, in particular comprising a deletion at positions H183+G184 and further comprising one or more mutations at positions 405, 421, 422 and / or 428. (g) A variant described in WO 2014 / 099523, in particular one that exhibits at least 60% amino acid sequence identity with the “PcuAmyl α-amylase” from Paenibacillus curdlanolyticus YK9 (SEQ ID NO: 3 in WO 2014099523). (h) variants described in WO 2014 / 099523, in particular "CspAmy2 amylase" from Cytophaga species (showing at least 60% amino acid sequence identity with SEQ ID NOs: 1 and 6 in WO 2014 / 164777, in particular comprising one or more of the following deletions and / or mutations based on SEQ ID NO: 1 in WO 2014 / 164777: R178 * , G179 * , T38N, N88H, N126Y, T129I, N134M, F153W, L171R, T180D, E187P, I203Y, G476K, G477E, Y303D. (i) A variant exhibiting at least 85% identity to Bacillus subtilis (SEQ ID NO: 1 in WO 2009 / 149271). (j) A variant showing at least 90% identity to the wild-type amylase derived from Bacillus sp. KSM-K38 under accession number AB051102. (k) variants according to WO 2016 / 180748, in particular those which exhibit at least 80% identity with the mature amino acid sequence of AAI10 from Bacillus species according to SEQ ID NO: 7 in WO 2016 / 180748; those which exhibit at least 80% identity with the mature amino acid sequence of amylase from Alicyclobacillus species according to SEQ ID NO: 8 in WO 2016 / 180748, and those which exhibit at least 80% identity with the mature amino acid sequence of SEQ ID NO: 13 in WO 2016 / 180748, in particular those which have the following mutations: * , N54S, V56T, K72R, G109A, F113Q, R116Q, W167F, Q172G, A174S, G184T, N195F, V206L, K391A, P473R, G476K. (l) Variants described in WO 2018 / 060216, in particular variants exhibiting at least 70% identity to the mature amino acid sequence of SEQ ID NO: 4 in WO 2018 / 060216, fusion molecules of Bacillus amyloliquefaciens and Bacillus licheniformis. In particular, those containing one or more substitutions at positions H1, N54, V56, K72, G109, F113, R116, T134, W140, W159, W167, Q169, Q172, L173, A174, R181, G182, D183, G184, W189, E194, N195, V206, G255, N260, F262, A265, W284, F289, S304, G305, W347, K391, Q395, W439, W469, R444, F473, G476, and G477.

[0125] A preferred amylase is a genetically engineered enzyme in which one or more of the amino acids susceptible to bleaching oxidation are replaced by amino acids that are less susceptible to oxidation. In particular, it is preferred that the methionine residue is replaced by any other amino acid. In particular, it is preferred that the methionine that is most susceptible to oxidation is replaced. Preferably, the methionine at position corresponding to 202 in SEQ ID NO: 11 is replaced. Preferably, the methionine at this position is replaced by threonine or leucine, preferably leucine.

[0126] Suitable commercially available alpha-amylases include DURAMYL®, LIQUEZYME®, TERMAMYL®, TERMAMYL ULTRA®, NATALASE®, SUPRAMYL®, STAINZYME®, STAINZYME PLUS®, FUNGAMYL®, ATLANTIC®, ACHIEVE ALPHA®, AMPLIFY® PRIME, INTENSA® and BAN® (Novozymes A / S, Bagsvaerd, Denmark), KEMZYM® AT 9000 (Biozym Biotech Trading GmbH, Wehlistrasse 27b A-1200 Wien Austria), RAPIDASE®, PURASTAR®, ENZYSIZE®, OPTISIZE HT PLUS®, POWERASE®, PREFERENZ S (registered trademark) series (including PREFERENZ S1000 (registered trademark) and PREFERENZ S2000 (registered trademark)), as well as PURASTAR OXAM (registered trademark) (DuPont., Palo Alto, California), and KAM (registered trademark) (Kao, 14-10 Nihonbashi Kayabacho, 1-chome, Chuo-ku Tokyo 103-8210, Japan).

[0127] Preferably, the composition contains at least 0.01 mg, preferably about 0.05 to about 10, more preferably about 0.1 to about 6, especially about 0.2 to about 5 mg of active amylase per gram of composition.

[0128] Peroxidases / Oxidases: Suitable peroxidases / oxidases include those of plant, bacterial, or fungal origin. They include chemically modified or genetically engineered variants of proteins. Examples of useful peroxidases include peroxidases from the genus Coprinus, such as peroxidases from C. cinereus and variants thereof, as described in WO 93 / 24618, WO 95 / 10602, and WO 98 / 15257.

[0129] Commercially available peroxidases include GUARDZYME® (Novozymes A / S).

[0130] Pectate lyases: Suitable pectate lyases include those sold under the trade names Pectawash®, Pectaway®, X-Pect®, (all from Novozymes A / S, Bagsvaerd, Denmark) and Preferenz® F1000 (DuPont Industrial Biosciences).

[0131] Mannanase: The composition preferably includes one or more additional mannanase enzymes. As used herein, the term "mannanase" or "galactomannanase" refers to a mannanase enzyme defined according to what is known in the art as mannan endo-1,4-beta-mannosidase, with the alternative names beta-mannanase and endo-1,4-mannanase, that catalyzes the hydrolysis of 1,4-beta-D-mannosidic linkages in mannans, galactomannans, glucomannans, and galactoglucomannans. Mannanase is classified as EC 3.2.1.78 according to enzyme nomenclature and belongs to glycosyl hydrolase families 5, 26, and 113. Many suitable mannanases belong to glycosyl hydrolase family 5. Commercially available mannanases include all those sold under the trade name Mannaway® (Novozymes A / S), such as Mannaway® 200L and Mannaway Evity 4.0T. Other commercially available mannanases include Effectenz® M1000, Mannastar® 375, Preferenz M100, and Purabrite® (all from DuPont Industrial Biosciences) and Biotouch M7 (AB enzyme). Other suitable mannanases belong to glycosyl hydrolase family 26, such as those described in WO 2018 / 191135, WO 2015 / 040159, WO 2017 / 021515, WO 2017 / 021516, WO 2017 / 021517, and WO 2019 / 081515. Suitable mixtures of mannanases include the combination of glycosyl hydrolase family 5 mannanase and glycosyl hydrolase family 26 mannanase described in WO 2019 / 081515.

[0132] Xanthan gum degrading enzyme: The composition may contain one or more xanthan gum degrading enzymes. Enzymes suitable for degrading xanthan gum-based stains include xanthan endoglucanase, optionally in combination with xanthan lyase. As used herein, the term "xanthan endoglucanase" refers to an enzyme that exhibits endo-β-1,4-glucanase activity that can catalyze the hydrolysis of the 1,4-linked β-D-glucose polymer backbone of xanthan gum, optionally in combination with a suitable xanthan lyase enzyme. Suitable xanthan endoglucanases are described in WO 2013 / 167581, WO 2015 / 181299, WO 2015 / 181292, WO 2017 / 046232, WO 2017 / 046260, WO 2018 / 37062, WO 2018 / 37065, WO 2019 / 038059, and WO 2019 / 162000. As used herein, the term "xanthan lyase" refers to an enzyme that cleaves the β-D-mannosyl-β-D-1,4-glucuronosyl bond of xanthan gum. Such enzymes belong to EC 4.2.2.12. Suitable xanthan lyases are described in WO 2015 / 001017, WO 2018 / 037061, WO 2018 / 37064, WO 2019 / 038060, WO 2019 / 162000, and WO 2019 / 038057.

[0133] Nuclease: Preferably, the composition comprises a nuclease, such as RNase or DNase, or a mixture thereof. A nuclease enzyme is an enzyme capable of cleaving phosphodiester bonds between nucleotide subunits of nucleic acids. The nuclease enzyme herein is preferably a deoxyribonuclease or ribonuclease enzyme or a functional fragment thereof. By functional fragment or portion is meant the part of the nuclease enzyme that catalyzes the cleavage of phosphodiester bonds in the DNA backbone, and thus is the region of said nuclease protein that retains catalytic activity. It therefore includes truncated but functional versions of the enzyme and / or variants and / or derivatives and / or homologues whose function is maintained.

[0134] Preferably, the nuclease enzyme is a deoxyribonuclease preferably selected from any of the following classes: EC 3.1.21.x (wherein x=1, 2, 3, 4, 5, 6, 7, 8 or 9), EC 3.1.22.y (wherein y=1, 2, 4 or 5), EC 3.1.30.z (wherein z=1 or 2), EC 3.1.31.1, and mixtures thereof.

[0135] DNase: Suitable DNases include wild-type and mutant DNases defined by SEQ ID NOs: 1, 2, 3, 4, 5, 6, 7, 8, and 9 in WO 2017 / 162836 (Novozymes), which is incorporated herein by reference, and mutants of Bacillus cibi DNase, including those described in WO 2018 / 011277 (Novozymes). Preferred DNases are as claimed in co-pending European Patent Application No. 18202967.

[0136] RNases: Suitable RNases include wild-type and mutant versions of DNases defined by SEQ ID NOs: 3, 6, 9, 12, 15, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 72, and 73 in WO 2018 / 178061 (Novozymes), which are incorporated herein by reference.

[0137] Hexosaminidase: The composition may contain one or more hexosaminidases. The term "hexosaminidase" includes "dispersant" and the abbreviation "Dsp", that is, a polypeptide having hexosaminidase activity (EC 3.2.1) that catalyzes the hydrolysis of β-1,6-glycosidic bonds of N-acetyl-glucosamine polymers found in soils of microbial origin. The term "hexosaminidase" includes polypeptides having N-acetylglucosaminidase activity and β-N-acetylglucosaminidase activity. Hexosaminidase activity may be determined according to Assay II described in WO 2018 / 184873. Suitable hexosaminidases include those described in WO 2017 / 186936, WO 2017 / 186937, WO 2017 / 186943, WO 2017 / 207770, WO 2018 / 184873, WO 2019 / 086520, WO 2019 / 086528, WO 2019 / 086530, WO 2019 / 086532, WO 2019 / 086521, WO 2019 and those disclosed in WO 2020 / 086526, WO 2020 / 002604, WO 2020 / 002608, WO 2020 / 007863, WO 2020 / 007875, WO 2020 / 008024, WO 2020 / 070063, WO 2020 / 070249, WO 2020 / 088957, WO 2020 / 088958, and WO 2020 / 207944. Variants of Teribacillus saccharophilus hexosaminidase as defined by SEQ ID NO: 1 of WO 2020 / 207944 may be preferred, particularly variants with improved thermostability as disclosed therein.

[0138] Galactanase: Preferably, the composition comprises a galactanase, i.e. an extracellular polymer degrading enzyme comprising an endo-beta-1,6-galactanase enzyme. The term "endo-beta-1,6-galactanase" or "polypeptide having endo-beta-1,6-galactanase activity" refers to an endo-beta-1,6-galactanase activity (EC 3.2.1.164) from glycoside hydrolase family 30 that catalyzes the hydrolytic cleavage of 1,6-3-D-galactooligosaccharides with a degree of polymerization (DP) higher than 3 and their acidic derivatives bearing a 4-O-methyl glucosyluronate or glucosyluronate group at the non-reducing end. For the purposes of this disclosure, endo-beta-1,6-galactanase activity is determined in Assay I according to the procedure described in WO 2015 / 185689. Suitable examples from classification EC 3.2.1.164 are described in WO 2015 / 185689, e.g. mature polypeptide SEQ ID NO:2.

[0139] The additional enzymes may be included in the detergent composition by adding a separate enzyme additive containing the additional enzymes or a mixed enzyme additive containing two or some or all of the additional enzymes. Such enzyme additives may be in the form of granules, liquids, or slurries, and preferably further comprise an enzyme stabilizer.

[0140] Preferably, each additional enzyme is present in at least about 0.0001 to about 0.1% weight percent of pure active enzyme protein based on the weight of the composition, for example, in an amount of about 0.0001% to about 0.01%, about 0.001% to about 0.01%, or about 0.001% to about 0.01% pure active enzyme protein.

[0141] Other enzymes The enzyme system may include other enzymes. Suitable enzymes provide cleaning performance and / or fabric care benefits. Examples of other suitable enzymes include, but are not limited to, hemicellulase, peroxidase, protease, cellulase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, licheninase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanases, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, and known amylases, or combinations thereof. A preferred enzyme system further includes a cocktail of conventional detergent enzymes, such as proteases, lipases, cutinases, and / or cellulases, in combination with amylase. Detergent enzymes are described in more detail in U.S. Pat. No. 6,579,839.

[0142] Enzyme-Containing Compositions: The enzyme-containing compositions described herein may optionally comprise from about 0.001% to about 10%, in some examples from about 0.005% to about 8%, and in other examples from about 0.01% to about 6% by weight of the composition of an enzyme stabilization system. The enzyme stabilization system may be any stabilization system compatible with the detersive enzyme. In the case of aqueous detergent compositions containing proteases, reversible protease inhibitors such as boron compounds, including borate, 4-formylphenylboronic acid, phenylboronic acid, and derivatives thereof, or compounds such as calcium formate, sodium formate, and 1,2-propanediol may be added to further improve stability.

[0143] Builder: The compositions of the present invention may optionally include a builder. Built compositions typically include at least about 1% builder by weight based on the total weight of the composition. Liquid compositions may include up to about 10% builder by weight of the total composition, and in some examples up to 8% builder. Granular compositions may include up to about 30% builder by weight of the composition, and in some examples up to 5% builder by weight.

[0144] Builders selected from aluminosilicates (e.g. zeolite builders such as zeolite A, zeolite P, and zeolite MAP) and silicates assist in controlling the mineral hardness of the wash water, especially calcium and / or magnesium, or in removing particulate soils from surfaces. Suitable builders may be selected from the group consisting of phosphates such as polyphosphates (e.g. sodium tri-polyphosphate), especially the sodium salts thereof; carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sesquicarbonates; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types, and phytic acid. These may be complemented, for example, by borates for pH buffering purposes, or by sulfates, especially sodium sulfate, and any other fillers or carriers that may be important in the engineering of a stable surfactant and / or builder-containing composition. Additional suitable builders may be selected from citric acid, lactic acid, fatty acids, polycarboxylate builders, such as copolymers of acrylic acid, copolymers of acrylic acid and maleic acid, and copolymers of acrylic acid and / or maleic acid and other suitable ethylenic monomers with various types of additional functional groups. Also suitable for use as builders herein are synthetic crystalline ion exchange materials or hydrates thereof having a chain structure and a composition represented by the following general anhydrous form x(M2O)·ySiO2·zM'O, where M is Na and / or K, M' is Ca and / or Mg, y / x is 0.5-2.0, and z / x is 0.005-1.0.

[0145] Alternatively, the composition may be substantially free of builders.

[0146] Structurants / Thickeners: Suitable structurants / thickeners include: i. Dibenzylidene polyol acetal derivatives ii. Bacterial cellulose iii. Coated bacterial cellulose iv. Cellulose fibers derived from non-bacterial cellulose v. Non-polymeric crystalline hydroxy-functional materials vi. Polymeric structuring agents vii. Diamide gelling agent viii. Any combination of the above.

[0147] Polymeric dispersants: The composition may include one or more polymeric dispersants. Examples are carboxymethylcellulose, poly(vinyl-pyrrolidone), poly(ethylene glycol), poly(vinyl alcohol), poly(vinylpyridine-N-oxide), poly(vinylimidazole), polycarboxylates such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0148] The composition has the following general structure: bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H 2x -N + The composition may include one or more amphiphilic cleaning polymers, such as a compound having the formula -(CH3)-bis((C2H5O)(C2H4O)n), where n=20-30 and x=3-8, or a sulfated or sulfonated variant thereof.

[0149] The composition may include amphiphilic alkoxylated grease cleaning polymers that have balanced hydrophilic and hydrophobic properties to remove grease particles from fabrics and surfaces. Specific embodiments of the amphiphilic alkoxylated grease cleaning polymers of the present invention include a core structure and a plurality of alkoxylate groups attached to the core structure. These may include alkoxylated polyalkyleneimines, for example, having an inner polyethylene oxide block and an outer polypropylene oxide block.

[0150] Alkoxylated polyamines can be used for grease and particulate removal. Such compounds can include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated versions thereof. Polypropoxylated derivatives can also be included. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees. A useful example is the 600 g / mole polyethyleneimine core, which is ethoxylated to 20 EO groups per NH, available from BASF.

[0151] The composition may comprise a hydrophilic backbone comprising monomers such as, for example, unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyalcohols such as glycerol, and mixtures thereof, and one or more C4-C 25 Mention may be made of random graft polymers containing hydrophobic side chains such as alkyl groups, polypropylene, polybutylene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acid, and mixtures thereof. Specific examples of such graft polymers based on polyalkylene oxides and vinyl esters, especially vinyl acetate. These polymers are typically prepared by polymerizing vinyl esters in the presence of polyalkylene oxides, with the initiator being dibenzoyl peroxide, dilauroyl peroxide, or diacetyl peroxide.

[0152] The composition may contain blocks of ethylene oxide, propylene oxide. Examples of such block polymers include ethylene oxide-propylene oxide-ethylene oxide (EO / PO / EO) triblock copolymers, where the copolymer contains a first EO block, a second EO block, and a PO block, and the first EO block and the second EO block are connected to the PO block. The blocks of ethylene oxide, propylene oxide, butylene oxide may also be arranged in other ways, such as (EO / PO) diblock copolymers, (PO / EO / PO) triblock copolymers, etc. The block polymer may also contain an additional butylene oxide (BO) block.

[0153] Carboxylate polymers - The compositions of the present invention may also include one or more carboxylate polymers, such as maleate / acrylate random copolymers or polyacrylate homopolymers. In one embodiment, the carboxylate polymer is a polyacrylate homopolymer having a molecular weight of 4,000 Da to 9,000 Da or 6,000 Da to 9,000 Da.

[0154] Soil Release Polymer: The compositions described herein may comprise from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, and in some embodiments, from about 0.2% to about 3.0%, by weight of the composition, of a soil release polymer (also known as a polymeric soil release agent or "SRA").

[0155] Soil release polymers typically have a hydrophilic segment for hydrophilizing the surface of hydrophobic fibers such as polyester and nylon, and a hydrophobic segment that deposits on the hydrophobic fibers and remains attached there until completion of washing and rinsing cycles, thereby serving as an anchor for the hydrophilic segment. This can make the soil that is lifted after treatment with the soil release agent more easily washable in the subsequent washing procedure. It is also believed that promoting soil release helps improve or maintain the wicking properties of fabrics.

[0156] The structure and charge distribution of the soil release polymer may be tailored for application to different types of fibers or fabrics, and for formulation in different detergent or detergent additive products. The soil release polymer may be linear, branched, or star shaped.

[0157] The soil release polymer may also comprise various charged (e.g., anionic or cationic) and / or uncharged (e.g., nonionic) monomer units. Typically, when the SRP is used in combination with a cationic fabric conditioning active, such as a quaternary ammonium ester compound, a nonionic SRP may be particularly preferred to avoid potentially negative interactions between the SRP and the cationic active.

[0158] The soil release polymers may contain end-capping moieties that are particularly effective in controlling the molecular weight of the polymer or altering the physical or surface active properties of the polymer.

[0159] One preferred class of suitable soil release polymers includes terephthalate-derived polyester polymers comprising structural units (I) and / or (II): (I)-[(OCHR 1 -CHR 2 ) a -O-OC-Ar-CO-] d (II)-[(OCHR 3 -CHR 4 ) b -O-OC-sAr-CO-] e During the ceremony, a and b are 1 to 200; d and e are 1 to 50; Ar is 1,4-substituted phenylene; sAr is a 1,3-substituted phenylene substituted at the 5-position with SO3M; M is Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetra-alkylammonium (alkyl groups are C1-C 18Alkyl or C2-C 10 hydroxyalkyl), or mixtures thereof; R 1 , R 2 , R 3 , R 4 are independently H or C1-C 18 selected from n-alkyl or iso-alkyl, Optionally, the polymer further comprises one or more end groups (III) derived from a polyalkylene glycol monoalkyl ether, preferably selected from structure (IV-a):

[0160] [ka] During the ceremony, R7 is a linear or branched C 1~30 Alkyl, C2-C 30 alkenyl, or a cycloalkyl group having 5 to 9 carbon atoms, or C8 to C 30 Aryl group or C6-C 30 Arylalkyl groups, preferably C 1~4 alkyl, more preferably methyl; c, d, and e are numbers independently selected from 0 to 200 based on a molar average, and the sum of c+d+e is 2 to 500; The [C2H4-O], [C3H6-O] and [C4H8-O] groups of the terminal group (IV-a) may be arranged blockwise, alternatingly, periodically and / or statistically, preferably blockwise and / or statistically, and any of the [C2H4-O], [C3H6-O] and [C4H8-O] groups of the terminal group (IV-a) may be linked to -R7 and / or -O.

[0161] Optionally, the polymer further comprises one or more anionic terminal units (IV) and / or (V) as described in EP 3222647. M is a counterion selected from Na, Li, K, Mg / 2, Ca / 2, Al / 3, ammonium, mono-, di-, tri-, or tetraalkylammonium, the alkyl groups being C1-C 18Alkyl or C2-C 10 hydroxyalkyl, or mixtures thereof.

[0162] [ka]

[0163] Optionally, the polymer may contain crosslinked multifunctional structural units having at least three functional groups capable of esterification reactions, such as acid, alcohol, ester, anhydride, or epoxy groups.

[0164] Optionally, the polymer may contain other di- or polycarboxylic acids, such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,6,-dicarboxylic acid, tetrahydrophthalic acid, trimellitic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decane-1,10-dicarboxylic acid, fumaric acid, succinic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid, or salts thereof or (di)alkyl esters thereof, preferably (C1-C4)-(di)alkyl esters thereof, more preferably (di)methyl esters thereof, or mixtures thereof, or their salts or (di)alkyl esters thereof can be used in the polyesters of the present invention.

[0165] Preferably, suitable terephthalate-derived soil release polymers are non-ionic and do not include structure (II) above. Further specific preferred non-ionic terephthalate-derived soil release polymers have a structure according to the following formula:

[0166] [ka] During the ceremony, R5 and R6 are independently selected from H or CH3. More preferably, one of R5 and R6 is H and the other is CH3. c and d are numbers independently selected from 0 to 200 based on the molar average, and the sum of c+d is 2 to 400; More preferably, d is 0 to 50 and c is 1 to 200. More preferably, d is 1 to 10 and c is 5 to 150. R7 is C 1~4 is alkyl, more preferably methyl; n is 1 to 50 on a molar average basis.

[0167] In one example of the most preferred terephthalate-derived soil release polymer, one of R5 and R6 is H and the other is CH3, d is 0, c is 5 to 100, and R7 is methyl.

[0168] Suitable terephthalate-derived soil release polymers can also be described as sulfonated and non-sulfonated PET / POET (polyethylene terephthalate / polyoxyethylene terephthalate) polymers, both end-capped and non-end-capped. Examples of suitable soil release polymers include TexCare® polymers supplied by Clariant, including TexCare® SRA-100, SRA-300, SRN-100, SRN-170, SRN-240, SRN-260, SRN-300, SRN UL50, and SRN-325.

[0169] Other suitable terephthalate-derived soil release polymers are described in WO 2014 / 019903, WO 2014 / 019658, and WO 2014 / 019659.

[0170] Another class of soil release polymers includes modified celluloses.Suitable modified celluloses can include non-ionic modified cellulose derivatives such as cellulose alkyl ethers and cellulose hydroxyalkyl ethers.Examples of such cellulose alkyl ethers and cellulose hydroxyalkyl ethers include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, and hydroxybutyl methyl cellulose.In some embodiments, the modified cellulose can include C4 or higher hydrocarbons, with the preferred length of the alkyl group being C4, C6, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C210, C220, C23, C24, C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46, ​​C47, C48, C49, C50, C51, C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70, C71, C72, C73, C74, C75, C75, C76, C77, C78, ​​C79, C81, C82, C83, C84, C85, C86, C87, C88, C89, C91, C92, C93, C94, C95, C96, C97, C98, C99, C99, C100 10 , C 12 , C 14 , C 16 , C 18 Examples of suitable modified celluloses are described in WO 2019 / 111948 and WO 2019 / 111949. In some embodiments, the modified cellulose may include an additional cationic modification, examples of suitable modified celluloses with additional cationic modifications are described in WO 2019 / 111946 and WO 2019 / 111947.

[0171] Another example of commercially available soil release polymers is the REPEEL O-TEX® line of polymers supplied by Rhodia, such as REPEEL O-TEX® SF, SF-2, and SRP6. Other suitable soil release polymers are the Marloquest® polymers supplied by Sasol, such as Marloquest® SL, HSCB, L235M, B, G82, etc. Further suitable soil release polymers of different types include the commercially available materials ZELCON 5126 (DuPont) and MILEASE T (ICI), Sorez 100 (ISP).

[0172] Cellulosic polymer: The compositions herein may comprise from about 0.1% to about 10%, typically from about 0.5% to about 7%, and in some embodiments, from about 3% to about 5% of a cellulosic polymer, by weight of the composition.

[0173] Suitable cellulosic polymers include alkyl cellulose, alkyl alkoxy alkyl cellulose, carboxy alkyl cellulose, and alkyl carboxy alkyl cellulose. In some embodiments, the cellulosic polymer is selected from carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, and mixtures thereof. In some embodiments, the cellulosic polymer is carboxymethyl cellulose having a degree of carboxymethyl substitution of about 0.5 to about 0.9 and a molecular weight of about 100,000 Da to about 300,000 Da.

[0174] Carboxymethylcellulose polymers include hydrophobically modified carboxymethylcelluloses such as Finnfix® GDA (sold by CP Kelko), an alkyl ketene dimer derivative of carboxymethylcellulose sold, for example, under the trade name Finnfix® SH1 (CP Kelko), or a block-based carboxymethylcellulose sold under the trade name Finnfix® V (sold by CP Kelko).

[0175] Additional amines: Various amines may be used in the compositions described herein to enhance the removal of grease and particles from soiled materials. The compositions described herein may include from about 0.1% to about 10%, in some examples from about 0.1% to about 4%, and in other examples from about 0.1% to about 2% by weight of the composition of additional amines. Non-limiting examples of additional amines may include, but are not limited to, polyamines, oligoamines, triamines, diamines, pentamines, tetraamines, or combinations thereof. Specific examples of suitable additional amines include tetraethylenepentamine, triethylenetetraamine, diethylenetriamine, or mixtures thereof.

[0176] For example, alkoxylated polyamines can be used for grease and particulate removal. Such compounds can include, but are not limited to, ethoxylated polyethyleneimine, ethoxylated hexamethylenediamine, and sulfated versions thereof. Polypropoxylated derivatives can also be included. A wide variety of amines and polyalkyleneimines can be alkoxylated to various degrees. A useful example is 600 g / mole polyethyleneimine core, ethoxylated to 20 EO groups per NH, available from BASF. The compositions described herein may comprise from about 0.1% to about 10%, in some examples from about 0.1% to about 8%, and in other examples from about 0.1% to about 6% by weight of the composition of the alkoxylated polyamine.

[0177] Alkoxylated polycarboxylates may also be used in the compositions herein to remove grease. Chemically, these materials include polyacrylates with one ethoxy side chain for every 7-8 acrylate units. The side chains have the formula -(CH2CH2O) m (CH2) nCH3, where m is 2-3 and n is 6-12. The side chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure. The molecular weight can vary, but may be in the range of about 2000 to about 50,000. The compositions described herein may comprise from about 0.1% to about 10%, in some examples from about 0.25% to about 5%, and in other examples from about 0.3% to about 2% by weight of the composition of the alkoxylated polycarboxylate.

[0178] Bleaching Compounds, Bleaching Agents, Bleach Activators, and Bleaching Catalysts: The compositions described herein may contain a bleaching agent, or a bleaching composition containing a bleaching agent and one or more bleach activators. The bleaching agent may be present in a concentration of about 1% to about 30% by weight, and in some examples, about 5% to about 20% by weight, based on the total weight of the composition. If present, the amount of bleach activator may be about 0.1% to about 60% by weight, and in some examples, about 0.5% to about 40% by weight of the bleaching composition including the bleaching agent plus the bleach activator.

[0179] Examples of bleaching agents include oxygen bleaches, perborate bleaches, percarboxylic acid bleaches and their salts, peroxygen bleaches, persulfate bleaches, percarbonate bleaches, and mixtures thereof.

[0180] In some examples, the composition may also include a transition metal bleach catalyst.

[0181] Bleaching agents other than oxygen bleaches are also known in the art and can be used in the compositions. They include, for example, photoactivated bleaches, or preformed organic peracids such as peroxycarboxylic acids or their salts, or peroxysulfonic acids or their salts. A suitable organic peracid is phthaloyl imido peroxycaproic acid. If used, the compositions described herein may typically contain such bleaches, and in some examples, zinc phthalocyanine sulfonate, at about 0.025% to about 1.25% by weight of the composition.

[0182] Brightening agents: Fluorescent or other brightening or whitening agents may be incorporated into the compositions described herein at a concentration of about 0.01% to about 1.2% by weight of the composition. Commercially available optical brightening agents that may be used herein can be divided into subgroups that include, but are not necessarily limited to, derivatives of stilbenes, pyrazolines, coumarins, benzoxazoles, carboxylic acids, methinecyanines, dibenzothiphene-5,5-dioxides, azoles, 5- and 6-membered heterocycles, and various other agents.

[0183] In some examples, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (brightener 15, commercially available under the trade name Tinopal AMS-GX by Ciba Geigy Corporation), disodium 4,4'-bis{[4-anilino-6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the trade name Tinopal UNPA-GX by Ciba-Geigy Corporation), disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation), or disodium 4,4'-bis{[4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate (commercially available under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation). More preferably, the optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate.

[0184] The whitening agent may be added in particulate form or as a premix with a suitable solvent, such as a non-ionic surfactant, monoethanolamine, propanediol.

[0185] Fabric hueing agents: The compositions may include fabric hueing agents (sometimes called shading agents, bluing agents, or whitening agents). Typically, the hueing agents impart a blue or blue-purple hue to the fabric. The hueing agents may be used either alone or in combination to create a particular hue shade and / or tint different types of fabric. This may be achieved, for example, by mixing red and green-blue dyes to produce a blue or purple shade. The hueing agent may be selected from any known chemical class of dyes, including, but not limited to, acridines, anthraquinones (including polycyclic quinones), azines, azos including premetallized azos (e.g., monoazos, diazos, trisazos, tetrakisazos, polyazos), benzodifuranes and benzodifuranones, carotenoids, coumarins, cyanines, diazahemicyanines, diphenylmethanes, formazans, hemicyanines, indigoids, methanes, naphthalimides, naphthoquinones, nitro and nitroso, oxazines, phthalocyanines, pyrazoles, stilbenes, styryls, triarylmethanes, triphenylmethanes, xanthenes, and mixtures thereof.

[0186] Dye transfer inhibitors: The composition may also include one or more substances effective in preventing the transfer of dye from one fabric to another during the washing process. Generally, such dye transfer inhibitors can include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. When used, these agents may be used at a concentration of about 0.0001% to about 10% by weight of the composition, in some examples, about 0.01% to about 5% by weight of the composition, and in other examples, about 0.05% to about 2% by weight of the composition.

[0187] Chelating agents: The compositions described herein may also contain one or more metal ion chelating agents. Suitable molecules include copper, iron, and / or manganese chelating agents and mixtures thereof. Such chelating agents may be selected from the group consisting of phosphonates, aminocarboxylates, aminophosphonates, succinates, polyfunctionally substituted aromatic chelating agents, 2-pyridinol-N-oxide compounds, hydroxamic acids, carboxymethyl inulin, and mixtures thereof. The chelating agents may be present in the form of an acid or a salt, including alkali metal salts, ammonium salts, and substituted ammonium salts thereof, and mixtures thereof.

[0188] The chelating agent may be present in the compositions disclosed herein from about 0.005% to about 15%, from about 0.01% to about 5%, from about 0.1% to about 3.0%, or from about 0.2% to about 0.7%, or from about 0.3% to about 0.6% by weight of the composition.

[0189] Aminocarboxylates useful as chelating agents include ethylenediaminetetracetate (EDTA), N-(hydroxyethyl)ethylenediaminetriacetate (HEDTA), nitrilotriacetate (NTA), ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriamine-pentaacetate (DTPA), methylglycinediacetic acid (MGDA), glutamic acid diacetate (GLDA), ethanol diglycine, triethylenetetraaminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (ETA), and the like. acid, EDTP), and derivatives thereof.

[0190] Encapsulating agent: The composition may comprise an encapsulating agent. In some embodiments, the encapsulating agent comprises a core, a shell having an inner surface and an outer surface, the shell encapsulating the core.

[0191] In certain embodiments, the encapsulant comprises a core and a shell, the core comprises a material selected from perfumes, brighteners, dyes, insect repellents, silicones, waxes, fragrances, vitamins, fabric softeners, skin care agents, such as paraffin, enzymes, antimicrobials, bleaches, sensates, or mixtures thereof, and the shell comprises a material selected from polyethylene, polyamides, polyvinyl alcohols, optionally containing other co-monomers, polystyrene, polyisoprene, polycarbonates, polyesters, polyacrylates, polyolefins, polysaccharides, such as alginates and / or chitosan, gelatin, shellac, epoxy resins, vinyl polymers, water insoluble inorganic materials, silicones, amino resins, or mixtures thereof. In some embodiments where the shell comprises an aminoplast, the aminoplast comprises a polyurea, polyurethane, and / or polyurea urethane. The polyurea may comprise polyoxymethylene urea and / or melamine formaldehyde.

[0192] The fabric and home care products are typically suitable for (a) finished textile care, finished textile laundering, finished textile sanitization, finished textile disinfection, detergents, stain removers, softeners, fabric enhancers, stain removal or finished textile treatment, pre-wash and post-wash treatment, washing machine cleaning and maintenance (finished textile is intended to include clothing and fabric articles); (b) care of dishes, glasses, china, pots, pans, utensils, cutlery, and the like, in automatic dishwashers, such as detergents, pre- and post-treatment and equipment cleaning and maintenance products for dishwashers, both the water used and their contents; or (c) hand dishwashing detergents.

[0193] Fabric and home care products typically include additional fabric and home care ingredients such as those described in more detail above.

[0194] Liquid laundry detergent compositions. The fabric and home care products may be laundry detergent compositions, such as liquid laundry detergent compositions. Suitable liquid laundry detergent compositions include non-soap surfactants, which may include anionic non-soap surfactants and non-ionic surfactants. The laundry detergent composition may include 10% to 60%, or 20% to 55% non-soap surfactants, by weight of the laundry detergent composition. The non-soap anionic surfactants are 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1. Suitable non-soap anionic surfactants include linear alkyl benzene sulfonates, alkyl sulfates, or mixtures thereof. The linear alkyl benzene sulfonate to alkyl sulfate weight ratio may be 1:2 to 9:1, 1:1 to 7:1, or 1:1 to 5:1, or 1:1 to 4:1. Suitable linear alkyl benzene sulfonates include C 10 ~C 16 Alkylbenzene sulfonic acid, or C 11 ~C 14 The alkyl benzene sulfonic acid. Suitable alkyl sulfate anionic surfactants include alkoxylated alkyl sulfates, non-alkoxylated alkyl sulfates, and mixtures thereof. Preferably, the HLAS surfactant has a C of greater than 50%. 12 , preferably more than 60%, preferably more than 70% C 12 , more preferably more than 75% C 12Suitable alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Suitable alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants having a molar average degree of ethoxylation of 1 to 5, 1 to 3, or 2 to 3. The alkyl alkoxylated sulfates can have a broad or peaked alkoxy distribution. The alkyl moiety of the AES can contain, on average, 13.7 to about 16, or 13.9 to 14.6 carbon atoms. At least about 50%, or at least about 60%, of the AES molecules can contain alkyl moieties having 14 or more carbon atoms, preferably 14 to 18, or 14 to 17, or 14 to 16, or 14 to 15 carbon atoms. The alkyl sulfate anionic surfactants may include non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, and the molar average degree of ethoxylation of the alkyl sulfate anionic surfactants is 1 to 5, 1 to 3, or 2 to 3. The alkyl fraction of the alkyl sulfate anionic surfactants may be derived from fatty alcohols, oxo-synthetic alcohols, Guerbet alcohols, or mixtures thereof. Preferred alkyl sulfates include, optionally, 2-alkyl branched primary alcohol sulfates, especially 2-branched C 12~15 Primary alcohol sulfates, linear primary alcohol sulfates, especially linear C 12~14 and ethoxylated alcohol sulfates, including primary alcohol sulfates, and mixtures thereof.The laundry detergent composition may comprise from 10% to 50%, or from 15% to 45%, or from 20% to 40%, or from 30% to 40% of a non-soap anionic surfactant, by weight of the laundry detergent composition.

[0195] Suitable nonionic surfactants may be selected from broad or narrow range alkoxylated alcohols, oxo synthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. The laundry detergent composition may comprise from 0.01% to 10%, from 0.01% to 8%, from 0.1% to 6%, or from 0.15% to 5% of a nonionic surfactant by weight of the liquid laundry detergent composition.

[0196] The laundry detergent composition comprises from 1.5% to 20%, or from 2% to 15%, or from 3% to 10%, or from 4% to 8%, by weight of the laundry detergent composition, of a soap, such as a fatty acid salt. Such soaps may be amine neutralized, for example, using an alkanolamine, such as monoethanolamine.

[0197] The laundry detergent composition may comprise adjunct ingredients selected from the group including builders including citrates, enzymes, bleaches, bleach catalysts, dyes, hueing dyes, leuco dyes, brighteners, cleaning polymers including alkoxylated polyamines and polyethyleneimines, amphiphilic copolymers, soil release polymers, surfactants, solvents, dye transfer inhibitors, chelating agents, diamines, perfumes, encapsulated perfumes, polycarboxylates, structurants, pH adjusters, antioxidants, antibacterial agents, antimicrobial agents, preservatives, and mixtures thereof.

[0198] The laundry detergent composition may have a pH of from 2 to 11, or from 6.5 to 8.9, or from 7 to 8, the pH of the laundry detergent composition being measured at a 10% product concentration in demineralized water at 20°C.

[0199] The liquid laundry detergent compositions may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0200] In liquid laundry detergent compositions, the composition may comprise from 5% to 99%, or from 15% to 90%, or from 25% to 80% water by weight of the liquid detergent composition.

[0201] The detergent composition according to the present invention may be a liquid laundry detergent composition. The following is an exemplary liquid laundry detergent formulation. Preferably, the liquid laundry detergent composition comprises 0.1% to 4.0%, preferably 0.5% to 3%, more preferably 1% to 2.5% of sulfated esteramine by weight of the detergent composition according to the present invention.

[0202] [Table 1] Explanation of superscript numbers: 1. C12-15 EO2.5S alkyl ethoxy sulfate, in which the alkyl portion of AES contains from about 13.9 to about 14.6 carbon atoms. 2PE-20 available from BASF 3 The nuclease enzyme is as claimed in co-pending European patent application 19219568.3 4 Antioxidant 1 is 3,5-bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid, methyl ester [6386-38-5] 5 Antioxidant 2 is Tinogard TS, available from BASF 6 The sanitizer is Tinosan HP100, available from BASF. 7 Defoamer blend supplied by Dow Corning, 80-92% ethylmethyl, methyl(2-phenylpropyl) siloxane, 5-14% MQ resin in octyl stearate, 3-7% modified silica. 8 The optical brightener is disodium 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt.

[0203] Water-soluble unit dose article The fabric and home care product may be a water-soluble unit dose article. The water-soluble unit dose article comprises at least one water-soluble film oriented to create at least one unit dose inner compartment, and at least one unit dose inner compartment comprises a detergent composition. The water-soluble film preferably comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer, such as a blend of polyvinyl alcohol homopolymer and / or polyvinyl alcohol copolymer, such as a copolymer selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, especially carboxylated anionic polyvinyl alcohol copolymers, such as a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer. In some embodiments, the water-soluble film may be one supplied by Monosol under product references M8630, M8900, M8779, M8310. The detergent product comprises a detergent composition, more preferably a laundry detergent composition. Preferably, the laundry detergent composition enclosed in the water-soluble unit dose article comprises 0.1% to 8%, preferably 0.5% to 7%, more preferably 1.0% to 6.0% by weight of the detergent composition of the present invention of sulfated esteramine. Preferably, the soluble unit dose laundry detergent composition comprises a non-soap surfactant, the non-soap surfactant comprising an anionic non-soap surfactant and a non-ionic surfactant. More preferably, the laundry detergent composition comprises 10% to 60%, or 20% to 55% by weight of the laundry detergent composition of non-soap surfactant. The weight ratio of non-soap anionic surfactant to non-ionic surfactant is preferably 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1. The non-soap anionic surfactant preferably comprises linear alkyl benzene sulfonate, alkyl sulfate, or mixtures thereof. The weight ratio of linear alkylbenzene sulfonate to alkyl sulfate is preferably 1:2 to 9:1, 1:1 to 7:1, 1:1 to 5:1, or 1:1 to 4:1. Exemplary linear alkylbenzene sulfonates include C 10 ~C 16 Alkylbenzene sulfonic acid or C11 ~C 14It is an alkylbenzene sulfonic acid. "Linear" as used herein means that the alkyl group is linear. Exemplary alkyl sulfate anionic surfactants may include alkoxylated alkyl sulfates, or non-alkoxylated alkyl sulfates, or mixtures thereof. Exemplary alkoxylated alkyl sulfate anionic surfactants include ethoxylated alkyl sulfate anionic surfactants. Exemplary alkyl sulfate anionic surfactants may include ethoxylated alkyl sulfate anionic surfactants having a molar average degree of ethoxylation of 1-5, 1-3, or 2-3. Exemplary alkyl sulfate anionic surfactants may include non-ethoxylated alkyl sulfates and ethoxylated alkyl sulfates, where the molar average degree of ethoxylation of the alkyl sulfate anionic surfactant is 1-5, 1-3, or 2-3. Exemplary alkyl fractions of the alkyl sulfate anionic surfactant are derived from fatty alcohols, oxo-synthetic alcohols, Guerbet alcohols, or mixtures thereof. Preferably, the laundry detergent composition comprises 10% to 50%, 15% to 45%, or 20% to 40%, or 30% to 40% of the non-soap anionic surfactant by weight of the laundry detergent composition. In some embodiments, the nonionic surfactant is selected from alcohol alkoxylates, oxo-synthetic alcohol alkoxylates, Guerbet alcohol alkoxylates, alkylphenol alcohol alkoxylates, or mixtures thereof. Preferably, the laundry detergent composition comprises 0.01% to 10%, 0.01% to 8%, or 0.1% to 6%, or 0.15% to 5% of the nonionic surfactant by weight of the liquid laundry detergent composition. Preferably, the laundry detergent composition comprises from 1.5% to 20%, from 2% to 15%, from 3% to 10%, or from 4% to 8% soap, in some examples a fatty acid salt, in some examples an amine neutralized fatty acid salt, in some examples the amine is an alkanolamine, preferably monoethanolamine. Preferably, the liquid laundry detergent composition comprises less than 15%, or less than 12% water, by weight of the liquid laundry detergent composition.Preferably, the laundry detergent composition comprises from 10% to 40%, or from 15% to 30%, by weight of the liquid laundry detergent composition, of a non-aqueous solvent selected from 1,2-propanediol, dipropylene glycol, tripropylene glycol, glycerol, sorbitol, polyethylene glycol, or mixtures thereof. Preferably, the liquid laundry detergent composition comprises from 0.1% to 10%, preferably from 0.5% to 8%, by weight of the detergent composition, of a further soil release polymer, preferably selected from the group of nonionic and / or anionic modified polyester terephthalate soil release polymers commercially available under the Texcare brand name from Clariant, amphiphilic graft polymers such as those based on polyalkylene oxides and vinyl esters, polyalkoxylated polyethyleneimines, and mixtures thereof. Preferably, the liquid detergent composition further comprises from 0.1% to 10%, preferably from 1% to 5%, of a chelating agent. In some examples, the laundry detergent composition comprises adjunct ingredients selected from the group comprising citrates, enzymes, bleaches, bleach catalysts, dyes, hueing dyes, brighteners, cleaning polymers including (zwitterionic) alkoxylated polyamines, surfactants, solvents, dye transfer inhibitors, perfumes, encapsulated perfumes, polycarboxylates, structurants, pH adjusters, and builders including mixtures thereof. Preferably, the liquid laundry detergent composition has a pH of 6-10, 6.5-8.9, or 7-8, the pH of the liquid laundry detergent composition being measured as a 10% product concentration in demineralized water at 20° C. When liquid, the laundry detergent composition may be Newtonian or non-Newtonian, preferably non-Newtonian.

[0204] Below is an exemplary water-soluble unit dose formulation: The composition may be part of a single chamber water-soluble unit dose article or may be divided across multiple compartments resulting in the following "overall compartment averaged" total article composition: The composition is encapsulated with a polyvinyl alcohol based water-soluble body, where the polyvinyl alcohol comprises a blend of a polyvinyl alcohol homopolymer and an anionic, e.g., carboxylated, polyvinyl alcohol copolymer.

[0205] [Table 2] Superscript explanation: * The nuclease enzyme is as claimed in co-pending European patent application 19219568.3. ** A polyethylene glycol grafted polymer comprising a polyethylene glycol backbone (Pluriol E6000) and hydrophobic vinyl acetate side chains, the polyethylene glycol grafted polymer comprising 40% by weight of the polymer system of the polyethylene glycol backbone polymer and 60% by weight of the polymer system of the grafted vinyl acetate side chains.

[0206] Liquid composition for hand washing dishes The fabric and home care product may be a dishwashing detergent composition, such as a hand dishwashing detergent composition, more preferably a liquid hand dishwashing detergent composition. Preferably, the liquid hand dishwashing detergent composition comprises 0.1% to 5.0%, preferably 0.5% to 4%, more preferably 1.0% to 3.0% of sulfated ester amine by weight of the detergent composition of the present invention. The liquid hand dishwashing detergent composition is preferably an aqueous composition comprising 50% to 90%, preferably 60% to 75% of water by weight of the total composition. Preferably, the pH of the detergent composition of the present invention, measured as a 10% product concentration in demineralized water at 20° C., is adjusted to 3 to 14, more preferably 4 to 13, more preferably 6 to 12, most preferably 8 to 10. The composition of the present invention may be a Newtonian or non-Newtonian fluid, but is preferably a Newtonian fluid. Preferably, the composition has a viscosity of from 10 mPa·s to 10,000 mPa·s, preferably from 100 mPa·s to 5,000 mPa·s, more preferably from 300 mPa·s to 2,000 mPa·s, or most preferably from 500 mPa·s to 1,500 mPa·s, or a combination thereof. Viscosity is measured at 20° C. using a Brookfield RT viscometer using spindle 31 with the viscometer RPM adjusted to achieve a torque of 40% to 60%.

[0207] The composition comprises 5% to 50% by weight of the surfactant system, preferably 8% to 45% by weight, more preferably 15% to 40% by weight of the total composition. The surfactant system preferably comprises 60% to 90% by weight, more preferably 70% to 80% by weight of the surfactant system, of anionic surfactant. The alkyl sulfated anionic surfactant is preferably selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates, preferably alkyl ethoxy sulfates, and mixtures thereof. The alkyl sulfated anionic surfactant preferably has an average alkyl chain length of 8 to 18, preferably 10 to 14, more preferably 12 to 14, most preferably 12 to 13 carbon atoms. The alkyl sulfated anionic surfactant preferably has an average degree of alkoxylation, preferably an ethoxylation degree, of less than 5, preferably less than 3, more preferably 0.5 to 2.0, most preferably 0.5 to 0.9. The alkyl sulfate anionic surfactant preferably has a weight average degree of branching of more than 10%, preferably more than 20%, more preferably more than 30%, even more preferably 30% to 60%, most preferably 30% to 50%. Suitable counterions include alkali metal cations, alkaline earth metal cations, alkanolammonium, or ammonium or substituted ammonium, preferably sodium. Suitable examples of commercially available alkyl sulfate anionic surfactants include those derived from alcohols sold by Shell under the trade name Neodol® or by Sasol under the trade names Lial®, Isalchem®, and Safol®, or some of the natural alcohols produced by Procter & Gamble Chemicals.

[0208] The surfactant system preferably comprises from 0.1% to 20%, more preferably from 0.5% to 15%, especially from 2% to 10% by weight of the liquid hand dishwashing detergent composition of a co-surfactant. Preferred co-surfactants are selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof. The weight ratio of anionic surfactant to co-surfactant may be from 1:1 to 8:1, preferably from 2:1 to 5:1, more preferably from 2.5:1 to 4:1. The co-surfactant is preferably an amphoteric surfactant, more preferably an amine oxide surfactant. Preferably, the amine oxide surfactant is selected from the group consisting of alkyl dimethyl amine oxides, alkyl amido propyl dimethyl amine oxides, and mixtures thereof, most preferably C 12 ~C 14 Alkyl dimethylamine oxide. Suitable zwitterionic surfactants include betaine surfactants, preferably cocamidopropyl betaine.

[0209] Preferably, the surfactant system of the composition of the present invention further comprises from 1% to 25%, preferably from 1.25% to 20%, more preferably from 1.5% to 15%, most preferably from 1.5% to 5% by weight of the surfactant system of a non-ionic surfactant. Suitable non-ionic surfactants may be selected from the group consisting of alkoxylated non-ionic surfactants, alkyl polyglucoside (APG) surfactants, and mixtures thereof. Suitable alkoxylated non-ionic surfactants are linear or branched primary or secondary alkyl alkoxylated, preferably alkyl ethoxylated, non-ionic surfactants containing an average of 9 to 15, preferably 10 to 14 carbon atoms in the alkyl chain and containing an average of 5 to 12, preferably 6 to 10, most preferably 7 to 8 ethylene oxide units per mole of alcohol. Most preferably, the alkyl polyglycoside surfactant has an average alkyl carbon chain length of 10 to 16, preferably 10 to 14, most preferably 12 to 14, and an average degree of polymerization of 0.5 to 2.5, preferably 1 to 2, most preferably 1.2 to 1.6. 16Alkyl polyglycosides are commercially available from several sources (e.g., Simusol® surfactants from Seppic Corporation, and Glucopon® 600 CSUP, Glucopon® 650 EC, Glucopon® 600 CSUP / MB, and Glucopon® 650 EC / MB from BASF Corporation).

[0210] The liquid hand dishwashing detergent compositions herein may optionally contain builders (e.g., preferably citrate), chelating agents (e.g., preferably GLDA), conditioning polymers, cleaning polymers comprising polyalkoxylated polyalkyleneimines, surface modifying polymers, soil flocculating polymers, foaming polymers comprising EO-PO-EO triblock copolymers, grease cleaning polymers comprising cyclic polyamines, structurants, emollients, humectants, skin rejuvenation actives, enzymes, carboxylic acids, scrubbing particles, bleach and bleach activators, fragrances, malodor control agents, facial cleansing agents, and the like. The compositions may also include many other auxiliary ingredients such as pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, organic solvents, inorganic cations such as alkaline earth metals such as Ca / Mg ions, antimicrobial agents, preservatives, viscosity modifiers (e.g., salts such as NaCl and other mono-, di-, and trivalent salts), and pH adjusters and buffering means (e.g., carboxylic acids such as citric acid, HCl, NaOH, KOH, alkanolamines, phosphoric and sulfonic acids, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates, borates, silicates, phosphates, imidazoles, etc.).

[0211] Below is an exemplary liquid hand dishwashing detergent formulation: The formulation can be made by standard mixing of the individual ingredients.

[0212] [Table 3]

[0213] Solid free-flowing particulate laundry detergent composition The fabric and home care product may be a solid free-flowing particulate laundry detergent composition. The following are exemplary solid free-flowing particulate laundry detergent compositions:

[0214] [Table 4]

[0215] How to use The present invention includes a method for cleaning a target surface. As used herein, "target surface" may include such surfaces as fabrics, dishes, glasses, and other cooking surfaces, hard surfaces, hair, or skin. As used herein, "hard surface" includes hard surfaces found in a typical household, such as hard wood, tiles, ceramics, plastics, leather, metal, glass, and the like. Such a method includes contacting a composition comprising a modified polyol compound, either in undiluted form or diluted in a cleaning solution, with at least a portion of the target surface, and then optionally rinsing the target surface. Preferably, the target surface is subjected to a cleaning step before any of the above-mentioned rinsing steps. For the purposes of the present invention, cleaning includes, but is not limited to, scrubbing, wiping, and mechanical agitation.

[0216] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in home care (hard surface cleaning compositions) and / or laundry applications.

[0217] The pH of the composition solution is selected to be most complementary to the target surface being cleaned over a wide pH range of about 3 to about 11. In personal care, such as skin and hair cleaning, the pH of such compositions preferably has a pH of about 5 to about 8, with laundry cleaning compositions having a pH of about 5 to about 11. The compositions are preferably used at a concentration of about 200 ppm to about 10,000 ppm in solution. Water temperatures preferably range from about 5°C to about 100°C.

[0218] For use in laundry cleaning compositions, the compositions are preferably employed at a concentration of from about 200 ppm to about 10,000 ppm in solution (or wash liquor). Water temperatures preferably range from about 5° C. to about 60° C. The water to fabric ratio is preferably from about 1:1 to about 20:1.

[0219] The method may include contacting a nonwoven substrate impregnated with an embodiment of the composition of the present invention. As used herein, "nonwoven substrate" may include any conventional nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Examples of suitable commercially available nonwoven substrates include those sold under the trade name SONTARA® by DuPont and POLYWEB® by James River Corp.

[0220] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in liquid dishwashing compositions. A method for using the liquid dishwashing compositions of the present invention comprises contacting soiled dishes with an effective amount, typically about 0.5 mL to about 20 mL (per 25 dishes to be treated), of the liquid dishwashing composition of the present invention diluted in water. EXAMPLES

[0221] Synthesis example: The following examples are carried out according to the procedures described and with the results obtained shown (see also Table 5).

[0222] Example 1 HMDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (HMDA+1 PO / NH+0.25 Caprolactone / NH+8 ​​PO / NH)

[0223] Example 1a: HMDA + 1 PO per mole of NH functional group A 2 L autoclave was charged with 245.0 g of hexamethylenediamine and 12.3 g of water. The reactor was purged with nitrogen three times and heated to 110° C. 489.8 g of propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was post-reacted at 110° C. for 5 hours. Volatile compounds were removed in vacuum at 90° C. A viscous yellow oil (730.0 g) was obtained. 1 H-NMR indicated complete conversion.

[0224] Example 1b: HMDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel, and reflux condenser, 278.8 g of hexamethylenediamine + 1 PO per mole of NH functional group (Example 1a) was placed and heated to 110°C. 91.3 g of caprolactone was added within 10 min. The reaction mixture was heated to 160°C and stirred at 160°C for 8 h. 370.0 g of a brown viscous oil was obtained. 1 H-NMR indicated complete conversion of the caprolactone.

[0225] Example 1c: HMDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 185.1 g of hexamethylenediamine + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group (Example 1b) and 1.9 g of potassium tertbutoxide were placed and the mixture was heated to 140°C. The vessel was purged with nitrogen three times. 743.4 g of propylene oxide were added in portions within 12 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 927.0 g of a light brown oil was obtained. The identity is given in CDCl3. 1 Confirmed by H-NMR.

[0226] Example 2 HMDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (HMDA+1PO / NH+0.5caprolactone / NH+8PO / NH)

[0227] Example 2a: HMDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel and reflux condenser, 139.4 g of hexamethylenediamine + 1 PO per mole of NH functionality (Example 1a) was placed and heated to 70°C. 91.3 g of caprolactone was added within 15 min. The reaction mixture was heated to 160°C and stirred at 160°C for 8 h. 223.0 g of an orange viscous oil was obtained. 1 H-NMR indicated complete conversion of the caprolactone.

[0228] Example 2b: HMDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 115.4 g of hexamethylenediamine + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group (Example 2a) and 1.0 g of potassium tertbutoxide were placed and the mixture was heated to 140°C. The vessel was purged with nitrogen three times. 371.7 g of propylene oxide were added in portions within 6 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 490.0 g of a light brown oil was obtained. The identity was determined by the addition of 1.2 g of propylene oxide in CDCl3. 1 Confirmed by H-NMR.

[0229] Example 3 EDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (EDA+1PO / NH+0.25caprolactone / NH+8PO / NH)

[0230] Example 3a: EDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel, and reflux condenser, 146.2 g of ethylenediamine + 1 PO per mole of NH functionality (Quadrol L purchased from BASF) was placed and heated to 40°C. 57.1 g of caprolactone was added within 5 min. The reaction mixture was heated to 160°C and stirred at 160°C for 8 h. 202.0 g of an orange viscous oil was obtained. 1 H-NMR indicated 98.5% conversion of caprolactone.

[0231] Example 3b: EDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 101.6 g of ethylenediamine + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group (Example 3a) and 1.1 g of potassium tertbutoxide were placed and the mixture was heated to 140°C. The vessel was purged with nitrogen three times. 464.6 g of propylene oxide were added in portions within 8 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 570.0 g of a light brown oil was obtained. The identity was determined by the addition of 1.0 g of ethylenediamine in CDCl3. 1 Confirmed by H-NMR.

[0232] Example 4 HMDA + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (HMDA+1EO / NH+0.25caprolactone / NH+8PO / NH)

[0233] Example 4a: HMDA + 1 EO per mole of NH functional group A 2 L autoclave was charged with 348.6 g of hexamethylenediamine and 17.4 g of water. The reactor was purged with nitrogen three times and heated to 90° C. 528.6 g of ethylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was post-reacted at 90° C. for 5 hours. Volatile compounds were removed in vacuum at 90° C. A beige wax (875.0 g) was obtained. 1 H-NMR indicated complete conversion.

[0234] Example 4b: HMDA + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 263.2 g of hexamethylenediamine + 1 EO per mole of NH functional group (Example 4a) was placed and heated to 80°C. 102.7 g of caprolactone was added at once at 80°C. The reaction mixture was heated to 160°C and stirred at 160°C for 13 hours. 360.0 g of a brown oil was obtained. 1H-NMR in MeOD indicated 93% conversion of caprolactone.

[0235] Example 4c: HMDA + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 162.6 g of hexamethylenediamine + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group (Example 4b) and 1.9 g of potassium tertbutoxide were placed and the mixture was heated to 140°C. The vessel was purged with nitrogen three times. 743.4 g of propylene oxide were added in portions within 12 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 895.0 g of a light brown oil was obtained. The identity was determined by the addition of 1.2 g of propylene oxide in CDCl3. 1 Confirmed by H-NMR.

[0236] Example 5 HMDA + 1 EO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (HMDA+1EO / NH+0.5caprolactone / NH+8PO / NH)

[0237] Example 5a: HMDA + 1 EO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel and reflux condenser, 131.6 g of hexamethylenediamine + 1 EO per mole of NH functional group (Example 4a) was placed and heated to 70 ° C. 102.7 g of caprolactone was added within 5 min. The reaction mixture was heated to 160 ° C and stirred at 160 ° C for 8 h. 227.6 g of dark brown oil was obtained. 1H-NMR in MeOD indicated 94% conversion of caprolactone.

[0238] Example 5b: HMDA + 1 EO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 134.0 g of hexamethylenediamine + 1 EO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group (Example 5a) and 1.2 g of potassium tertbutoxide were placed and the mixture was heated to 140°C. The vessel was purged with nitrogen three times. 478.3 g of propylene oxide were added in portions within 8 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 610.0 g of a light brown oil was obtained. The identity was determined by the addition of 1.0 g of ethyl acetate in CDCl3. 1 Confirmed by H-NMR.

[0239] Example 6 PDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group (PDA + 1PO / NH + 0.25caprolactone / NH + 8PO / NH)

[0240] Example 6a: 1 PO per mole of PDA + NH functional groups A 2 L autoclave was charged with 222.4 g of 1,3-propanediamine and 11.2 g of water. The reactor was purged with nitrogen three times and heated to 110° C. 697.0 g of propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was post-reacted at 110° C. for 5 hours. Volatile compounds were removed in vacuum at 90° C. A viscous light brown oil (919.0 g) was obtained. 1 H-NMR indicated complete conversion.

[0241] Example 6b: PDA + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel, and reflux condenser, 306.4 g of 1,3-propanediamine + 1 PO per mole of NH functional group (Example 6a) was placed and heated to 50°C. 114.1 g of caprolactone was added within 50 min. The reaction mixture was heated to 160°C and stirred at 160°C for 4 h. 420 g of a brown viscous oil was obtained. 1 H-NMR indicated complete conversion of the caprolactone.

[0242] Example 6c: PDA + 1 PO per mole of NH functional groups + 0.25 caprolactone per mole of NH functional groups + 8 PO per mole of NH functional groups In a 2 L autoclave, 168.2 g of 1,3-propanediamine + 1 PO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group (Example 6b) and 1.8 g of potassium tertbutoxide were placed and the mixture was heated to 140° C. The vessel was purged with nitrogen three times. 743.4 g of propylene oxide were added in portions within 12 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90° C. for 2 hours. 915.0 g of a light brown oil was obtained. The identity is given by the formula: 1Confirmed by H-NMR.

[0243] Example 7 N4 amine + 1 PO per mole of NH functional group + 0.33 per mole of NH functional group Caprolactone + 8 PO per mole of NH functional group (N4 amine + 1PO / NH + 0.33 caprolactone / NH + 10.7PO / NH)

[0244] Example 7a: N4 amine + 1 PO per mole of NH functionality A 2 L autoclave was charged with 261.4 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) and 13.0 g of water. The reactor was purged with nitrogen three times and heated to 110° C. 522.7 g of propylene oxide was added within 10 hours. To complete the reaction, the reaction mixture was post-reacted at 110° C. for 5 hours. Volatile compounds were removed in vacuum at 90° C. A viscous light brown oil (784.0 g) was obtained. 1 1 H-NMR indicated complete conversion.

[0245] Example 7b: N4 amine + 1 PO per mole of NH functional group + 0.33 caprolactone per mole of NH functional group A three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel and reflux condenser was charged with 200.0 g of N4 amine + 1 PO per mole of NH functional group (Example 7a) and heated to 50°C. 87.4 g of caprolactone was added within 50 min. The reaction mixture was heated to 160°C and stirred at 160°C for 5 h. 420 g of a brown viscous oil was obtained. 1 H-NMR indicated 96% conversion of caprolactone.

[0246] Example 7c: N4 amine + 1 PO per mole of NH functional group + 0.33 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 150.2 g of N4 amine + 1 PO + 0.33 caprolactone per mole of NH functional group (Example 7b) and 1.0 g of potassium tertbutoxide were placed and the mixture was heated to 140° C. The vessel was purged with nitrogen three times. 743.4 g of propylene oxide were added in portions within 12 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90° C. for 2 hours. 900.0 g of a light brown oil was obtained. The identity was determined by the addition of 1.0 g of propylene oxide in CDCl3. 1 Confirmed by H-NMR.

[0247] Example 8 EDA + 1 EO per mole of NH functional group + 0.25 PO per mole of NH functional group Caprolactone + 8 PO per mole of NH functional group (EDA+1EO / NH+0.25caprolactone / NH+8PO / NH)

[0248] Example 8a: EDA + 1 EO per mole of NH functional group A 2 L autoclave was charged with 199.0 g of ethylenediamine and 9.9 g of water. The reactor was purged with nitrogen three times and heated to 110° C. 583.4 g of ethylene oxide was added within 12 hours. To complete the reaction, the reaction mixture was post-reacted at 110° C. for 5 hours. Volatile compounds were removed in vacuum at 90° C. A pale viscous oil (780.0 g) was obtained. 1 1 H-NMR indicated complete conversion.

[0249] Example 8b: EDA + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group In a three-necked reaction vessel equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, 141.8 g of ethylenediamine + 1 EO per mole of NH functionality (Example 8a) was placed and heated to 80°C. 68.4 g of caprolactone was added at once at 80°C. The reaction mixture was heated to 160°C and stirred at 160°C for 8 hours. 210.0 g of an orange oil was obtained. 1H-NMR in MeOD indicated 99% conversion of caprolactone.

[0250] Example 8c: EDA + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 106.9 g of ethylenediamine + 1 EO per mole of NH functional group + 0.25 caprolactone per mole of NH functional group (Example 8b) and 1.4 g of potassium tertbutoxide were placed and the mixture was heated to 140 ° C. The vessel was purged with nitrogen three times. 567.4 g of propylene oxide were added in portions within 12 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140 ° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90 ° C. for 2 hours. 670.0 g of a light brown oil was obtained. The identity is given by the formula: 1 Confirmed by H-NMR.

[0251] Example 9 HMDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 2 EO per mole of NH functional group + 8 PO per mole of NH functional group (HMDA+1PO / NH+0.5caprolactone / NH+2EO / NH+8PO / OH)

[0252] In a 2 L autoclave, 151.0 g of hexamethylenediamine + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group (Example 2a) and 1.5 g of potassium tertbutoxide were placed and the mixture was heated to 140° C. The vessel was purged with nitrogen three times. 92.2 g of ethylene oxide were added within 2 hours. The reaction mixture was stirred at 140° C. for 2 hours and then 486.6 g of propylene oxide were added within 10 hours. To complete the reaction, the mixture was reacted for another 5 hours at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90° C. for 2 hours. 720.0 g of a light brown oil is obtained. The identity is given by the formula: 1 Confirmed by H-NMR.

[0253] Example 10 EDA + 1 per mole of NH functional group PO + 0.5 per mole of NH functional group Caprolactone + 2 per mole of NH functional group EO + 8 per mole of NH functional group () (EDA+1PO / NH+0.5caprolactone / NH+2EO / NH+8PO / NH)

[0254] Example 10a: EDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group A three-necked reaction vessel equipped with stirrer, thermometer, dropping funnel, and reflux condenser was charged with 251.4 g of ethylenediamine + 1PO per mole of NH functionality (Quadrol L, purchased from BASF) and 0.45 g of tin(II) 2-ethylhexanoate and heated to 100°C. 196.3 g of caprolactone were added within 5 min. The reaction mixture was heated to 160°C and stirred at 160°C for 4 h. 377.0 g of an orange viscous oil was obtained. 1 H-NMR indicated 97.5% conversion of caprolactone.

[0255] Example 10b: EDA + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group + 2 EO per mole of NH functional group + 8 PO per mole of NH functional group In a 2 L autoclave, 156.2 g of ethylenediamine + 1 PO per mole of NH functional group + 0.5 caprolactone per mole of NH functional group (Example 10a) and 1.6 g of potassium tertbutoxide were placed and the mixture was heated to 140° C. The vessel was purged with nitrogen three times. 105.7 g of ethylene oxide were added within 1.5 hours. The reaction mixture was stirred at 140° C. for 2 hours and then 557.6 g of propylene oxide were added within 12 hours. To complete the reaction, the mixture was reacted for another 10 hours at 140° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90° C. for 2 hours. 821.0 g of a light brown oil is obtained. The identity is given by the formula: 1 Confirmed by H-NMR.

[0256] The following comparative examples were carried out and the procedures described were followed with the results shown (see also Table 5).

[0257] Comparative Example 1 Polyethylenimine, molecular weight 800 g / mol, ethoxylated with 20 mol of ethylene oxide per mol of NH functionality (PEI800+20EO / NH), synthesized as described in WO 9532272.

[0258] Comparative Example 1a Polyethylenimine, molecular weight 800 g / mol, ethoxylated with 1 mol of ethylene oxide per mol of NH functional group. A 5 L autoclave is charged with 1943.0 g of polyethyleneimine with an average molecular weight of 800 g / mol and 97.0 g of water. The reactor is purged three times with nitrogen and heated to 110° C. 1789.0 g of ethylene oxide are added within 14 hours. The mixture is reacted for 5 hours in order to complete the reaction. The water and volatile compounds are removed in a vacuum at 90° C. A highly viscous yellow oil (3688.0 g, water content: 2.6%, pH: 11.05 (5% in water)) is obtained.

[0259] Comparative example 1b Polyethylenimine, molecular weight 800 g / mol, ethoxylated with 20 mol of ethylene oxide per mol of NH functionality The same product as in Comparative Example 1a (144.6 g, 92.7% in water) and 4.34 g of potassium hydroxide (50% in water) are placed in a 2 L autoclave. The mixture is heated to 120° C. under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor is purged with nitrogen three times and the mixture is heated to 140° C. 1470.7 g of ethylene oxide are added within 14 hours. The mixture is reacted for 5 hours to complete the reaction. Volatile compounds are removed in vacuum. 1615.0 g of a slightly brown solid is obtained (melting point: 35.4° C.).

[0260] Comparative Example 2 HMDA + 8PO per mol of NH functional group (HMDA+8PO / NH)

[0261] A 5L autoclave was charged with 672.9g of hexamethylenediamine + 1PO per mole of NH functionality (prepared as in Example 1a) and 16.0g of potassium hydroxide (50% in water). The vessel was purged with nitrogen three times and heated to 120°C. A vacuum was applied and the mixture was dehydrated at 120°C and <20mbar for 2 hours. The vacuum was removed with nitrogen and the temperature was increased to 140°C. 3089.9g of propylene oxide was added within 35 hours. To complete the reaction, the mixture was reacted for another 10 hours at 140°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuum at 90°C for 2 hours. 3370.0g of a light brown oil was obtained. The identity was confirmed by 1H-NMR in CDCl3.

[0262] [Table 5]

[0263] In the following examples showing the applications and other test results of certain inventive polymers, whenever a "polymer example" and number is referred to, it is meant that the final product, i.e., the resulting "alkoxylated polyamine," is utilized.

[0264] Polymer Biodegradable Polymer biodegradation in wastewater was tested in triplicate using the OECD 301F manometric respirometry method. 30 mg / mL of the test substance is inoculated into wastewater taken from the Mannheim Wastewater Treatment Plant and incubated in closed flasks at 25°C for 28 days. Oxygen consumption during this period is measured as the pressure change inside the flask using an OxiTopC (WTW). A NaOH solution is used to absorb the released CO2. The amount of oxygen consumed by the microbial population during the biodegradation of the test substance, after correction using blanks, is expressed as % of ThOD (theoretical oxygen demand).

[0265] The biodegradation data for the polymers of the present invention at 28 days in the OECD 301F test are summarized in Table 6.

[0266] [Table 6]

[0267] Anti-redeposition performance of polymers in laundry detergents The following liquid laundry detergent compositions (Table 7) were used as base detergents to test the anti-redeposition performance of the polymers. The anti-redeposition performance of the polymers was tested under the following conditions: Tested using 3000 ppm clay, 688 ppm base detergent / 25° C. / 1 mM hardness / 19.6 ppm polymer.

[0268] [Table 7] a The optical brightener is 4,4'-bis{[4-anilino-6-morpholino-s-triazin-2-yl]-amino}-2,2'-stilbenedisulfonate or 2,2'-([1,1'-biphenyl]-4,4'-diyldi-2,1-ethenediyl)bis-benzenesulfonic acid disodium salt. b 3,5-Bis(1,1-dimethylethyl)-4-hydroxybenzenepropanoic acid methyl ester [6386-38-5] c Dow Corning supplies an antifoam blend of 80-92% ethylmethyl, methyl(2-phenylpropyl) siloxane, 5-14% MQ resin in octyl stearate, and 3-7% modified silica.

[0269] Exam Preparation: The following fabrics are provided for whiteness benefit testing: NA polyester: PW19 available from Empirical Manufacturing Company, Cincinnati, OH; Cotton knit 1: Test fabric, Inc 403 cotton interlock knit tubular CW120, available from Empirical Manufacturing Company, Cincinnati, OH, USA. Polycotton

[0270] The "washed and FE treated" fabric was prepared by the following method: 400g fabric was washed in a WE Miniwasher Electrolux EWC1350 (3.5 litres of water) using 18.6g Ariel™ compact powder detergent at 60°C using a short program (45 minutes wash cycle followed by 3 rinse cycles, total program time 90 minutes), 2 times at 60°C using a short program without detergent, followed by 8.2g Lenor™ concentrate (fabric softener) at 40°C, 3 times in addition to each main wash. The fabric was then dried using an overdry tumble dryer until dry.

[0271] The "washed" fabric was prepared by the following method: 400 g of fabric was washed in a WE Miniwasher Electrolux EWC1350 (3.5 liters of water) using 18.6 g of Ariel™ compact powder detergent at 60° C. using a short program (45 minute wash cycle followed by 3 rinse cycles, total program time 90 minutes) and twice at 60° C. using a short program without detergent. The fabric was then dried in an overdry tumble dryer until dry.

[0272] Test Method Four fabric samples: washed polycotton, washed cotton knit, washed and FE treated NA polyester, washed and FE treated cotton knit.

[0273] Each sample was placed in a 96-well plate that mimicked a washing system using magnetic bearings to simulate the agitation of a typical full-scale washing machine with the following conditions: 750 ppm detergent concentration, 150 μL water per well, 25° C., 1.0 mM water hardness (2:1 Ca+2:Mg+2 molar ratio), wash pH of 8.3, and 3000 ppm Arizona test dust (supplied by PTI, Powder Technology Inc).

[0274] Each fabric is washed for 60 minutes and dried in the dark under ambient conditions. For each wash condition, there are two 96-well plates and eight internal replicates per 96-well plate (a total of 16 internal replicates per wash condition).

[0275] When the samples were dry, a Spectrolino imaging system (Gretag Macbeth, Spectro Scan3.273) was used to measure the L concentration at each 96-well plate spot. * , a * , b * , and CIE WI are measured. For each treatment, the average CIE WI is determined. Delta CIE WI, as reported in the table below, is the difference in the average CIE WI of the sample relative to the average CIE WI of the control sample without the test polymer.

[0276] For the Whiteness Index, the CIE Whiteness Index formula was used and Delta WI was calculated as follows: Delta WI of material=WI Tech-No WI Tech.

[0277] The results, shown in Table 8, demonstrate that the polymers of the present invention can provide clear anti-redeposition performance.

[0278] [Table 8]

[0279] Polymer cleaning performance of laundry detergent Laundry detergent polymer cleaning performance was carried out with the formulations listed in Table 7 and the wash conditions for single wash cycle performance can be summarized as follows: Machine: Launder-o-meter Cleaning solution 500mL Cleaning time: 30 minutes Wash temperature 25℃ Detergent concentration: 0.688g / L Water hardness 1mmol / L(Ca:Mg):HCO3(4:1):8 Ballast: White cotton fabric (CFT cotton double-sided knit tubular) 7 x 21 cm Soiled fabrics: PC-S 94, WFK 20D, PC-S 132 from CFT After one cycle, the soiled fabric was rinsed twice with water, followed by a brief spin dry and drying at room temperature for a period of 12 hours.

[0280] To evaluate the primary cleaning power of different soils, the soil removal index (SRI) formula according to ASTM D4265 was used to determine each soiled fabric before and after washing. To obtain the reflectance value of each fabric both before and after washing using a Spectrolino imaging system (GretagMacbeth, Spectro Scan 3.273), an average of six different measurement points was taken before and after washing, respectively. A higher delta reflectance value indicates a better primary cleaning power.

[0281] ASTM D4265-14: Evaluation of stain removal performance in home laundering Stain Removal Index = SRI SRI = 100 × (((Delta E * (Before Cleaning - Unsoiled) - Delta E * (After cleaning - not dirty) / Delta E * (Before cleaning - not dirty))) Delta E * = ((Delta L * ) 2 +(Delta a * ) 2 +(Delta b * )2 ) 1 / 2 Average Delta SRI = (Total Delta SRI all stains) / Number of stains

[0282] The cleaning performance of the inventive polymers is summarized in Table 9. The inventive polymers can provide clear improvements in stain removal, especially for stains containing sebum (PCS94, WFK20D, and PCS132).

[0283] [Table 9]

[0284] Polymer Brightness Performance Whiteness maintenance, also called whiteness retention, is the ability of a detergent to prevent white items from losing whiteness when washed in the presence of soil. White clothing may appear dirty / dull over time as soil is removed from soiled clothing and suspended in the wash water, and these soils may then be redeposited on the clothing, causing the clothing to lose whiteness each time it is washed.

[0285] The whiteness benefits of the polymers of the present disclosure are evaluated using an automated tergotometer with 10 pots for laundry formulation testing.

[0286] To simulate consumer soiling levels (a mixture of body soils, food, dirt, etc.), SBL2004 test soil strips supplied by WFK Testgewebe GmbH are used. On average, 8 g of soil is loaded per SBL2004 strip. The SBL2004 test soil strips were cut into 5 x 5 cm squares for use in the tests.

[0287] Additionally, Black Todd clay is used to further stress the system. 0.25g of clay is added per litre of cleaning solution. The clay is supplied by Warwick Equest Ltd.

[0288] The white fabric swatches in Table 10 below, purchased from WFK Testgewebe GmbH, are used as whiteness tracers.

[0289] [Table 10]

[0290] Additional ballast (background fabric swatches) are also used to simulate the fabric load and provide mechanical energy during the actual washing process. The ballast load consists of cotton and polycotton knit swatches with a size of 5 x 5 cm.

[0291] Four wash cycles are required to complete the test. Cycle 1: The desired amount of detergent is completely dissolved by mixing with 1 L of water (defined hardness) in each tergotometer port. Also at this point, 0.25 g of Black Todd clay is added. 60 grams of fabric (four types, four replicates) containing whiteness tracer, ten pieces of 5x5 cm SBL2004, and ballast are washed and rinsed in the tergotometer pot under defined conditions. For testing of the water-soluble unit dose composition, the wash concentration is 2000 ppm. The wash temperature is 30° C. and the water hardness is 7 gpg. Cycle 2: After the process of cycle 1, the whiteness tracer and ballast of each pot are then washed and rinsed again with a new set of SBL2004 (5×5 cm, 10 pieces). All other conditions remain the same as cycle 1. Cycle 3: After the process of cycle 1, the whiteness tracer and ballast of each pot are then washed and rinsed again with a new set of SBL2004 (5×5 cm, 10 pieces). All other conditions remain the same as cycle 1. Cycle 4: Then, after the process of cycle 1, the whiteness tracer and ballast of each port are washed and rinsed again with a new set of SBL2004 (5×5 cm, 10 pieces). All other conditions remain the same as cycle 1.

[0292] After cycle 4, all the whiteness tracers and ballast are laid flat to dry until dry, then the tracers are measured using a Konica Minolta CM-3610D spectrophotometer. The whiteness index (WI(CIE)) is part of the Konica Minolta report.

[0293] The following liquid detergent compositions E and F are prepared by conventional means known to those skilled in the art by mixing the listed ingredients (Table 11).

[0294] The whiteness maintenance of the inventive and comparative polymers is evaluated by a method to evaluate the whiteness performance of the polymer by directly comparing the whiteness performance of the reference composition E and the test composition F. The ΔWI(CIE) of composition F versus composition E is reported in Table 11 below as an indication of the advantage of the polymer whiteness performance. The inventive polymers can provide a distinct advantage in whiteness.

[0295] [Table 11]

[0296] [Table 12]

[0297] Polymer foam durability performance in hand dishwashing detergents The following method was used to evaluate the suds persistence of hand dishwashing compositions and to evaluate the cleaning polymer suds persistence performance. The purpose of the Foam Persistence Index test is to compare the development over time of foam volume generated for different test formulations at specified water hardness, solution temperature, and formulation concentration while under the influence of periodic soil injection. The data is compared and expressed as a Foam Persistence Index relative to a reference composition (the reference composition has a Foam Persistence Index of 100). The steps of the method are as follows: 1) Depending on the target composition concentration (0.12 wt%), a defined amount of test composition is dispensed through a plastic pipette at a flow rate of 0.67 mL / sec into a stream of water (water hardness: 2 gpg, water temperature: 35° C.) filling a sink to 4 L at a constant pressure of 4 bar, at a height of 37 cm above the sink bottom (dimensions: diameter 300 mm and height 288 mm). 2) Initial foam volume generated (measured as average foam height x sink surface area, cm 3 (expressed as ) is recorded immediately after filling is completed. 3) A fixed amount (6 mL) of soil is immediately poured into the center of the sink. 4) Mix the resulting solution using a metal blade (10 cm x 5 cm) positioned in the center of the sink at the air-liquid interface at a 45 degree angle, rotating 20 times at 85 RPM. 5) Another measurement of the total lather volume is recorded immediately after the blade rotation has finished. 6) The measured total foam volume is 400 cm 3 Repeat steps 3 to 5 until the minimum level of 400 cm is reached. 3 The amount of soil added required to reach a level of foam persistence is considered the foam persistence of the test composition. 7) Each test composition is tested four times per test condition (i.e., water temperature, composition concentration, water hardness, soil type). 8) Calculate the average foam persistence as the average of four replicates for each sample. 9) Calculate the foam persistence index by comparing the average persistence of the test composition samples to the reference composition samples. The calculation is as follows:

[0298]

number

[0299] A stain composition is prepared by standard mixing of the ingredients set out in Table 13.

[0300] [Table 13]

[0301] Polymer performance in hand dishwashing detergents The following hand dishwashing detergent compositions are prepared by conventional means known to those skilled in the art by mixing the listed ingredients. The effect of the polymer of the present invention on suds mileage is evaluated by comparing the suds mileage of formulations A (reference) and B (reference with the polymer of the present invention) in Table 14. The method for evaluating suds mileage of hand dishwashing compositions described below is used to evaluate the suds mileage performance and the suds mileage index is reported in Table 15.

[0302] [Table 14] * Measured as a 10 w / w% product dilution in demineralized water at 22°C.

[0303] As shown in Table 15, the polymers of the present invention can provide distinct foam persistence advantages.

[0304] [Table 15]

Claims

1. An alkoxylated polyamine for use in a laundry or dishwashing detergent composition, comprising up to 6 amine groups, obtainable by a process comprising the following steps a) to c) and, optionally, step d): a) reaction of i) at least one polyamine containing up to 6 amine groups with ii) at least one first alkylene oxide (AO1) to obtain a first intermediate (I1), in which 0.25 to 2.0 mol of alkylene oxide (AO1) are used per mol of NH functional groups of the polyamine, AO1 being ethylene oxide and / or propylene oxide, b) reacting said first intermediate (I1) with caprolactone to obtain a second intermediate (I2), in which 0.25 to 3 mol of caprolactone is used per mol of NH functional groups of the polyamine (used in step a)), c) reaction of said alkoxylated polyamine or, if optional step d) is used, said second intermediate (I2) with at least one second alkylene oxide (AO2) to obtain a third intermediate (I3), in which 1 mol to 14.5 mol of alkylene oxide (AO2) are used per mol of NH functional groups of the polyamine (used in step a)), AO2 being ethylene oxide and / or propylene oxide, d) optional reaction of said third intermediate (I3) with at least one second alkylene oxide (AO2) to obtain said alkoxylated polyamine, in which at least 1 mol of alkylene oxide (AO2) is used per mol of NH functional groups of the polyamine (used in step a)), and if only one second alkylene oxide (AO2) is used in step d), said second alkylene oxide (AO2) in this step is different from ethylene oxide, the alkylene oxides AO1 and / or AO2 are selected such that at least 10 weight percent of the total amount of moieties in the alkoxylated polyamine derived from alkylene oxide (i.e., from AO1 and AO2) is derived from a C3 alkylene oxide; the total amount of alkylene oxide used is from 1 to a maximum of 17 mol per mol of NH functional groups of the polyamine (i.e. the polyamine used in step a), The at least one polyamine used in step a) has the general formula (I) 【Chemistry 1】 wherein the variables are defined as follows: y is an integer having a value ranging from 0 to 4; Alkoxylated polyamines, where R is the same or different, a C 2 -C 6 -alkylene group selected from ethylene, propylene and hexamethylene.

2. General formula (IIa) 【Chemistry 2】 wherein the variables are defined as follows: R １ is C ２ 〜C3-(1,2-alkylene) group, R ２ represents hydrogen, R ３ represents a linear C5 alkylene group, R ４ is C ２ 〜C3-(1,2-alkylene) group, R ５ represents 1,2-ethylene, m is an integer having a value of at least 1 and at most 10; n is an integer having a value of at least 1 and at most 25; o is an integer having a value from 0 up to 25; p is an integer having a value of at least 1 and at most 5; provided that the sum of n+o+p is at most 25; Residue R in the alkoxylated polyamine １ , R ４ at least 50 weight percent of the total amount of moieties is derived from C3-alkylene oxide; If o is not 0, R １ and R ５ is R １ and R ５ The moieties containing R １ and R ５ wherein the selected alkylene oxide is selected from R １ and R ５ and wherein the arrangement of said alkylene oxides is different when both are the same.

3. General formula (IIb) 【Chemistry 3】 wherein the variables are defined as follows: R １ is C ２ 〜C3-(1,2-alkylene) group, R ２ represents hydrogen, R ３ represents a linear C5 alkylene group, R ５ represents 1,2-ethylene, m is an integer having a value of at least 1 and at most 10; n is an integer having a value of at least 1 and at most 25; o is an integer having a value from 0 up to 25; Residue R in the alkoxylated polyamine １ and, if the residue of formula IIa is also present, R ４ at least 50 weight percent of the total amount of moieties is derived from C3-alkylene oxide; R １ and R ５ is R １ and R ５ The moieties containing R １ and R ５ wherein the selected alkylene oxide is R １ and R ５ and the arrangement of said alkylene oxides is different when the two are the same; 3. The alkoxylated polyamine of claim 1, wherein the sum of n+o is at most 25.

4. General formula (IIc) 【Chemistry 4】 wherein the variables are defined as follows: R １ is C ２ 〜C3-(1,2-alkylene) group, R ２ represents hydrogen, R ５ represents 1,2-ethylene, n is an integer having a value of at least 5 and at most 100; o is an integer having a value of at least 0 to 100; at least 50 weight percent of the total amount of moieties in the alkoxylated polyamine that are derived from alkylene oxide (i.e., the residues R1 and, if the residue of Formula IIa is also present, R4) are derived from a C3-alkylene oxide; 4. The alkoxylated polyamine of claim 1, containing at least one residue according to the formula:

5. The alkoxylated polyamine according to any one of claims 1 to 4, wherein step a) is carried out in the presence of water and / or in the presence of a base catalyst.

6. The alkoxylated polyamine of any one of claims 1 to 5, wherein the number of amine groups in the polyamine is up to 5 amine groups.

7. The alkoxylated polyamine of any one of claims 1 to 6, wherein y is an integer having a value ranging from 0 to 3.

8. 8. The alkoxylated polyamine of claim 1, wherein the residue (IIa) accounts for at least 80 percent by weight of all residues (IIa), (IIb) and (IIc) bonded to the amino groups of the polyamine used in step a).

9. An alkoxylated polyamine according to any one of claims 1 to 8, wherein in step c) the second alkylene oxide (AO2) is propylene oxide or a mixture of ethylene oxide and propylene oxide.

10. i) in step a) 0.5 to 2 mol of alkylene oxide (AO1) are used per mol of NH functional groups of the polyamine, and / or ii) in step b) 0.5 to 3 mol of caprolactone are used per mol of NH functional groups of the polyamine (used in step a)); and / or iii) In step c) 5 to 14.5 mol of alkylene oxide (AO2) are used per mol of NH functional groups of polyamine (used in step a)).

11. Use of an alkoxylated polyamine according to any one of claims 1 to 10 in a laundry detergent composition or a dishwashing detergent composition.

12. i) clay removal; and / or ii) soil removal of particulate stains; and / or iii) dispersing and / or emulsifying the soil; and / or iv) modification of the treated surface to improve removal upon subsequent recontamination; and / or v) improved whiteness; 12. The use according to claim 11 in a laundry detergent composition or a dishwashing detergent composition for

13. A laundry detergent composition comprising at least one alkoxylated polyamine according to any one of claims 1 to 10.

14. A dishwashing detergent composition comprising at least one alkoxylated polyamine according to any one of claims 1 to 10.

15. i) clay removal; and / or ii) soil removal of particulate stains; and / or iii) dispersing and / or emulsifying the soil; and / or iv) modification of the treated surface to improve removal upon subsequent recontamination; and / or v) Improved whiteness 15. Use of the laundry detergent composition according to claim 13 or the dishwashing detergent composition according to claim 14 for:

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