Composition and its use

Abstract

(A) (a) a core having 1 to 3 moieties of general formula (I) (wherein Z is different or the same, and C2 to C 12 -Alkylene and C3-C 12 -cycloalkylene, wherein the C2 to C 12 -Alkylene or C3-C 12 -cycloalkylene, each of which may be unsubstituted or substituted with one or more O—C1-C4-alkyl groups, 12 -cycloalkylene may have 1 to 3 methyl groups, A 1 are different or the same and C1~C 12 -Alkylene, C6-arylene, and C3-C 12 -cycloalkylene, C2-C 12 -Alkylene and C3-C 12 -Cycloalkylene may be unsubstituted or substituted with one or more O-C1-C4-alkyl or OH groups, and C3-C 12 -cycloalkylene may have 1 to 3 methyl groups, or may be based on citric acid, X 1 is selected from hydrogen, methyl, and ethyl, and combinations of at least two of the foregoing, and n ranges from 1 to 100; and (b) at least one polymer comprising a polyalkylene oxide chain. TIFF2023537833000029.tif24160

Description

[Technical Field]

[0001] The present invention provides (A) at least one polymer, (a) a core having 1 to 3 moieties of general formula (I);

[0002] [ka] (Wherein, Z is different or the same, C2 to C 12 -Alkylene and C3-C 12 -cycloalkylene, wherein the C2 to C 12 -Alkylene or C3-C 12 -cycloalkylene, each of which may be unsubstituted or substituted with one or more O—C1-C4-alkyl groups, 12 -cycloalkylene may have 1 to 3 methyl groups; A 1 are different or the same, and C1 to C 12 -Alkylene, C6-arylene, and C3-C 12 -cycloalkylene, C2-C 12 -Alkylene and C3-C 12 -Cycloalkylene may be unsubstituted or substituted by one or more O-C1-C4-alkyl or OH groups, and may be C3-C 12 -cycloalkylene may have 1 to 3 methyl groups; Or based on citric acid, X 1 is selected from hydrogen and methyl and ethyl, and combinations of at least two of the foregoing; (n is in the range of 1 to 100) (b) Polyalkylene oxide chain a polymer comprising The present invention relates to a composition comprising:

[0003] Additionally, the present invention relates to polymers useful in such compositions and methods for making such polymers. Summary of the Invention

[0004] Laundry detergents must meet several requirements. They must remove all types of stains from laundry, including all types of pigments, soils, and fatty stains, as well as dyes from foods and beverages, such as red wine, tea, coffee, and fruits, including berry juice. They must also exhibit a certain level of storage stability. In particular, laundry detergents that are liquid or contain hygroscopic ingredients often lack good storage stability, for example, enzymes tend to be inactivated.

[0005] Greasy soils remain a challenge in laundry. Many proposals for removal have been made (polymers, enzymes, surfactants), but finding a solution that works well remains a challenge. The use of lipases has been proposed to aid in grease removal, but many builders do not work well with lipases, especially in liquid laundry detergents.

[0006] It was therefore an object to provide detergent compositions that meet the requirements discussed above. It was a further object to provide ingredients that meet the above requirements, and to provide methods of making such ingredients and detergent compositions.

[0007] Thus, a composition as defined at the beginning has been found, hereinafter also referred to as the composition of the invention or the composition according to the invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] The composition of the present invention comprises: (A) comprises at least one polymer, hereinafter also referred to as polymer (A), and such polymer (A) comprises: (a) a core having 1 to 3 moieties according to general formula (I)

[0009] [ka] wherein Z is different or the same; C2~C 12 -Alkylene, for example -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, -(CH2) 12 -, and preferred are -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, and -(CH2)6-, and the C2 to C 12 - alkylene may be linear or branched, unsubstituted or substituted with one or more O-C1-C4-alkyl groups, and C3~C 12 -cycloalkylene, preferably C5-C6-cycloalkylene, where C3-C 12 -Cycloalkylene, preferably C5-C6-cycloalkylene, may be unsubstituted or substituted with one or more O-C1-C4-alkyl groups, 12 -Cycloalkylene, preferably C5-C6-cycloalkylene, may have 1 to 3 methyl groups, preferably C5-C 10 - cycloalkylene, for example 1,3-cyclopentylene, 1,2-cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-methyl-2,4-cyclohexylene, 1-methyl-2,6-cyclohexylene, 1,3-cycloheptylene, 1,4-cyclooctylene, 1,5-cyclooctylene, is selected from X 1 is selected from hydrogen, methyl, ethyl and combinations of at least two of the foregoing, preferably methyl and combinations of methyl and hydrogen, more preferably hydrogen; A 1 are different or the same, and C1 to C 12 -Alkylene, preferably C2-C4-alkylene, for example -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, -(CH2) 12-, preferably -CH2CH2-, -(CH2)3-, -(CH2)4-, further C6-arylene, and C3-C 12 -Cycloalkylene, C2-C 12 -Alkylene and C3-C 12 -Cycloalkylene may be unsubstituted or substituted by one or more O-C1-C4-alkyl or OH groups, and may be C3-C 12 -cycloalkylene may have 1 to 3 methyl groups; or citric acid, e.g., based on -CH2-C(CO2H)(OH)-CH2- or -CH2-C(OH)(CH2-COOH)- Includes.

[0010] In one embodiment of the present invention, A in polymer (A) 1 is a mixture of C2-C4-alkylene and citric acid-based residues, for example in a molar ratio of 1:10-15:1, preferably 1:5-10:1.

[0011] n is in the range of 1 to 100, preferably 10 to 75.

[0012] The free valence on the nitrogen atom in formula (I) is a polyalkylene chain (b) or -CH2-CH(X 1 )-O(CO)-A 1 -(CO)-O-CHX 1 In an embodiment in which the molecular weight Mw is 10,000 g / mol or more, the free valence on the nitrogen atom in formula (I) is a polyalkylene chain (b) or a -CH-CH(X 1 )-O-CHX 1 Contains -CH2-NZN units.

[0013] Preferably, Z are isomers of each other and / or differ only in variable n. Even more preferably, Z are isomers.

[0014] A preferred example of Z is the formula

[0015] [ka] and is therefore a mixture of isomers.

[0016] In one embodiment of the present invention, polymer (A) may further comprise one or more structural units according to general formula (X).

[0017] [ka]

[0018] In one embodiment of the present invention, the polymer (A) has an average molecular weight M in the range of 2,500 to 300,000 g / mol, preferably 5,000 to 250,000 g / mol. w The average molecular weight can be determined, for example, by gel permeation chromatography (GPC) in tetrahydrofuran (THF) as the mobile phase using linear polymethyl methacrylate ("PMMA") as a standard.

[0019] In one embodiment of the present invention, the polymer (A) has a molecular weight distribution M in the range of 1.1 to 2.5. w / M n It has.

[0020] In one embodiment of the present invention, polymer (A) has a Hazen color number in the range of 20 to 500, determined in a 10% by weight aqueous solution.

[0021] In one embodiment of the present invention, polymer (A) has an OH number in the range of 20 to 650 mg KOH, preferably 30 to 100 mg KOH per gram of polymer (A), measured according to DIN 53240 (2013).

[0022] In one embodiment of the present invention, polymer (A) has a total amine number, determined in accordance with ASTM D2074-07, in the range of 10 to 650 mg KOH, preferably 10 to 510 mg KOH, more preferably 10 to 80 mg KOH per gram of polymer (A).

[0023] The polymer (A) is (b) Polyalkylene oxide chain Further includes:

[0024] The polyalkylene oxide side chains can be derived from C2-C4-alkylene oxides. Examples of C2-C4-alkylene oxides are ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BuO"), and mixtures of at least two of the foregoing, such as ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide. Preferred are propylene oxide and ethylene oxide, more preferred is ethylene oxide.

[0025] In one embodiment of the present invention, the weight ratio of core (a) to polyalkylene oxide chain (b) in polymer (A) ranges from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0026] In one embodiment of the present invention, the composition of the present invention comprises at least one enzyme. The enzyme is identified by its polypeptide sequence (also referred to herein as its amino acid sequence). The polypeptide sequence specifies the three-dimensional structure of the enzyme, including the "active site," and therefore determines the catalytic activity of the enzyme. The polypeptide sequence may be identified by a SEQ ID NO:. In accordance with the World Intellectual Property Organization (WIPO) Standard ST.25 (1998), amino acids herein are represented using three-letter codes with the first letter capitalized, or the corresponding single-letter codes.

[0027] Enzymes according to the present invention refer to parent and / or variant enzymes, both of which have enzymatic activity. An enzyme with enzymatic activity is enzymatically active or effects an enzymatic transformation, meaning that the enzyme acts on substrates and converts them into products. The term "enzyme" herein excludes inactive variants of an enzyme.

[0028] A "parent" sequence (of a parent protein or enzyme, also called a "parent enzyme") is a starting sequence for introducing changes into the sequence (e.g., by introducing one or more amino acid substitutions, insertions, deletions, or a combination thereof) to result in a "variant" of the parent sequence. The term parent enzyme (or parent sequence) includes wild-type enzymes (sequences) and synthetically produced sequences (enzymes) that are used as starting sequences for introducing (further) changes.

[0029] The terms "enzyme variant" or "sequence variant" or "variant enzyme" refer to an enzyme that differs to some extent in amino acid sequence from a parent enzyme. Unless otherwise specified, a variant enzyme that is "enzymatically active" means that the variant enzyme has the same type of enzymatic activity as the respective parent enzyme.

[0030] When describing the variants of the present invention, the following nomenclature is used: Amino acid substitutions are described by providing the original amino acid of the parent enzyme, followed by the position number in the amino acid sequence, followed by the substituted amino acid. Amino acid deletions are described by providing the original amino acid of the parent enzyme, followed by the position number in the amino acid sequence, followed by the substituted amino acid. *Amino acid insertions are described by providing the original amino acid of the parent enzyme, followed by the position number in the amino acid sequence, followed by the original amino acid and the additional amino acid. For example, an insertion of a lysine at position 180 next to a glycine would be designated "Gly180GlyLys" or "G180GK." When a substitution and insertion occur at the same position, this can be designated as S99SD+S99A or simply S99AD. Degeneracy in nomenclature occurs when an amino acid residue identical to an existing amino acid residue is inserted. For example, if a glycine is inserted after the glycine in the above example, this would be designated as G180GG. When different changes can be introduced at a position, the different changes are separated by commas, e.g., "Arg170Tyr,Glu" represents a substitution of arginine at position 170 with tyrosine or glutamic acid. Alternatively, different modifications or optional substitutions may be indicated in parentheses, for example Arg170[Tyr,Gly] or Arg170{Tyr,Gly}, or simply R170[Y,G] or R170{Y,G}, or longer R170Y,R170G.

[0031] Enzyme variants can be defined by their sequence identity compared to the parent enzyme. Sequence identity is usually provided as "% sequence identity" or "% identity." To calculate sequence identity, the first step is to create a sequence alignment. According to the present invention, a pairwise global alignment must be created, which means that two sequences must be aligned over their entire length, and this is usually created by using a mathematical approach called an alignment algorithm. According to the present invention, the alignment is generated by using the Needleman and Wunsch algorithm (J. Mol. Biol. (1979) 48, 443-453). Preferably, the program "NEEDLE" (The European Molecular Biology Open Software Suite (EMBOSS)) is used for the purposes of the present invention using the program's default parameters (gap open = 10.0, gap extension = 0.5, and matrix = EBLOSUM62).

[0032] According to the present invention, the following calculation of % identity is applied: % identity = (identical residues / length of the alignment region representing each sequence of the present invention over its full length) x 100.

[0033] According to the present invention, enzyme variants may be described as amino acid sequences that are at least n% identical to the amino acid sequence of their respective parent enzymes, where "n" is an integer between 10 and 100. In one embodiment, the variant enzyme is at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical to the full-length amino acid sequence of the parent enzyme, and the enzyme variant has enzymatic activity.

[0034] "Enzyme activity" refers to the catalytic effect exerted by an enzyme in terms of molecules of substrate converted per minute per molecule of enzyme (molecular activity), usually expressed as units per milligram of enzyme (specific activity). A variant enzyme may have an enzymatic activity according to the present invention if the enzyme variant exhibits at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or 100% of the enzymatic activity of the respective parent enzyme.

[0035] In one embodiment, the enzyme is selected from hydrolases, preferably from proteases, amylases, lipases, cellulases, and mannanases.

[0036] In one embodiment of the present invention, the composition of the present invention comprises: (B) It comprises at least one hydrolase, hereinafter also referred to as hydrolase (B), which hydrolase is preferably chosen from lipases, hereinafter also referred to as lipase (B).

[0037] The terms "lipase," "lipolytic enzyme," and "lipid esterase" all refer to enzymes in EC class 3.1.1 ("carboxylic ester hydrolase"). Such lipases (B) may have lipase activity (or lipolytic activity; triacylglycerol lipase, EC 3.1.1.3), cutinase activity (EC 3.1.1.74; enzymes with cutinase activity may be referred to herein as cutinases), sterol esterase activity (EC 3.1.1.13), and / or wax ester hydrolase activity (EC 3.1.1.50). Lipases (B) include those of bacterial or fungal origin.

[0038] Commercially available lipases (B) include, but are not limited to, those sold under the trade names Lipolase™, Lipex™, Lipolex™ and Lipoclean™ (Novozymes A / S), Preferenz™ L (DuPont), Lumafast (originally made by Genencor) and Lipomax (Gist-Brocades / now DSM).

[0039] In one aspect of the invention, the lipase (B) is selected from the following: a lipase from the genus Humicola (syn. Thermomyces), such as H. lanuginosa (T. lanuginosus), as described in EP 258068, EP 305216, WO 92 / 05249 and WO 2009 / 109500, or H. insolens, as described in WO 96 / 13580; Rhizomucor miehei, as described in WO 92 / 05249; lipases from Pseudomonas (some of which have now been renamed Burkholderia), such as P. alcaligenes or P. pseudoalcaligenes (EP 218272, WO 94 / 25578, WO 95 / 30744, WO 95 / 35381, WO 96 / 00292), P. cepacia (EP 331376), P. stutzeri (GB 1372034), P. fluorescens, Pseudomonas Lipases from P. sp. seed strain SD705 (WO 95 / 06720 and WO 96 / 27002), P. wisconsinensis (WO 96 / 12012), Pseudomonas mendocina (WO 95 / 14783), P. glumae (WO 95 / 35381, WO 96 / 00292); Streptomyces griseus (WO 2011 / 150157) and S. pristinaspiralis (S.lipases from Streptomyces sp. (WO 2012 / 137147), GDSL-type Streptomyces lipases (WO 2010 / 065455); lipases from Thermobifida fusca as disclosed in WO 2011 / 084412; lipases from Geobacillus stearothermophilus as disclosed in WO 2011 / 084417; Bacillus lipases, e.g., as disclosed in WO 00 / 60063, Dartois et al. (1992), Biochemica et Biophysica Lipases derived from B. subtilis, B. stearothermophilus (JP 64-074992 A) or B. pumilus (WO 91 / 16422 A) as disclosed in Acta, 1131, 253-360 or WO 2011 / 084599; and lipases derived from Candida antarctica (WO 94 / 01541 A). Suitable lipases (B) also include variants of the above lipases that have lipolytic activity. Such suitable lipase variants are, for example, those developed by the methods disclosed in WO 95 / 22615, WO 97 / 04079, WO 97 / 07202, WO 00 / 60063, WO 2007 / 087508, EP 407225, and EP 260105. Suitable lipase variants are, for example, those developed by the methods disclosed in WO 95 / 22615, WO 97 / 04079, WO 97 / 07202, WO 00 / 60063, WO 2007 / 087508, EP 407225, and EP 260105.

[0040] Suitable lipases (B) also include variants of the lipases described above that have lipolytic activity. Suitable lipase variants include variants having at least 40-100% identity when compared to the full-length polypeptide sequence of the parent enzyme disclosed above. In one embodiment, the lipase variant with lipolytic activity can be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical when compared to the full-length polypeptide sequence of the parent enzyme disclosed above.

[0041] Lipase (B) has "lipolytic activity." Methods for determining lipolytic activity are well known in the literature (see, e.g., Gupta et al. (2003), Biotechnol. Appl. Biochem. 37, pp. 63-71). For example, lipase activity can be measured by ester bond hydrolysis of the substrate para-nitrophenyl palmitate (palmitate-pNP, C:16), releasing pNP, which is yellow and can be detected at 405 nm.

[0042] In one embodiment, the lipase (B) is selected from fungal triacylglycerol lipases (EC class 3.1.1.3). The fungal triacylglycerol lipase may be selected from Thermomyces lanuginosa lipases. In one embodiment, the at least one Thermomyces lanuginosa lipase is selected from the triacylglycerol lipases according to amino acids 1-269 of SEQ ID NO: 2 of U.S. Pat. No. 5,869,438 and variants thereof having lipolytic activity.

[0043] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity that are at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical to the full-length polypeptide sequence of amino acids 1 to 269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438.

[0044] The Thermomyces lanuginosa lipase can be selected from variants with lipolytic activity that contain only conservative mutations that do not involve the functional domain of amino acids 1-269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438. The lipase variants of this embodiment with lipolytic activity can be at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% similar when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438.

[0045] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the following amino acid substitutions: T231R and N233R, when compared to amino acids 1-269 of SEQ ID NO:2 in U.S. Patent No. 5,869,438. The lipase variant may further comprise one or more of the following amino acid exchanges: Q4V, V60S, A150G, L227G, and P256K, when compared to amino acids 1-269 of SEQ ID NO:2 in U.S. Patent No. 5,869,438.

[0046] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the amino acid substitutions T231R, N233R, Q4V, V60S, A150G, L227G, and P256K within the polypeptide sequence of amino acids 1 to 269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438, and is at least 95%, at least 96%, or at least 97% similar when compared to the full-length polypeptide sequence of amino acids 1 to 269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438.

[0047] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising the amino acid substitutions T231R and N233R within amino acids 1-269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438, and is at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% similar when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Patent No. 5,869,438.

[0048] The Thermomyces lanuginosa lipase may be a variant of amino acids 1-269 of SEQ ID NO:2 in U.S. Patent No. 5,869,438 having lipolytic activity, characterized in that the variant of amino acids 1-269 of SEQ ID NO:2 in U.S. Patent No. 5,869,438 contains the amino acid substitutions T231R and N233R. Such lipase may be referred to herein as Lipex.

[0049] In one embodiment of the present invention, a combination of at least two of the aforementioned lipases (B) may be used.

[0050] In one embodiment of the present invention, lipase (B) is included in the composition of the present invention in an amount such that the finished composition of the present invention has a lipolytic enzyme activity in the range of 100 to 0.005 LU per mg of composition, preferably 25 to 0.05 LU per mg of composition. A lipase unit (LU) is the amount of lipase that produces 1 μmol of titrated fatty acid per minute in a pH stat under the following conditions: temperature 30°C, pH = 9.0, substrate 13 mmol / L Ca in 5 mmol / L Tris buffer. 2+ and an emulsion of 3.3 wt % olive oil and 3.3% gum arabic in the presence of 20 mmol / l NaCl.

[0051] In one embodiment of the present invention, the composition of the present invention comprises: (D) Contains at least one protease (D), hereinafter also referred to as protease (D).

[0052] In one embodiment, the at least one protease (D) is selected from the group of serine endopeptidases (EC 3.4.21), most preferably from the group of subtilisin-type proteases (EC 3.4.21.62). Serine proteases or serine peptidases are characterized by having a serine in the catalytic active site, which forms a covalent adduct with the substrate during catalysis. A serine protease in the context of the present invention may be selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC 3.4.21.78 or EC 3.4.21.79), kallikrein (e.g., EC 3.4.21.34, EC 3.4.21.35, EC 3.4.21.118 or EC 3.4.21.119), plasmin (e.g., EC 3.4.21.7), trypsin (e.g., EC 3.4.21.4), thrombin (e.g., EC 3.4.21.5) and subtilisin. Subtilisins are also known as subtilopeptidases, e.g., EC 3.4.21.62, which is also referred to hereinafter as "subtilisin." The subtilisin-related class of serine proteases share a common amino acid sequence that defines a catalytic triad that distinguishes them from the chymotrypsin-related class of serine proteases. Both subtilisins and chymotrypsin-related serine proteases have a catalytic triad containing aspartate, histidine, and serine.

[0053] A protease is an active protein that exerts "protease activity" or "proteolytic activity." Proteolytic activity relates to the rate of degradation of a protein by a protease or proteolytic enzyme over a defined time course.

[0054] Methods for analyzing proteolytic activity are well known in the literature (see, e.g., Gupta et al. (2002), Appl. Microbiol. Biotechnol. 60, 381-395). Proteolytic activity can be determined by using succinyl-Ala-Ala-Pro-Phe-p-nitroanilide as a substrate (Suc-AAPF-pNA, short AAPF; see, e.g., DelMar et al. (1979), Analytical Biochem 99, 316-320). pNA is cleaved from the substrate molecule by proteolytic cleavage, resulting in the release of a yellow color of free pNA, and an OD 405 This can be quantified by measuring

[0055] Proteolytic activity may be provided in units per gram of enzyme. For example, 1 U of protease may correspond to the amount of protease that liberates 1 μmol of Folin-positive amino acids and peptides (as tyrosine) per minute at pH 8.0 and 37° C. (using casein as a substrate).

[0056] Subtilisin-type proteases (EC 3.4.21.62) are proteases from the genera Bacillus, Clostridium, Enterococcus, Geobacillus, Lactobacillus, Lactococcus, Oceanobacillus, Staphylococcus, Streptococcus, and Streptomyces. The protease may be a bacterial protease or a Gram-negative bacterial polypeptide derived from a microorganism selected from the group consisting of Campylobacter, E. coli, Flavobacterium, Fusobacterium, Helicobacter, Ilyobacter, Neisseria, Pseudomonas, Salmonella, and Ureaplasma.

[0057] In one embodiment of the present invention, the at least one protease (D) is selected from the group consisting of Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus circulans, Bacillus clausii, Bacillus coagulans, Bacillus firmus, Bacillus gibsonii, Bacillus lautus, Bacillus lentus, Bacillus licheniformis, Bacillus megaterium, Bacillus The protease is selected from Bacillus megaterium, Bacillus pumilus, Bacillus sphaericus, Bacillus stearothermophilus, Bacillus subtilis, or Bacillus thuringiensis.

[0058] In one embodiment of the present invention, the at least one protease (D) is selected from the following: subtilisin from Bacillus amyloliquefaciens BPN' (described by Vasantha et al. (1984) J. Bacteriol. Volume 159, pp. 811-819 and J.A. Wells et al. (1983) Nucleic Acids Research, Volume 11, pp. 7911-7925); subtilisin from Bacillus licheniformis (subtilisin Carlsberg; E.L. Smith et al. (1968) J. Biol. Chem., Volume 243, pp. 2184-2191 and Jacobs et al. (1985) in Nucleic Acids Res., Vol. 13, pp. 8913-8926); subtilisin PB92 (the original sequence of alkaline protease PB92 is described in European Patent Application Publication No. 283075A2); subtilisins 147 and / or 309 (Esperase® and Savinase®, respectively) disclosed in WO 89 / 06279; subtilisins derived from Bacillus lentus disclosed in WO 91 / 02792, such as subtilisin derived from Bacillus lentus DSM 5483 or variants of Bacillus lentus DSM 5483 described in WO 95 / 23221; subtilisin derived from Bacillus alkalophilus disclosed in German Patent No. 10064983; subtilisins from Bacillus gibsonii (DSM 14391) disclosed in WO 2003 / 054184; subtilisins from Bacillus sp. (DSM 14390) disclosed in WO 2003 / 056017; and subtilisins from Bacillus sp. disclosed in WO 2003 / 055974.) (DSM 14392); the subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003 / 054184; the subtilisin having SEQ ID NO: 4 described in WO 2005 / 063974, the subtilisin having SEQ ID NO: 4 described in WO 2005 / 103244; the subtilisin having SEQ ID NO: 7 described in WO 2005 / 103244, and the subtilisin having SEQ ID NO: 2 described in German Patent Application No. 102005028295.4.

[0059] Examples of proteases useful according to the present invention include variants described in WO 92 / 19729, WO 95 / 23221, WO 96 / 34946, WO 98 / 20115, WO 98 / 20116, WO 99 / 11768, WO 01 / 44452, WO 02 / 088340, WO 03 / 006602, WO 2004 / 03186, WO 2004 / 041979, WO 2007 / 006305, WO 2011 / 036263, WO 2011 / 036264 and WO 2011 / 072099. Suitable examples include SEQ ID NO: 22 (Bacillus lentus) as described in EP 1921147, which has an amino acid substitution at one or more of the following positions: 3, 4, 9, 15, 24, 27, 33, 36, 57, 68, 76, 77, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 118, 120, 123, 128, 129, 130, 131, 154, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 (according to BPN numbering), which has particular proteolytic activity. In one embodiment, the sequence of the mature alkaline protease from B. lentus DSM 5483 is not mutated at positions Asp32, His64, and Ser221 (according to BPN numbering).

[0060] In one embodiment, the at least one protease (D) is a proteolytically active protease having a sequence according to SEQ ID NO: 22 as described in EP 1921147 or at least 80% identical thereto. In one embodiment, said protease is characterized by having the amino acid glutamic acid, or aspartic acid, or asparagine, or glutamine, or alanine, or glycine, or serine at position 101 (according to BPN numbering) and has proteolytic activity. In one embodiment, the protease comprises one or more further substitutions: (a) threonine at position 3 (3T), (b) isoleucine at position 4 (4I), (c) alanine, threonine or arginine at position 63 (63A, 63T or 63R), (d) aspartic acid or glutamic acid at position 156 (156D or 156E), (e) proline at position 194 (194P), (f) methionine at position 199 (199M), (g) isoleucine at position 205 (205I), (h) aspartic acid, glutamic acid or glycine at position 217 (217D, 217E or 217G), or (i) a combination of two or more amino acids from (a)-(h).

[0061] At least one protease (D) may be at least 80% identical to SEQ ID NO: 22 described in EP 1 921 147 and is characterized by comprising one amino acid (according to (a) to (h)) or a combination according to (i) together with amino acids 101E, 101D, 101N, 101Q, 101A, 101G, or 101S (according to BPN numbering). In one embodiment, said protease comprises the mutations (according to BPN numbering) R101E, or S3T + V4I + V205I, or R101E and S3T, V4I and V205I, or S3T + V4I + V199M + V205I + L217D, and is characterized by having proteolytic activity. A protease having a sequence according to SEQ ID NO: 22 described in EP 1 921 147 together with 101E may be referred to herein as Lavergy.

[0062] In one embodiment, the protease according to SEQ ID NO: 22 described in EP 1921147 comprises the mutations (according to BPN numbering) S3T+V4I+S9R+A15T+V68A+D99S+R101S+A103S+I104V+N218D and is characterized by having proteolytic activity.

[0063] The compositions of the present invention may comprise a combination of at least two proteases, preferably selected from the group of serine endopeptidases (EC 3.4.21), more preferably selected from the group of subtilisin-type proteases (EC 3.4.21.62), all of which are disclosed above.

[0064] It is preferred to use a combination of lipase (B) and protease (D) in the composition, for example 1% to 2% by weight of protease (D) and 0.1% to 0.5% by weight of lipase (B), both relative to the total weight of the composition.

[0065] In the context of the present invention, a lipase (B) and / or a protease (D) is considered to be called stable if its enzymatic activity "available in use" is equal to at least 60% compared to the initial enzymatic activity before storage. An enzyme may be called stable in the present invention if its enzymatic activity available in use is at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, or at least 99.5% compared to the initial enzymatic activity before storage.

[0066] Subtracting a % from 100% gives the "loss of enzyme activity during storage" compared to the initial enzyme activity before storage. In one embodiment, an enzyme is stable according to the present invention if essentially no loss of enzyme activity occurs during storage, i.e., the loss of enzyme activity is equal to 0% compared to the initial enzyme activity before storage. Essentially no loss of enzyme activity in the present invention can mean that the loss of enzyme activity is less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, or less than 5%.

[0067] In one embodiment of the present invention, the composition of the present invention comprises: (C) At least one anionic surfactant is contained, and hereinafter, this is also referred to as anionic surfactant (C).

[0068] Examples of the anionic surfactant (C) include C8 to C 18 -Alkali metal and ammonium salts of alkyl sulfates, C8-C 18 Alkali metal and ammonium salts of fatty alcohol polyether sulfates, ethoxylated C4-C 12 -Alkali metal and ammonium salts of sulfuric acid half esters of alkylphenols (ethoxylated: 1 to 50 mol ethylene oxide / mol), C 12 ~C 18 Sulfofatty acid alkyl esters, such as C 12 ~C 18 Alkali metal and ammonium salts of sulfo fatty acid methyl esters, and further C 12 ~C 18 -Alkali metal and ammonium salts of alkylsulfonic acids, and C 10 ~C 18 - alkali metal and ammonium salts of alkylarylsulfonic acids. The alkali metal salts of the aforementioned compounds are preferred, with the sodium salts being particularly preferred.

[0069] Further examples of anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylic acids and alkyl ether phosphates.

[0070] In a preferred embodiment of the present invention, the anionic surfactant (C) is selected from compounds according to the general formula (II): R 1 -O(CH2CH2O) x -SO3M (II) During the ceremony, R 1 nC 10 ~C 18 -alkyl, in particular having an even number of carbon atoms, for example n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, preferably C 10 -C 14 -alkyl, even more preferably nC 12 -alkyl, x is a number ranging from 1 to 5, preferably from 2 to 4, and even more preferably 3; M is selected from alkali metals, preferably potassium, and even more preferably sodium.

[0071] In the anionic surfactant (C), x may be an average number and therefore n is not necessarily an integer, whereas in the individual molecules according to formula (I), x represents an integer.

[0072] In one embodiment of the present invention, the composition of the present invention may contain 0.1% by weight to 60% by weight, preferably 5% by weight to 50% by weight of an anionic surfactant (C).

[0073] The compositions of the present invention may contain ingredients other than those previously mentioned. Examples are nonionic surfactants, fragrances, dyes, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.

[0074] Preferred compositions of the present invention may contain one or more non-ionic surfactants.

[0075] Preferred nonionic surfactants are alkoxylated alcohols, di- and multi-block copolymers of ethylene oxide and propylene oxide, and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APGs), hydroxyalkyl mixed ethers, and amine oxides.

[0076] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (IIIa):

[0077] [ka] wherein the variables are as defined below: R 2 are the same or different and are hydrogen and linear C1-C 10 alkyl, preferably identical in each case, ethyl, particularly preferably hydrogen or methyl, R 3 is a branched or straight chain C8-C 22 Alkyl, e.g., n-CH 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 , or nC 18 H 37 is selected from R 4 is C1~C 10 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl.

[0078] The variables e and f range from zero to 300, with the sum of e and f being at least 1, preferably ranging from 3 to 50. Preferably, e ranges from 1 to 100 and f ranges from 0 to 30.

[0079] In one embodiment, the compound of general formula (II) can be a block copolymer or a random copolymer, with block copolymers being preferred.

[0080] Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (IIIb):

[0081] [ka] wherein the variables are as defined below: R 2 are identical or different and are selected from hydrogen and linear C1-C0 alkyl, preferably identical in each case and are ethyl, particularly preferably hydrogen or methyl, R 5 is a branched or straight chain C6-C 20 Alkyl, specifically n-CH 17 , nC 10 H 21 , nC 12 H 25 , nC 13 H 27 , nC 15 H 31 , nC 14 H 29 , nC 16 H 33 , nC 18 H 37 is selected from a is a number ranging from zero to 10, preferably from 1 to 6; b is a number ranging from 1 to 80, preferably from 4 to 20; d is a number ranging from 0 to 50, preferably from 4 to 25.

[0082] The sum of a+b+d is preferably in the range of 5-100, and even more preferably in the range of 9-50.

[0083] The compound of general formula (III) can be a block copolymer or a random copolymer, with block copolymers being preferred.

[0084] Further suitable nonionic surfactants are selected from di- and multi-block copolymers composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-C 16 -Alkyl polyglucosides and branched C8-C 14 Likewise suitable are alkyl polyglycosides, for example compounds of the general formula (IV),

[0085] [ka] During the ceremony: R 6 is C1-C4-alkyl, in particular ethyl, n-propyl or isopropyl, R 7 -(CH2)2-R 6 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, y ranges from 1.1 to 4, and y is the average number.

[0086] Further examples of nonionic surfactants are compounds of general formulae (V) and (VI):

[0087] [ka] AO is selected from ethylene oxide, propylene oxide and butylene oxide; EO is ethylene oxide, CH2CH2-O, R 8 is a branched or straight chain C8-C 18-alkyl, and R 5 is as defined above.

[0088] A 3 O is selected from propylene oxide and butylene oxide; w is a number ranging from 15 to 70, preferably from 30 to 50; w1 and w3 are numbers ranging from 1 to 5, w2 is a number in the range of 13 to 35.

[0089] An overview of suitable further nonionic surfactants can be found in European Patent Application No. A0851023 and German Patent Application No. A19819187.

[0090] Mixtures of two or more different nonionic surfactants selected from the foregoing may also be present.

[0091] Other surfactants which may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants, and mixtures thereof.

[0092] An example of an amphoteric surfactant is one that has positive and negative charges in the same molecule under the conditions of use.A preferred example of an amphoteric surfactant is so-called betaine surfactant.Many examples of betaine surfactants have one quaternary nitrogen atom and one carboxylic acid group per molecule.A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0093] An example of an amine oxide surfactant is a compound of the general formula (VII): R 9 R 10 R 11 N → O (VII) In the formula, R 9 , R 10 , and R 11 are each independently an aliphatic, alicyclic or C2-C4-alkylene C 10 ~C 20-alkylamide moieties. Preferably, R 9 is C8~C 20 -Alkyl or C2-C4-alkylene C 10 ~C 20 -alkylamide, and R 10 and R 11 are both methyl.

[0094] A particularly preferred example is lauryl dimethylamine oxide, sometimes called lauramine oxide. An even more particularly preferred example is cocamidyl propyl dimethylamine oxide, sometimes called cocamidopropyl amine oxide.

[0095] In one embodiment of the present invention, the composition of the present invention may contain 0.1% by weight to 60% by weight of at least one surfactant selected from nonionic surfactants, amphoteric surfactants, and amine oxide surfactants.

[0096] In a preferred embodiment, the solid detergent compositions of the present invention for cleaners, and particularly for automatic dishwashing, do not contain anionic surfactants.

[0097] The composition of the present invention may contain at least one bleaching agent, also called bleach. The bleaching agent may be selected from chlorine bleaches and peroxide bleaches, and the peroxide bleaches may be selected from inorganic peroxide bleaches and organic peroxide bleaches. Preferred are inorganic peroxide bleaches selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates.

[0098] Examples of organic peroxide bleaching agents are organic percarboxylic acids, especially organic percarboxylic acids.

[0099] In the compositions of the present invention, alkali metal percarbonates, especially sodium percarbonate, are preferably used in coated form. Such coating agents can be organic or inorganic in nature. Examples are glycerol, sodium sulfate, silicates, sodium carbonate, and combinations of at least two of the foregoing, such as a combination of sodium carbonate and sodium sulfate.

[0100] Suitable chlorine-containing bleaches are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

[0101] The compositions of the present invention may contain, for example, in the range of 3% to 10% by weight of a chlorine-containing bleaching agent.

[0102] The compositions of the present invention may contain one or more bleaching catalysts. The bleaching catalyst may be selected from bleach-enhancing transition metal salts or complexes, such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen complexes, or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper complexes with nitrogen-containing tripodal ligands, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, may also be used as bleaching catalysts.

[0103] The compositions of the present invention may include one or more bleach activators, such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quats (trimethylammonium acetonitrile salts).

[0104] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0105] Examples of fragrances are benzyl salicylate, 2-(4-tert.-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0106] Examples of dyes are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101, Acid Green 1, Solvent Green 7, and Acid Green 25.

[0107] The compositions of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent compositions of the present invention due to attack by microorganisms. Examples of biocides and preservatives include BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT"), 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), benzoic acid, sorbic acid, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH"), and dibromodimethylhydantoin ("DBDMH").

[0108] Examples of viscosity modifiers are agar, carrageenan, tragacanth, gum arabic, alginate, pectin, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, such as polyacrylic acid crosslinked with bis-(meth)acrylamide, as well as silicic acid, clays, such as, but not limited to, montmorillonite, zeolite, dextrin, and casein.

[0109] A hydrotrope in the context of the present invention is a compound that promotes the dissolution of compounds that exhibit limited solubility in water. Examples of hydrotropes include, but are not limited to, organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and other organic solvents that are miscible with water under normal conditions. Further examples of suitable hydrotropes are the sodium salts of toluenesulfonic acid, xylenesulfonic acid, and cumenesulfonic acid.

[0110] Examples of polymers other than polymer (A) are in particular polyacrylic acids and their respective alkali metal salts, in particular their sodium salts. Suitable polymers in particular have an average molecular weight M preferably in the range of 2,000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. w and polyacrylic acid, each partially or completely neutralized with an alkali, especially sodium. Also suitable are copolymer polycarboxylates, particularly copolymers of acrylic acid and methacrylic acid, and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid. Polyacrylic acid and its respective alkali metal salts can function as soil redeposition inhibitors.

[0111] A further example of a polymer is polyvinylpyrrolidone (PVP), which may function as a color transfer inhibitor.

[0112] Further examples of polymers are polyethylene terephthalate, polyoxyethylene terephthalate, and polyethylene terephthalate endcapped with one or two hydrophilic groups per molecule, the hydrophilic groups being selected from CH2CH2CH2-SONa, CH2CH(CH2-SONa)2, and CH2CH(CH2SONa)CH2-SONa.

[0113] Examples of buffering agents are monoethanolamine and N,N,N-triethanolamine.

[0114] An example of a defoaming agent is silicone.

[0115] The compositions of the present invention are not only good at cleaning soiled laundry with respect to organic fatty stains, such as grease. The liquid detergent compositions of the present invention are also very useful for removing non-bleachable stains from laundry, including, but not limited to, stains from various fruit juices, such as red wine, tea, coffee, vegetable, and berry juice. They also do not leave residue on clothing.

[0116] A further aspect of the present invention is therefore the use of the compositions of the present invention for laundry care, where laundry care in this context includes laundry washing.

[0117] In another aspect, the compositions of the present invention are useful for cleaning hard surfaces. Thus, a further aspect of the present invention is the use of the compositions of the present invention for cleaning hard surfaces.

[0118] In the context of the present invention, the term "hard surface cleaning composition" includes cleaners for home care and industrial or institutional use. The term "hard surface cleaning composition" includes compositions for dishwashing, especially hand-washing and automatic dishwashing and utensil washing, as well as compositions for hard surface cleaning, such as, but not limited to, bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, car washing, including truck washing, open plant cleaning, cleaning-in-place, metal cleaning, disinfecting cleaning, farm cleaning, and pressure washing, but is not a laundry detergent composition. A particular embodiment of a hard surface cleaning composition is an automatic dishwashing composition.

[0119] In the context of the present invention, the terms "hard surface cleaning composition" and "hard surface cleaner composition" are used interchangeably.

[0120] In the context of the present invention, and unless otherwise specified, percentages in the context of ingredients of laundry detergent compositions are percentages by weight and are based on the total solids content of the respective laundry detergent composition. In the context of the present invention, and unless otherwise specified, percentages in the context of ingredients of detergent compositions for hard surface cleaners are percentages by weight and are based on the total solids content of the detergent composition for hard surface cleaning.

[0121] When the compositions of the present invention are used in automatic dishwashing, they preferably (E) Contains at least one builder component selected from aminopolycarboxylic acids and preferably their alkali metal salts, also referred to in the context of the present invention as complexing agent (E) or sequestering agent (E). In the context of the present invention, the terms sequestering agent and chelating agent are used interchangeably.

[0122] Examples of the sequestering agent (E) include alkali metal salts of MGDA (methylglycine diacetate), GLDA (glutamic acid diacetate), IDS (iminodisuccinic acid), EDTA, and polymers having complexing groups, for example, polymers in which 20 to 90 mol% of the N atoms are substituted with at least one CH2COO - groups, and the respective alkali metal salts thereof, in particular the sodium salts thereof, such as MGDA-Na3, GLDA-Na4, or IDS-Na4.

[0123] Preferred sequestering agents are those of the general formula (IXa) [CH3-CH(COO)-N(CH2-COO)2]M 3-x H x (IXa) This is due to wherein M is selected from the same or different ammonium and alkali metal cations, such as sodium, potassium cations, and combinations of at least two of the foregoing. Ammonium may be alkyl substituted, but is not limited to unsubstituted ammonium NH4 +Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium, and it is even more preferred that in the compounds according to general formula (IIa) all M are the same and they are all Na; In formula (IIa), x is in the range of 0 to 1.0; or (IXb) [OOC-CH2CH2-CH(COO)-N(CH2-COO)2]M 4-x H x (IXb) This is due to wherein M is as defined above, and x in formula (IXb) ranges from zero to 2.0, preferably 1.0; or (IXc) [OOC-CH2-CH(COO)]-N-CH(COO)-CH2-COO]M 4-x H x (IXc) This is due to wherein M is as defined above, and x in formula (IIc) ranges from zero to 2.0, preferably 1.0.

[0124] In one embodiment of the invention, the composition of the invention comprises a combination of at least two of the foregoing, for example a combination of a chelating agent according to general formula (IXa) and a chelating agent according to general formula (IXb).

[0125] The chelating agents according to the general formulae (IXa) and (IXb) are preferred. Even more preferred are the chelating agents according to the general formula (IXa).

[0126] In one embodiment of the present invention, the compound according to general formula (IXa) is selected from the ammonium or alkali metal salts of racemic MGDA and the ammonium and alkali metal salts of a mixture of L- and D-enantiomers according to formula (IXa), said mixture containing predominantly the respective L-isomers, with an enantiomeric excess (ee) ranging from 5% to 99%, preferably from 5% to 95%, more preferably from 10% to 75%, and even more preferably from 10% to 66%.

[0127] In one embodiment of the present invention, the compound according to general formula (IXb) is selected from at least one alkali metal salt of a mixture of L- and D-enantiomers according to formula (IXb), said mixture being a racemic mixture or preferably containing predominantly the respective L-isomer, e.g., with an enantiomeric excess (ee) in the range of 5% to 99%, preferably 15% to 95%.

[0128] The enantiomeric excess of the compound of general formula (IXa) can be determined by measuring polarized light (polarimetry) or preferably by chromatography, for example by HPLC with a chiral column, for example using one or more cyclodextrins as the stationary phase or using a chiral stationary phase of the ligand exchange (Pirkle-brush) concept. Preference is given to determining the ee by HPLC using an immobilized optically active amine, for example D-penicillamine in the presence of copper(II) salts. The enantiomeric excess of the compound of general formula (IXb) salt can be determined by measuring polarized light (polarimetry).

[0129] Due to environmental concerns arising in the context of the use of phosphates, advantageous compositions are preferably phosphate-free. "Phosphate-free" in the context of the present invention should be understood to mean that the phosphate and polyphosphate content is in the range of from the detection level to 1% by weight, preferably 10 ppm to 0.2% by weight in total, determined by gravimetric methods.

[0130] In one embodiment of the present invention, the composition of the present invention contains a sequestering agent (E) in the range of 0.5% to 50% by weight, preferably 1% to 35% by weight, relative to the total solid content.

[0131] To be suitable as a liquid laundry composition, the compositions of the present invention may be in bulk form or as unit doses, for example in the form of a sachet or pouch. Suitable materials for pouches are water-soluble polymers, for example polyvinyl alcohol.

[0132] In a preferred embodiment of the present invention, the composition of the present invention is in liquid or gel form at ambient temperature. In another preferred embodiment of the present invention, the composition of the present invention is in solid form, such as a powder or tablet, at ambient temperature.

[0133] In one embodiment of the invention, the compositions of the invention are liquid or gel type and have a pH value in the range of 7 to 9, preferably 7.5 to 8.5. In embodiments in which the compositions of the invention are solid, their pH value may be in the range of 7.5 to 11, determined at ambient temperature after dissolving 1 g per 100 ml in distilled water. In embodiments in which the compositions of the invention are used for hard surfaces such as tiles, e.g., bathroom tiles, their pH value may even be acidic, e.g., 3 to 6.

[0134] In one embodiment of the present invention, the composition of the present invention is liquid or gel type and has a total solids content ranging from 8% to 80%, preferably from 10% to 50%, as measured by drying at 80°C under vacuum.

[0135] Another aspect of the present invention relates to a polymer (A), hereinafter also referred to as the polymer (A) of the present invention or simply as the polymer (A). The polymer (A) of the present invention is (a) a core having 1 to 3 moieties according to general formula (I);

[0136] [ka] wherein Z is different or the same; C2~C 12 -Alkylene, for example -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, -(CH2) 12 -, and preferred are -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, and -(CH2)6-, and the C2 to C 12 - alkylene may be linear or branched, unsubstituted or substituted with one or more O-C1-C4-alkyl groups, and C3~C 12 -cycloalkylene, preferably C5-C6-cycloalkylene, 12 -Cycloalkylene, preferably C5-C6-cycloalkylene, may be unsubstituted or substituted with one or more O-C1-C4-alkyl groups, 12 -Cycloalkylene, preferably C5-C6-cycloalkylene, may have 1 to 3 methyl groups, preferably C5-C 10 -cycloalkylene, for example 1,3-cyclopentylene, 1,2-cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 1-methyl-2,4-cyclohexylene, 1-methyl-2,6-cyclohexylene, 1,3-cycloheptylene, 1,4-cyclooctylene, 1,5-cyclooctylene, X 1 is selected from hydrogen, methyl, ethyl and combinations of at least two of the foregoing, preferably methyl and combinations of methyl and hydrogen, more preferably hydrogen; A 1 are different or the same, and C1 to C 12 -Alkylene, preferably C2-C4-alkylene, for example -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)8-, -(CH2) 10 -, -(CH2) 12 -, preferably -CH2CH2-, -(CH2)3-, -(CH2)4-, further C6-arylene, and C3-C 12 -Cycloalkylene, C2-C 12 -Alkylene and C3-C 12 -Cycloalkylene may be unsubstituted or substituted by one or more O-C1-C4-alkyl or OH groups, and may be C3-C 12 -cycloalkylene may have 1 to 3 methyl groups; or based on citric acid, for example -CH2-C(CO2H)(OH)-CH2- or -CH2-C(OH)(CH2-COOH)-.

[0137] In one embodiment of the present invention, A in polymer (A) 1 is a mixture of C2-C4-alkylene and citric acid-based residues, for example in a molar ratio of 1:10-15:1, preferably 1:5-10:1.

[0138] n is in the range of 1 to 100, preferably 10 to 75.

[0139] The free valence on the nitrogen atom in formula (I) is a polyalkylene chain (b) or -CH-CH(X 1 )-O(CO)-A 1 -(CO)-O-CHX 1 In an embodiment in which the molecular weight Mw is 10,000 g / mol or more, the free valence on the nitrogen atom in formula (I) is a polyalkylene chain (b) or a -CH-CH(X 1 )-O-CHX 1 Contains -CH2-NZN units.

[0140] Preferably, Z are isomers of each other and / or differ only in variable n. Even more preferably, Z are isomers.

[0141] A preferred example of Z is the formula

[0142] [ka] and is therefore a mixture of isomers.

[0143] In one embodiment of the present invention, the polymer (A) has an average molecular weight M in the range of 2,500 to 300,000 g / mol, preferably 5,000 to 250,000 g / mol. w The average molecular weight can be determined, for example, by gel permeation chromatography (GPC) in tetrahydrofuran (THF) as the mobile phase using linear polymethyl methacrylate ("PMMA") as a standard.

[0144] In one embodiment of the present invention, the polymer (A) has a molecular weight distribution M in the range of 1.1 to 2.5. w / M n It has.

[0145] In one embodiment of the present invention, polymer (A) has a Hazen color number in the range of 20 to 500, determined in a 10% by weight aqueous solution.

[0146] In one embodiment of the present invention, polymer (A) has an OH number in the range of 20 to 650 mg KOH, preferably 30 to 100 mg KOH per gram of polymer (A), measured according to DIN 53240 (2013).

[0147] In one embodiment of the present invention, polymer (A) has a total amine value in the range of 10 to 650 mg KOH, preferably 10 to 510 mg KOH, more preferably 10 to 80 mg KOH per gram of polymer (A), determined according to ASTM D2074-07.

[0148] The polymer of the present invention is (b) Polyalkylene oxide chain Further includes:

[0149] The polyalkylene oxide side chains can be derived from C2-C4 alkylene oxides. Examples of C2-C4 alkylene oxides are ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BuO"), and mixtures of at least two of the foregoing, such as ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide. Preferred are propylene oxide and ethylene oxide, more preferred is ethylene oxide.

[0150] In one embodiment of the present invention, the weight ratio of core (a) to polyalkylene oxide chain (b) in polymer (A) ranges from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0151] In one embodiment of the present invention, the polymer (A) of the present invention may further comprise one or more structural units according to the general formula (X).

[0152] [ka]

[0153] The polymer (A) of the present invention is highly suitable for use as the composition of the present invention or for the preparation thereof. The polymer (A) of the present invention is biodegradable.

[0154] In one aspect, the present invention relates to a method for improving the cleaning performance of a liquid detergent composition by adding a polymer (A) according to the present invention to a detergent composition preferably comprising at least one lipase and / or at least one protease.

[0155] The term "improved cleaning performance" herein may indicate that the polymer (A) provides better or improved stain removal properties under comparable cleaning conditions compared to the cleaning performance of a detergent composition lacking the polymer (A). In one embodiment, "improved cleaning performance" refers to improved cleaning performance of a detergent comprising the polymer (A) and at least one enzyme, preferably at least one hydrolase (B), in particular at least one lipase (B) and / or at least one protease (D), compared to the cleaning performance of a detergent comprising the polymer (A) but without any enzyme. In one embodiment, "improved cleaning performance" refers to improved cleaning performance of a detergent comprising the polymer (A) and an enzyme, preferably a hydrolase (B), more preferably a lipase (B) and / or a protease (D), compared to the cleaning performance of a detergent comprising at least one enzyme, preferably at least one hydrolase (B), preferably a lipase (B) and / or at least one protease (D), but without the polymer (A).

[0156] The term "relevant washing conditions" in this specification refers to the conditions, in particular the washing temperature, time, washing mechanism, soapy water concentration, detergent type and water hardness, that are actually used in a washing machine, automatic dishwasher or manual washing process.

[0157] A further aspect of the present invention relates to a method for preparing the polymer (A) of the present invention, hereinafter also referred to as the inventive method, which comprises steps (α), (β), and (γ): (α) reacting a diamine according to the general formula HN-Z-NH with an alkylene oxide in a molar ratio of alkylene oxide:diamine of 4:1 to 1:1, preferably 2.5:1 to 1:0.7, even more preferably wherein the alkylene oxide is selected from ethylene oxide and propylene oxide, thereby forming an intermediate; (β) reacting the intermediate from step (α) with at least one dicarboxylic or tricarboxylic acid, or a mixture of the aforementioned, or in each case with the respective anhydride or C1-C4-alkyl ester, thereby obtaining an ester, (γ) reacting the ester from step (β) with at least one C2-C4-alkylene oxide in one or more steps Includes.

[0158] Steps (α), (β) and (γ) are described in more detail below.

[0159] In step (α), a diamine of the general formula H-N-Z-NH is reacted with an alkylene oxide. The variable Z is defined above. For purposes of this invention, a mixture of isomeric diamines is considered a "diamine." For example, diamino-methylcyclohexane is typically produced as a mixture of various isomers.

[0160] [ka]

[0161] The alkylene oxide reacted in step (α) is selected from ethylene oxide (“EO”), propylene oxide (“PO”), and mixtures of the foregoing. Preferred are propylene oxide and ethylene oxide, and more preferred is ethylene oxide.

[0162] In step (α), the molar ratio of alkylene oxide to diamine is in the range of 4:1 to 1:1, preferably 2.5:1 to 1:0.7.

[0163] In step (a) based on methylcyclohexanediamine, the following compound:

[0164] [ka] and a mixture of compounds containing each isomer based on 2,6-diamine is formed.

[0165] Step (α) may be carried out with or without a solvent. In embodiments where the diamine of general formula H2-NZ-NH2 is a liquid at the reaction temperature, it is preferred to use the diamine in bulk. In embodiments where the diamine of general formula H2-NZ-NH2 is a solid at the reaction temperature, it is preferred to use a solvent. Suitable solvents are aprotic solvents, such as hydrocarbons, e.g., toluene, and ethers, e.g., di-n-butyl ether.

[0166] In one embodiment of the present invention, step (α) may comprise diluting a diamine of general formula H2-NZ-NH2 with water prior to alkoxylation, for example in a diamine:water weight ratio of 100:1 to 1:1, in particular 20:1 to 5:1.

[0167] Preferably, step (α) is carried out in the absence of a catalyst.

[0168] In one embodiment of the present invention, step (α) is carried out at a reaction temperature of 90 to 150°C, preferably 100 to 135°C.

[0169] In one embodiment of the present invention, step (α) may be carried out at a pressure of up to 15 bar, preferably up to 10 bar, for example from 1 to 8 bar. Preferred vessels for carrying out step (α) are autoclaves and tubular reactors.

[0170] In one embodiment of the present invention, step (α) has a duration ranging from 30 minutes to 10 hours, preferably from 1 hour to 7 hours.

[0171] Step (α) may be carried out under an inert gas atmosphere, such as nitrogen or a noble gas. In another embodiment, step (α) is carried out under an alkylene oxide atmosphere. An inert gas atmosphere is preferred. From step (α), an intermediate is formed. For example, the intermediate can be worked up by removing unreacted alkylene oxide and water, if present, or the intermediate from step (α) can be used without further workup. The removal of unreacted alkylene oxide and water, if present, can be carried out by evaporation at a pressure ranging from 500 mbar to 0 mbar, preferably from 100 mbar to 20 mbar, and at a temperature ranging from 20 to 120°C, preferably from 60 to 100°C. The intermediate from step (α) is usually a mixture of compounds, the main component of which is H-AO-NH-Z-NH-AO-H, where AO is CH2CH2-O or CH2CH(CH3)-O, and the degree of alkoxylation is usually an average number.

[0172] The intermediate is obtained from step (α).

[0173] In step (β), the intermediate from step (α) is reacted with at least one dicarboxylic or tricarboxylic acid, or with a mixture of the aforementioned, or in each case with the respective anhydride or C1-C4-alkyl ester, thereby obtaining an ester.

[0174] Step (β) may be carried out at a temperature in the range of 20 to 180°C. In embodiments where ester(s), particularly C1-C2-alkyl esters, such as diethyl adipate, diethyl succinate, dimethyl adipate, dimethyl succinate, triethyl citrate, etc., are used, temperatures in the range of 25 to 150°C are preferred. In embodiments where anhydride(s), such as succinic anhydride, are applied, temperatures in the range of 25 to 150°C are preferred. In embodiments where the respective free acid(s) are used, temperatures in the range of 100 to 180°C are preferred. In particular, in embodiments where temperatures above 100°C are applied, elevated temperatures are preferred.

[0175] Step (β) may be carried out at any pressure, for example from 10 mbar to 10 bar. Preferred are ambient pressure and lower pressures, for example from 10 to 500 mbar.

[0176] During step (β), water or alcohols, such as methanol or ethanol, are formed. Such by-products are preferably removed, for example, by distilling them off. Suitable apparatus are Dean-Stark apparatus, distillation columns, water removers, and other apparatuses that can serve to remove water or alcohols by distillation.

[0177] Step (β) may be carried out in the absence or presence of a solvent. Suitable solvents are aromatic solvents such as toluene, aliphatic hydrocarbons or cycloaliphatic solvents, such as decane, cyclohexane, n-heptane, etc. However, step (β) is preferably carried out in the absence of a solvent, especially when the reaction mixture is liquid at the reaction temperature.

[0178] In one embodiment of the present invention, step (β) is carried out in the presence of a catalyst.

[0179] Examples of suitable catalysts are especially acidic catalysts, such as inorganic and organic acids.

[0180] Acidic inorganic catalysts for the purposes of the present invention include, for example, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH value 5-6), and acidic alumina. For example, compounds of the general formula Al(OR 5 )3 and aluminum compounds of the general formula Ti(OR 5 ) 4 titanate esters are also suitable as acidic inorganic catalysts, with residues R 5 are the same or different, and the following C1~C 10 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl, C3~C 12 - cycloalkyl, for example independently selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, with cyclopentyl, cyclohexyl and cycloheptyl being preferred.

[0181] Preferably, Al(OR 5 )3 and Ti(OR 5 Residue R in 4 5 are the same and are selected from isopropyl or 2-ethylhexyl.

[0182] Preferred acidic organometallic catalysts include, for example, dialkyltin oxides (R 5 )2SnO, R 5 is as defined above. One particularly preferred representative acidic organometallic catalyst is di-n-butyltin oxide, which is commercially available in the oxo-tin form.

[0183] Preferred acidic organic catalysts are, for example, acidic organic compounds containing phosphoric acid groups, sulfonic acid groups, sulfuric acid groups, or phosphonic acid groups. Sulfonic acids, such as para-toluenesulfonic acid or methanesulfonic acid, are particularly preferred. Acidic ion exchangers can also be used as acidic organic catalysts, for example, polystyrene resins containing sulfonic acid groups and crosslinked with about 2 mol% divinylbenzene. Methanesulfonic acid is particularly preferred.

[0184] Combinations of two or more of the aforementioned catalysts can also be used. Another possibility is to use organic or organometallic or inorganic catalysts in the form of separate molecules, in immobilized form.

[0185] When the use of an acidic inorganic, organometallic or organic catalyst is desired, the amount of catalyst used according to the present invention is from 0.01% to 10% by weight, preferably from 0.1% to 2% by weight, more preferably from 0.2% to 1% by weight, based on the total amount of reactants, respectively.

[0186] In another embodiment of the present invention, step (β) is carried out without the use of a catalyst.

[0187] In one embodiment of the present invention, step (β) has a duration ranging from 30 minutes up to 15 hours.

[0188] By carrying out step (β), the ester is obtained.

[0189] In one embodiment of the present invention, the reaction of step (β) results in complete conversion of all carboxylic acid or ester or anhydride groups of the respective dicarboxylic or tricarboxylic acid, or mixtures thereof, or in each case the respective anhydride or C1-C4-alkyl ester. However, in many embodiments, the conversion of the ester or carboxylic acid or anhydride groups is incomplete, resulting in esters that still contain carboxylic acid or C1-C4-alkyl ester groups. The completeness of the reaction can be assessed, for example, by determining the acid number according to EN ISO 660:(2009).

[0190] In one embodiment of the present invention, further groups, such as citric acid or its C1-C4-esters, may be reacted with, for example, a hydroxyl group.

[0191] The ester resulting from step (β) can be isolated and purified, for example, by removal of the solvent, if applicable, or by neutralization of the acid. In particular, in embodiments of step (β) in which neither a catalyst nor a solvent was used, it is preferred to carry the resulting ester to step (γ) without further purification steps.

[0192] In step (γ), the ester from step (β) is reacted with at least one C2-C4-alkylene oxide. Examples of C2-C4-alkylene oxides are ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BuO"), and mixtures of at least two of the foregoing. Preferred are propylene oxide and ethylene oxide, more preferred is ethylene oxide.

[0193] In one embodiment of the present invention, the weight ratio of alkylene oxide in step (γ) to ester from step (β) corresponds to the ratio of core (a) to side chain (b) and is therefore from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0194] Step (γ) is preferably carried out in the presence of a catalyst, such as a base or a double-metal cyanide.

[0195] In one embodiment of the present invention, step (γ) is carried out in the presence of a base. Suitable bases include potassium hydroxide, sodium hydroxide, sodium alkoxides, or potassium alkoxides, such as potassium methylate (KOCH), potassium tert-butoxide, sodium ethoxide, and sodium methylate (NaOCH), preferably potassium hydroxide and sodium hydroxide. Further examples of catalysts include alkali metal hydrides and alkaline earth metal hydrides, such as sodium hydride and calcium hydride, and alkali metal carbonates, such as sodium carbonate and potassium carbonate. Alkali metal hydroxides are preferred, including potassium hydroxide, sodium hydroxide, and alkali metal alkoxides, with potassium tert-butoxide in tert-butanol, sodium n-hexanoate in n-hexanol, and sodium methanolate in n-nonanol being particularly preferred. A typical amount of base used is 0.05% to 10% by weight, in particular 0.5% to 2% by weight, based on the total amount of condensate and C2-C4-alkylene oxide from step (β).

[0196] In one embodiment of the present invention, step (γ) is carried out in the presence of a double metal cyanide. A double metal cyanide, hereinafter also referred to as a double metal cyanide compound or DMC compound, usually comprises at least two different metals, at least one of which is selected from transition metals and the other from transition metals and alkaline earth metals, and also a cyanide counterion. Particularly suitable catalysts for alkoxylation are double metal cyanides containing zinc, cobalt, or iron, or two of these. For example, Berlin blue is particularly suitable.

[0197] It is preferred to use a crystalline DMC compound. In a preferred embodiment, a crystalline DMC compound of the Zn-Co type containing zinc acetate as an additional metal salt component is used as the catalyst. Such compounds crystallize in a monoclinic structure and have platelet-like properties.

[0198] In one embodiment of the present invention, the synthesis of the present invention is carried out in the presence of at least one double metal cyanide selected from hexacyanocobaltates.

[0199] In one embodiment of the present invention, the synthesis of the present invention comprises the step of preparing a compound according to general formula (VIII) M 1 r1 [M 2 (CN) r2 (A) r3 ] r4 ·r 6 M 1 r7 X 2 m1 ·r 8 (H2O)·r 5 L·kP (VIII) In the presence of at least one double metal cyanide selected from During the ceremony, M 1 Zn 2+ , Fe 2+ , Fe 3+ , Co 3+ , Ni 2+ , Mn 2+ , Co 2+ , Sn 2+ , Pb 2+ , Mo 4+ , Mo 6+ , Al 3+ , V 4+ , V 5+ , Sr 2+ , W 4+ , W 6+ , Cr 2+ , Cr 3+ , Cd 2+ , Hg 2+ , Pd 2+ , Pt 2+ , V 2+ , Mg 2+ , Ca2+ , Ba 2+ , Cu 2+ , La 3+ , Ce 3+ , Ce 4+ ,EU 3+ , Ti 3+ , Ti 4+ , Ag + , Rh 2+ , Rh 3+ , Ru 2+ , Ru 3+ at least one metal ion selected from the group consisting of M 2 is Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , Mn 2+ , Mn 3+ , V 4+ , V 5+ , Cr 2+ , Cr 3+ , Rh 3+ , Ru 2+ , Ir 3+ at least one metal ion selected from the group consisting of and M 1 and M 2 are not identical in any way, A and X 2 are, independently of one another, anions selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, thiocyanate, isocyanate, cyanate, carboxylate, oxalate, nitrate, nitrosyl, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate or hydrogen carbonate, L is a ligand selected from the group consisting of alcohols, aldehydes, ketones, ethers, polyethers, esters, polyesters, polycarbonates, ureas, amides, primary, secondary and tertiary amines, ligands with pyridine nitrogen, nitriles, sulfides, phosphides, phosphites, phosphanes, phosphonates and phosphates; k is equal to or greater than zero up to a maximum of 6. The variable k can be an integer or a fraction.

[0200] P is an organic additive selected from, for example, polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly(acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylamide-co-maleic acid), polyacrylonitrile, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl acetate, polyvinyl alcohols, poly-N-vinylpyrrolidone, poly(N-vinylpyrrolidone-co-acrylic acid), polyvinyl methyl ketone, poly(4-vinylphenol), poly(acrylic acid-co-styrene), oxazoline polymers, maleic acid and maleic anhydride copolymers, hydroxyethyl cellulose, polyacetates, ionic surface-active and interface-active compounds, bile acids or their salts, esters or amides, carboxylic acid esters of polyhydric alcohols and glycosides.

[0201] r1, r2, r3, r4, r 7 and m1 are selected so as to ensure the electroneutrality of compound (I), and each of f and r 3 can be 0, r 5 is the number of ligand molecules, e.g., a fraction or integer greater than zero, or zero; r6 and r6 are, independently of one another, fractional or integer numbers greater than zero, or zero.

[0202] In one embodiment, r 5 , r 6 , and r 8 The upper limit of each is 6.

[0203] The double metal cyanide compounds can be used as powders, pastes or suspensions, or can be formed to obtain moldings, incorporated into moldings, foams, etc., or applied to moldings, foams, etc.

[0204] Preferably, the DMC catalyst used in step (γ) is 5 to 2000 ppm (i.e. 5 to 2000 mg of catalyst per kg of product), based on the polycondensate obtained in step (β), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm, ppm referring to ppm (parts per million) by mass of the polycondensate obtained in step (β).

[0205] Step (γ) may be carried out in bulk in embodiment (i) or in an organic solvent in embodiment (ii). In embodiment (i), water can be removed from the polycondensate obtained in step (β). Such water removal can be carried out by heating to a temperature in the range of 80 to 150°C under a reduced pressure in the range of 0.01 to 0.5 bar and distilling off the water.

[0206] In one embodiment of the present invention, step (γ) is carried out at a reaction temperature in the range of 70 to 200°C, preferably 100 to 180°C.

[0207] In one embodiment of the present invention, step (γ) is carried out once per synthesis of the inventive polymer (A). In an alternative embodiment, step (γ) is carried out several times, for example up to four times, per synthesis of the inventive polymer (A), for example using the same or preferably different C2-C4-alkylene oxides. For example, it is possible to subject the polycondensate obtained in step (β) to a first alkoxylation (γ1) with ethylene oxide, and the product from step (γ1) to a second alkoxylation (γ2), for example with propylene oxide.

[0208] In one embodiment of the present invention, step (γ) is carried out at a pressure of up to 10 bar, in particular up to 8 bar, for example between 1 and 8 bar.

[0209] In one embodiment of the present invention, the reaction time in step (γ) is generally in the range of 0.5 to 12 hours.

[0210] Examples of suitable organic solvents for embodiment (ii) of step (γ) include non-polar and polar aprotic organic solvents. Particularly suitable examples of non-polar aprotic solvents include aliphatic and aromatic hydrocarbons, such as hexane, cyclohexane, toluene and xylene. Particularly suitable examples of polar aprotic solvents are ethers, particularly cyclic ethers, such as tetrahydrofuran and 1,4-dioxane, as well as N,N-dialkylamides, such as dimethylformamide and dimethylacetamide, and N-alkyllactams, such as N-methylpyrrolidone. Likewise, it is possible to use a mixture of at least two of the above organic solvents. Preferred organic solvents are xylene and toluene.

[0211] In embodiment (ii), the solution obtained in the first step is dehydrated before or after the addition of the catalyst and the solvent and before being subjected to alkylene oxide, the water removal being advantageously carried out at a temperature in the range of 120 to 180°C, preferably supported by a nitrogen stream. The subsequent reaction with alkylene oxide can be achieved as in embodiment (i). In embodiment (i), the alkoxylated polyalkyleneimine according to the invention can be obtained directly in bulk and, if desired, dissolved in water. In embodiment (ii), as a workup, the organic solvent is typically replaced with water. Alternatively, the alkoxylated polyalkyleneimine (B) according to the invention can be isolated in bulk.

[0212] An "optional" post-treatment step may include deactivation of the catalyst used in step (γ), in the case of a basic catalyst, by neutralization.

[0213] The process of the present invention does not require a bleaching step or reductive removal of impurities. [Example]

[0214] The present invention is further illustrated by the examples.

[0215] Overview: Reactions were carried out under a nitrogen atmosphere unless otherwise stated. Percentages refer to weight percent unless otherwise specified. GPC was performed using THF as the mobile phase, linear PMMA as the internal standard, and hexafluoroisopropanol ("HFIP") as the solvent. The hydroxyl number (OH number) was determined according to 53240 (2013). Amine number was determined according to ASTM D2074-07. The Hazen color index was determined by spectrophotometric detection in accordance with DIN ISO 6271, ASTM D 1209 (2° standard observer, standard light, layer thickness 11 mm, against distilled water). rpm: revolutions per minute

[0216] I. Synthesis of the Polymers of the Invention I.1 Synthesis of intermediates Step (α.1) In a 3.5 liter steel autoclave, add 2,4-diamine and 2,6-diamine:

[0217] [ka] 1.6 kg of methylcyclohexyldiamine (MCDA, 12.5 mol) as a 4:1 mixture and 160 g of water were charged and then heated to 100°C. Next, 50 g of ethylene oxide was charged to the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Subsequently, 1,051 g of ethylene oxide ("EO") was charged to the autoclave within 12 hours, for a total of 25 mol of EO. The system was maintained at 100°C for an additional 6 hours. The mixture was then removed from the autoclave, and residual EO and water were stripped under reduced pressure (20 mbar) at 80°C for 2 hours. 2.7 kg of intermediate ITM.1 was obtained as a yellow, viscous liquid. analysis: OH value: 908 mg KOH / g Amine value: Total amines: 438 mg KOH / g

[0218] Step (α.2) In a 3.5 liter steel autoclave, add 2,4-diamine and 2,6-diamine:

[0219] [ka] 1.28 kg of methylcyclohexyldiamine (MCDA, 10 mol) as a 4:1 mixture and 128 g of water were charged and then heated to 100°C. Next, 50 g of propylene oxide was charged to the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Subsequently, 879 g of propylene oxide ("PO") was charged to the autoclave within 15 hours, for a total of 16 mol of PO. The system was held at 100°C for an additional 6 hours. The mixture was then removed from the autoclave, and the remaining PO and water were stripped under reduced pressure (20 mbar) at 80°C for 2 hours. 2.2 kg of intermediate ITM.2 was obtained as a yellow, viscous liquid. analysis: OH value: 856 mg KOH / g, Amine value: Total amine: 556 mg KOH / g

[0220] Step (α.3): The protocol of step (α.1) was followed, but 831 g of EO was used instead of 1.051 kg of EO. A quantity of 2.48 kg of intermediate ITM.3 was obtained as a yellow viscous liquid. analysis: OH value: 919 mg KOH / g, Amine value: Total amine: 556 mg KOH / g

[0221] Step (α.4) The protocol of step (α.1) was followed, but 769 g of EO was used instead of 1.16 g of MCDA, and 1.007 kg was used instead of 1.501 kg of EO. A quantity of 1.82 kg of intermediate ITM.4 was obtained as a yellow viscous liquid. analysis: OH value: 727 mg KOH / g, Amine value: Total amine: 376 mg KOH / g

[0222] I.2 Synthesis of Core (a) Step (β.1): ITM.1: Citric acid: Adipic acid: 1: 0.1: 0.88 A 500 ml flask equipped with a mechanical stirrer, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (13.35 g, 6.95 mmol) and adipic acid (91.4 g, 62.5 mmol). ITM.1 (155.3 g, 71.2 mmol) was heated to 60°C, and the resulting liquid was added to the Dean-Stark flask. The reaction mixture was stirred at 60 rpm under a nitrogen atmosphere and heated to 100°C over 15 minutes. As the temperature increased and the viscosity decreased, the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 120°C (internal temperature). Mild bubbling and an exothermic reaction were observed, and the temperature rose to 145°C. Water was distilled off and collected. Stirring at 140°C was continued under nitrogen for 4.8 hours. The reaction mixture was then slowly cooled. The resulting ester (a.1) was collected as a solid red material (148 g). GPC:M in HFIP n 1120 g / mol, M w 10386g / mol Acid value: 91.8mgKOH / g OH value: 337 mg KOH / g

[0223] Step (β.2): ITM.1: Citric acid: Sebacic acid: 1:0.1:0.9 A 500 ml flask equipped with a mechanical stirrer, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (12.42 g, 6.46 mmol) and sebacic acid (117.7 g, 58.2 mmol). ITM.1 (139.9 g, 64.2 mmol) was heated to 60°C, and the resulting liquid was added to the flask. The reaction mixture was stirred at 60 rpm under a nitrogen atmosphere and heated to 100°C over 15 minutes. As the temperature increased and the viscosity decreased, the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 120°C (internal temperature). Gentle effervescence was observed. Water was distilled off and collected. Stirring was continued under nitrogen for 6.5 hours. The reaction mixture was then slowly cooled. The resulting ester, Core (a.2), was collected as a solid red material. GPC:M in HFIP n 1925g / mol, M w 26095g / mol Acid value: 61.75mgKOH / g OH value: 209.1 mg KOH / g

[0224] Step (β.3): ITM.1 and triethyl citrate, molar ratio 1:0.35 A 1000 ml flask equipped with a blade stirrer, liquid divider, nitrogen inlet, and internal thermometer was charged with triethyl citrate (110 g, 0.39 mol) and ITM.1 (241.4 g, 1.11 mol). The temperature rose to 30°C during stirring. The resulting clear, viscous mixture was then degassed under vacuum for 3 minutes and then heated to 110°C and then to 130°C (oil bath temperature) over 30 minutes with stirring. After 5 hours, the temperature was reduced to 110°C (oil bath temperature) and the flask was placed under vacuum. After 7 minutes, the evacuation and heating were stopped, and the reaction mixture was allowed to cool to ambient temperature. The resulting ester, Core (a.3), was collected as a solid, reddish-brown material (280 g). GPC:M in HFIP n 1449 g / mol, M w 6491g / mol Acid value: 29mgKOH / g OH value: 513 mg KOH / g

[0225] Step (β.4): ITM.1, triethyl citrate and diethyl sebacate, molar ratio 1:0.066:0.9 A 1000 ml flask equipped with a blade stirrer, liquid divider, nitrogen inlet, and internal thermometer was charged with triethyl citrate (18.23 g, 0.066 mol), diethyl sebacate (232.6 g, 0.9 mol), and ITM.1 (217 g, 1 mol). The temperature rose to 30°C during stirring. The resulting clear, viscous mixture was then degassed under vacuum for 15 minutes and then heated to 115°C and then to 140°C (oil bath temperature) over 33 minutes with stirring. After 5 hours, the temperature was increased to 160°C (oil bath temperature), and stirring was continued for 8.6 hours. Heating was then stopped, and the reaction was cooled to ambient temperature. The resulting ester, Core (a.4), was collected as a solid, reddish-brown material (376 g). GPC:M in HFIP n 1110g / mol, M w 13144g / mol Acid value: 1.7mgKOH / g OH value: 304 mg KOH / g

[0226] Step (β.5): ITM.1, triethyl citrate and diethyl sebacate, molar ratio 1:0.342:0.5 A 1000 ml flask equipped with a blade stirrer, liquid divider, nitrogen inlet, and internal thermometer was charged with triethyl citrate (94.5 g, 0.342 mol), diethyl sebacate (132.8 g, 0.51 mol), and ITM.1 (222.2 g, 1.019 mol). The temperature rose to 30°C during stirring. The resulting clear, viscous mixture was then degassed under vacuum for 20 minutes and then heated to 140°C (oil bath temperature) with stirring. After 10.7 hours, the temperature was reduced to 110°C (oil bath temperature), and the flask was placed under vacuum. After 15 minutes, the vacuum and heating were removed, and the reaction was allowed to cool to ambient temperature. The resulting ester, Core (a.5), was collected as a solid, reddish-brown material (365 g). GPC:M in HFIP n 991g / mol, M w 10312g / mol Acid value: 4.8mgKOH / g OH value: 393 mg KOH / g

[0227] Step (β.6): ITM.2, citric acid and sebacic acid, molar ratio 1:0.1:0.96 A 500 ml flask equipped with a mechanical stirrer, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (12.0 g, 6.25 mmol) and sebacic acid (113.9 g, 56.3 mmol). ITM.2 (144 g, 58.5 mmol) was warmed to 60°C and added to the flask. The reaction mixture was stirred at 60 rpm under a nitrogen atmosphere and heated to 100°C over 15 minutes. As the temperature increased and the viscosity decreased, the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 140°C (internal temperature). Water was distilled off and collected. Stirring was continued under nitrogen for 14 hours. The reaction mixture was then slowly cooled. The resulting ester, Core (a.6), was collected as a solid reddish-brown material. GPC:M in HFIP n 1470 g / mol, M w 7134g / mol Acid value: 57.3mgKOH / g OH value: 262 mg KOH / g

[0228] Step (β.7): ITM.3, citric acid and adipic acid, molar ratio 1:0.09:0.82 A 500 ml flask equipped with a mechanical stirrer, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (13.4 g, 6.94 mmol) and adipic acid (91.4 g, 62.5 mmol). ITM.3 (165.3 g, approximately 75.5 mmol) was warmed to 60°C and added to the flask. The reaction mixture was stirred at 60 rpm under a nitrogen atmosphere and heated to 100°C over 15 minutes. As the temperature increased and the viscosity decreased, the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 120°C (internal temperature). Water was distilled off and collected. Stirring was continued under nitrogen for 13.75 hours. The reaction mixture was then slowly cooled. The resulting ester, Core (a.7), was collected as a solid reddish-brown material. GPC:M in HFIP n 504 g / mol, M w 7695g / mol Acid value: 79.6mgKOH / g OH value: 326 mg KOH / g

[0229] [Table 1]

[0230] Step (γ.1): A 3.5 L autoclave was charged with 185.0 g of the core (a.1) and 4.6 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120°C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130°C, and 50 g of ethylene oxide was charged within 10 minutes. Next, 929 g of ethylene oxide was added to the reaction mixture within 24 hours. The resulting reaction mixture was reacted at 130°C for another 6 hours. The autoclave was then cooled to 100°C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80°C. As a result, 1169 g of polymer (A.1.1) was obtained as a dark brown solid.

[0231] Step (γ.2): A 3.5 L autoclave was charged with 1.1 kg of polymer (A.1.1) and 8.3 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 915 g of propylene oxide was added to the reaction mixture within 20 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 2.07 kg of polymer (A.1.2) was obtained as a dark brown liquid.

[0232] Step (γ.3): A 3.5 L autoclave was charged with 182.0 g of the core (a.2) and 4.6 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120°C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130°C, and 50 g of ethylene oxide was charged within 10 minutes. Next, 549 g of ethylene oxide was added to the reaction mixture within 12 hours. The resulting reaction mixture was reacted at 130°C for another 6 hours. The autoclave was then cooled to 100°C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80°C. As a result, 780 g of polymer (A.2.1) was obtained as a dark brown solid.

[0233] Step (γ.4): A 3.5 L autoclave was charged with 638 g of polymer (A.2.1) and 4.6 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 465 g of propylene oxide was added to the reaction mixture within 10 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1.15 kg of polymer (A.2.2) was obtained as a dark brown liquid.

[0234] Step (γ.5): A 3.5 L autoclave was charged with 200 g of the core (a.3) and 7.2 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of ethylene oxide was charged within 10 minutes. 1,561 g of ethylene oxide was then added to the reaction mixture within 24 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1,816 g of polymer (A.3.1) was obtained as a dark brown solid.

[0235] Step (γ.6): A 3.5 L autoclave was charged with 990 g of polymer (A.3.1) and 7.7 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 880 g of propylene oxide was added to the reaction mixture within 30 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1.92 kg of polymer (A.3.2) was obtained as a dark brown liquid.

[0236] Step (γ.7): A 3.5 L autoclave was charged with 270 g of core (a.4) and 6.2 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of ethylene oxide was charged within 10 minutes. Next, 1,239 g of ethylene oxide was added to the reaction mixture within 24 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1.56 kg of polymer (A.4.1) was obtained as a dark brown solid.

[0237] Step (γ.8): A 3.5 L autoclave was charged with 800 g of polymer (A.4.1) and 6.0 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 648 g of propylene oxide was added to the reaction mixture within 12 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1.5 kg of polymer (A.4.2) was obtained as a dark brown liquid.

[0238] Step (γ.9): A 3.5 L autoclave was charged with 200 g of the core (a.5) and 5.4 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of ethylene oxide was charged within 10 minutes. Next, 1,184 g of ethylene oxide was added to the reaction mixture within 24 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1,438 g of polymer (A.5.1) was obtained as a dark brown solid.

[0239] Step (γ.10): A 3.5 L autoclave was charged with 990 g of polymer (A.5.1) and 6.2 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 693 g of propylene oxide was added to the reaction mixture within 12 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1.57 kg of polymer (A.5.2) was obtained as a dark brown liquid.

[0240] Step (γ.11): A 3.5 L autoclave was charged with 188 g of the core (a.6) and 3.8 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of ethylene oxide was charged within 10 minutes. Next, 723 g of ethylene oxide was added to the reaction mixture within 17 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 948 g of polymer (A.6.1) was obtained as a dark brown solid.

[0241] Step (γ.12): A 3.5 L autoclave was charged with 300 g of polymer (A.6.1) and 2.2 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 30 g of propylene oxide was charged within 10 minutes. Next, 225 g of propylene oxide was added to the reaction mixture within 4 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 545 g of polymer (A.6.2) was obtained as a dark brown liquid.

[0242] Step (γ.13): A 2 L autoclave was charged with 120 g of the core (a.7) and 2.9 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 140 °C, and 30 g of ethylene oxide was charged within 10 minutes. Next, 584 g of ethylene oxide was added to the reaction mixture within 9 hours. The resulting reaction mixture was reacted at 140 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 1258 g of polymer (A.7.1) was obtained as a dark brown solid.

[0243] Step (γ.14): A 2 L autoclave was charged with 500 g of polymer (A.7.1) and 3.8 g of aqueous potassium hydroxide solution (50% wt). The autoclave was heated to 120 °C under reduced pressure and flushed with nitrogen to remove water. The autoclave was heated to 130 °C, and 50 g of propylene oxide was charged within 10 minutes. Next, 392 g of propylene oxide was added to the reaction mixture within 5 hours. The resulting reaction mixture was reacted at 130 °C for another 6 hours. The autoclave was then cooled to 100 °C. The reaction mixture was stripped with nitrogen, and volatile compounds were removed in vacuo at 80 °C. As a result, 938 g of polymer (A.7.2) was obtained as a dark brown liquid.

[0244] [Table 2]

[0245] II. Washing performance ( II.1 Laundry washing A laundry liquor was prepared using water with a hardness of 14° dH (2.5 mmol / L; Ca:Mg:HCO3 4:1:8) containing 3.0 g / L of liquid test detergent L.1 (see composition in Table 3) and 2.0% of the inventive polymers (A.1.1) to (A.5.2) according to Table 2, and the main washing performance of the inventive polymers was tested in a washing machine.

[0246] [Table 3]

[0247] For performance testing in a washing machine (Miele SOFTTRONIC W 1935 WTL, 30°C, short program, 1200 rpm, 3.5 kg ballast load), three multi-stain monitors (M1, M2, M3) were washed together with four SBL-2004 sheets (wfk Testgewebe GmbH, DE; equivalent to 64 grams of ballast soil) as additional soil ballast.

[0248] Table 4. Multiple stain monitor for washing machine testing M1 (circular stain, 5cm diameter): CFT PC-H144: Red china clay on polyester / cotton (65:35) CFT KC-H115: Standard clay on cotton knit fabric CFT PC-H145: Polyester / cotton (65:35) on tennis court clay CFT KC-H018: Clay and soil stains on cotton knit fabric M2: CFT CS-10: Butterfat with colorant on cotton CFT CS-62: Lard on cotton, colored CFT CS-78: Soybean oil with pigment on cotton EMPA 112: Cocoa on cotton EMPA 141 / 1: Lipstick on cotton EMPA 125: Soils on cotton sensitive to surfactants and lipases wfk20D: Pigments and sebaceous fats on polyester / cotton blend fabrics CFT CS-70: Chocolate / Mousse Cream on Cotton M3: wfk20D: Pigments and sebaceous fats on polyester / cotton blend fabrics EMPA 101: Cotton stained with carbon black / olive oil EMPA 141 / 2: Lipstick stained polyester / cotton (65:35) CFT PC-S-04: Olive oil, coloring EMPA 114: Red wine stained cotton EMPA 112: Cocoa stained cotton EMPA 116: Blood / Milk / Ink Stained Cotton CFT CS-01: Aged blood on cotton CFT CS-08: Grass on Cotton CFT C-10: Pigment / Oil / Milk on Cotton CFT PC-05: Blood / Milk / Ink on Polyester / Cotton (65:35)

[0249] Color measurements were used to evaluate the overall level of cleaning. A spherical reflectance spectrometer (Model SF 500, Datacolor, USA, wavelength range 360-700 nm, optical geometry d / 8°) equipped with a UV cut filter at 460 nm was used to measure the reflectance values ​​of the stains on the monitor. In this case, the CIE-Lab color space classification method was used to measure the luminance L * , value a on the red-green axis * and value b on the yellow-blue axis * was measured before and after washing and averaged for each stain in the monitor.

[0250]

number

[0251] A higher Delta E value indicates better cleaning. For each stain, a difference of 1 unit can be visually detected by an expert. A non-expert can easily visually detect a difference of 2 units. The Delta E values ​​of the formulations for 4, 8, and 11 stains corresponding to M1 and M2 plus M3 and for some selected single stains are shown in Table 5.

[0252] [Table 4]

[0253] In this test, cleaning performance benefits are seen in terms of ΔE for both M1 and M2 plus M3 monitors using polyesteramines of the present invention. Higher benefits can be seen for the first ethoxylated, then propoxylated polymers (γ.2, γ.4, γ.6, γ.8, γ.10) against oil-containing stains such as sebum and lipstick (wfk20D and EMPA141 / 2).

[0254] II.2 Hard surface cleaning Nonionic surfactant: (IV.1): nC where y is about 1.3 16 -Alkyl / nC 18 -Alkyl-polyglucosides II.2.1 Preparation of Comparative Formulation C-HSC.1 80 g of water was placed in a 250 ml container. 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene glycol (BDG) were then added, followed by 2 g of a 50% aqueous solution of (IV.1). Homogenization was achieved by gentle stirring (magnetic) for 5 minutes at ambient temperature. Comparative formulation C-HSC.1 was obtained.

[0255] II.2.2 Preparation of the formulation HSC.2 according to the invention 80 g of water was placed in a 250 ml container. 6 g of aqueous NaOH (50%) and 8 g of butylene glycol (BDG) were then added, followed by 2 g of a 50% aqueous solution of (IV.1) and 4 g of the inventive polymer (A.5.2). Homogenization was achieved by gentle stirring (magnetic) for 5 minutes at ambient temperature. Inventive formulation HSC.2 was obtained.

[0256] II.2.3 Preparation of the formulation HSC.3 according to the invention 80 g of water was placed in a 250 ml container. 6 g of aqueous NaOH (50%) and 8 g of butylene glycol (BDG) were then added, followed by 5 g of a 41 wt % solution of MGDA-Na3, 2 g of a 50% aqueous solution of (IV.1) and 2 g of the polymer of the present invention (A.5.2). Homogenization was achieved by gentle stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.3 of the present invention was obtained.

[0257] II.2.4 Preparation of the formulation HSC.4 according to the invention 80 g of water was placed in a 250 ml container. 6 g of aqueous NaOH (50%) and 8 g of butylene glycol (BDG) were then added, followed by 5 g of a 41 wt % solution of MGDA-Na3, 2 g of a 50% aqueous solution of (IV.1) and 2 g of the polymer of the present invention (A.6.2). Homogenization was achieved by gentle stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.4 of the present invention was obtained.

[0258] For cleaning performance, performance was evaluated on a stainless steel surface at ambient temperature.

[0259] Test stain: A greasy stain was prepared by mixing 25.0% butter, 25.0% lard, 25.0% margarine, 20.0% ketchup, 2.5% mustard and 2.5% potato starch under continuous stirring at 40-45°C. A greasy stain was obtained.

[0260] Stainless steel plates (15 x 10 cm) were pre-cleaned with ethanol and then weighed. Approximately 1.5 g of greasy soil was evenly applied to each plate with a roller. The plates were then heated to 200°C in an oven for 2 hours. The plates were then allowed to cool to ambient temperature and stored for 2 hours. Finally, a cleaning test was performed.

[0261] 2 g of the inventive formulation / comparative formulation was sprayed evenly onto the stained stainless steel plate with a trigger sprayer and allowed to act for 2 minutes, and the stained plate surface was then wiped with a moist cellulose sponge (without applying pressure).

[0262] The stain removal evaluation was performed visually and refers to the average of three experiments: 1 No removal 2 Weak removal (10-30% of the surface is cleaned) 3 Average removal (40-70% of the surface is cleaned) 4. Good removal (70-90% of the surface is cleaned) 5. Excellent removal (>90% surface clean) Percentages are relative to surface.

[0263] The results are summarized in Table 6.

[0264] [Table 5]

[0265] II.3 Detergents for automatic dishwashers: The following detergent composition for automatic dishwashers can be made by mixing the ingredients according to Table 7. All amounts are in grams. The resulting detergent mixture can be converted into 20g tablets.

[0266] [Table 6]

[0267] III. Biodegradation Test General: Tests were performed in accordance with OECD guidelines. According to OECD guidelines, the test is valid for: 1. The reference material reaches 60% within 14 days. 2. The extremes of the test replicates vary by less than 20% by the end of the test. 3. The oxygen uptake of the inoculum blank should be 20-30 mg O2 / L and should not exceed 60 mg O2 / L. 4. The pH value measured at the end of the test must be between 6 and 8.5.

[0268] Description of test methods used in the context of the present invention: Biodegradation in sewage was tested in triplicate using the OECD 301F pressure respirometry method. OECD 301F is an aerobic test that measures the biodegradation of sewage samples by measuring oxygen consumption. To a measured volume of sewage, 100 mg / L of the test substance, nominally the sole carbon source, was added along with an inoculum (aerated sludge from a public sewage treatment plant in Mannheim, Germany). The sludge was stirred in a sealed flask at a constant temperature (25°C) for 28 days. Oxygen consumption was determined by measuring the pressure change in the sealed flask using an Oxi TopC. Evolved carbon dioxide was absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent oxygen consumption by nitrification. The amount of oxygen uptake by the microbial consortium during biodegradation of the test substance (corrected for uptake by a parallel blank inoculum) was expressed as a percentage of ThOD (theoretical oxygen demand, determined by elemental analysis of the compound). A positive control, glucose / glutamate, is run as a reference for each cabinet along with the test samples. Calculation: Theoretical oxygen demand: The amount of O2 required to oxidize a compound to its final oxidation product. This is calculated using elemental analysis data. %biodegradable Experimental O2 uptake x 100, divided by theoretical oxygen demand.

[0269] The results of the biodegradability tests are summarized in Table 8.

[0270] [Table 7]

[0271] In each test, the reference material was more than 60% biodegradable.

Claims

1. (A) at least one polymer, (a) a core having 1 to 3 moieties of general formula (I); 【Chemical 1】 wherein Z is different or the same, and C 2 ~C 12 -Alkylene and C 3 ~C 12 -cycloalkylene, wherein C 2 ~C 12 -Alkylene or C 3 ~C 12 -cycloalkylene is unsubstituted or has one or more O-C groups. 1 ~C 4 - optionally substituted with an alkyl group, C 3 ~C 12 -cycloalkylene may have 1 to 3 methyl groups; A 1 are different or the same, and C 1 ~C 12 -Alkylene, C 6 -arylene, and C 3 ~C 12 -cycloalkylene, C 2 ~C 12 -Alkylene and C 3 ~C 12 -cycloalkylene is unsubstituted or has one or more O-C groups 1 ~C 4 - may be substituted with an alkyl group or an OH group, C 3 ~C 12 -cycloalkylene may have 1 to 3 methyl groups; Or based on citric acid, X 1 is selected from hydrogen and methyl and ethyl, and combinations of at least two of the foregoing; (n ranges from 1 to 100) (b) Polyalkylene oxide chain a polymer comprising A detergent composition comprising:

2. 2. The composition of claim 1, wherein all Z's are selected from cyclohexylene and cyclopentylene, each of which is unsubstituted or substituted with 1 to 2 methyl or methoxy groups.

3. (B) at least one hydrolytic enzyme 3. The composition of claim 1 or 2, further comprising:

4. 4. The composition according to claim 3, wherein the hydrolase (B) is a lipase (B) selected from triacylglycerol lipases (EC 3.1.1.3).

5. The polymer (A) has an average molecular weight M in the range of 2,500 to 80,000 g / mol. w 5. The composition of claim 1, wherein

6. Z, 【Chemistry 2】 6. The composition of claim 1, wherein the combination is selected from the group consisting of:

7. 7. Use of a composition according to any one of claims 1 to 6 for laundry care or hard surface cleaning.

8. (a) a core having 1 to 3 moieties of general formula (I); 【Chemistry 3】 wherein Z is different or the same, and C 2 ~C 12 -Alkylene and C 3 ~C 12 -cycloalkylene, wherein C 2 ~C 12 -Alkylene or C 3 ~C 12 -cycloalkylene is unsubstituted or has one or more O-C groups. 1 ~C 4 - optionally substituted with an alkyl group, C 3 ~C 12 -cycloalkylene may be unsubstituted or bear 1 to 3 methyl groups; A 1 are different or the same, and C 1 ~C 12 -Alkylene, C 6 -arylene, and -CH 2 C(CO 2 X 2 )(OH)-CH 2 - and C 3 ~C 12 -cycloalkylene, C 2 ~C 12 -Alkylene and C 3 ~C 12 -cycloalkylene is unsubstituted or has one or more O-C groups 1 ~C 4 - may be substituted with an alkyl group or an OH group, C 3 ~C 12 -cycloalkylene may have 1 to 3 methyl groups or may be based on citric acid; X 1 is selected from hydrogen and methyl and ethyl, and combinations of at least two of the foregoing; n ranges from 1 to 100; X 2 is C 1 ~C 4 -Alkyl, hydrogen, and CH(X 1 )-CH 2 -NZ-) (b) a polyalkylene oxide chain derived from propylene oxide or ethylene oxide A polymer comprising:

9. Average molecular weight M in the range of 2,500 to 80,000 g / mol w 9. The polymer of claim 8, having the formula:

10. 10. The polymer of claim 8, wherein all Z are selected from cyclohexylene and cyclopentylene, each of which is unsubstituted or substituted with 1 to 2 methyl or methoxy groups.

11. Z, 【Chemistry 4】 11. The polymer according to claim 8, wherein the polymer is selected from the combination of:

12. A 1 C 1 ~C 4 12. The polymer of claim 8, wherein the aryl group is selected from the group consisting of -alkylene.

13. 13. A method of making a polymer according to any one of claims 8 to 12, comprising: (α) General formula H 2 NZ-NH 2 reacting the diamine according to formula (I) with an alkylene oxide in a molar ratio of alkylene oxide:diamine of from 4:1 to 1:1, wherein the alkylene oxide is selected from ethylene oxide and propylene oxide, thereby forming an intermediate; (β) reacting the intermediate from step (α) with at least one dicarboxylic or tricarboxylic acid, or a mixture of the foregoing, or in each case with the respective anhydride or C 1 ~C 4 with an alkyl ester, thereby obtaining the ester, (γ) reacting the ester from step (β) with at least ethylene oxide or propylene oxide in one or more steps; A method comprising:

14. In step (β), the intermediate from step (α) is converted to a di-C of succinic acid, malonic acid, or adipic acid. 1 ~C 2 14. The method of claim 13, wherein the hydroxybenzoate is reacted with an alkyl ester and optionally with the triethyl ester of citric acid.

15. 13. A method for improving the cleaning performance of a liquid detergent composition by adding a polymer (A) according to any one of claims 8 to 12 to the detergent composition comprising at least one lipase and / or at least one protease.

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