Compositions containing polymers, polymers and uses thereof

Abstract

The present invention relates to (A) at least one polymer comprising (a) 1 to 50 moieties of general formula (I) and a group of general formula (II) [Formula 1] TIFF2025505571000025.tif57170 (where the asterisk stands for X 2 or a C1-C4 alkyl, or a group of formula (II), or a polyalkylene oxide chain (b), linked via X 1 are the same or different and are selected from C1-C2-alkyl and hydrogen; X 2 are the same or different and are selected from linear or branched C2-C6-alkylenes that are unsubstituted or substituted with one or more hydroxyl groups, ester or ether groups of carboxylic acids. and (b) at least one polymer that comprises a polyalkylene oxide chain.

Description

[Technical field]

[0001] The present invention relates to (A) at least one polymer, (a) General formula (I) [ka] 1 to 50 moieties of the general formula [ka] Based on (wherein the asterisk represents X 2 or a C1-C4-alkyl, or a group of formula (II), or a polyalkylene oxide chain (b), X 1 are the same or different and are selected from C1-C2-alkyl and hydrogen, X 2 are the same or different and are selected from linear or branched C2-C6-alkylenes that are unsubstituted or substituted with one or more hydroxyl groups, ester or ether groups of carboxylic acids. A core carrying the (b) Polyalkylene oxide chain At least one polymer comprising The present invention relates to a detergent composition comprising:

[0002] Furthermore, the present invention is directed to a polymer (A) and a process for making such a polymer (A). [Background technology]

[0003] Laundry detergents must meet several requirements: they must remove all kinds of stains from laundry, including all kinds of pigments, clays, greasy stains and dyes from food and beverages such as red wine, tea, coffee and fruits, including berry juices. They must also exhibit a certain storage stability. In particular, laundry detergents that are liquid or contain moisture-absorbing ingredients often lack good storage stability, e.g. enzymes tend to become inactivated.

[0004] Greasy soils remain a challenge in laundry. Many suggestions have been made for removal (polymers, enzymes, surfactants), but a solution that works well is still of interest. The use of lipases to aid in the removal of grease has been suggested, but many builders do not work well with lipases, especially in liquid laundry detergents.

[0005] In addition, graying of laundry remains a significant problem. The cause of graying is the redeposition of dirt during washing. To reduce the redeposition of dirt, certain natural or modified polysaccharides have been developed, such as polysaccharides treated with gaseous or liquid SO2. Many ingredients with different structures have been suggested, see for example WO 2015 / 091160, EP 3266858 A1 and EP 3226858 A1, but there is still room for improvement and the anti-graying performance of such compounds is still not sufficient. Therefore, there is a continuous need for improved anti-graying agents that can be used in the washing process. In particular, it is desirable to provide an anti-graying agent that reduces the graying of washed fabrics.

[0006] Several polymers have been suggested as additives, however many of them suffer from rapid degradation and therefore short shelf life. Summary of the Invention [Problem to be solved by the invention]

[0007] It was therefore an object to provide detergent compositions that meet the above demands. It was further an object to provide ingredients that meet the above demands, and to provide processes for making such ingredients and detergent compositions. [Means for solving the problem]

[0008] Accordingly, a detergent composition as defined at the beginning has been found, hereinafter also referred to as the composition of the present invention or the composition according to the present invention.The composition of the present invention comprises at least one polymer (A) comprising a core (a) and a side chain (b).The polymer (A) and the detergent composition comprising the polymer (A) are described in more detail below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The polymer (A) is (a) General formula (I) [ka] and 1 to 50, preferably 3 to 25, moieties of the general formula [ka] Based on (wherein the asterisk represents X 2 or C1-C4-alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl or sec-butyl, with methyl being the preferred C1-C4-alkyl, or The asterisk represents a group of formula (II) or a polyalkylene oxide chain (b), X 1 are different or preferably the same and are selected from hydrogen and C1-C2-alkyl, preferably all X 1 is hydrogen, and even more preferably, all X 1 is hydrogen, X 2are the same or different and are selected from linear or branched C2-C6-alkylenes which are unsubstituted or substituted with one or more hydroxyl groups, preferably tertiary hydroxyl groups, ester groups of carboxylic acids, such as COOCH3, COOC2H5 or ether groups, such as -OCH3 or -OC2H5. Examples of linear C2-C6-alkylenes are -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5- and -(CH2)6-, and substituted examples are residues based on citric acid, -CH2-C(OH)(COO-)-CH2- a core carrying a group (b) Polyalkylene oxide chain Includes.

[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 mixtures of at least two of the above, 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.

[0011] In a preferred embodiment, the majority of the alkylene oxides in the polyalkylene oxide chain (b) are EO, with the remainder being PO or BU. In a more preferred embodiment, all of the alkylene oxides in the polyalkylene oxide chain (b) are EO.

[0012] In one embodiment of the present invention, the weight ratio of core (a) to polyalkylene oxide chain (b) in polymer (A) ranges from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0013] In one embodiment of the present invention, the polymer (A) has the formula (CH2) z1 -[N(CH2) z2 ] z4 -N(CH2)z3 - group, where the variables z1, z2 and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, each CH2 group may be unsubstituted or substituted with 1 to 2 methyl or methoxy groups, and the free valence of the N atom carries a chain (b). Said additional groups thus constitute part of the core (a).

[0014] Preferably, the variables are selected as follows: z1 and z3 are both 3, z2 is 2 and z4 is 1, or z1 is 2, z4 is 0, z3 is 3 and z2 is 2-4.

[0015] In one embodiment of the present invention, a group of formula (I) and a group of formula (CH2) z1 -[N(CH2) z2 ] z4 -N(CH2) z3 The numerical ratio of - groups is in the range of 2:1 to 6:1.

[0016] The polyalkylene oxide chain (b) may have a hydrogen atom at the end (so-called no capping) and may have a C1-C 10 It may be capped with -alkyl, especially methyl, or -SO3Na.

[0017] In one embodiment of the present invention, the average molecular weight M of the polymer (A) w is at least 1,500 g / mol, preferably in the range of 2,500 to 80,000 g / mol. The average molecular weight can be determined by gel permeation chromatography ("GPC") in 0.1 M aqueous NaCl solution containing 0.05% by weight of potassium trifluoroacetate as the mobile phase or in hexafluoroisopropanol ("HFIP") containing 0.05% by weight of potassium trifluoroacetate as the mobile phase, preferably using TSKgel as the stationary phase in each case.

[0018] In one embodiment of the present invention, the polydispersity Q of the polymer (A) is w / M n is in the range of 1 to 10, preferably 1.5 to 6.

[0019] 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.

[0020] In one embodiment of the present invention, polymer (A) has an OH number (measured according to DIN 53240 (2013)) in the range of 1 to 1000, preferably 5 to 350 mg KOH / g polymer (A).

[0021] 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 including the "active site" of the enzyme, which thus determines the catalytic activity of the enzyme. The polypeptide sequence can be identified by a sequence number. In accordance with the World Intellectual Property Organization (WIPO) standard ST.25 (1998), amino acids are represented herein using three-letter code with the first letter capitalized or the corresponding one-letter code.

[0022] Any enzyme according to the invention relates 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 conversion, meaning that the enzyme acts on a substrate and converts it into a product. As used herein, the term "enzyme" excludes inactive variants of the enzyme.

[0023] A "parent" sequence (of a parent protein or enzyme, also called a "parent enzyme") is a starting sequence for introducing changes into the sequence (e.g., by introducing one or more amino acid substitutions, insertions, deletions or a combination thereof) to result in a "variant" of the parent sequence. The term parent enzyme (or parent sequence) includes wild-type enzymes (sequences) and synthetically produced sequences (enzymes) that are used as starting sequences for introducing (further) changes.

[0024] The term "enzyme variant" or "sequence variant" or "mutant enzyme" refers to an enzyme that differs to some extent in its amino acid sequence from its parent enzyme. Unless otherwise specified, a mutant enzyme that is "enzymatically active" means that the mutant enzyme has the same type of enzymatic activity as the corresponding parent enzyme.

[0025] In describing the variants of the present invention, the nomenclature explained below is used.

[0026] Amino acid substitutions are described by giving the original amino acid of the parent enzyme, then the position number in the amino acid sequence, then the replaced amino acid. Amino acid deletions are described by giving the original amino acid of the parent enzyme, then the position number in the amino acid sequence, then a *. Amino acid insertions are described by giving the original amino acid of the parent enzyme, then the position number in the amino acid sequence, then 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 the substitution and insertion occur at the same position, this can be designated as S99SD+S99A or S99AD for short. Degeneracy in nomenclature occurs when an amino acid residue identical to an existing amino acid residue is inserted. For example, if in the above example a glycine was inserted after the glycine, this would be designated as 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 optional substitutions may be indicated in parentheses, for example, Arg170[Tyr,Gly] or Arg170{Tyr,Gly}, or short, R170[Y,G] or R170{Y,G}, or long, R170Y,R170G.

[0027] Enzyme variants can be defined by their sequence similarity when compared to the parent enzyme. Sequence identity is usually indicated as "% sequence identity" or "% identity". For sequence identity calculation, a sequence alignment must be generated in the first step. 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 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, and the program default parameters (gap start = 10.0, gap extension = 0.5 and matrix = EBLOSUM62) are used.

[0028] According to the present invention, the following calculation of % identity is applied: % identity = (identical residues / length of the alignment region showing each sequence of the present invention over its full length) * 100.

[0029] 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 a corresponding parent enzyme, where "n" is an integer between 10 and 100. In one embodiment, the mutant enzyme is at least 70%, at least 75%, at least 80%, at least 81%, at least 83%, at least 84%, at least 85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical to the full-length amino acid sequence of the parent enzyme, and the enzyme variant has enzymatic activity.

[0030] "Enzyme activity" refers to the catalytic effect exerted by an enzyme and is usually expressed as units per milligram of enzyme (specific activity) and is related to the molecules of substrate converted per molecule of enzyme per minute (molecular activity). An enzyme variant may have an enzymatic activity according to the invention if it 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 corresponding parent enzyme.

[0031] In one embodiment the enzyme is selected from hydrolases, preferably proteases, amylases, lipases, cellulases and mannanases.

[0032] In one embodiment of the present invention, the composition of the present invention comprises: (A) at least one hydrolase, hereinafter also called hydrolase (B), preferably chosen from lipases, hereinafter also called lipases (B); Includes.

[0033] "Lipase", "lipolytic enzyme", "lipid esterase" all refer to enzymes in EC class 3.1.1 ("carboxylic acid ester hydrolases"). 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.

[0034] 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).

[0035] In one aspect of the invention, the lipase (B) is selected from: lipases from the genus Humicola (synonym Thermomyces), such as those from H. lanuginosa (T. lanuginosus), as described in EP 258068, EP 305216, WO 92 / 05249 and WO 2009 / 109500, or from H. insolens, as described in WO 96 / 13580; lipases from strains of the genus Pseudomonas (some of which have now been renamed Burkholderia), such as P. alcaligenes or P. pseudoalcaligenes (EP 218272, WO 94 / 25578, WO 95 / 30744, WO 95 / 35381, WO 96 / 00292), P. cepacia (EP 331376), P. stutzeri (GB 1372034), P. fluorescens, Pseudomonas species sp. strain SD705 (WO 95 / 06720 and WO 96 / 27002), P. wisconsinensis (WO 96 / 12012), Pseudomonas mendocina (WO 95 / 14783), P. glumae (WO 95 / 35381, WO 96 / 00292); Streptomyces griseus (WO 2011 / 150157) and S.lipases from S. pristinaespiralis (WO 2012 / 137147), GDSL-type Streptomyces lipases (WO 2010 / 065455); lipases from Thermobifida fusca as disclosed in WO 2011 / 084412; lipases from Geobacillus stearothermophilus as disclosed in WO 2011 / 084417; Bacillus lipases, such as those disclosed in WO 00 / 60063, Dartois et al. (1992), Biochemica et Biophysica Lipases from B. subtilis, B. stearothermophilus (JP 64-074992) or B. pumilus (WO 91 / 16422) as disclosed in Acta, 1131, 253-360 or WO 2011 / 084599; lipases from Candida antarctica as disclosed in WO 94 / 01541. Suitable lipases (B) also include variants of the above lipases that have lipolytic activity.

[0036] Suitable lipases (B) also include variants of the above lipases that have lipolytic activity. Suitable lipase variants include variants that have at least 40-100% identity when compared to the full-length polypeptide sequence of the parent enzyme disclosed above. In one embodiment, the lipase variants with lipolytic activity can be at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full-length polypeptide sequence of the parent enzyme disclosed above.

[0037] 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 hydrolysis of the ester bond in the substrate para-nitrophenyl palmitate (pNP-palmitate, C:16), releasing pNP, which is yellow in color and can be detected at 405 nm.

[0038] 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.

[0039] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity that are at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 in U.S. Pat. No. 5,869,438.

[0040] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity that contain only conservative mutations not related 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 having 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.

[0041] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the following amino acid substitutions, T231R and N233R, when compared to amino acids 1-269 of SEQ ID NO:2 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, when compared to amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438.

[0042] The Thermomyces lanuginosa lipase can 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 is 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.

[0043] 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.

[0044] The Thermomyces lanuginosa lipase may be a lipolytically active variant of amino acids 1-269 of SEQ ID NO:2 of US Patent No. 5,869,438, characterized in that the variant of amino acids 1-269 of SEQ ID NO:2 of US Patent No. 5,869,438 contains the amino acid substitutions T231R and N233R. Said lipase may be referred to herein as Lipex.

[0045] In one embodiment of the present invention, a combination of at least two of the above lipases (B) may be used.

[0046] In one embodiment of the present invention, lipase (B) is included in the composition of the present invention in an amount such that the final composition of the present invention has a lipolytic enzymatic activity in the range of 100 to 0.005 LU / mg of the composition, preferably 25 to 0.05 LU / mg. A lipase unit (LU) is calculated as the lipase activity measured at a temperature of 30°C, pH=9.0, and with a substrate of 13 mmol / l Ca in 5 mmol / l Tris buffer. 2+ and the amount of lipase that produces 1 μmol of titratable fatty acid per minute on a pH stat in an emulsion of 3.3 wt.% olive oil and 3.3% gum arabic in the presence of 20 mmol / l NaCl.

[0047] In one embodiment of the present invention, the composition of the present invention comprises: (D) at least one protease (D), hereinafter also referred to as protease (D); Includes.

[0048] In one embodiment, at least one protease (D) is selected from the group of serine endopeptidases (EC 3.4.21), most preferably from the group of subtilisin-type proteases (EC 3.4.21.62). Serine proteases or serine peptidases are characterized by having a serine in the catalytic active site, which forms a covalent adduct with the substrate during the catalytic reaction. In the context of the present invention, the serine protease 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 subtilisins and chymotrypsin-related serine proteases have a catalytic triad that includes aspartic acid, histidine, and serine.

[0049] 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 defined period of time.

[0050] Methods for analyzing proteolytic activity are well known in the literature (see, e.g., Gupta et al. (2002), Appl. Microbiol. Biotechnol. 60:381-395). Proteolytic activity can be determined by using succinyl-Ala-Ala-Pro-Phe-p-nitroanilide (Suc-AAPF-pNA, short AAPF, see, e.g., DelMar et al. (1979), Analytical Biochem 99, 316-320) as a substrate. pNA is cleaved from the substrate molecule by proteolytic cleavage, resulting in the release of free pNA, which is yellow in color, and an increase in OD 405 It can be quantified by measuring

[0051] Proteolytic activity can be expressed in units per gram of enzyme, for example, 1 U protease can 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).

[0052] Subtilisin type proteases (EC 3.4.21.62) are proteases from the genera Bacillus, Clostridium, Enterococcus, Geobacillus, Lactobacillus, Lactococcus, Oceanobacillus, Staphylococcus, Streptococcus or Streptomyces. The protease may be a bacterial protease or a Gram-negative polypeptide of microbial origin selected from the group consisting of proteases from the genus Campylobacter, E. coli, Flavobacterium, Fusobacterium, Helicobacter, Ilyobacter, Neisseria, Pseudomonas, Salmonella and Ureaplasma.

[0053] 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, and the like. The protease is selected from Bacillus megaterium, Bacillus pumilus, Bacillus sphaericus, Bacillus stearothermophilus, Bacillus subtilis or Bacillus thuringiensis.

[0054] In one embodiment of the present invention, the at least one protease (D) is selected from the group consisting of subtilisin from Bacillus amyloliquefaciens BPN' (described in Vasantha et al. (1984) J. Bacteriol. Volume 159, p. 811-819 and J. A. Wells et al. (1983), Nucleic Acids Research, Volume 11, p. 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. 11, pp. 2185-2192). 13, p. 8913-8926); subtilisin PB92 (the native sequence of alkaline protease PB92 is described in EP 283075 A2); subtilisins 147 and / or 309 (Esperase®, Savinase®, respectively) disclosed in WO 89 / 06279; subtilisins from Bacillus lentus disclosed in WO 91 / 02792, such as those from Bacillus lentus DSM 5483 or mutants of Bacillus lentus DSM 5483 described in WO 95 / 23221; Bacillus alkalophilus disclosed in DE 10064983 A1. 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); subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003 / 054184; subtilisin having SEQ ID NO: 4 described in WO 2005 / 063974; subtilisin having SEQ ID NO: 4 described in WO 2005 / 103244; subtilisin having SEQ ID NO: 7 described in WO 2005 / 103244; as well as subtilisin having SEQ ID NO: 2 described in application DE 102005028295.4.

[0055] A suitable example is in particular SEQ ID NO: 22, which is described in EP 1921147 (which is derived from Bacillus lentus). lentus) DSM 5483) which have amino acid substitutions at one or more of the following positions: 3, 4, 9, 15, 24, 27, 33, 36, 57, 68, 76, 77, 87, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 106, 118, 120, 123, 128, 129, 130, 131, 154, 160, 167, 170, 194, 195, 199, 205, 206, 217, 218, 222, 224, 232, 235, 236, 245, 248, 252 and 274 (according to the BPN' numbering) and have proteolytic activity. In one embodiment, such a protease is not mutated at positions Asp32, His64 and Ser221 (according to the BPN' numbering).

[0056] In one embodiment, at least one protease (D) has a sequence according to SEQ ID NO: 22 as described in EP 1 921 147 or a protease that 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 BPN' numbering) and has proteolytic activity. In one embodiment, the protease comprises one or more further substitutions: (a) threonine (3T) at position 3; (b) isoleucine (4I) at position 4; (c) alanine, threonine or arginine (63A, 63T or 63R) at position 63; (d) aspartic acid or glutamic acid (156D or 156E) at position 156; (e) proline (194P) at position 194; (f) methionine (199M) at position 199; (g) isoleucine (205I) at position 205; (h) aspartic acid, glutamic acid or glycine (217D, 217E or 217G) at position 217; (i) a combination of two or more amino acids from (a)-(h).

[0057] At least one protease (D) may be at least 80% identical to SEQ ID NO: 22 described in EP 1921147 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 is characterized in that it 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. The protease having the sequence according to SEQ ID NO: 22 described in EP 1921147 together with 101E may be referred to herein as Lavergy.

[0058] In one embodiment the protease according to SEQ ID NO: 22 described in EP 1 921 147 is characterised in that it comprises the mutations (according to BPN' numbering) S3T+V4I+S9R+A15T+V68A+D99S+R101S+A103S+I104V+N218D and has proteolytic activity.

[0059] The compositions of the invention may comprise a combination of at least two proteases (all as disclosed above), 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).

[0060] 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 relative to the total weight of the composition.

[0061] In the context of the present invention, a lipase (B) and / or a protease (D) is considered to be stable if its enzymatic activity "available for application" is at least equal to 60% when compared to the initial enzymatic activity before storage. An enzyme can be called stable in 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 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or at least 99.5% when compared to the initial enzymatic activity before storage.

[0062] Subtracting a% from 100% gives the "loss of enzyme activity during storage" compared to the initial enzyme activity before storage. In one embodiment, an enzyme is stable according to the present invention if substantially no loss of enzyme activity occurs during storage, i.e. the loss in enzyme activity is equal to 0% compared to the initial enzyme activity before storage. In the present invention, substantially 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%.

[0063] 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) Includes.

[0064] Examples of anionic surfactants (C) are C8 to C 18 -Alkyl sulfate, C8~C 18 -Fatty alcohol polyether sulfate, ethoxylated C4~C 12 - 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 Sulfo fatty acid methyl esters, and further C 12 ~C 18 -Alkyl sulfonic acid and C 10 ~C 18 -Alkylarylsulfonic acids, alkali metal and ammonium salts. The alkali metal salts of the above compounds are preferred, in particular the sodium salts.

[0065] Further examples of anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, carboxylic ether and alkyl ether phosphates.

[0066] In a preferred embodiment of the present invention, the anionic surfactant (C) is represented by the general formula (III) R 1 -O(CH2CH2O) x -SO3M (III) wherein: R 1 nC 10 ~C 18 -Alkyl, especially those having an even number of carbon atoms, such as n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, preferably C 10 ~C 14 -alkyl, more preferably nC 12 -alkyl, x is a number ranging from 1 to 5, preferably from 2 to 4, and even more preferably 3; M is selected from alkali metals, preferably potassium, and even more preferably sodium.

[0067] In the anionic surfactant (C), x may be an average number, and therefore n is not necessarily an integer, but in each individual molecule of formula (I), x represents an integer.

[0068] 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.

[0069] The compositions of the present invention may contain ingredients other than those listed above, such as nonionic surfactants, fragrances, dyes, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, antifoam agents and anticorrosion additives.

[0070] Preferred compositions of the present invention may contain one or more non-ionic surfactants.

[0071] Preferred nonionic surfactants are alkoxylated alcohols, diblock and multiblock 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.

[0072] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (IIIa) [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 -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.

[0073] 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.

[0074] Other preferred examples of alkoxylated alcohols include those represented by the general formula (IIIb) [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.

[0075] The sum of a+b+d is preferably in the range of 5-100, and more preferably in the range of 9-50.

[0076] The compound of general formula (III) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0077] 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 polyglucosides and branched C8-C 14 Likewise suitable are -alkyl polyglycosides, for example 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 -(CH2)2-R 6 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, y ranges from 1.1 to 4 and is an average number.

[0078] Further examples of non-ionic surfactants include those represented by the general formulas (V) and (VI): [ka] is a compound of 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 defined above. A 3 O is selected from propylene oxide and butylene oxide; w is a number ranging from 15 to 70, preferably from 30 to 50; w1 and w3 are numbers ranging from 1 to 5, w2 is a number in the range of 13 to 35.

[0079] Overviews of further suitable non-ionic surfactants can be found in EP-A-0851023 and DE-A-19819187.

[0080] Mixtures of two or more different nonionic surfactants selected from those listed above may also be present.

[0081] Other surfactants which may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants, and mixtures thereof.

[0082] Examples of amphoteric surfactants are those that have positive and negative charges in the same molecule under the conditions of use.Preferred examples of amphoteric surfactants are so-called betaine surfactants.Many examples of betaine surfactants have one quaternized nitrogen atom and one carboxylic acid group per molecule.A particularly preferred example of amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0083] Examples of amine oxide surfactants include those represented by the general formula (VII): R 9 R 10 R 11 N → O (VII) wherein R 9 , R 10 and R 11 are each independently an aliphatic, alicyclic or C2-C4 alkylene C 10 ~C 20 -alkylamide moieties. Preferably, R 9 is C8~C 20 -Alkyl or C2-C4-alkylene C 10 ~C 20 -alkylamide; R 10 and R 11 are both methyl.

[0084] 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.

[0085] 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.

[0086] In a preferred embodiment, the solid detergent composition of the present invention for cleaning applications, especially for automatic dishwashing applications, does not contain any anionic surfactants.

[0087] The composition of the present invention may contain at least one bleaching agent, also called bleaching agent. 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.

[0088] Examples of organic peroxide bleaching agents are organic percarboxylic acids, especially organic percarboxylic acids.

[0089] In the composition of the present invention, alkali metal percarbonate, especially sodium percarbonate, is preferably used in coating form.Such coating agents can be organic or inorganic.Examples include glycerol, sodium sulfate, silicate, sodium carbonate and combinations of at least two of the above, such as the combination of sodium carbonate and sodium sulfate.

[0090] Suitable chlorine-containing bleaching agents 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.

[0091] The composition of the present invention may contain, for example, a chlorine-containing bleaching agent in the range of 3 to 10% by weight.

[0092] The composition of the present invention may contain one or more bleaching catalysts. The bleaching catalysts may be selected from bleach-accelerating transition metal salts or transition metal complexes, such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen or -carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleaching catalysts.

[0093] 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 quaternary ammonium (trimethylammonium acetonitrile salts).

[0094] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0095] Examples of fragrances are benzyl salicylate, 2-(4-tert.-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0096] 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.

[0097] The compositions of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent compositions of the present invention due to attack 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"), 2-butyl-benzo[d]isothiazol-3-one (BBIT), 2-octyl-2H-isothiazol-3-one (OIT); benzoic acid, Sorbic acid and its salts, such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate, calcium sorbate, sodium sorbate, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH"), and dibromodimethylhydantoin ("DBDMH").

[0098] Of particular interest are the following antimicrobials and / or preservatives: 4,4'-dichloro 2-hydroxydiphenyl ether, further name: 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP (commercially available as a 30 wt % solution of 4,4'-dichloro 2-hydroxydiphenyl ether in 1,2 propylene glycol); 2-Phenoxyethanol, further names: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether), 2-Bromo-2-nitropropane-1,3-diol, further name: 2-Bromo-2-nitro-1,3-propanediol, glutaraldehyde (CAS number 111-30-8, further names: 1-5-pentanediol, pentane-1,5-dial, glutaral, glutaric dialdehyde, glyoxal (further names: ethanediol, oxylaldehyde, 1,2-ethanediol), Mixture of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (CMIT / MIT mixture), potassium (E,E)-hexa-2,4-dienoate (potassium sorbate), lactic acid and its salts, in particular sodium lactate, in particular L-(+)-lactic acid, Salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate and TEA salicylate. Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, didecyldimethylammonium chloride (DDAC), N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine), peracetic acid and hydrogen peroxide.

[0099] The biocides or preservatives may be added to the compositions of the invention in a concentration of 0.001 to 10% relative to the total weight of the composition.

[0100] Preferably, the composition of the present invention contains 2-phenoxyethanol at a concentration of 0.1 to 2% or 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0101] Thus, the present invention further relates to a method of protecting an aqueous composition of the present invention from microbial contamination or growth comprising the addition of 2-phenoxyethanol.

[0102] Thus, the present invention further relates to a method of providing antimicrobial benefit to fabrics after treatment with a solid laundry detergent, e.g., powder, granules, capsules, tablets, bars, etc.), liquid laundry detergent, fabric softener or post-rinse agent containing 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP).

[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, etc.), dextrin and casein.

[0104] In the context of the present invention, a hydrotrope is a compound that promotes the dissolution of compounds that exhibit limited water solubility. 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 standard 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 of 2,000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. w Each is partially or completely neutralized with alkali, especially sodium. Polycarboxylate copolymers are also suitable, especially 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 function 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 ("MEA") and N,N,N-triethanolamine.

[0109] An example of an antifoaming agent is silicone.

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

[0111] A further aspect of the present invention is therefore the use of the compositions of the present invention for the care of laundry. In this context, the care of laundry includes the washing of laundry.

[0112] In another aspect, the compositions of the invention are useful for cleaning hard surfaces. Thus, a further aspect of the invention is the use of the compositions of the invention for cleaning hard surfaces.

[0113] In the context of the present invention, the term "compositions for cleaning hard surfaces" includes detergents for home care and industrial or institutional applications. The term "compositions for cleaning hard surfaces" includes compositions for dishwashing, especially manual and automatic dishwashing and ware washing, and compositions for cleaning hard surfaces, such as but not limited to bathroom washing, kitchen washing, floor washing, pipe descaling, window washing, car washing, including truck washing, as well as open plant cleaning cleaning in place, metal washing, disinfecting washing, farm washing, pressure washing, but does not include laundry detergent compositions. A special embodiment of the composition for cleaning hard surfaces is an automatic dishwashing composition.

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

[0115] In the context of this invention and unless expressly stated otherwise, percentages relating to ingredients of laundry detergent compositions are percentages by weight and refer to the total solids of the respective laundry detergent compositions.In the context of this invention and unless expressly stated otherwise, percentages relating to ingredients of detergent compositions for hard surface cleaners are percentages by weight and refer to the total solids of the detergent compositions for cleaning hard surfaces.

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

[0117] Examples of the sequestering agent (E) are MGDA (methylglycine diacetate), GLDA (glutamic acid diacetate), IDS (iminodisuccinic acid), alkali metal salts of EDTA, and polymers having a complexing group, for example, a polymer having 20 to 90 mol % of N atoms of at least one CH2COO -Polyethylenimines bearing groups and their corresponding alkali metal salts, in particular the sodium salts, such as MGDA-Na3, GLDA-Na4 or IDS-Na4.

[0118] Preferred sequestering agents are those of the general formula (IXa) [CH3-CH(COO)-N(CH2-COO)2]M 3-x H x (IXa) where M is selected from ammonium cations and alkali metal cations, such as sodium, potassium, and combinations of at least two of the above, and may be the same or different. Ammonium may be substituted with alkyl, 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 even more preferably in the compounds of general formula (IIa), all M are the same, they are all Na, and In formula (IIa), x is in the range of 0 to 1.0; or (IXb) [OOC-CH2CH2-CH(COO)-N(CH2-COO)2]M 4-x H x (IXb) (wherein M is as defined above, and x in formula (IXb) is in the range of 0 to 2.0, preferably to 1.0), or (IXc) [OOC-CH2-CH(COO)]-N-CH(COO)-CH2-COO]M 4-x H x (IXc) (wherein M is as defined above, and x in formula (IIc) is in the range of 0 to 2.0, preferably 1.0). It is of the following.

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

[0120] The chelating agents of the general formulae (IXa) and (IXb) are preferred, and 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 the ammonium and alkali metal salts of a mixture of the L- and D-enantiomers of formula (IXa), said mixture containing predominantly the respective L-isomer with an enantiomeric excess (ee) in the range of 5-99%, preferably 5-95%, more preferably 10-75%, even more preferably 10-66%.

[0122] In one embodiment of the invention, the compound of general formula (IXb) is selected from at least one alkali metal salt of a mixture of the L-enantiomer and the D-enantiomer of formula (IXb), 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 (IXa) can be determined by measuring polarized light (polarimetry) or preferably by chromatography, for example by HPLC using a chiral column, for example using one or more cyclodextrins as stationary phase or using a ligand exchange (Pirkle-brush) concept chiral stationary phase. Determination of ee by HPLC using immobilized optically active amines such as D-penicillamine in the presence of copper(+II) salts is preferred. The enantiomeric excess of the salt of the compound of general formula (IXb) can be determined by measuring polarized light (polarimetry).

[0124] Due to the environmental concerns raised in connection with the use of phosphates, it is preferred that the advantageous composition is phosphate-free. "Phosphate-free" in the context of the present invention should be understood to mean that the content of phosphates and polyphosphates is in the range of from the detection level to 1% by weight, preferably from 10 ppm to 0.2% by weight, measured 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 of the invention is in liquid or gel form at ambient temperature. In another preferred embodiment of the invention, the composition of the invention is in solid form, such as a powder or tablet, at ambient temperature.

[0128] In one embodiment of the invention, the composition of the invention is in liquid or gel form and has a pH value in the range of 7 to 9, preferably 7.5 to 8.5. In an embodiment in which the composition of the invention is a solid, its pH value may be in the range of 7.5 to 11, determined at ambient temperature after dissolving 1 g / 100 ml in distilled water. In an embodiment in which the composition of the invention is used on hard surfaces such as tiles, for example bathroom tiles, its pH value may even be acidic, for example 3 to 6.

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

[0130] Another aspect of the present invention relates to polymer (A), hereinafter also referred to as inventive polymer (A) or simply polymer (A). Inventive polymer (A) comprises:

[0131] The polymer (A) is (c) General formula (I) [ka] and 1 to 50, preferably 3 to 25, moieties of the general formula [ka] (wherein the asterisk represents X 2 or C1-C4-alkyl, such as methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl or sec-butyl, with methyl being a preferred C1-C4-alkyl, or , the asterisk represents a group of formula (II) or a polyalkylene oxide chain (b), X 1 are different or preferably the same and are selected from hydrogen and C1-C2-alkyl, preferably all X 1 is hydrogen, and even more preferably, all X 1 is hydrogen, X 2 are the same or different and are selected from linear or branched C2-C6-alkylenes which are unsubstituted or substituted with one or more hydroxyl groups, preferably tertiary hydroxyl groups, ester groups of carboxylic acids, such as COOCH3, COOC2H5 or ether groups, such as -OCH3 or -OC2H5. Examples of linear C2-C6-alkylenes are -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5- and -(CH2)6-, and substituted examples are residues based on citric acid, -CH2-C(OH)(COO-)-CH2- a core carrying a group (b) Polyalkylene oxide chain Includes.

[0132] 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 above, 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.

[0133] In a preferred embodiment, the majority of the alkylene oxides in the polyalkylene oxide chain (b) are EO, with the remainder being PO or BU. In a more preferred embodiment, all of the alkylene oxides in the polyalkylene oxide chain (b) are EO.

[0134] In one embodiment of the present invention, the weight ratio of the core (a) to the polyalkylene oxide chain (b) in the polymer (A) of the present invention ranges from 1:100 to 1:2, preferably from 1:40 to 1:3.

[0135] In one embodiment of the present invention, the polymer (A) of the present invention has the formula (CH2) z1 -[N(CH2) z2 ] z4 -N(CH2) z3 - group, where the variables z1, z2 and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, each CH2 group may be unsubstituted or substituted with 1 to 2 methyl or methoxy groups, and the free valence of the N atom carries a chain (b). Said additional groups thus constitute part of the core (a).

[0136] Preferably, the variables are selected as follows: z1 and z3 are both 3, z2 is 2 and z4 is 1, or z1 is 2, z4 is 0, z3 is 3 and z2 is 2-4.

[0137] In one embodiment of the present invention, a group of formula (I) and a group of formula (CH2) z1 -[N(CH2) z2 ] z4 -N(CH2) z3 The numerical ratio of - groups is in the range of 2:1 to 6:1.

[0138] The polyalkylene oxide chain (b) may have a hydrogen atom at the end (so-called no capping) and may have a C1-C 10 It may be capped with -alkyl, especially methyl, or -SO3Na.

[0139] In one embodiment of the present invention, the average molecular weight M of the polymer (A) of the present invention w is at least 1,500 g / mol, preferably in the range of 2,500 to 80,000 g / mol. The average molecular weight can be determined by gel permeation chromatography ("GPC") in 0.1 M aqueous NaCl solution containing 0.05% by weight of potassium trifluoroacetate as the mobile phase or in HFIP containing 0.05% by weight of potassium trifluoroacetate as the mobile phase, preferably using TSKgel as the stationary phase in each case.

[0140] In a preferred embodiment of the present invention, the polymer (A) of the present invention is water-soluble, which means that at ambient temperature, at least 50 of the polymer (A) can be dissolved in 1 liter of distilled water without forming an emulsion.

[0141] In one embodiment of the present invention, the polydispersity Q of the polymer (A) of the present invention is w / M n is in the range of 2 to 10, preferably 2.5 to 6.

[0142] Further details of the polymer (A) of the present invention are described above.The polymer (A) of the present invention not only shows excellent cleaning properties, but also has a better shelf life.Its degradation under storage conditions is improved without significantly hindering biodegradation in wastewater.

[0143] 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. The inventive process comprises the steps of: (α) providing a mixture comprising at least one alkoxylated, preferably ethoxylated, amine, diamine, oligoamine or polyamine and at least one aliphatic C2-C6-diol or C3-C6-triol not carrying N atoms, (β) reacting the mixture from step (α) with a dialkyl carbonate; (γ) reacting the carbonate from step (β) with at least one C2-C4-alkylene oxide in one or more steps or otherwise, (γ') The carbonate from step (β) is converted to C1-C 10 -Cated with an alkyl group or an aliphatic C2-C 20 -Alkyl fatty acid or C 10 ~C 20 - reacting with a polyalkylene oxide which has been esterified with an alkenyl fatty acid Includes.

[0144] The process of the present invention is described in more detail below: Steps (α), (β) and (γ) or (γ') are also referred to as step (α), step (β), step (γ) or step (γ'), respectively, or simply as (α), (β) and (γ) and (γ').

[0145] Examples of alkoxylated, preferably ethoxylated, amines are monoethanolamine, N,N-diethanolamine, N-methylethanolamine, N-methyldiethanolamine, N,N-dimethyl-ethanolamine, N,N,N-triethanolamine and 2-propanol-1-amine.

[0146] Examples of alkoxylated, preferably ethoxylated, diamines are bisalkoxylated ethylenediamines, in particular bisethoxylated ethylenediamine, bisalkoxylated 1,3-propylenediamines, in particular bisethoxylated 1,3-propylenediamine and bisalkoxylated α,ω-C4-C6-alkylenediamines, in particular bisethoxylated α,ω-C4-C6-alkylenediamines, tetraalkoxylated ethylenediamines, in particular tetraethoxylated ethylenediamine.

[0147] Further examples of alkoxylated, preferably ethoxylated, diamines are the bis-ethoxylates of cyclic compounds, especially 2,4-diamino-1-methylcyclohexane and 2,6-diamino-1-methylcyclohexane, and mixtures thereof.

[0148] Examples of alkoxylated, preferably ethoxylated, oligoamines are H2N-(CH2) z1 -[NH(CH2) z2 ] z4 -NH(CH2) z3 Alkoxylated amines and especially ethoxylated amines of -NH2, where the variables z1, z2 and z3 are independently selected from 2 to 4, z4 is selected from 0 to 2, and each CH2 group can be unsubstituted or substituted with 1 to 2 methyl or methoxy groups. Preferred oligoamines are H2N-(CH2)3-NH(CH2)2-NH(CH2)3-NH2 ("N4-amines") and H2N-(CH2)3-NH(CH2)2-NH2 ("N3-amines") and mixtures thereof, for example in a molar ratio of 9:1.

[0149] The examples of ethoxylated N4-amines are usually mixtures of compounds. Specific examples include: [ka] and depending on the ratio of EO to N, [ka] [ka] and the respective monoethoxylates.

[0150] Specific examples of ethoxylated oligoamines are bis-ethoxylated N4-amine and bis-ethoxylated N3-amine.

[0151] Examples of alkoxylated, preferably ethoxylated, polyamines are poly-alkoxylated, preferably ethoxylated, polyethyleneimines and poly-alkoxylated, preferably ethoxylated, polypropyleneimines and alkoxylated, preferably ethoxylated, polyvinylamines. The base polyethyleneimines or polypropyleneimines can be linear or preferably branched, and the base polyethyleneimines or polypropyleneimines or polyvinylamines have an average molecular weight M in the range of 500 to 2,500 g / mol. w may have:

[0152] The alkoxylation - preferably ethoxylation - preferably refers to 0.3 to 2 moles of alkoxide, preferably ethylene oxide, per NH function of the base amine.

[0153] The mixture provided in step (α) further contains at least one aliphatic C2-C6-diol or C3-C6-triol carrying no N atoms, examples of which are ethylene glycol, 1,2-propylene glycol, 1,4-propylene glycol, 2,3-butanediol, 1,5-pentanediol, 2,2-dimethylpropane-1,3-diol, 1,6-hexanediol, glycerol and 1,3,5-pentanediol.

[0154] The mixture provided in step (α) may consist of 33-100 mol %, preferably 70-80 mol % of alkoxylated, preferably ethoxylated, amines, diamines, oligoamines or polyamines and 0-67 mol %, preferably 15-30 mol % of at least one aliphatic C2-C6-diol or C3-C6-triol not carrying N atoms.

[0155] The mixture can be provided by mixing the components or, if two alkoxylated amines are provided, by alkoxylating two or more amines together in the absence or presence of a diol or triol.

[0156] In one embodiment of the present invention, the mixture provided in step (α) is a compound of the formula H2N-(CH2) z1 -[NH(CH2) z2 ] z4 -NH(CH2) z3 The compounds include alkoxylated amines based on the formula -NH2, where the variables z1, z2 and z3 are independently selected from 2 to 4, and z4 is selected from 0 to 2, and each CH2 group can be unsubstituted or substituted with 1 to 2 methyl or methoxy groups.

[0157] Preferred amines are N4-amines and N3-amines and mixtures thereof.

[0158] The mixture may be provided in bulk or with a solvent. Examples of suitable solvents are hydrocarbons, such as aromatic or aliphatic or cycloaliphatic hydrocarbons. Specific examples include cyclohexane, toluene, benzene and n-heptane. Preferably, the mixture is provided in bulk.

[0159] In step (β), the mixture from step (α) is reacted with a dialkyl carbonate, such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, diisopropyl carbonate, preferably a di-C1-C2-alkyl carbonate, such as dimethyl carbonate or diethyl carbonate.

[0160] In one embodiment of the present invention, step (β) is carried out at a temperature in the range of 80-180° C., preferably 100-175° C. It is preferred to increase the temperature during step (β).

[0161] During step (β) an alcohol is formed, for example when diethyl carbonate is used ethanol is formed. It is preferred to remove the alcohol, for example by distillative removal.

[0162] In one embodiment of the invention, step (β) is carried out at ambient pressure, however, to facilitate the removal of the alcohol, it is preferred to carry out step (β) at reduced pressure, for example between 10 and 500 mbar.

[0163] In one embodiment of the present invention, step (β) has a duration ranging from 1 hour to 2 days.

[0164] In a preferred embodiment of the present invention, step (β) is carried out in the presence of a catalyst. Inorganic and organic bases such as KOH and K2CO3 can function as catalysts. Preferred catalysts are tertiary amines, especially bicyclic amines. Examples thereof are triethylamine and 1,5,7-triazabicyclo[4,4,0]dec-5-ene and 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0165] The catalyst or mixture of catalysts may be applied in an amount of 0.1 to 10% by weight relative to the mixture provided in step (α).

[0166] After step (β), an intermediate is formed which in the context of the present invention is referred to as core (a).

[0167] In step (γ), the core (a) 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 above. Propylene oxide and ethylene oxide are preferred, and ethylene oxide is more preferred.

[0168] In one embodiment of the present invention, the weight ratio of core (a) to alkylene oxide in step (γ) 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.

[0169] Step (γ) is preferably carried out in the presence of a catalyst, such as a base or a double metal cyanide.

[0170] In one embodiment of the present invention, step (γ) is carried out in the presence of a base. Suitable bases include, for example, potassium hydroxide, sodium hydroxide, sodium or potassium alkoxides, such as 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 and 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. The typical amount of base used is 0.05 to 10% by weight, in particular 0.5 to 2% by weight, based on the total amount of condensate of step (β) and C2-C4-alkylene oxide.

[0171] In one embodiment of the present invention, step (γ) is carried out in the presence of a double metal cyanide. A double metal cyanide, hereinafter also called a double metal cyanide compound or DMC compound, usually comprises at least two different metals, at least one of which is selected from transition metals, and the other is selected from transition metals and alkaline earth metals, as well as a cyanide counterion. Particularly suitable catalysts for alkoxylation are double metal cyanide compounds containing zinc, cobalt or iron, or two of them. For example, Berlin blue is particularly suitable.

[0172] It is preferred to use crystalline compounds of DMC. In a preferred embodiment, crystalline compounds of DMC of the Zn-Co type, containing zinc acetate as an additional metal salt component, are used as catalysts. Such compounds crystallize in the monoclinic structure and have a platelet-like crystal habit.

[0173] 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.

[0174] The double metal cyanide compounds can be used as powders, pastes or suspensions, or can be formed into moldings, incorporated into moldings or foams, or the like, or applied to moldings or foams, or the like.

[0175] Preferably, the DMC catalyst used in step (γ) is present in an amount of 5 to 2000 ppm (i.e. mg catalyst / kg product), based on the cores (a) obtained in step (β), preferably less than 1000 ppm, in particular less than 500 ppm, particularly preferably less than 100 ppm, for example less than 50 ppm or 35 ppm, particularly preferably less than 25 ppm, ppm referring to ppm (parts per million) by mass of the polycondensate obtained in step (β).

[0176] 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). Such water removal can be carried out by heating at a temperature in the range of 80-150° C. under reduced pressure in the range of 0.01-0.5 bar and distilling off the water.

[0177] In one embodiment of the present invention, step (γ) is carried out at a reaction temperature in the range of 70-200°C, preferably 100-180°C.

[0178] In one embodiment of the invention, step (γ) is carried out once per synthesis of the inventive polymer (A). In another 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 the product of step (γ1) to a second alkoxylation (γ2), for example with propylene oxide.

[0179] In one embodiment of the invention, step (γ) is carried out at a pressure of up to 10 bar, in particular up to 8 bar, for example from 1 to 8 bar.

[0180] In one embodiment of the present invention, the reaction time of step (γ) generally ranges from 0.5 to 12 hours.

[0181] 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, especially 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.

[0182] In embodiment (ii), the solution obtained in the first step is dehydrated before or after the addition of catalyst and solvent and before being subjected to alkylene oxide, said water removal being advantageously carried out by removing water at a temperature in the range of 120-180° C., preferably with the aid of a nitrogen stream. The subsequent reaction with alkylene oxide can be carried out as in embodiment (i). In embodiment (i), the alkoxylated polyalkylenimine according to the invention can be obtained directly in bulk and dissolved in water if necessary. In embodiment (ii), for the workup, the organic solvent is usually replaced by water. The alkoxylated polyalkylenimine (B) according to the invention can alternatively be isolated in bulk.

[0183] The optional post-treatment step may comprise deactivating the catalyst used in step (γ) by neutralization, in the case of a basic catalyst.

[0184] In an alternative embodiment, step (γ′) may be performed. Step (γ′) comprises a core (a) and C1 to C 10 -alkyl, in particular methyl, capped, with a polyalkylene glycol carboxylic acid, preferably in which at least 50 mol-% of the alkylene groups are ethylene oxide.

[0185] The respective carboxylic acids, in particular the carboxylic acids of polyalkylene oxides in which at least 50 mol % of the alkylene oxide units are ethylene oxide, can be prepared by oxidation of one hydroxyl group of the corresponding polyalkylene glycol using Pt on carbon as a catalyst.

[0186] Each Mono - C1~C 10 -Alkyl-capped carboxylic acids can be synthesized by oxidation of the corresponding monomethyl-capped polyalkylene glycols using, for example, Pt on carbon as a catalyst.

[0187] In one embodiment of the present invention, step (γ′) is carried out in the presence of a catalyst.

[0188] Step (γ') can be carried out at a temperature in the range of 20 to 180° C. In embodiments where esters, especially C1-C2-alkyl esters, such as diethyl adipate, diethyl succinate, dimethyl adipate, dimethyl succinate, dimethyl sebacate, diethyl sebacate, diethyl or triethyl citrate, 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 respective free acid is 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 increase the temperature.

[0189] Step (γ′) can be carried out at any pressure, for example between 10 mbar and 10 bar. Ambient pressure and below is preferred, for example between 10 and 500 mbar.

[0190] During step (γ') water is formed. Such water is preferably removed, for example, by distillative removal. Suitable tools are Dean-Stark apparatus, distillation bridges, water removal devices and other devices that can serve to remove water by distillation.

[0191] Step (γ') can be carried out in the absence or presence of a solvent. Suitable solvents are aromatic solvents such as toluene, aliphatic hydrocarbons or cycloaliphatic solvents such as decane, cyclohexane and n-heptane. 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.

[0192] Examples of suitable catalysts are especially acidic catalysts, such as inorganic and organic acids.

[0193] Acidic inorganic catalysts for the purposes of the present invention include, for example, sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH value 5-6) and acidic alumina. Acidic inorganic catalysts include, for example, compounds of the general formula Al(OR b )3 and aluminum compounds of the general formula Ti(OR b Titanate esters of the formula 4 are also suitable, with the residue R b are the same or different and are independently selected from the following: 10 - alkyl, for example 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 to C6 12 -cycloalkyl, examples of which are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, with cyclopentyl, cyclohexyl and cycloheptyl being preferred.

[0194] Preferably, Al(OR 5 )3 and Ti(OR 5 ) Residue R of 4 5 are each the same and are selected from isopropyl or 2-ethylhexyl.

[0195] Preferred acidic organometallic catalysts are, for example, dialkyltin oxides (R b )2SnO, R b is as defined above. One particularly preferred representative of the acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available in the oxo-tin form.

[0196] Preferred acidic organic catalysts are, for example, acidic organic compounds containing phosphoric acid, sulfonic acid, sulfuric acid 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.

[0197] It is also possible to use a combination of two or more of the above catalysts. Another possibility is to use those organo- or organometallic- or inorganic catalysts in the form of discrete molecules in immobilized form.

[0198] When the use of an acidic inorganic, organometallic or organic catalyst is desired, the amount of catalyst used according to the present invention is from 0.01 to 10% by weight, preferably from 0.1 to 2% by weight, more preferably from 0.2 to 1% by weight, based on the total amount of reactants.

[0199] In another embodiment of the present invention, step (γ′) is carried out without a catalyst.

[0200] In one embodiment of the present invention, step (γ′) has a duration ranging from 30 minutes to 15 hours.

[0201] A further aspect of the present invention is directed to a method for improving the cleaning performance of a liquid detergent composition by adding the polymer (A) of the present invention to a detergent composition comprising at least one lipase and / or at least one protease.

[0202] The term "improved cleaning performance" herein may indicate that the polymer (A) provides better, i.e. improved, stain removal properties under suitable cleaning conditions when compared to the cleaning performance of a detergent composition lacking 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 when compared to the cleaning performance of a detergent comprising a polymer (A) but without an 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 when compared to the cleaning performance of a detergent comprising at least one enzyme, preferably at least one hydrolase (B), preferably a lipase (B) and / or at least one protease (D), but without a polymer (A).

[0203] 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 mechanism, soap concentration, detergent type and water hardness.

[0204] The polymers (A) according to the invention are eminently suitable as compositions according to the invention or for the preparation of compositions according to the invention.The polymers (A) according to the invention exhibit remarkable biodegradability. EXAMPLES

[0205] General Notes: Unless otherwise stated, percentages are percent by weight. rpm: Revolutions per minute.

[0206] Molecular weights were determined by GPC using 0.05 wt% potassium trifluoroacetate (potassium trifluoroacetate salt) in HFIP as the mobile phase and TSKgel as the stationary phase.

[0207] I. Synthesis of Polymer (A) of the Invention I.1 Synthesis of the polymers (A.1.1) and (A.1.2) of the invention Synthesis of the core (a.1): Step (α.1): A three-necked round-bottom flask equipped with a mechanical stirrer, a dropping funnel and a condenser attached to a vacuum line was charged with 1,5-pentanediol (11.49 g, 0.11 mol, 1.0 eq.), N,N,N-triethanolamine (37.04 g, 0.248 mol, 2.25 eq.) and N4-amine ethoxylated with 1.0 ethylene oxide / NH (37.18 g, 0.085 mol, eq.). The mixture was heated to 100° C. and a vacuum of 500 mbar was applied for 5 hours to distill off water from the reaction product.

[0208] Step (β.1): Next, the vacuum was stopped and 1,5,7-triazabicyclo[4,4,0]dec-5-ene (0.30 g, 2.15 10 -3 mol, 0.02 eq.) was added to the mixture, the apparatus was exposed to a nitrogen flow for 1 h, then diethyl carbonate (62.95 g, 0.533 mol) was added through the dropping funnel over 1 h. The dropping funnel was removed and the reaction mixture was stirred at 140° C. for 16 h. A distillation bridge was installed to distill off the formed ethanol and excess diethyl carbonate. A vacuum of up to 50 mbar was then applied and the reaction was carried out for another 12 h. A black highly viscous crude product was obtained, which was purified by precipitation into cold ethyl acetate to give the dark brown polymer core (a.1). M n : 1500g / mol, M w : 4550g / mol, M w / M n : 3.0; OH value: 831.4 mg KOH / g

[0209] Step (γ.1): 34.4 g of core (a.1) was mixed with 2.0 g of KOH 50% ig (0.2% of A.1.1). Water was then distilled off under vacuum at 100° C. The residue was transferred to a 2 liter reactor inerted with N2, pressurized at 2 bar (absolute pressure) and dissolved in 55.6 g of methyl ethyl ketone. The reactor was heated to 130° C. and 50 grams of ethylene oxide were introduced for 10 minutes at a stirring speed of 100 rpm.

[0210] An additional 398 g of ethylene oxide was added (0.6 g / min) within 8 hours, also at 130° C. and a stirring speed of 200 rpm. The resulting mixture was then heated at 130° for an additional 6 hours to terminate the reaction. After rotary evaporation, 483 grams of polymer (A.1.1) was obtained. Yield 99.8%. M w = 2470 g / mol, M n = 1610 g / mol, M w / M n = 1.5, OH value: 82mgKOH / g, amine value: 25mgKOH / g, H2O: 0.3%

[0211] Step (γ.2): 218 g of the polymer of the invention (A.1.1) was mixed with 1.7 g of KOH 50% ig (0.2% of (A.1.1)). Water was then distilled off under vacuum at 100° C. The residue was transferred to a 3.5 liter reactor inerted with N2 and pressurized at 2 bar (absolute). The reactor was then heated to 130° C. and 10 grams of propylene oxide were introduced over a period of 10 minutes at a stirring speed of 100 rpm.

[0212] An additional 208 grams of propylene oxide was added within 3 hours (1 g / min) at 130° C. and a stirring speed of 200 rpm. The mixture was then heated at 130° for an additional 6 hours. After cooling to ambient temperature, 421 g of the inventive polymer (A.1.2) was obtained after rotary evaporation. Yield 97.2%. M w = 3130 g / mol, M n = 1950 g / mol and M w / M n= 1.6, OH value: 65 mg KOH / g, amine value: 14 mg KOH / g, H2O: 0.3%.

[0213] I.2 Synthesis of the polymer (A.2) of the invention Synthesis of the core (a.2): Step (α.2): 1,5-pentanediol (52.56 g, 0.5 mol, 2.0 eq.), triethanolamine (37.3 g, 0.25 mol, 1.0 eq.) were placed in a three-necked round-bottom flask equipped with a mechanical stirrer, a dropping funnel, and a condenser attached to a vacuum line. The mixture was heated to 100° C. and a vacuum of 500 mbar was applied for 5 hours to distill off water from the reaction product.

[0214] Step (β.2): Next, the vacuum was stopped and 1,5,7-triazabicyclo[4,4,0]dec-5-ene (0.19 g, 1.36 10 -3 mol, 5.4 10 -3 To the mixture was added (118.13 g, 1.0 mol, 4.0 eq.), the apparatus was exposed to a nitrogen stream for 1 h, and then diethyl carbonate (118.13 g, 1.0 mol, 4.0 eq.) was added through the dropping funnel over 1 h. The dropping funnel was removed and the reaction mixture was stirred at 140° C. for about 14 h.

[0215] Step (γ'.1): The reaction mixture of step (β.2) was cooled to ambient temperature. n 750g (18g, 7.0g, 0.25mol, 1.0eq.) was added. The reaction mixture was heated to 165°C under reflux for 2 hours and then vacuum distilled at a maximum pressure of 75mbar for 12 hours. A light brown to brown polymer of the invention (A.2) was obtained. n : 17600g / mol, M w : 37400g / mol, M w / M n :2.1

[0216] I.3 Synthesis of the polymer (A.3) of the invention Synthesis of the core (a.3): Step (α.3): 1,5-pentanediol (42.05 g, 0.4 mol, 1.15 eq.), triethanolamine (52.5 g, 0.35 mol, 1.0 eq.) were placed in a three-necked round-bottom flask equipped with a mechanical stirrer, a dropping funnel, and a condenser attached to a vacuum line. The mixture was heated to 100° C. and a vacuum of 500 mbar was applied for 5 hours to distill off water from the reaction product.

[0217] Step (β.3): Next, the vacuum was stopped and 1,5,7-triazabicyclo[4,4,0]dec-5-ene (0.19 g, 1.36 10 -3 mol, 5.4 10 -3 To the mixture was added (147.66 g, 1.25 mol, 5.0 eq.), the apparatus was exposed to a nitrogen stream for 1 h, and then diethyl carbonate (147.66 g, 1.25 mol, 5.0 eq.) was added through the dropping funnel over 1 h. The dropping funnel was removed and the reaction mixture was stirred at 140° C. for about 14 h.

[0218] Step (γ'.2): The reaction mixture of step (β.3) was cooled to ambient temperature. n 750 g (187.0 g, 0.25 mol, 0.71 eq.) was added. The reaction mixture was heated to 165° C. under reflux for 2 hours and then vacuum distilled at a maximum pressure of 75 mbar for 12 hours. A light brown to brown polymer of the invention (A.3) was obtained. n : 15900g / mol, M w : 42800g / mol, M w / M n :2.7

[0219] I.4 Synthesis of the polymer (A.4) according to the invention Synthesis of the core (a.4): Step (α.4): 1,5-pentanediol (31.54 g, 0.3 mol, 0.67 eq.), triethanolamine (67.5 g, 0.45 mol, 1.0 eq.) were placed in a three-necked round-bottom flask equipped with a mechanical stirrer, a dropping funnel, and a condenser attached to a vacuum line. The mixture was heated to 100° C. and a vacuum of 500 mbar was applied for 5 hours to distill off water from the reaction product.

[0220] Step (β.4): Next, the vacuum was stopped and 1,5,7-triazabicyclo[4,4,0]dec-5-ene (0.19 g, 1.36 10 -3 mol, 5.4 10 -3 To the mixture was added 147.66 g (1.25 mol, 2.78 eq.), the apparatus was exposed to a nitrogen stream for 1 h, and then diethyl carbonate (147.66 g, 1.25 mol, 2.78 eq.) was added through the dropping funnel over 1 h. The dropping funnel was removed and the reaction mixture was stirred at 140° C. for about 14 h.

[0221] Step (γ'.3): The reaction mixture of step (β.4) was cooled to ambient temperature. n 750 g (187.0 g, 0.25 mol, 0.561 eq.) was added. The reaction mixture was heated to 165° C. under reflux for 2 hours and then vacuum distilled at a maximum pressure of 75 mbar for 12 hours. A light brown to brown polymer of the invention (A.4) was obtained. n : 14900g / mol, M w :38900g / mol, M w / M n :2.6

[0222] II. Washing performance II.1 Washing laundry The primary washing performance of the inventive polymers was tested in a washing machine by preparing a washing liquor containing 3.0 g / L of test liquid detergent L.1 in water (2.5 mmol / L; Ca:Mg:HCO3 4:1:8) with a hardness of 14° dH, see the compositions in Table 2.1 or 2.2 and 2.0% of the inventive polymer (A) in Table 3.

[0223] [Table 1]

[0224] [Table 2]

[0225] (D.1): [ka]

[0226] The polymer (A) of the invention was added to a polymer-free laundry liquor (addition of 2.5 wt. % of liquid model detergent) containing either the liquid model composition L.1 or L.2, respectively, together with a stained fabric commercially available from the Center of Test Materials CFT Vlaardingen, P-H108. Three monitors with multiple stains, MSM1, MSM2 and MSM3, and 5 g of a commercially available soil ballast sheet, wfk SBL2004 (wfk Testgewebe GmbH Brueggen). Wash conditions were 2.5 g / L detergent for L.1 and 2.0 g / L detergent for L.2, 250 mL of liquor, 30 min, 40°C, 4x dose. After washing, the fabrics were rinsed and dried. The fabrics were instrumentally evaluated before and after washing using a MACH5 multi-area color measuring instrument from ColourConsult, which provides laboratory measurements. From these laboratory measurements, the ΔE values ​​between the unwashed and washed stains were calculated. The higher the ΔE value, the better the performance. To better judge the pure washing effect of each polymer sample itself, the obtained values ​​were further expressed as ΔΔE values ​​relative to a reference without polymer (baseline correction for the simple washing effect of detergent only). Again, the higher the respective observed ΔΔE value, the better the performance.

[0227] Table 3. Monitors with multiple stains for washing machine testing MSM1 (circular stain, diameter 5 cm): CFT PC-H144: Red clay for ceramics on polyester / cotton (65:35) CFT KC-H115: Standard clay for cotton knit CFT PC-H145: Polyester / cotton (65:35) with tennis court clay CFT KC-H018: Clay on cotton stockinette, dirt on ground 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: For cotton fabrics, stains sensitive to the action of surfactants and lipases wfk20D: Polyester / cotton blend fabric with pigment and sebum-based fat CFT CS-70: Chocolate / Mousse cream on cotton MSM3: wfk20D: Polyester / cotton blend fabric with pigment and sebum-based fat EMPA 101: Cotton stained with carbon black / olive oil EMPA 141 / 2: Lipstick stained polyester / cotton (65:35) CFT PC-S-04: Olive oil, colored EMPA 114: Red wine stained cotton EMPA 112: Cocoa-stained cotton EMPA 116: Blood / Milk / Ink Stained Cotton CFT CS-01: Blood on cotton after a period of time CFT CS-08: Cotton and Grass CFT C-10: Pigment / Oil / Milk on cotton CFT PC-05: Blood / milk / ink on polyester / cotton (65:35)

[0228] Color measurements were used to evaluate the overall level of cleaning. The reflectance values ​​of the monitor stains were measured using a sphere reflectance spectrometer (Datacolor, USA SF500 model, wavelength range 360-700 nm, optical geometry d / 8°) equipped with a 460 nm UV cutoff filter. Here, the lightness L*, a* value on the red-green axis, and b* value on the yellow-blue axis were measured before and after washing using the CIE-Lab color space classification, and the average values ​​were calculated for each stain on the monitor. The values ​​were determined by the color evaluation tool and expressed as follows:

number

[0229] A higher Delta E value indicates better cleaning. For each stain, a person skilled in the art can visually detect a difference of 1 unit. A non-expert can easily visually detect 2 units. The ΔΔE and ΔΔL values ​​of the formulations for 4, 8 and 11 stains corresponding to MSM1 and MSM2 plus MSM3 and for some selected single stains are shown in Table 4.

[0230] [Table 3]

[0231] III. Biodegradability Test Summary: The test was performed according to the OECD guidelines. According to the OECD guidelines, the test is valid in the following cases: 1. The reference reaches 60% within 14 days. 2. The difference in extreme values ​​between replicate tests by the end of the test is less than 20%. 3. The oxygen uptake of the inoculum blank should be 20-30 mgO2 / l and should not exceed 60 mgO2 / l. 4. The pH value measured at the end of the test must be between 6 and 8.5.

[0232] Description of the test methods used in connection with the present 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. A measured amount of wastewater was spiked with 100 mg / L of the test substance, nominally the sole 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 consumption of oxygen is determined by measuring the change in pressure in the closed flask using an Oxi TopC. The evolved carbon dioxide was absorbed in a solution of sodium hydroxide. 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 / glutamate, is run as a reference along with the test samples in each cabinet. Calculations: 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. %biodegradable Experimental O2 uptake x 100 and divide by theoretical oxygen demand.

[0233] The results of the biodegradability tests are summarized in Table 5.

[0234] [Table 4]

[0235] In each test, the reference material had a biodegradability of greater than 60%.

Claims

1. (A) at least one polymer, (a) General formula (I) 【Chemistry 1】 and 1 to 50 moieties of the general formula 【Chemistry 2】 Based on (wherein the asterisk represents X ２ or another group of general formula (I) linked via C １ ~C ４ -alkyl, or a group of formula (II), or a polyalkylene oxide chain (b), X １ are the same or different, and C １ ~C ２ - selected from alkyl and hydrogen, X ２ are the same or different and are linear or branched C groups that are unsubstituted or substituted with one or more hydroxyl groups, ester or ether groups of a carboxylic acid. ２ ~C ６ -alkylene) a core carrying the (b) Polyalkylene oxide chain At least one polymer comprising A detergent composition comprising:

2. The polymer (A) is a polymer having the formula (CH ２ ) ｚ１ -[N(CH ２ ) ｚ２ ] ｚ４ -N(CH ２ ) ｚ３ - group, 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 2. The composition of claim 1, wherein the group can be unsubstituted or substituted with one to two methyl or methoxy groups, the free valence of the N atom carrying the chain (b).

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

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 3. The composition of claim 1 or 2, wherein

6. The composition of claim 1 or 2, further comprising a surfactant.

7. 3. Use of a composition according to claim 1 or 2 for the care of laundry or for cleaning hard surfaces.

8. A polymer comprising: (a) General formula (I) 【Transformation 3】 and 1 to 50 moieties of the general formula 【Chemistry 4】 Based on (wherein the asterisk represents X ２ or another group of general formula (I) linked via C １ ~C ４ -alkyl, or a group of formula (II), or a polyalkylene oxide chain (b), X １ are the same or different, and C １ ~C ２ - selected from alkyl and hydrogen, X ２ are the same or different and are linear or branched C groups that are unsubstituted or substituted with one or more hydroxyl groups, ester or ether groups of a carboxylic acid. ２ ~C ６ -alkylene) a core carrying the (b) Polyalkylene oxide chain A polymer comprising:

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

10. Formula (CH ２ ) ｚ１ -[N(CH ２ ) ｚ２ ] ｚ４ -N(CH ２ ) ｚ３ - group, 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. Polymer according to claim 8 or 9, wherein the group can be unsubstituted or substituted with one to two methyl or methoxy groups, the free valence of the N atom carrying the chain (b).

11. X １ is an unsubstituted straight or branched chain C １ ~C ６ 10. The polymer according to claim 8, wherein the aryl group is selected from the group consisting of aryl, aryl, aryl- ...

12. 10. A process for making the polymer of claim 8 or 9, comprising: (α) at ​​least one alkoxylated amine, diamine, oligoamine or polyamine, ２ ~C ６ -diol or C ３ ~C ６ - providing a mixture comprising with a triol, (β) reacting the mixture from step (α) with a dialkyl carbonate; (γ) treating the carbonate from step (β) with at least one C ２ ~C ４ - reacting in one or more steps or otherwise with an alkylene oxide, (γ′) The carbonate from step (β) is reacted with C １ ~C １０ - alkyl group or aliphatic C ２ ~C ２０ -Alkyl fatty acid or C １０ ~C ２０ - reacting with a polyalkylene oxide which has been esterified with an alkenyl fatty acid A process involving:

13. In step (β), the mixture from step (α) is reacted with di-C carbonate. １ ~C ２ 13. The process of claim 12, wherein the hydroxyl group is reacted with an alkyl group.

14. The mixture provided in step (α) is a compound of formula H ２ N-(CH ２ ) ｚ１ -[NH(CH ２ ) ｚ２ ] ｚ４ -NH(CH ２ ) ｚ３ -NH ２ wherein the variables z1, z2, and z3 are independently selected from 2 to 4, and z4 is selected from 0 to 2; and each CH ２ The process of claim 12, wherein the group can be unsubstituted or substituted with one to two methyl or methoxy groups.

15. 10. A method for improving the cleaning performance of a liquid detergent composition by adding the polymer (A) according to claim 8 or 9 to the detergent composition comprising at least one lipase and / or at least one protease.

Images