Composition and its application

Abstract

The present invention relates to (A) at least one polymer, (a) a core carrying 1 to 3 moieties of general formula (I), [Formula 1] TIFF2024546896000025.tif25170, where Z is different or the same, and C5 to C 20 alkylene, and the above C5 to C 20 In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, and the above C5-C 20 C atoms in the alkylene may be unsubstituted or substituted with one or more O-C1-C4 alkyl groups; A 1 are different or the same, and C1 to C 12 Alkylene, C6 arylene, and C3-C 12 cycloalkylene, wherein C1 to 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 may be C3-C4 alkyl or OH groups. 12 The cycloalkylene may carry 1 to 3 methyl groups; Or based on citric acid, X1 is selected from hydrogen, methyl, ethyl, and combinations of at least two of the foregoing; n is in the range of 1 to 100; and and (c) a polyalkylene oxide chain.

Description

[Technical field]

[0001] The present invention provides a liquid detergent composition comprising: (A) at least one polymer, (a) a core carrying 1 to 3 moieties of general formula (I), [ka] In the formula, Z is different or the same and is C5 to C 20 alkylene, and the above C5 to C 20 In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, and the above C5-C 20 C atoms in the alkylene may be unsubstituted or substituted with one or more O-C1-C4 alkyl groups; A 1 are different or the same, and C1 to C 12 Alkylene, C6 arylene, and C3-C 12 cycloalkylene, wherein C1 to 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 may be C3-C4 alkyl or OH groups. 12 The cycloalkylene may carry 1 to 3 methyl groups; Or based on citric acid, X 1 is selected from hydrogen, methyl, and ethyl, and combinations of at least two of the foregoing; n is in the range of 1 to 100; and (b) a polyalkylene oxide chain.

[0002] Additionally, the present invention relates to polymers useful in such compositions and processes for making such polymers. [Background technology]

[0003] Laundry detergents are required to meet several requirements. They need to remove all kinds of stains from laundry, such as all kinds of pigmented, clay, greasy stains, and dyes, such as food and beverage dyes, such as red wine, tea, coffee, and fruit dyes, including berry juice. Laundry detergents also need to show a certain storage stability. In particular, laundry detergents that contain liquid or moisture-absorbing ingredients often do not have good storage stability, for example enzymes tend to be inactivated.

[0004] Greasy soils remain a challenge in washing. Many proposals for removal have been made (polymers, enzymes, surfactants) but a well-performing solution is still of interest. The use of lipases has been proposed to aid in grease removal, but many builders do not cooperate well with lipases, especially in liquid laundry detergents. Summary of the Invention [Problem to be solved by the invention]

[0005] Thus, one object was to provide a detergent composition that meets the requirements set forth above. A further object was to provide ingredients that meet the above requirements, and one object was to provide processes for making such ingredients and detergent compositions.

[0006] As a result, a liquid detergent composition as defined at the outset has been discovered, hereinafter also referred to as the composition of the invention or the composition according to the invention. [Means for solving the problem]

[0007] The composition of the present invention comprises (A) at least one polymer (hereinafter also referred to as polymer (A)), such polymer (A) comprising: (a) a core carrying 1 to 3 moieties of general formula (I), [ka] wherein Z is different or the same; Straight or branched chain C5-C 20 Alkylene, preferably C6-C 12 alkylene, and the above C5 to C 20 Alkylene or C6-C 12 In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, for example comprising a core in which 1 to 3 C atoms are replaced.

[0008] In addition to the above, C5~C 20 Alkylene or C6-C 12 Alkylene may be otherwise unsubstituted or substituted with one or more O-C1-C4 alkyl groups. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] In one embodiment of the present invention, all Z are (CH) z1 -[N(CH2) z2 ] z4 -N(CH2) z3 -, wherein the variables z1, z2, and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, and each CH2 group may be substituted with 1 to 2 methyl or methoxy groups or is preferably unsubstituted.

[0010] The polyalkylene oxide side chains may be derived from C2-C4 alkylene oxides. Examples of C2-C4 alkylene oxides are ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BuO"), and combinations of at least two of the foregoing, such as ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide, preferably in each case the majority of the alkylene oxide units are EO. Propylene oxide and ethylene oxide (majority ethylene oxide) are preferred, with ethylene oxide being more preferred.

[0011] In one embodiment of the invention, all Z are -(CH2)3-N-(CH2)2-, and It is selected from -(CH2)3-N-(CH2)3 and -(CH2)3-N-(CH2)2-N-(CH2)3-. Preferably, all Z are the same.

[0012] X 1 is selected from hydrogen, methyl and ethyl, and combinations of at least two of the foregoing, with methyl and combinations of methyl and hydrogen being preferred, and hydrogen being more preferred.

[0013] A 1 are different or the same, and C1 to C 12 Alkylene, preferably C2 to 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, where C1-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 may be C3-C4 alkyl or OH groups. 12 The cycloalkylene may carry 1 to 3 methyl groups; Alternatively, it is based on citric acid, for example, -CH2-C(CO2H)(OH)-CH2- or -CH2-C(OH)(CH2-COOH)-.

[0014] 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.

[0015] The value of n is within the range of 1 to 100, and preferably 10 to 75.

[0016] The free valence on the nitrogen atom of formula (I) is a polyalkylene chain (b) or -CH2-CH(X 1 )-O(CO)-A 1 -(CO)-O-CHX 1 -CH2-NZN units or hydrogen atoms. Molecular weight M w In the embodiment where the free valence on the nitrogen atom of formula (I) is a polyalkylene chain (b) or -CH-CH(X 1 )-O-CHX 1 It carries -CH2-NZN units.

[0017] In one embodiment of the present invention, the polymer (A) may further carry one or more structural units of general formula (X). [ka]

[0018] In one embodiment of the present invention, the polymer (A) has an average molecular weight M w in the range of 2,500 to 300,000 g / mol, preferably 5,000 to 250,000 g / mol, and even more preferably up to 80,000 g / mol. 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 the standard.

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

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

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

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

[0023] The polymer (A) further comprises (b) Contains a polyalkylene oxide chain.

[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. Propylene oxide and ethylene oxide are preferred, with ethylene oxide being more preferred.

[0025] In one embodiment of the present invention, the weight ratio of core (a) to polyalkylene oxide chains (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 amino acid sequence). The polypeptide sequence specifies the three-dimensional structure of the enzyme, including the "active site", which in turn determines its catalytic activity. The polypeptide sequence may be identified by a sequence number. According to the World Intellectual Property Office (WIPO) standard ST.25 (1998), amino acids herein are represented using three-letter symbols with the first letter capitalized, or the corresponding single letters.

[0027] Any enzyme of the present invention is related to a parent enzyme and / or a variant enzyme, both of which have enzymatic activity. An enzyme with enzymatic activity is enzymatically active or effects an enzymatic transformation, i.e., the enzyme acts on substrates to convert them into products. The term "enzyme" herein does not encompass 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 modifications 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), which are used as starting sequences for introducing (further) changes.

[0029] The term "enzyme variant" or "sequence variant" or "variant enzyme" refers to an enzyme whose amino acid sequence differs to a particular degree from its parent enzyme. Unless otherwise indicated, 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] In describing the variants of the present invention, the nomenclature described below is used.

[0031] Amino acid substitutions are described by providing the original amino acid of the parent enzyme, followed by the number of the position 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 number of the position in the amino acid sequence, followed by *. Amino acid insertions are described by providing the original amino acid of the parent enzyme, followed by the number of the position in the amino acid sequence, followed by the original amino acid and the additional amino acid. For example, the insertion of a lysine at position 180 next to a glycine would be designated as "Gly180GlyLys" or "G180GK". If a substitution and an insertion are in the same position, this can be indicated as S99SD+S99A or in short 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 indicated by G180GG. When different modifications can be introduced at a position, the different modifications are separated by commas, for example, "Arg170Tyr,Glu" represents the substitution of arginine at position 170 with tyrosine or glutamic acid. Alternatively, the different modifications or any substitutions can be indicated in brackets (e.g., Arg170[Tyr,Gly] or Arg170{Tyr,Gly}, or short R170[Y,G] or R170{Y,G}, or long R170Y, R170G).

[0032] Enzyme variants can be defined by their sequence identity compared to the parent enzyme. Sequence identity is usually indicated as "% sequence identity" or "% identity". To calculate sequence identity, in the first step, a sequence alignment must be generated. According to the present invention, a pairwise global alignment must be generated, which means that two sequences must be aligned over their full length, which is usually generated by using a mathematical method 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, p. 443-453). Preferably, the program "NEEDLE" (European Molecular Biology Open Software Suite (EMBOSS)) is used for the present invention, using the program's default parameters (gap open = 10.0, gap extension = 0.5, and matrix = EBLOSUM62).

[0033] According to the present invention, the following calculation of % identity is applied: % identity = (identical residues / length of the alignment region showing the respective sequences of the present invention over their entire length) * 100.

[0034] According to the present invention, an enzyme variant can be described as an amino acid sequence that is at least n% identical to the amino acid sequence of the respective parent enzyme, 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 82%, at least 84%, at least 86%, at least 88%, at least 90%, at least 92%, at least 93%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical compared to the full-length amino acid sequence of the parent enzyme, wherein the enzyme variant has enzymatic activity.

[0035] "Enzyme activity" refers to the catalytic effect exerted by an enzyme, which is related to the 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 of the invention when said 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.

[0036] In one embodiment, the enzyme is selected from hydrolases, preferably from proteases, amylases, lipases, cellulases, and mannanases.

[0037] In one embodiment of the present invention, the composition of the present invention comprises: (B) At least one hydrolase, hereinafter also referred to as hydrolase (B), which is preferably selected from lipases, hereinafter also referred to as lipases (B).

[0038] "Lipase", "lipolytic enzyme", "lipid esterase" all refer to enzymes in EC class 3.1.1 ("carboxylester 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.

[0039] 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 from Genencor), and Lipomax (Gist-Brocades / now DSM).

[0040] Suitable lipases (B) also include variants of the above lipases having lipolytic activity. Suitable lipase variants include variants having at least 40-100% identity compared to the full-length polypeptide sequence of the parent enzyme disclosed above. In one embodiment, the lipase variant having lipolytic activity may be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 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 the parent enzyme disclosed above.

[0041] Lipase (B) has "lipolytic activity". Methods for determining lipolytic activity are well known in the literature (see, for example, Gupta et al. (2003), Biotechnol. Appl. Biochem. 37, p. 63-71). For example, lipase activity can be measured by ester bond hydrolysis in the substrate para-nitrophenyl palmitate (pNP-palmitate, C:16), releasing pNP, which is yellow in color and detectable 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 lipase according to amino acids 1-269 of SEQ ID NO: 2 of US Pat. No. 5,869,438 and variants thereof having lipolytic activity.

[0043] The Thermomyces lanuginosa lipase may be selected from variants having 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 lipolytic activity when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 in U.S. Pat. No. 5,869,438.

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

[0045] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the following amino acid substitutions: T231R and N233R, as compared to amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438. The lipase variant may further comprise one or more of the following amino acid exchanges: Q4V, V60S, A150G, L227G, P256K, as compared to amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. 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, P256K within the polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438, and which are at least 95%, at least 96%, or at least 97% similar when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438.

[0047] The Thermomyces lanuginosa lipase can 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. Pat. No. 5,869,438, and which are at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% similar when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438.

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

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

[0050] In one embodiment of the invention, lipase (B) is included in the composition of the invention in an amount such that the finished composition of the invention has a lipolytic enzymatic activity in the range of 100-0.005 LU / mg of the composition, preferably 25-0.05 LU / mg. 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; 13 mmol / l Ca in 5 mmol / l Tris buffer. 2+ and that the substrate was an emulsion of 3.3 wt % olive oil and 3.3 wt % 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, at least one protease (D) is selected from the group of serine endopeptidases (EC 3.4.21), more 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 the catalytic reaction. A serine protease in the context of the present invention may be selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC 3.4.21.78 or EC 3.4.21.79), kallikrein (e.g., EC 3.4.21.34, EC 3.4.21.35, EC 3.4.21.118, or EC 3.4.21.119), plasmin (e.g., EC 3.4.21.7), trypsin (e.g., EC 3.4.21.4), thrombin (e.g., EC 3.4.21.5), and subtilisin. Subtilisins are also known as subtilopeptidases, e.g., EC 3.4.21.62, the latter of which will hereinafter also be referred to as "subtilisins". 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 subtilisin and chymotrypsin-related serine proteases have a catalytic triad that includes aspartic acid, histidine, and serine.

[0053] A protease is an active protein that exerts "protease activity" or "proteolytic activity." Proteolytic activity is related to the rate of degradation of a protein by a protease or proteolytic enzyme in a given period of time.

[0054] Methods for analyzing proteolytic activity are well known in the literature (see, for example, 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, for example, DelMar et al. (1979), Analytical Biochem 99, 316-320). pNA is cleaved from the substrate molecule by proteolytic cleavage and is expressed as OD 405 This results in the release of yellow free pNA which can be quantified by measurement of

[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. (casein as 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 derived from a microorganism selected from proteases, or a Gram-negative bacterial polypeptide, such as, for example, Campylobacter, E. coli, Flavobacterium, Fusobacterium, Helicobacter, lyobacter, Neisseria, Pseudomonas, Salmonella, and Ureaplasma.

[0057] In one embodiment of the 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 invention, the at least one protease (D) is selected from the group consisting of 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) Nucl. Acids Res, Vol. 1, pp. 2185-2192). 13, p. 8913-8926), subtilisin PB92 (the original sequence of alkaline protease PB92 is described in EP 283075 A2), subtilisin 147 and / or 309 (Esperase®, Savinase®, respectively) disclosed in WO 89 / 06279, subtilisins from Bacillus lentus disclosed in WO 91 / 02792, e.g. subtilisins from Bacillus lentus DSM 5483 described in WO 95 / 23221 or mutants of Bacillus lentus DSM 5483, Bacillus alcalophilus as disclosed in DE 10064983, alcalophilus (DSM 11233), subtilisins from Bacillus gibsonii (DSM 14391) disclosed in WO 2003 / 054184, subtilisins from Bacillus sp. (DSM 14390) disclosed in WO 2003 / 056017, 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 invention include the 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. A suitable example is in particular the Bacillus lentus variant of SEQ ID NO: 22 described in EP 1 921 147 B1, which has amino acid substitutions at one or more of the following positions, having proteolytic activity: lentus) DSM 5483) which is the sequence of the mature alkaline protease from DSM 5483) at 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 the BPN numbering). In one embodiment, such proteases are not mutated at positions Asp32, His64, and Ser221 (according to the BPN numbering).

[0060] In one embodiment, at least one protease (D) has the sequence SEQ ID NO: 22 as described in EP 1921147 or is at least 80% identical thereto and has proteolytic activity. 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 the BPN numbering) and has proteolytic activity. In one embodiment, the protease comprises one or more further substitutions: (a) a threonine (3T) at position 3; (b) an isoleucine (4I) at position 4; (c) an alanine, threonine or arginine (63A, 63T or 63R) at position 63; (d) an aspartic acid or glutamic acid (156D or 156E) at position 156; (e) a proline (194P) at position 194; (f) a methionine (199M) at position 199; (g) an isoleucine (205I) at position 205; (h) an aspartic acid, glutamic acid or glycine (217D, 217E or 217G) at position 217; (i) a combination of two or more amino acids according to (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 in that it comprises 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 has proteolytic activity. A protease having the sequence of SEQ ID NO: 22 described in EP 1 921 147 containing 101E may be referred to herein as Lavergy.

[0062] In one embodiment the protease of SEQ ID NO: 22 described in EP 1 921 147 is characterised in that it comprises the mutations (according to the BPN numbering) S3T+V4I+S9R+A15T+V68A+D99S+R101S+A103S+I104V+N218D and has 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 as disclosed above.

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

[0065] In the context of the present invention, a lipase (B) and / or a protease (D) is considered stable if its enzymatic activity "available for application" is at least equal to 60% compared to the initial enzymatic activity before storage. An enzyme can be said to be stable in the context of the present invention if its enzymatic activity available for application is at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 92%, at least 94%, at least 95%, at least 96%, 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 "amount of enzyme activity lost during storage" compared to the initial enzyme activity before storage. In one embodiment, an enzyme is stable according to the present invention when 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. In the present invention, essentially no loss of enzyme activity 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%, less than 5%.

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

[0068] Examples of anionic surfactants (C) are 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: 1-50 mol ethylene oxide / mol), C 12 ~C 18 Sulfofatty acid alkyl esters, e.g. C 12 ~C 18 Alkali metal and ammonium salts of sulfo fatty acid methyl esters, as well as 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 above mentioned compounds are preferred, with the sodium salts being particularly preferred.

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

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

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

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

[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 include 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 (III a) [ka] where the variables are defined as follows: 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 linear 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 is selected from alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, or isodecyl. The variables e and f are in the range of 0 to 300, and the sum of e and f is at least 1, preferably in the range of 3 to 50. Preferably, e is in the range of 1 to 100, and f is in the range of 0 to 30.

[0077] In one embodiment, the compound of general formula (II) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0078] Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (III b) [ka] where the variables are defined as follows: R 2 are identical or different and selected from hydrogen and linear C1-C0 alkyl, preferably are identical in each case and are ethyl, particularly preferably hydrogen or methyl, R 5 is a branched or linear C6-C 20 Alkyl, especially 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 0 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.

[0079] The sum of a+b+d is preferably within the range of 5-100, and even more preferably within the range of 9-50.

[0080] The compound of general formula (III) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0081] Further suitable non-ionic surfactants are selected from diblock and multiblock copolymers composed of ethylene oxide and propylene oxide. Further suitable non-ionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-C 16 Alkyl polyglycosides and branched C8-C 14 Likewise suitable are alkyl polyglycosides, such as compounds of the general average formula (IV): [ka] During the ceremony, R 6 is C1-C4 alkyl, in particular ethyl, n-propyl or isopropyl; R 7 is -(CH)-R 6 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, y is in the range of 1.1 to 4, where y is an average number.

[0082] Further examples of non-ionic surfactants are compounds of the general formulae (V) and (VI) [ka] AO is selected from ethylene oxide, propylene oxide, and butylene oxide; EO is ethylene oxide, CH2CH2-O; R 8 is a branched or linear C8-C 18 alkyl; R 5 is as defined above.

[0083] A 3is 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.

[0084] An overview of suitable further nonionic surfactants can be found in EP-A-0 851 023 and DE-A-198 19 187.

[0085] Mixtures of two or more different nonionic surfactants selected from the above may also be present.

[0086] Other surfactants which may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants, and mixtures thereof.

[0087] An example of an amphoteric surfactant is a surfactant that has positive and negative charges in the same molecule under the conditions of use.A preferred example of an amphoteric surfactant is the so-called betaine surfactant.Many examples of betaine surfactants have one quaternized nitrogen atom and one carboxylic acid group per molecule.A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0088] Examples of amine oxide surfactants are compounds of 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 Preferably, R 9 is C8~C 20 Alkyl or C2-C4 alkylene C 10 ~C 20alkylamides, R 10 and R 11 Both are methyl.

[0089] A particularly preferred example is lauryl dimethylamine oxide, sometimes called lauramine oxide. A further particularly preferred example is cocamidyl propyl dimethylamine oxide, sometimes called cocamidopropylamine oxide.

[0090] In one embodiment of the present invention, the composition of the present invention may contain 0.1 to 60% by weight of at least one surfactant selected from nonionic surfactants, amphoteric surfactants, and amine oxide surfactants.

[0091] In a preferred embodiment, the cleaning solid detergent composition, particularly the automatic dishwashing solid detergent composition, of the present invention does not contain any anionic surfactants.

[0092] The compositions of the present invention may contain at least one bleaching agent, also referred to as 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. Inorganic peroxide bleaches selected from alkali metal percarbonates, alkali metal perborates, and alkali metal persulfates are preferred.

[0093] Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.

[0094] In the compositions of the present invention, alkali metal percarbonates, especially sodium percarbonate, are preferably used in the form of a coating. Such coatings can be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicates, sodium carbonate, and combinations of at least two of the above, such as sodium carbonate and sodium sulfate.

[0095] 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.

[0096] The compositions of the invention may contain, for example, 3 to 10% by weight of a chlorine-containing bleach.

[0097] The composition of the present invention may contain one or more bleach catalysts. The bleach catalyst may be selected from bleach-boosting transition metal salts or transition metal 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 tripod ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes may be used as bleach catalysts.

[0098] 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).

[0099] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0100] Examples of fragrances are benzyl salicylate, 2-(4-tert-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0101] 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.

[0102] The composition of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent composition of the present invention due to attack from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT"), and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), benzoic acid, sorbic acid, 1,5-pentanedial, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH"), and dibromodimethylhydantoin ("DBDMH"). Further examples of preservatives are 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether ("diclosan").

[0103] Examples of viscosity modifiers are agar, carrageenan, tragacanth, gum arabic, alginates, 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 (including but not limited to montmorillonite, zeolite, dextrin, and casein).

[0104] A hydrotrope in the context of the present invention is a compound that promotes the dissolution of compounds that have limited solubility in water. Examples of hydrotropes are, but are not limited to, organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and further 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.

[0105] Examples of polymers other than the polymer (A) are especially polyacrylic acids and their corresponding alkali metal salts, especially their sodium salts. Suitable polymers are especially polyacrylic acids, preferably having average molecular weights M in the range from 2,000 to 40,000 g / mol, preferably from 2,000 to 10,000 g / mol, in particular from 3,000 to 8,000 g / mol. w Each is partially or completely neutralized with alkali, in particular with sodium. Likewise suitable copolymeric polycarboxylates are in particular 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 corresponding alkali metal salts can function as soil redeposition inhibitors.

[0106] A further example of a polymer is polyvinylpyrrolidone (PVP), which may act as a dye transfer inhibitor.

[0107] 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.

[0108] Examples of buffers are monoethanolamine and N,N,N-triethanolamine.

[0109] An example of a defoamer is silicone.

[0110] The composition of the present invention is not only good for organic greasy stains such as oil in washing dirty laundry.The liquid detergent composition of the present invention is very useful for removing non-bleachable stains from laundry, such as but not limited to stains from red wine, tea, coffee, vegetables, and various fruit juices such as berry juice.Moreover, the liquid detergent composition of the present invention does not leave any residue on fabric.

[0111] Thus, a further aspect of the present invention is the use of the compositions of the present invention in laundry care. Laundry care in this context includes laundry washing.

[0112] 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 in cleaning hard surfaces.

[0113] In the context of the present invention, the term "hard surface cleaning compositions" includes home care and institutional cleaning agents. The term "hard surface cleaning compositions" includes compositions for dishwashing, especially manual and automatic dishwashing and ware washing, as well as compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, automobile cleaning, including truck washing, as well as open plant cleaning, cleaning-in-place, metal cleaning, germicidal cleaning, farm cleaning, high pressure cleaning, but does not include laundry detergent compositions. A special embodiment of the hard surface cleaning composition is an automatic dishwashing composition.

[0114] In the context of the present invention, the terms "hard surface cleaning composition" and "hard surface cleaner composition" are used interchangeably.

[0115] 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 of the corresponding 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 of the detergent composition for cleaning hard surfaces.

[0116] The compositions of the present invention, when used in automatic dishwashing, It is preferred to contain (E) at least one builder component (also called complexing agent (E) or sequestering agent (E) in the context of the present invention) selected from aminopolycarboxylic acids and preferably their alkali metal salts. In the context of the present invention, the terms sequestering agent and chelating agent are used interchangeably.

[0117] Examples of the sequestering agent (E) include MGDA (methylglycine diacetate), GLDA (glutamic acid diacetate), IDS (iminodisuccinate), EDTA, and, for example, 20 to 90 mol % of the N atoms are CH2COO - Suitable complexing groups include the alkali metal salts of polymers having complexing groups, such as polyethyleneimines containing groups, and their corresponding alkali metal salts, in particular their sodium salts, for example MGDA-Na3, GLDA-Na4, or IDS-Na4.

[0118] Preferred sequestering agents are of the general formula (IX a) [CH3-CH(COO)-N(CH2-COO)2]M 3-x H x (IX a) where M is selected from the same or different ammonium and alkali metal cations, such as sodium, potassium, 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 further preferred that all M in the compounds of formula (II a) are the same and are all Na; In formula (II a), x is in the range of 0 to 1.0; Or (IX b) [OOC-CH2CH2-CH(COO)-N(CH2-COO)2]M 4-x H x (IX b) (wherein M is as defined above, and x in formula (IX b) is in the range of 0 to 2.0, preferably 0 to 1.0), or (IX c) [OOC-CH2-CH(COO)]-N-CH(COO)-CH2-COO]M 4-x H x (IX c) (wherein M is as defined above, and in formula (IIc), x is in the range of 0 to 2.0, preferably 0 to 1.0).

[0119] In one embodiment of the invention, the composition of the invention as described above contains a combination of at least two of the foregoing, for example a combination of a chelating agent of general formula (IX a) with a chelating agent of general formula (IX b).

[0120] The chelating agents of the general formulae (IXa) and (IXb) are preferred. The chelating agents of the general formula (IXa) are even more preferred.

[0121] In one embodiment of the present invention, the compound of general formula (IXa) is selected from the ammonium or alkali metal salts of racemic MGDA and from the ammonium and alkali metal salts of a mixture of L- and D-enantiomers of formula (IXa), said mixtures predominantly containing the respective L-isomers with an enantiomeric excess (ee) in the range of 5-99%, preferably 5-95%, more preferably 10-75%, and even more preferably 10-66%.

[0122] In one embodiment of the invention, the compound of general formula (IX b) is selected from at least one alkali metal salt of a mixture of L- and D-enantiomers of formula (IX b), said mixture being a racemic mixture or preferably containing predominantly the respective L-isomer, for example with an enantiomeric excess (ee) in the range of 5-99%, preferably 15-95%.

[0123] The enantiomeric excess of the compound of general formula (IX a) 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 stationary phase or using a chiral stationary phase of the ligand exchange (Pirkle brush) concept. Determination of ee by HPLC with immobilized optically active amines such as D-penicillamine in the presence of copper(II) salts is preferred. The enantiomeric excess of the compound of general formula (IX b) salt can be determined by measuring polarized light (polarimetry).

[0124] Due to the environmental concerns that arise in the context of their use, advantageous compositions are preferably phosphate-free. In the context of the present invention, "phosphate-free" is understood to mean that the phosphate and polyphosphate content is within the detection level of up to 1% by weight in total, preferably between 10 ppm and 0.2% by weight, as determined gravimetrically.

[0125] 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, based on the total solids content.

[0126] To be suitable as a liquid laundry composition, the compositions of the present invention may be in bulk form or in unit dose form, such as a sachet or pouch. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.

[0127] In a preferred embodiment of the invention, the composition according to the invention is of liquid or gel type at ambient temperature. In another preferred embodiment of the invention, the composition according to the invention is in solid form at ambient temperature, for example a powder or a tablet.

[0128] In one embodiment of the invention, the compositions of the invention are of 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 in solid form, their pH values ​​may be in the range of 7.5 to 11, determined at ambient temperature after dissolution at 1 g / 100 ml in distilled water. In embodiments in which the compositions of the invention are used on hard surfaces such as tiles, for example bathroom tiles, their pH values ​​may even be acidic, for example 3 to 6.

[0129] In one embodiment of the present invention, the composition of the present invention is liquid or gel type and has a total solids content in the range of 8-80%, preferably 10-50%, as determined by drying under vacuum at 80°C.

[0130] Another aspect of the present invention relates to a polymer (A), hereinafter also referred to as inventive polymer (A) or simply as polymer (A). The inventive polymer (A) is (a) a core carrying 1 to 3 moieties of general formula (I), [ka] wherein Z is different or the same; Straight or branched chain C5-C 20 Alkylene, preferably C6-C 12 alkylene, and the above C5 to C 20 Alkylene or C6-C 12 In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, for example comprising a core in which 1 to 3 C atoms are replaced.

[0131] In addition to the above, C5~C 20 Alkylene or C6-C 12Alkylene may be otherwise unsubstituted or substituted with one or more O-C1-C4 alkyl groups.

[0132] In one embodiment of the present invention, all Z are (CH) z1 -[N(CH2) z2 ] z4 -N(CH2) z3 -, wherein the variables z1, z2, and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, and each CH2 group may be substituted with 1 to 2 methyl or methoxy groups or is preferably unsubstituted.

[0133] The polyalkylene oxide side chains may be derived from C2-C4 alkylene oxides. Examples of C2-C4 alkylene oxides are ethylene oxide ("EO"), propylene oxide ("PO"), butylene oxide ("BuO"), and combinations of at least two of the foregoing, such as ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide, preferably in each case the majority of the alkylene oxide units are EO. Propylene oxide and ethylene oxide with a majority of ethylene oxide are preferred, with ethylene oxide being more preferred.

[0134] In one embodiment of the invention, all Z are -(CH2)3-N-(CH2)3-, and It is selected from -(CH2)3-N-(CH2)2- and -(CH2)3-N(CH2)2-N-(CH2)3-. Preferably, all Z are the same.

[0135] X 1 is selected from hydrogen, methyl and ethyl, and combinations of at least two of the foregoing, with methyl and combinations of methyl and hydrogen being preferred, and hydrogen being more preferred. A 1 are different or the same, and C1 to C 12Alkylene, preferably C2 to 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, where C1-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 may be C3-C4 alkyl or OH groups. 12 The cycloalkylene may carry 1 to 3 methyl groups; Alternatively, it is based on citric acid, for example, -CH2-C(CO2H)(OH)-CH2- or -CH2-C(OH)(CH2-COOH)-.

[0136] In one embodiment of the present invention, A in the polymer (A) of the present invention 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.

[0137] The value of n is within the range of 1 to 100, and preferably 10 to 75.

[0138] The free valence on the nitrogen atom of formula (I) is a polyalkylene chain (b) or -CH2-CH(X 1 )-O(CO)-A 1 -(CO)-O-CHX 1 -CH2-NZN units or hydrogen atoms. Molecular weight M w In embodiments where the free valence on the nitrogen atom of formula (I) is a polyalkylene chain (b) or -CH-CH(X 1 )-O-CHX 1 It carries -CH2-NZN units.

[0139] In one embodiment of the present invention, the polymer (A) of the present invention may further carry one or more structural units of general formula (X). [ka]

[0140] In one embodiment of the present invention, the polymer (A) of the present invention has an average molecular weight M w in the range of 2,500 to 300,000 g / mol, preferably 5,000 to 250,000 g / mol. The average molecular weight can be determined, for example, by GPC in THF as the mobile phase using linear PMMA as the standard.

[0141] In one embodiment of the present invention, the polymer (A) of the present invention has a molecular weight distribution M w / M n is in the range of 1.1 to 2.5.

[0142] In one embodiment of the present invention, the polymer (A) of the present invention has a Hazen color number in the range of 20-500 as determined in a 10% by weight aqueous solution.

[0143] In one embodiment of the present invention, the inventive polymer (A) has an OH number, measured according to DIN 53240 (2013), in the range of 20 to 650, preferably 30 to 100 mg KOH per g of polymer (A).

[0144] In one embodiment of the present invention, the polymer (A) of the present invention has a total amine number in the range of 10 to 650, preferably 10 to 510, more preferably 10 to 80 mg KOH per gram of polymer (A), determined according to ASTM D2074-07.

[0145] The polymer (A) of the present invention further comprises (b) Contains a polyalkylene oxide chain.

[0146] 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. Propylene oxide and ethylene oxide are preferred, with ethylene oxide being more preferred.

[0147] In one embodiment of the present invention, the weight ratio of core (a) to polyalkylene oxide chains (b) in the polymer (A) of the present invention is in the range of from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0148] The polymer (A) of the present invention is highly suitable for producing the composition of the present invention. The polymer (A) of the present invention exhibits biodegradability.

[0149] In one aspect, the present invention relates to a method for improving the cleaning performance of a liquid detergent composition by adding the polymer (A) of the present invention to said detergent composition, preferably comprising at least one lipase and / or at least one protease.

[0150] The term "improved cleaning performance" herein may indicate that the polymer (A) provides better, i.e. improved stain removal properties under suitable washing conditions compared to the cleaning performance of a detergent composition that does not contain the polymer (A). In one embodiment, "improved cleaning performance" means that the cleaning performance of a detergent comprising a 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), is improved compared to the cleaning performance of a detergent comprising a polymer (A) and no enzyme. In one embodiment, "improved cleaning performance" means that the cleaning performance of a detergent comprising a polymer (A) and an enzyme, preferably a hydrolase (B), more preferably a lipase (B) and / or a protease (D), is improved 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), and no polymer (A).

[0151] The term "suitable washing conditions" in this specification refers to the conditions actually used in a washing machine, automatic dishwasher or manual washing process, in particular the washing temperature, time, washing equipment, foam concentration, detergent type and water hardness.

[0152] A further aspect of the present invention relates to a process for making the inventive polymer (A), hereinafter also referred to as the inventive process, which comprises the following steps (α), (β) and (γ). (α) forming an intermediate by reacting an amine of general formula H2N-Z'-NH2 with an alkylene oxide, even more preferably selected from ethylene oxide and propylene oxide, in a molar ratio of alkylene oxide:N atom of 3:1 to 1:3, preferably 1.5:1.0 to 1.0:2.5. (β) A step of obtaining an ester by reacting the intermediate from step (α) with at least one di- or tricarboxylic acid, or with a mixture of the aforementioned, or in each case with their corresponding anhydride or C1-C4 alkyl ester. (γ) reacting the ester from step (β) with at least one C2-C4 alkylene oxide in one or more steps.

[0153] Steps (α), (β), and (γ) are described in more detail below.

[0154] In step (α), an amine of general formula H2N-Z'-NH2 is reacted with an alkylene oxide. The variable Z' is defined as Z, but the N atom carries an H instead of a polyalkylene oxide chain. In the present invention, a mixture of isomeric amines is considered as "an amine".

[0155] Preferred examples of amines H2N-Z'-NH2 are H2N-(CH2)3-NH-(CH2)3-NH2, H2N-(CH2)3-NH-(CH2)2-NH2 ("N3 amines"), and (N,N'-bis-(3-aminopropyl)-ethylenediamine ("N4 amines"), H2N-(CH2)3-NH-(CH2)2-NH-(CH2)3-NH2, and combinations of N3 and N4 amines (e.g., in molar ratios ranging from 1:9 to 9:1).

[0156] The alkylene oxide reacted in step (α) is selected from ethylene oxide ("EO"), propylene oxide ("PO"), and mixtures of the foregoing. Propylene oxide and ethylene oxide are preferred, with ethylene oxide being more preferred.

[0157] In an exemplary process (α) based on N4 amines and ethylene oxide, the following compound [ka] And depending on the ratio of EO to N, one or more of the following: [ka] As well as the corresponding monoethoxylate-containing compounds, a mixture of compounds is formed.

[0158] Step (α) may be carried out with or without a solvent. In embodiments where the amine of general formula H2N-Z'-NH2 is liquid at the reaction temperature, it is preferred to use said amine in bulk. In embodiments where the amine of general formula H2N-Z'-NH2 is solid at the reaction temperature, it is preferred to use a solvent. Suitable solvents are aprotic solvents, such as hydrocarbons, for example toluene, and ethers, for example di-n-butyl ether.

[0159] In one embodiment of the present invention, step (α) may comprise diluting the amine of general formula H2N-Z'-NH2 with water prior to alkoxylation, for example in an amine:water ratio of from 100:1 to 1:1, in particular from 20:1 to 5:1, by weight.

[0160] Preferably, step (α) is carried out without a catalyst.

[0161] 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.

[0162] In one embodiment of the present invention, step (α) may be carried out under 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.

[0163] 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.

[0164] Step (α) may be carried out under an inert gas atmosphere, for example 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. The intermediate can be worked up, for example by removing unreacted alkylene oxide and water, if present, or the intermediate from step (α) can be used without further workup. The removal of said 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.

[0165] The intermediate is obtained in step (α).

[0166] In step (β), the intermediate from step (α) is reacted with at least one di- or tricarboxylic acid, or a mixture of the aforementioned, or in each case with their corresponding anhydrides or C1-C4 alkyl esters to obtain the esters. Preferred di- and tricarboxylic acids are C2-C 10 Alkylenedicarboxylic acids and C4-C 10 Alkylene tricarboxylic acid and one C4-C 10 Alkylene tricarboxylic acid and at least one C2-C 10 Combinations with alkylene dicarboxylic acids and the corresponding C1-C4 alkyl esters. Preferred esters are the corresponding methyl and ethyl esters.

[0167] C2~C 10 Alkylene and C4-C 10 Alkylene can be unsubstituted or substituted, for example, with methyl or hydroxyl.

[0168] In one embodiment of step (β), the intermediate from step (α) is reacted with a di-C1-C2 alkyl ester of succinic acid, malonic acid, sebacic acid, or adipic acid, and, optionally, triethyl ester of citric acid.

[0169] In another embodiment of step (β), the intermediate from step (α) is reacted with succinic acid, malonic acid, sebacic acid, aspartic acid, or adipic acid, and optionally citric acid.

[0170] Step (β) may be carried out at a temperature in the range of 20 to 180° C. In embodiments where esters, 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 anhydrides, such as succinic anhydride, are applied, temperatures in the range of 25 to 150° C. are preferred. In embodiments where the corresponding free acids are used, temperatures in the range of 100 to 180° C. are preferred. In particular in embodiments where temperatures above 100° C. are applied, it is preferred to ramp up the temperature.

[0171] Step (β) can be carried out at any pressure, for example from 10 mbar to 10 bar. Ambient pressure and for example pressures from 10 to less than 500 mbar are preferred.

[0172] During step (β), water or alcohol, such as methanol or ethanol, is formed. It is preferable to remove such by-products, for example by distillation. Suitable tools are Dean-Stark apparatus, distillation bridges, water removers, and other devices that can help remove water or alcohol by distillation.

[0173] Step (β) may be carried out in the presence or absence of a solvent. Suitable solvents are aromatic solvents such as toluene, aliphatic hydrocarbons, or cycloaliphatic solvents such as decane, cyclohexane, n-heptane, etc. However, it is preferred to carry out step (β) in the absence of a solvent, especially when the reaction mixture is liquid at the reaction temperature.

[0174] In one embodiment of the present invention, step (β) is carried out in the presence of a catalyst.

[0175] Examples of suitable catalysts are especially acidic catalysts, such as inorganic and organic acids.

[0176] Examples of acidic inorganic catalysts for the present invention include sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH 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 Titanates of the formula R 5 are each the same or different and, independently of one another, 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 selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, preferably cyclopentyl, cyclohexyl and cycloheptyl.

[0177] Preferably, Al(OR 5 )3 and Ti(OR 5 Residue R in 4 5 are each the same and are selected from isopropyl or 2-ethylhexyl.

[0178] Preferred acidic organometallic catalysts are, for example, dialkyltin oxides (R 5)2SnO, R 5 is as defined above. One particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available in the form of oxo-tin.

[0179] Preferred acidic organic catalysts are, for example, acidic organic compounds containing phosphoric acid groups, sulfonic acid groups, sulfuric acid groups or phosphonic acid groups. Particularly preferred are sulfonic acids, such as para-toluenesulfonic acid or methanesulfonic acid. Acidic ion exchangers can also be used as acidic organic catalysts, an example of which is a polystyrene resin containing sulfonic acid groups and crosslinked with about 2 mol% divinylbenzene. Particularly preferred is methanesulfonic acid.

[0180] It is also possible to use a combination of two or more of the abovementioned catalysts. Another possibility is to use those organic or organometallic or inorganic catalysts that are in the form of discrete molecules in immobilized form.

[0181] When the use of an acidic inorganic catalyst, an organometallic catalyst, or an organic catalyst is desired, the amount of catalyst used in accordance with the present invention is from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight, and more preferably from 0.2 to 1% by weight, based on the total amount of reactants, respectively.

[0182] In another embodiment of the present invention, step (β) is carried out without a catalyst.

[0183] In one embodiment of the present invention, step (β) has a duration ranging from 30 minutes up to 15 hours.

[0184] By carrying out step (β), an ester is obtained.

[0185] In one embodiment of the present invention, the reaction in step (β) leads to the complete conversion of all carboxylic acid or ester or anhydride groups of the corresponding di- or tricarboxylic acid or mixtures of the aforementioned, or in each case to their corresponding anhydrides or C1-C4 alkyl esters. However, in many embodiments, it is observed that the conversion of the ester or carboxylic acid or anhydride groups is incomplete, so that the esters still bear 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.

[0186] In one embodiment of the invention, a further group of, for example, citric acid or its C1-C4 ester may react with, for example, a hydroxyl group.

[0187] The ester obtained from step (β) can be isolated and purified, for example by removing the solvent or by neutralizing the acid. In particular in the embodiment of step (β) where no catalyst or solvent was used, the obtained ester is preferably sent to step (γ) without further purification steps.

[0188] 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. Propylene oxide and ethylene oxide are preferred, with ethylene oxide being more preferred.

[0189] In one embodiment of the present invention, the weight ratio of alkylene oxide of step (γ) to ester of 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.

[0190] Step (γ) is preferably carried out in the presence of a catalyst, such as a base or a double metal cyanide.

[0191] In one embodiment of the present invention, step (γ) is carried out in the presence of a base. A suitable base, such as potassium hydroxide, sodium hydroxide, sodium or potassium alkoxide, for example potassium methylate (KOCH3), potassium tert-butoxide, sodium ethoxide, and sodium methylate (NaOCH3), preferably potassium hydroxide and sodium hydroxide. Further examples of catalysts are alkali metal hydrides and alkaline earth metal hydrides, such as sodium hydride and calcium hydride, and alkali metal carbonates, such as sodium carbonate and potassium carbonate. Alkali metal hydroxides are preferred, potassium hydroxide and sodium hydroxide as well as alkali metal alkoxides are preferred, with potassium tert-butoxide in tert-butanol, sodium n-hexanolate in n-hexanol, and sodium methanolate in n-nonanol being particularly preferred. A typical amount of base used is 0.05-10% by weight, specifically 0.5-2% by weight, based on the total amount of condensate and C2-C4 alkylene oxide from step (β).

[0192] In one embodiment of the present invention, step (γ) is carried out in the presence of a double metal cyanide. Double metal cyanides (hereinafter also referred to as double metal cyanide compounds or DMC compounds) usually contain at least two different metals, at least one of which is selected from transition metals and the other one is selected 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 them. Berlin blue, for example, is particularly suitable.

[0193] It is preferred to use crystalline DMC compounds. In a preferred embodiment, crystalline DMC compounds of the Zn-Co type containing zinc acetate as a further metal salt component are used as catalysts. Such compounds crystallize in a monoclinic structure and have a platelet-like habit.

[0194] 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, for example with zinc.

[0195] The double metal cyanide compounds may be used as a powder, a paste or a suspension, may be moulded to obtain moulded articles, may be introduced into moulded articles, foams etc. or may be applied to moulded articles, foams etc.

[0196] Preferably, the DMC catalyst used in step (γ) is 5 to 2000 ppm (i.e. 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, where ppm refers to ppm (parts per million) by mass of the polycondensate obtained in step (β).

[0197] Step (γ) can be carried out in bulk (embodiment (i)) or in an organic solvent (embodiment (ii)). In embodiment (i), water can be removed from the polycondensate obtained in step (β). This can be done by heating to a temperature in the range of 80 to 150° C. under reduced pressure in the range of 0.01 to 0.5 bar and distilling off the water.

[0198] 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.

[0199] In one embodiment of the 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 with 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 to subject the product from step (γ1) to a second alkoxylation (γ2), for example with propylene oxide.

[0200] In one embodiment of the invention, step (γ) is carried out under a pressure of up to 10 bar, in particular up to 8 bar, for example from 1 to 8 bar.

[0201] In one embodiment of the present invention, the reaction time in step (γ) is generally in the range of 0.5 to 12 hours.

[0202] Examples of suitable organic solvents for embodiment (ii) of step (γ) are 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, in particular 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. It is also possible to use a mixture of at least two of the above organic solvents. Preferred organic solvents are xylene and toluene.

[0203] In embodiment (ii), the solution obtained in the first step is exposed to an alkylene oxide after dehydration, before or after the addition of the catalyst and the solvent, said water removal being advantageously carried out at a temperature ranging from 120 to 180 ° C, preferably supported by a nitrogen stream. The subsequent reaction with the alkylene oxide can be achieved analogously to embodiment (i). In embodiment (i), the alkoxylated polyalkyleneimine of the invention can be obtained directly in bulk and dissolved in water if necessary. In embodiment (ii), for the workup, the organic solvent is typically replaced by water. The alkoxylated polyalkyleneimine (B) of the invention can alternatively be isolated in bulk.

[0204] An optional post-treatment step may involve deactivation of the catalyst used in step (γ) (by neutralization, in the case of a basic catalyst).

[0205] The process of the present invention does not require a bleaching step or reductive removal of impurities.

[0206] The present invention is further illustrated by examples. EXAMPLES

[0207] Overview Reactions were carried out under a nitrogen atmosphere unless otherwise stated. Percentages refer to weight percent unless otherwise specified. GPC was performed using hexafluoroisopropanol ("HFIP") as the mobile phase and linear PMMA as the internal standard. The hydroxyl number (OH number) was determined according to DIN 53240 (2013). Amine number was determined according to ASTM D2074-07. The Hazen colour index was determined by spectrophotometric detection according to DIN ISO 6271, ASTM D 1209 (2° reference observer, standard light, layer thickness 11 mm, distilled water as reference). rpm: Revolutions per minute N,N'-bis-(3-aminopropyl)-ethylenediamine: N4 amine H2N-(CH2)3-NH-(CH2)2-NH2 ("N3 amine")

[0208] I. Synthesis of the Polymers of the Invention I.1 Synthesis of intermediates, step (α) I.1.1 Synthesis of ITM.1, step (α.1) A 3.5 liter steel autoclave was charged with 1.2 kg (6.88 moles) of N4 amine and 120 g of water, and then heated to 100° C. Then, 50 g of ethylene oxide was dosed into the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Then, 850 g of ethylene oxide ("EO") was dosed into the autoclave within 14 hours (total amount of EO: 20.45 moles). The system was maintained at 100° C. for another 6 hours. Then, the mixture was removed from the autoclave and the remaining EO and water were stripped under reduced pressure (20 mbar) at 80° C. for 2 hours. 2.1 kg of intermediate ITM.1 was obtained as a yellow wax.

[0209] I.1.2 Synthesis of ITM.2, step (α.2) A 3.5 liter steel autoclave was charged with 1.0 kg (5.7 moles) of N4 amine and 100 g of water, and then heated to 100° C. Then, 50 g of ethylene oxide was dosed into the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Then, 860 g of ethylene oxide ("EO") was dosed into the autoclave within 20 hours (total amount of EO: 20.7 moles). The system was maintained at 100° C. for another 6 hours. Then, the mixture was removed from the autoclave and the remaining EO and water were stripped under reduced pressure (20 mbar) at 80° C. for 2 hours. 1.91 kg of intermediate ITM.2 was obtained as a clear viscous liquid.

[0210] I.1.3 Synthesis of ITM.3, step (α.3) A 3.5 liter steel autoclave was charged with 1.0 kg (8.53 moles) of N3 amine and 100 g of water, and then heated to 100° C. Then, 50 g of ethylene oxide was dosed into the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Then, 889 g of ethylene oxide ("EO") was dosed into the autoclave within 14 hours (total amount of EO: 21.3 moles). The system was maintained at 100° C. for another 6 hours. Then, the mixture was removed from the autoclave and the remaining EO and water were stripped under reduced pressure (20 mbar) at 80° C. for 2 hours. 1.94 kg of intermediate ITM.3 was obtained as a viscous liquid.

[0211] I.1.4 Synthesis of ITM.4, step (α.4) A 3.5 liter steel autoclave was charged with 1.0 kg (5.74 moles) of N4 amine and 100 g of water, and then heated to 100° C. Then, 50 g of propylene oxide was dosed into the autoclave within 10 minutes. The onset of an exothermic reaction was observed. Then, 950 g of propylene oxide ("PO") was dosed into the autoclave within 20 hours (total amount of PO: 17.2 moles). The system was maintained at 100° C. for another 6 hours. Then, the mixture was removed from the autoclave and the remaining PO and water were stripped under reduced pressure (20 mbar) at 80° C. for 2 hours. 1.91 kg of intermediate ITM.4 was obtained as a clear viscous liquid.

[0212] I.2 Synthesis of Core (a) I.2.1 Process (β.1): ITM.1: Citric acid: Sebacic acid: 6:1:9 A 500 ml flask equipped with a stir bar, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (14.61 g, 0.076 mol), sebacic acid (138.39 g, 0.684 mol), and ITM.1 (127.0 g, 0.456 mol). The reaction mixture was stirred at 60 rpm under nitrogen and heated to 87 °C over 25 min. The stirring speed was adjusted to 210 rpm because the viscosity decreased with increasing temperature. The reaction mixture was then heated to 120-130 °C (internal temperature). Gentle effervescence was observed. Water was distilled off and collected. Stirring at 120-130 °C (internal temperature) under nitrogen was continued for a total of 9 h. The reaction mixture was then slowly cooled. The resulting ester ("core") (a.1) was collected as a clear amber viscous material.

[0213] I.2.2 Process (β.2): ITM.1: Citric acid: Sebacic acid: 10:1:9 A 500 ml flask equipped with a stir bar, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (11.22 g, 0.058 mol), sebacic acid (106.26 g, 0.525 mol), and ITM.1 (162.5 g, 0.584 mol). The reaction mixture was stirred at 60 rpm under nitrogen and heated to 88 °C over 30 min. The viscosity decreased with increasing temperature, so the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 120-130 °C (internal temperature). Effervescence was observed. Water was distilled off and collected. Stirring at 120-130 °C (internal temperature) under nitrogen was continued for a total of 25 h. The reaction mixture was then slowly cooled. The resulting ester, core (a.2), was collected as an amber viscous material.

[0214] I.2.3 Step (β.3): ITM.1: Citric acid: Adipic acid (5:1:4) A 500 ml flask equipped with a stir bar, Dean-Stark apparatus, nitrogen inlet, and internal thermometer was charged with citric acid (22.36 g, 0.116 mol), adipic acid (68.08 g, 0.466 mol), and ITM.1 (178.2 g, 0.582 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 100 °C over 1 h. The viscosity decreased with increasing temperature, so the stirring speed was adjusted to 210 rpm. The reaction mixture was then heated to 120-130 °C (internal temperature). Effervescence was observed. Water was distilled off and collected. Stirring at 120-130 °C (internal temperature) under nitrogen atmosphere was continued for a total of 2 h. The reaction mixture was then slowly cooled. The resulting ester, core (a.3), was collected as an amber viscous material.

[0215] Further cores were synthesized according to Table 1.

[0216] [Table 1]

[0217] Step (γ.1), ethoxylation of the core: A 3.5 L autoclave was charged with 107.0 g of the core (a.1) and 4.5 g of aqueous potassium hydroxide (50 wt%), and the autoclave was heated to 120° C. under reduced pressure with nitrogen flushing to remove moisture. The autoclave was heated to 130° C. and charged with 50 g of ethylene oxide within 10 minutes. Ethylene oxide as per table 2 was then 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 80° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed under reduced pressure at 80° C. As a result, the polymer of the present invention (A.1.1) was obtained as a dark amber solid.

[0218] Step (γ.2), propoxylation of the polymer of the invention: A 3.5 L autoclave was charged with 444 g of polymer (A.1.1) and 3.5 g of aqueous potassium hydroxide (50 wt%), and the autoclave was heated to 120° C. under reduced pressure with nitrogen flushing to remove moisture. The autoclave was heated to 130° C. and 50 g of propylene oxide was charged within 10 minutes. Propylene oxide as per table 2 was then 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 80° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed under reduced pressure at 80° C. As a result, polymer (A.1.2) was obtained as a dark amber solid.

[0219] [Table 2]

[0220] [Table 3]

[0221] II. Washing and cleaning performance II.1 Washing laundry The first wash performance of the polymers of the present invention was tested in a washing machine by preparing a wash solution 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 polymers of the present invention (A.1.1)-(A.1.2) of Table 2.

[0222] [Table 4]

[0223] [Table 5]

[0224] For the performance test in the 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 stain) as additional stain ballast.

[0225] Table 4. Multi-stain monitor test for washing machines MSM1 (circular stain, diameter 5 cm): CFT PC-H144: Red ceramic clay on polyester / cotton (65:35) CFT KC-H115: Standard clay on knitted cotton CFT PC-H145: Tennis court clay on polyester / cotton (65:35) CFT KC-H018: Soil clay on knitted cotton MSM2: CFT CS-10: Milk fat with colorant on cotton CFT CS-62: Colored lard on cotton CFT CS-78: Pigmented soybean oil on cotton EMPA 112: Cocoa on cotton EMPA 141 / 1: Lipstick on cotton EMPA 125: Soils on cotton susceptible to the action of surfactants and lipases. wfk20D: Pigments and sebum-based fats on polyester / cotton blends CFT CS-70: Chocolate / mousse cream on cotton MSM3: wfk20D: Pigments and sebum-based fats on polyester / cotton blends EMPA 101: Cotton stained with carbon black / olive oil EMPA 141 / 2: Lipstick stained polyester / cotton (65:35) CFT PC-S-04: Colored olive oil EMPA 114: Red wine stained cotton EMPA 112: Cocoa-stained cotton EMPA 116: Blood / Milk / Ink Stained Cotton CFT CS-01: Blood aged 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)

[0226] Color measurements were used to evaluate the overall degree of cleaning. The reflectance values ​​of the stains on the monitor were measured using a sphere reflectance spectrometer (model SF 500 from Datacolor, USA, wavelength range 360-700 nm, optical geometry d / 8°) equipped with a 460 nm UV cut-off filter. Here, the lightness L*, a* value on the red-green axis, and b* value on the yellow-blue axis were measured and averaged for each stain on the monitor before and after cleaning, using the CIE-Lab color space classification. The following formula is used:

number

[0227] A higher Delta E value indicates better cleaning. For any stain, a person skilled in the art can visually detect a difference of 1 unit. A non-trained person can easily visually detect a difference of 2 units. The ΔE values ​​of the formulations for the corresponding M1 and M2+M3 4, 8, and 11 stains, as well as several selected single stains, are shown in Table 5.

[0228] [Table 6]

[0229] In the tests, wash performance benefits could be seen in ΔE for both MSM1 and MSM2+MSM3 monitors using the polymers of the present invention. Higher benefits against oil-containing stains such as sebum and lipstick (wfk20D and EMPA141 / 2) were seen with the first ethoxylated and then propoxylated polymer (A).

[0230] II.2 Cleaning hard surfaces Nonionic surfactants: (IV.1): nC 16 -Alkyl / nC 18 -Alkyl-polyglucosides (y is about 1.3) II.2.1 Preparation of Comparative Formulation C-HSC.1 A 250 ml container was charged with 80 g of water. Then, 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene diglycol (BDG) were added, followed by 2 g of an aqueous solution of (IV.1) at 50%. Homogenization was achieved by medium stirring (magnetic) for 5 minutes at ambient temperature. Comparative formulation C-HSC.1 was obtained.

[0231] II.2.2 Preparation of the formulation HSC.2 according to the invention A 250 ml vessel was charged with 80 g of water. Then, 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene diglycol (BDG) were added, followed by 2 g of an aqueous solution of (IV.1) at 50% and 4 g of the polymer of the invention (A.3.2). Homogenization was achieved by medium stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.2 of the invention was obtained.

[0232] II.2.3. Preparation of the formulation HSC.3 according to the invention A 250 ml vessel was charged with 80 g of water. Then, 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene diglycol (BDG) were added, followed by 5 g of a 41% by weight solution of MGDA-Na3, 2 g of a 50% aqueous solution of (IV.1) and 2 g of the polymer of the invention (A.3.2). Homogenization was achieved by medium stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.3 of the invention was obtained.

[0233] II.2.4 Preparation of the formulation HSC.4 according to the invention A 250 ml vessel was charged with 80 g of water. Then, 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene diglycol (BDG) were added, followed by 5 g of a 41% by weight solution of MGDA-Na3, 2 g of a 50% aqueous solution of (IV.1) and 2 g of the polymer of the invention (A.5.2). Homogenization was achieved by medium stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.4 of the invention was obtained.

[0234] II.2.5 Preparation of the formulation HSC.5 according to the invention A 250 ml vessel was charged with 80 g of water. Then, 6 g of an aqueous solution of NaOH (50%) and 8 g of butylene diglycol (BDG) were added, followed by 5 g of a 41% by weight solution of MGDA-Na3, 2 g of a 50% aqueous solution of (IV.1) and 2 g of the polymer of the invention (A.9.2). Homogenization was achieved by medium stirring (magnetic) for 5 minutes at ambient temperature. Formulation HSC.5 of the invention was obtained.

[0235] The performance was evaluated for cleaning performance on stainless steel surfaces at ambient temperature.

[0236] Test stains: Oily stains were prepared by mixing 25.0% butter, 25.0% lard, 25.0% margarine, 20.0% ketchup, 2.5% mustard, and 2.5% potato starch with continuous stirring at 40-45°C. Oily stains were obtained.

[0237] Stainless steel plates (15x10cm) were pre-cleaned with ethanol and then weighed. Approximately 1.5g of oily soil was applied evenly to each plate with a roller. The plates were then heated to 200°C in an oven for 2 hours. The plates were then cooled to ambient temperature and stored for 2 hours. Finally, a cleaning test was performed.

[0238] 2g of the inventive formulation / or comparative formulation was sprayed evenly onto the soiled stainless steel plate with a trigger sprayer and left to act for 2 minutes.Furthermore, the surface of the soiled plate was wiped with a cellulose-type wet sponge (no pressure was applied).

[0239] The stain removal was evaluated visually and based on the average value of three experiments. 1 No removal 2 Slight removal (10-30% of the surface cleaned) 3 Average removal (40-70% of the surface cleaned) 4 Good removal (>70% - 90% of the surface was cleaned) 5 Excellent removal (>90% of the surface was cleaned) The percentages are based on the surface. The results are summarized in Table 6.

[0240] [Table 7]

[0241] III. Biodegradation Tests Summary: The test was performed according to the OECD guidelines. According to the OECD guidelines, the test is valid if: 1. The reference material reaches 60% within 14 days. 2. The difference in the extreme values ​​of test reproducibility by the end of the test is less than 20%. 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.

[0242] Description of the test methods used in the context of this invention: Biodegradation in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F, an aerobic test that measures the biodegradation of wastewater samples by measuring the consumption of oxygen. Measured amounts of wastewater were spiked with 100 mg / L of the test substance, nominally the only carbon source, together with an inoculum (aerated sludge taken from the municipal wastewater treatment plant in Mannheim, Germany). The sludge was stirred in a closed flask at constant temperature (25°C) for 28 days. The oxygen consumption is determined by measuring the change in pressure in a closed flask using an Oxi TopC. The released carbon dioxide is absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent the consumption of oxygen by nitrification. The amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for the uptake by a parallel blank inoculum) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). A positive control, glucose / glutamic acid, is run along with the test samples in each cabinet as a reference material.

[0243] Calculation: Theoretical Oxygen Demand: The amount of O2 required to oxidize a compound to its final oxidation product. This amount is calculated using elemental analysis data.

[0244] Biodegradation% Take the experimental O2 intake x 100 and divide by the theoretical oxygen demand.

[0245] The results of the biodegradability tests are summarized in Table 7.

[0246] [Table 8]

[0247] [Table 9]

Claims

1. 1. A liquid detergent composition comprising: (A) at least one polymer, (a) a core carrying 1 to 3 moieties of general formula (I), 【Chemistry 1】 where Z is different or the same, and C ５ ~C ２０ alkylene; ５ ~C ２０ In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, ５ ~C ２０ The C atoms in alkylene may be unsubstituted or may be substituted with one or more O—C １ ~C ４ It may be substituted with an alkyl group. A １ are different or the same, and C １ ~C １２ Alkylene, C ６ Arylene, and C ３ ~C １２ cycloalkylene, where C １ ~C １２ Alkylene and C ３ ~C １２ The cycloalkylene may be unsubstituted or may have one or more O—C １ ~C ４ It may be substituted with an alkyl group or an OH group, ３ ~C １２ The cycloalkylene may carry one to three methyl groups; Or based on citric acid, X １ is selected from hydrogen, methyl, and ethyl, and combinations of at least two of the foregoing; a core, n being in the range of 1 to 100; (b) a polyalkylene oxide chain; and A composition comprising a polymer comprising:

2. All the Zs are (CH ２ ) ｚ１ -[N(CH ２ ) ｚ２ ] ｚ４ -N(CH ２ ) ｚ３ -, wherein the variables z1, z2, and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, and each CH ２ The composition of claim 1, wherein the group is unsubstituted or substituted with one to two methyl or methoxy groups.

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

4. 4. The composition of 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 The composition according to any one of claims 1 to 4, having the formula:

6. All Z's are -(CH ２ ) ３ -N-(CH ２ ) ２ , -(CH ２ ) ３ -N-(CH ２ ) ３ - and -(CH ２ ) ３ -N(CH ２ ) ２ -N-(CH ２ ) ３ The composition according to any one of claims 1 to 5, wherein said compound is selected from the group consisting of

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

8. (a) a core carrying 1 to 3 moieties of general formula (I), 【Chemistry 2】 where Z is different or the same, and C ５ ~C ２０ alkylene; ５ ~C ２０ In the alkylene, at least one C atom is replaced by an N atom carrying a polyalkylene chain, ５ ~C ２０ The C atoms in alkylene may be unsubstituted or may be substituted with one or more O—C １ ~C ４ It may be substituted with an alkyl group. 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, where C １ ~C １２ Alkylene and C ３ ~C １２ The cycloalkylene may be unsubstituted or may have one or more O—C １ ~C ４ It may be substituted with an alkyl group or an OH group, ３ ~C １２ The cycloalkylene may carry one to three methyl groups; Or based on citric acid, X １ is selected from hydrogen, methyl, and ethyl, and combinations of at least two of the foregoing; n is in the range of 1 to 100; X ２ C １ ~C ４ Alkyl, hydrogen, and CH(X １ )-CH ２ A core selected from -N-Z-; (b) a polyalkylene oxide chain; and A polymer comprising:

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

10. All Z's are (CH ２ ) ｚ１ -[N(CH ２ ) ｚ２ ] ｚ４ -N(CH ２ ) ｚ３ -, wherein the variables z1, z2, and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, and each CH ２ 10. A polymer according to claim 8 or 9, wherein each group may be unsubstituted or substituted with one to two methyl or methoxy groups.

11. All Z's are -(CH ２ ) ３ -N-(CH ２ ) ２ , -(CH ２ ) ３ -N-(CH ２ ) ３ - and -(CH ２ ) ３ -N(CH ２ ) ２ -N-(CH ２ ) ３ The polymer according to any one of claims 8 to 10, which is selected from

12. A １ But, C １ ~C ４ The polymer according to any one of claims 8 to 11, selected from alkylene.

13. A process for making the polymer of any one of claims 8 to 12, comprising the steps of: (α) General formula H ２ N-Z'-NH ２ with an alkylene oxide in a molar ratio of alkylene oxide:N atom of 3:1 to 1:3, wherein the alkylene oxide is selected from ethylene oxide and propylene oxide, thereby forming an intermediate, wherein Z′ is defined as Z, but the N atom carries an H instead of a polyalkylene oxide chain; (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 their corresponding anhydrides or C １ ~C ４ with an alkyl ester to obtain an ester; (γ) treating the ester from step (β) in one or more steps with at least one C ２ ~C ４ reacting with an alkylene oxide; The process includes:

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

15. 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 said detergent composition comprising at least one lipase and / or at least one protease.

Images