Compositions, their preparation and use

Abstract

The present invention provides a composition comprising: (A) at least one combination of the following: (α) triethanolamine, (β) citrate, and (B) at least one water-soluble polymer having at least two ester groups per molecule; The present invention relates to a composition comprising:

Description

[Technical field]

[0001] The present invention provides a liquid laundry composition comprising: (A) at least one combination of the following: (α) triethanolamine, (β) citrate, and (B) at least one water-soluble polymer having at least two ester groups per molecule; The present invention relates to a liquid laundry composition comprising:

[0002] Furthermore, the present invention relates to the use of a combination of compound (α) and compound (β) in laundry detergents. [Background technology]

[0003] Laundry detergents must meet several requirements. They must remove all kinds of soils from laundry, including all kinds of pigments, clays, fatty soils, and dyes from foods and beverages, such as red wine, tea, coffee, and fruits, including berry juice. They must also exhibit certain storage stability. In particular, liquid laundry detergents or laundry detergents that contain hygroscopic ingredients often lack good storage stability, for example enzymes are easily deactivated.

[0004] The current requirement of detergent compositions is that the amount of non-biodegradable components is reduced.Therefore, it has been suggested that certain effect polymers are replaced by biodegradable polymers.However, it has been observed that biodegradable polymers can already undergo degradation before reaching the end user, and their beneficial effect in cleaning laundry or dishes is greatly reduced.

[0005] Therefore, one object of the present invention was to provide a composition containing an enzyme or a biodegradable polymer, which overcomes the above-mentioned drawbacks and has a good shelf life.Furthermore, it was an object to provide a method for improving the performance and shelf life of detergent compositions, and an object to provide a method for making such a composition.

[0006] In US 2014 / 0174480, specific formulations for cleaning hard surfaces are disclosed that do not contain enzymes or biodegradable polymers. Summary of the Invention [Means for solving the problem]

[0007] Thereby, a liquid laundry composition as defined at the outset is found, hereinafter also defined as the composition of the invention or the composition according to the invention. The composition of the invention comprises components (A), (B) and (C) as defined below: (A) at least one combination of compounds comprising: (α) triethanolamine, (β) citrate, and (B) at least one water-soluble polymer having at least two ester groups per molecule.

[0008] Components (A), (B) and (C) will now be described in more detail.

[0009] The compound (α) contains triethanolamine.

[0010] In one embodiment of the present invention, the combination (A) of the present invention has a boiling point at ambient pressure of 180° C. or higher, for example 180 to 300° C., and N—CH2CH(X 1) aliphatic or cycloaliphatic amines that do not have an -OH group (γ). Examples of aliphatic or cycloaliphatic amines (γ), hereafter also referred to as compounds (γ), are methyldiaminocyclohexane and N,N-bis(3-aminopropyl)-1,2-ethanediamine. In the context of aliphatic or cycloaliphatic amines (γ), diamines, triamines and tetramines are included in the term "amine". DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In one embodiment of the present invention, the molar ratio of compound (α) and compound (γ) is in the range of 20:1 to 1:3.

[0012] Additionally, the compositions of the present invention contain at least one (β) citrate.

[0013] The citrates may have free carboxylic acid groups or may be neutralized, for example with at least one carboxyl group per molecule of citrate present as an ammonium salt, where ammonium is selected from alkylammonium and alkanolammonium.

[0014] Citrates (β) that do not have an alkali metal as a counterion, such as sodium, on any of the carboxyl groups, are preferred.

[0015] In one embodiment of the present invention, the sodium content of the citrate (β) is 0.5 to 1.5% by weight or less, preferably 1% by weight or less, based on the total composition.

[0016] Some amines have an unpleasant odor. Here, it is preferred that the ammonium ion derived by protonation is selected from an amine having low volatility, for example a boiling point at ambient pressure higher than 180° C. Ammonium ions derived from amines that do not have an unpleasant odor are also preferred.

[0017] Counterions such as triethanolammonium, N,N-diethanolammonium, N-methyl-N,N-diethanolammonium, N,N-dimethyl-ethanolammonium, and ethanolammonium are preferred, with triethanolammonium being more preferred.

[0018] In one embodiment of the present invention, the molar ratio of amino groups in compound (α) to carboxylic acid groups from compound (β) is in the range of 1:10 to 10:1, preferably 5:3 to 2:3. The molar ratio is the ratio of N-CH2-CH(X) to the total carboxyl groups derived from citrate. 1 Thus, for example, if 0.3 moles of citrate and 0.5 moles of triethanolamine are used per liter of detergent composition, the total moles of N-CH2-CH(X)-OH groups in compound (α) are 1 The molar ratio of --OH groups to carboxylic acid groups from compound (β) is 1:0.9.

[0019] (B) The detergent compositions of the present invention further comprise at least one water-soluble polymer having at least two ester groups per molecule, such polymer being also referred to as polymer (B).

[0020] The ester groups are selected from carboxylic acid esters and (organic) carbonates.

[0021] In the context of the present invention, a polymer (B) is considered to be water-soluble if at least 50 g of such polymer is soluble in 1 liter of distilled water at 20° C. and forms a transparent solution or a stable dispersion that is visible to the naked eye.

[0022] In one embodiment, the detergent composition of the present invention comprises both a hydrolase (C) and one water-soluble polymer (B) having at least two ester groups per molecule.

[0023] The detergent composition of the present invention comprises at least one water-soluble polymer (hereinafter also referred to as polymer (B)) having at least two ester groups per molecule. The ester groups may be chosen from carboxylic acid esters and carbonates.

[0024] In the context of the present invention, the polymers have an average molecular weight M in the range of 1,000 to 50,000 g / mol, preferably 3,000 to 30,000 g / mol. n The molecular weight Mn is defined as an organic molecule having the formula: Mn=Mn / Mn / Mn. A suitable method for determining the average molecular weight Mn is gel permeation chromatography ("GPC"). As a mobile phase, an aqueous medium is suitable, for example, a 0.1 M NaCl solution in water containing 0.1 wt. % trifluoroacid or a fluorinated alcohol such as hexafluoroisopropanol ("HFIP") as the mobile phase. An example of a suitable stationary phase is TSKgel.

[0025] In one embodiment of the present invention, the polymer (B) has an average molecular weight M in the range of 2,500 to 100,000 g / mol, preferably 3,400 to 25,000 g / mol. w The average molecular weight can be determined, for example, by gel permeation chromatography ("GPC") in 0.1 M aqueous NaCl containing 0.1 wt. % trifluoroacid as the mobile phase, or in hexafluoroisopropanol ("HFIP"), preferably each time using TSKgel as the standard.

[0026] In one embodiment of the present invention, the polymer (B) has a molecular weight distribution M in the range of 1.1 to 6.0. w / M n has.

[0027] In one embodiment of the present invention, the polymer (B) is (B1) A polymer, (a) at least one backbone having 1 to 40 β-aminoalcohol groups or β-amino-(alkylene oxide) groups; The polymer is selected from the group consisting of (b) some β-amino alcohol groups or β-amino-(alkylene oxide) groups are esterified with a mono- or di-acid of a polyalkylene oxide in which at least 50 mol % of the alkylene oxide groups are ethylene oxide groups, or with the monomethyl ether of a mono-acid of a polyalkylene oxide in which at least 50 mol % of the alkylene oxide groups are ethylene oxide groups, and optionally (c) Some β-amino alcohol groups or β-amino-(alkylene oxide) groups are aliphatic C4-C 10 - esterified with a di- or tricarboxylic acid, such as adipic acid, sebacic acid, citric acid or a combination of at least two of the above.

[0028] The main chain (a) has 1 to 40 β-amino alcohol groups or β-amino-(alkylene oxide) groups.

[0029] The term β-amino alcohol group refers to the -N-CH(R a )-CH2-O- group, R a is selected from methyl and especially hydrogen. Specific examples are the N-CH2CH2OH-, N-(CH2CH2)2OH-, N-CH2CH(CH3)OH- and N-(CH2CH(CH3))2OH- groups, as well as combinations of at least two of the above. In the polymer (C1), after esterification, the hydrogens in the OH groups are replaced by carboxyl groups.

[0030] The term β-amino-(alkylene oxide) group refers to the -N(AO) x - group and -N[(AO) x ]2-group, where AO is a variable selected from ethylene oxide (EO) and propylene oxide (PO) and combinations, and x ranges from 2 to 10. In the embodiment where AO refers to a combination of EO and PO, they are usually arranged in blocks, not statistically. Preferably, at least half of all AO are EO. More preferably, all AO are EO.

[0031] In one embodiment of the present invention, the backbone (a) is selected from alkoxylated triethanolamine, alkoxylated N,N'-bis-(3-aminopropyl)-ethylenediamine, alkoxylated polyethyleneimine, alkoxylated N,N-bis(2-aminoethyl)-1,2-ethanediamine 1,1-bis(2-hydroxyethyl)-ethanolamine and alkoxylated compounds of methyldiaminocyclohexane (MCDA).

[0032] In the alkoxylated compounds of alkoxylated triethanolamine, alkoxylated N,N'-bis-(3-aminopropyl)-ethylenediamine, alkoxylated polyethyleneimine, alkoxylated N,N-bis(2-aminoethyl)-1,2-ethanediamine 1,1-bis(2-hydroxyethyl)-ethanolamine and methyldiaminocyclohexane ("MCDA"), the alkoxylation can be selected from, for example, propoxylation, butoxylation and ethoxylation, with ethoxylation and combinations of ethoxylation and propoxylation being preferred, and ethoxylation being even more preferred, thus involving neither propoxylation nor butoxylation. In the embodiment in which a combination of ethoxylation and propoxylation is provided, the ethylene oxide units and propylene oxide units are arranged in blocks rather than randomly.

[0033] The term "polyethyleneimine" in the context of the present invention refers not only to polyethyleneimine homopolymers, but also to polyalkyleneimines which contain the NH-CH-CH-NH structural element together with other alkylenediamine structural elements, such as the NH-CH-CH-CH-NH structural element, the NH-CH-CH(CH)-NH structural element, the NH-(CH)-NH structural element, the NH-(CH)-NH structural element, the NH-(CH)-NH structural element or the (NH-(CH)-NH structural element, with the proviso that the NH-CH-CH-NH structural element is in the majority in terms of molar distribution. Preferred polyethyleneimines contain the NH-CH-CH-NH structural element in the majority in terms of molar distribution, for example representing more than 60 mol %, more preferably at least 70 mol %, relative to all alkyleneimine structural elements. In a particular embodiment, the term polyethyleneimine refers to polyalkyleneimines which have only one or zero alkyleneimine structural elements per molecule different from NH-CH-CH-NH.

[0034] In one embodiment of the present invention, the average molecular weight M of the polyethyleneimine before alkoxylation is w The average molecular weight M of the polyethyleneimine is in the range of 500 to 100,000 g / mol, preferably up to 50,000 g / mol, more preferably from 800 up to 25,000 g / mol. w can be determined by gel permeation chromatography (GPC) using 1.5 wt % aqueous formic acid as the eluent and cross-linked polyhydroxyethyl methacrylate as the stationary phase.

[0035] In one embodiment of the present invention, the polyalkyleneimine prior to alkoxylation has a polydispersity Q=M of at least 3.5, preferably in the range of 3.5 to 10, more preferably in the range of 4 to 9, even more preferably in the range of 4.0 to 5.5. w / M n In another embodiment of the present invention, the polyalkyleneimine has a polydispersity Q=M of 3.4 or less, for example in the range of 1.1 to 3.0, more preferably in the range of 1.3 to 2.5, even more preferably in the range of 1.5 to 2.0. w / Mn Shows.

[0036] The polyethyleneimine before alkoxylation may have a linear or branched structure. The branches may be alkyleneamino groups, such as, but not limited to, -CH2-CH2-NH2 groups or (CH2)3-NH2- groups. Longer branches may be, for example, -(CH2)3-N(CH2CH2CH2NH2)2 or -(CH2)2-N(CH2CH2NH2)2 groups. Highly branched polyethyleneimines are, for example, polyethyleneimine dendrimers or related molecules with a degree of branching in the range of 0.25 to 0.95, preferably in the range of 0.30 to 0.80, particularly preferably at least 0.5. The degree of branching is preferably, for example, 0.2 to 0.95, preferably 0.3 to 0.80, in D2O. 13 C-NMR or 15 It can be determined by N-NMR spectroscopy and is defined as: DB=D+T / D+T+L Here, D (dendritic) corresponds to the fraction of tertiary amino groups, L (linear) corresponds to the fraction of secondary amino groups and T (terminal) corresponds to the fraction of primary amino groups.

[0037] Within the context of the present invention, branched polyethyleneimines are polyethyleneimines having a DB in the range of 0.25 to 0.95, particularly preferably in the range of 0.30 to 0.90%, very particularly preferably at least 0.5. Such branched polyethyleneimines can be prepared by polymerization of aziridines.

[0038] In the context of this invention, a CH3- group is not considered as branched.

[0039] Preferred polyethyleneimines are those which exhibit little or no branching and therefore a predominantly linear or linear polyethyleneimine backbone. In another embodiment, preferred polyethyleneimines are branched polyethyleneimines. When a diethoxylated MCDA-based backbone is provided as block (a), a mixture of the compounds listed above is typically provided.

[0040] The polymer (C1) may contain one or more main chains (a) having different or preferably identical structures and which may be linked to one another via blocks (b) or (c).

[0041] In one embodiment of the present invention, the polymer (C1) has 1 to 15 main chains (a) per molecule, preferably 3 to 7.

[0042] In the polymer (C1), some of the hydroxyl groups of the β-amino alcohol groups or of the β-amino-(alkylene oxide) groups are esterified with polyalkylene oxide mono- or diacids in which at least 50 mol % of the alkylene oxide groups are ethylene oxide groups (block (b)).

[0043] In block (b), the alkylene oxide groups which are not ethylene oxide are preferably selected from propylene oxide, in particular 1,2-propylene oxide ("PO"), and butylene oxide, in particular 1,2-butylene oxide ("BuO"). A preferred alkylene oxide other than ethylene oxide is PO.

[0044] Preferred mono- and diacids of polyalkylene oxides and preferred monomethyl ethers of polyalkylene oxide monoacids are represented by the general formula (I) X 2 -(AO') y -CH2-COOH (I) (In the formula, X 2 is HO-CH2-CH2-O- or CH3-O-CH2-CH2-O- or HO2C-CH2-O-, AO' is selected from ethylene oxide (EO), CH2-CH2-O, and combinations of EO and propylene oxide (PO) or butylene oxide (BuO), with at least 50 mol % of all AO' being EO. In the embodiment where AO' refers to a combination of EO and PO or BuO, they are usually arranged in blocks, not statistically. More preferably, all AO' are EO, The variable y ranges from 2 to 20, preferably from 4 to 15. The variable y may be an average value, in which case it refers to a number average.

[0045] In a preferred embodiment of the invention, the diacid of formula (I) contains, as impurities, for example up to 15 mol %, preferably 1 to 12 mol %, of the respective monoacid.

[0046] In a preferred embodiment of the invention, the monoacid of formula (II) contains as impurities, for example, a total of 50 mol % of both the respective diacid and the non-oxidized diol.

[0047] In the polymer (C1), some of the hydroxyl groups of the β-amino alcohol groups or β-amino-(alkylene oxide) groups of the main chain (a) are (c) aliphatic C4-C 10 -Can be esterified with di- or tricarboxylic acids.

[0048] Suitable aliphatic C4-C 10 Examples of aliphatic C4-C dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, pimelic acid, azelaic acid and sebacic acid. 10 -dicarboxylic acids may have functional groups other than carboxyl groups, for example alcohol groups. Suitable aliphatic C4-C 10 Examples of -dicarboxylic acids are tartaric acid and malic acid.

[0049] Aliphatic C4~C 10 Among the tricarboxylic acids, C6-C8-tricarboxylic acids are preferred. 10 An example of an aliphatic C4-C tricarboxylic acid is propane-1,2,3-tricarboxylic acid. 10-The tricarboxylic acid may have a functional group other than a carboxyl group, for example an alcohol group. 10 Examples of C6-C8 tricarboxylic acids are citric acid, isocitric acid and oxalosuccinic acid. Citric acid is particularly preferred as a C6-C8 tricarboxylic acid.

[0050] In one embodiment of the present invention, some of the hydroxyl groups are only one aliphatic C4-C 10 In another embodiment, some of the hydroxyl groups are esterified with aliphatic C4-C 10 -Dicarboxylic acids and aliphatic C4-C 10 - esterified with mixtures of tricarboxylic acids, for example a combination of adipic acid and citric acid or a combination of sebacic acid and citric acid or a combination of adipic acid with sebacic acid and citric acid.

[0051] In a preferred embodiment, at least one block (c) per molecule of polymer (C1), for example 1 to 5 blocks (c), is esterified with hydroxyl groups of β-aminoalcohol groups or β-amino-(alkylene oxide) groups of two different main chains (a).

[0052] In one embodiment of the present invention, the molar ratio of block (b) to block (c) ranges from 1:25 to 5:1, such as from 1:10 to 1:5.

[0053] In one embodiment of the present invention, all the carboxylic acid groups of block (c) are esterified, however, it is preferred that some carboxylic acid groups remain as free acids.

[0054] In one embodiment of the present invention, the polymer (B) is selected from the polymer (B2), alkoxylated and preferably polyethoxylated polyaspartic acid esters. Despite the name, such polymers are not synthesized from aspartic acid, but preferably from unsaturated polyesters (UPE) and primary amines by aza-Michael addition. The product of this reaction contains a polyester backbone with side chains linked to the backbone via secondary amino groups.

[0055] In one embodiment of the present invention, the polymer (B) is selected from polymers (B3) having an average molecular weight M of at least 1,500 g / mol. w which has the specific repeat unit: [ka] (In the formula, X 1 are different or preferably identical and are selected from hydrogen and methyl, preferably all Z 1 are identical and are hydrogen. R 1 are the same or different and are C2-C4-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, preferably unsubstituted CH3 or C2H5 or hydroxy or -NR 2a R 2b or C2H5 substituted with, R 2a and R 2b are different or preferably identical and are selected from C1-C4-alkyl, C1-C4-alkyl being as defined above, or NR 2a R 2b together form a C5-C6-cycloalkyleneamino or 1-imidazole group. 2a R 2b Preferred examples are -N(CH3)2, -N(C2H5)2, -N(CH2)4, and -N(CH2)5. The variable n is selected from 3 to 100, preferably 3 to 45. Z 1 is O and NR 3 Selected from R 3 is selected from hydrogen and methyl, preferably all Z 1 is oxygen, A 1 are the same or different and are selected from C2-C6-alkylene, for example, -(CH2)2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, preferably (AO) y1 (wherein AO is selected from ethylene oxide ("EO") and propylene oxide ("PO"), and combinations thereof; and y1 is selected from 2 to 200, preferably 2 to 10). Includes.

[0056] (AO) y1 In the embodiment where AO refers to a combination of EO and PO, such EO and PO may be arranged randomly or, preferably, blockwise, in two or three blocks. y1 In a preferred embodiment in which AO refers to a combination of EO and PO, at least 50 mol % of AO is EO, for example, 50 to 90 mol %, more preferably 65 to 90 mol %.

[0057] Even more preferably, (AO) y1 In other words, A 1 All AOs in are EOs.

[0058] The repeating units may be one per molecule, preferably up to two per molecule, for example those of the general formula: [ka] An asterisk represents a bond to another repeat unit or to an end-capping group according to * are connected to each other via

[0059] In formula (II), A 2 (AO) y2(wherein AO is selected from ethylene oxide and propylene oxide and combinations thereof, and y2 is 2 to 200, preferably 2 to 45); And Z 2 teeth, hydrogen, C1~C 10 an alkyl group, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, iso-amyl, n-hexyl, isohexyl, n-heptyl, isoheptyl, n-octyl, n-nonyl or n-decyl, preferably CH3 or C2H5, Aliphatic C2~C 20 -alkyl fatty acids, such as the carboxylates of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, or arachidic acid; or C 10 ~C 20 Alkenyl fatty acids are selected from the carboxylates of oleic acid, palmitoleic acid, linoleic acid, linoelaidic acid, and alpha-linolenic acid, preferably oleic acid, lauric acid, palmitic acid, and stearic acid. A 2 are the same or different, (AO) y2 (wherein AO is selected from ethylene oxide ("EO") and propylene oxide ("PO"), and combinations thereof; and y2 is selected from 2 to 200, preferably 2 to 45).

[0060] (AO) y2 In the embodiment where AO refers to a combination of EO and PO, such EO and PO are arranged randomly or, preferably, blockwise, in two or three blocks. y2 In a preferred embodiment in which AO refers to a combination of EO and PO, at least 50 mol % of AO is EO, for example, 50 to 90 mol %, more preferably 65 to 90 mol %.

[0061] Even more preferably, (AO) y2 In other words, A 2All AOs in are EOs.

[0062] Preferably, A 1 and A 2 are identical.

[0063] In the above formula, the asterisk indicates the moiety attached to the N atom of polymer (B3).

[0064] In one embodiment of the present invention, the polymer (B3) has per molecule at least one group of the following general formula: [ka] R 2a and R 2b are different or preferably identical and are selected from C1-C4-alkyl, C1-C4-alkyl being as defined above, or NR 2a R 2b together form a C5-C6-cycloalkyleneamino or 1-imidazole group. 2a R 2b Preferred examples are 1-imidazole, -N(CH3)2, -N(C2H5)2, -N(CH2)4, and -N(CH2)5.

[0065] The other variables are defined as above.

[0066] In one embodiment of the present invention, the polymer is selected from polymer (B4): (d) a core having 1 to 3 moieties of general formula (I); [ka] where the variables are defined as follows: Z 3 are different or identical, and C2 to C 12 -Alkylene and C3-C 12 -cycloalkylene, wherein the C2 to C 12 -Alkylene or C3-C 12-cycloalkylene may be unsubstituted or substituted with one or more O-C1-C4-alkyl groups, each of which may be C3-C4 12 -cycloalkylene may have 1 to 3 methyl groups; A 3 are different or identical, C1 to C 12 -Alkylene, C6-arylene, and C3-C 12 -cycloalkylene, where C to C 12 -Alkylene and C3-C 12 -Cycloalkylene is unsubstituted or substituted with one or more O-C1-C4-alkyl or OH groups, C3-C 12 -cycloalkylene may have 1 to 3 methyl groups; or based on citric acid, X 1 is selected from hydrogen, methyl, ethyl, and combinations of at least two of the foregoing; n is in the range of 1 to 100; (e) Polyalkylene oxide chain has.

[0067] Polymers (B4) and methods for preparing them are disclosed in WO 2022 / 008416.

[0068] In one embodiment of the present invention, the polymer (B) is selected from the polymer (B5). The polymer (B5) is obtained by first partially or completely oxidizing polyethylene glycol with a catalyst, such as palladium on charcoal, followed by esterification. In an embodiment in which the polyethylene glycol is partially oxidized, for example, under the formation of polyethylene glycol monocarboxylic acid, the addition of an alcohol component is not required. In an embodiment in which polyethylene glycol dicarboxylic acid is formed, a polyalkylene glycol, preferably polyethylene glycol, is added for esterification.

[0069] In one embodiment of the present invention, the polymer (B) is selected from polymers (B6) containing sulfonic acid groups and phthalic acid ester groups, which are disclosed in EP 2 504 380 A1.

[0070] In one embodiment, the composition of the present invention comprises: (C) hereinafter also referred to as protease (C), comprises at least one protease (C).

[0071] In one embodiment, the at least one protease (C) 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 and form covalent adducts with substrates during catalysis. A serine protease in the context of the present invention may be selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC 3.4.21.78 or EC 3.4.21.79), kallikrein (e.g., EC 3.4.21.34, EC 3.4.21.35, EC 3.4.21.118, or EC 3.4.21.119), plasmin (e.g., EC 3.4.21.7), trypsin (e.g., EC 3.4.21.4), thrombin (e.g., EC 3.4.21.5), and subtilisin. Subtilisins are also known as subtilopeptidases, e.g., EC 3.4.21.62, 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 an aspartate, a histidine, and a serine.

[0072] A protease is an active protein that exerts "protease activity" or "proteolytic activity." Proteolytic activity is related to the rate of degradation of a protein by a protease or proteolytic enzyme in a given period of time.

[0073] Methods for analyzing proteolytic activity are known in the literature (see, for example, Gupta et al. (2002), Appl. Microbiol. Biotechnol. 60:381-395). Proteolytic activity can be determined using Succinyl-Ala-Ala-Pro-Phe-p-nitroanilide (Suc-AAPF-pNA, abbreviated AAPF; see, for example, 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 has a yellow color, and is expressed by an OD 405 It can be quantified by measuring

[0074] Proteolytic activity can be provided in units per gram of enzyme. For example, 1 U of protease can correspond to the amount of protease that liberates 1 μmole of Folin-positive amino acids and peptides (as tyrosine) per minute at pH 8.0 and 37° C. (casein as substrate).

[0075] 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 derived from a microorganism selected from the group consisting of Campylobacter, E. coli, Flavobacterium, Fusobacterium, Helicobacter, Ilyobacter, Neisseria, Pseudomonas, Salmonella, and Ureaplasma.

[0076] In one embodiment of the invention, the at least one protease (C) is selected from the group consisting of Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus circulans, Bacillus clausii, Bacillus coagulans, Bacillus firmus, Bacillus gibsonii, Bacillus lautus, Bacillus lentus, Bacillus licheniformis, Bacillus megaterium, Bacillus The protease is selected from Bacillus megaterium, Bacillus pumilus, Bacillus sphaericus, Bacillus stearothermophilus, Bacillus subtilis or Bacillus thuringiensis.

[0077] In one embodiment of the invention, the at least one protease (C) is selected from: subtilisin from Bacillus amyloliquefaciens BPN'; subtilisin from Bacillus licheniformis (subtilisin Carlsberg); subtilisin PB92; subtilisin 147 and / or 309; subtilisin from Bacillus lentus as disclosed in WO 91 / 02792, such as subtilisin from Bacillus lentus DSM 5483 or variants of Bacillus lentus DSM 5483 as described in WO 95 / 23221; subtilisin from Bacillus gibsonii; subtilisin from Bacillus sp. (DSM 14390); subtilisin from Bacillus sp. (DSM 14392); subtilisin from Bacillus gibsonii (DSM 14393); subtilisin having SEQ ID NO: 4 as described in WO 2005 / 063974; subtilisin having SEQ ID NO: 4 as described in WO 2005 / 103244; subtilisin having SEQ ID NO: 7 as described in WO 2005 / 103244; and subtilisin having SEQ ID NO: 2 as described in DE 102005028295.4.

[0078] In one embodiment, at least one protease (C) has a sequence according to SEQ ID NO: 22 as described in EP 1921147 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 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) a threonine (3T) at position 3; (b) an isoleucine (4I) at position 4; (c) an alanine, threonine or arginine (63A, 63T or 63R) at position 63; (d) an aspartic acid or glutamic acid (156D or 156E) at position 156; (e) a proline (194P) at position 194; (f) a methionine (199M) at position 199; (g) an isoleucine (205I) at position 205; (h) an aspartic acid, glutamic acid or glycine (217D, 217E or 217G) at position 217; (i) a combination of two or more amino acids from (a)-(h).

[0079] At least one protease (C) may be at least 80% identical to SEQ ID NO: 22 described in EP 1 921 147 and is characterized by comprising one amino acid (according to (a) to (h)) or a combination according to (i) together with amino acids 101E, 101D, 101N, 101Q, 101A, 101G or 101S (according to BPN numbering). In one embodiment, said protease is characterized by comprising 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 having proteolytic activity. Proteases having a sequence according to SEQ ID NO: 22 with 101E described in EP 1 921 147 may be referred to herein as Lavergy.

[0080] In one embodiment the protease according to SEQ ID NO: 22 described in EP 1 921 147 is characterized by comprising the mutations (according to BPN numbering) S3T+V4I+S9R+A15T+V68A+D99S+R101S+A103S+I104V+N218D and having proteolytic activity.

[0081] The compositions of the present invention may comprise a combination of at least two proteases, preferably selected from the group of serine endopeptidases (EC 3.4.21), more preferably selected from the group of subtilisin-type proteases (EC 3.4.21.62), all of which have been previously disclosed.

[0082] It is preferred to use a combination of lipase (C) and protease (C) in the composition, for example 1-2% by weight of protease (C) and 0.1-0.5% by weight of lipase (C), both relative to the total weight of the composition.

[0083] In the context of the present invention, the lipase (C) and / or the protease (C) are considered stable if their enzymatic activity "available at the time of application" is at least equal to 60% compared to the initial enzymatic activity before storage. An enzyme may be called stable within the scope of the present invention if its enzymatic activity available at the time of 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% compared to the initial enzymatic activity before storage.

[0084] 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 when essentially no loss of enzyme activity occurs during storage, i.e. the loss of enzyme activity is equal to 0% compared to the initial enzyme activity before storage. Within the present invention, virtually 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%.

[0085] In one embodiment of the invention, the protease (C) is selected from lipases (C).

[0086] "Lipase", "lipolytic enzyme", "lipid esterase" all refer to enzymes in EC class 3.1.1 ("carboxylester hydrolase"). Such lipases (C) can 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 (C) include those of bacterial or fungal origin.

[0087] Commercially available lipases (C) 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).

[0088] Suitable lipases (B) also include variants of the above-mentioned lipases having lipolytic activity, such as those having at least 40-99% identity with the full-length polypeptide sequence of the parent enzymes described above.

[0089] Lipase (B) has "lipolytic activity". Methods for determining lipolytic activity are well known in the literature (see, e.g., Gupta et al. (2003), Biotechnol. Appl. Biochem. 37:63-71). For example, lipase activity can be measured by ester bond hydrolysis of the substrate paranitrophenyl palmitate (pNP-Palmitate, C:16), releasing the yellow colored pNP, detectable at 405 nm.

[0090] In one embodiment, the lipase (C) 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.

[0091] The Thermomyces lanuginosa lipase can be selected from variants having lipolytic activity that is at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 in U.S. Pat. No. 5,869,438.

[0092] The Thermomyces lanuginosa lipase can be selected from variants with lipolytic activity that contain only conservative mutations that do not belong to the functional domain of amino acids 1-269 of SEQ ID NO:2 of US 5,869,438. The lipase variants of this embodiment with lipolytic activity can be at least 95%, at least 96%, at least 97%, at least 98% or at least 99% similar when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of US 5,869,438.

[0093] The Thermomyces lanuginosa lipase can 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 US 5,869,438. The lipase variant can 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 US 5,869,438.

[0094] The Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the amino acid substitutions T231R, N233R, Q4V, V60S, A150G, L227G, P256K within the polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438, and which are at least 95%, at least 96% or at least 97% similar when compared to the full-length polypeptide sequence of amino acids 1-269 of SEQ ID NO:2 of U.S. Pat. No. 5,869,438.

[0095] 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.

[0096] The Thermomyces lanuginosa lipase may be a variant of amino acids 1-269 of SEQ ID NO:2 of US Patent No. 5,869,438 having lipolytic activity, characterized in that it contains the amino acid substitutions T231R and N233R. Said lipase may be referred to herein as Lipex.

[0097] In one embodiment of the present invention, a combination of at least two of the aforementioned lipases (B) can be used.

[0098] In one embodiment of the present invention, lipase (B) is included in the composition of the present invention in an amount such that the finished composition of the present invention has a lipolytic enzyme activity in the range of 100-0.005 LU / mg of the composition, preferably 25-0.05 LU / mg. A lipase unit (LU) is the amount of lipase that will produce 1 μmole of titratable fatty acid per minute in a pH stat under the following conditions: temperature 30°C; pH = 9.0; substrate is 13 mmol / L Ca 2+ and an emulsion of 3.3 wt % olive oil and 3.3% gum arabic in 5 mmol / L Tris buffer in the presence of 20 mmol / L NaCl.

[0099] In one embodiment of the invention, the composition according to the invention comprises at least one surfactant (D), such as an anionic surfactant (D) or a nonionic surfactant (D).

[0100] Examples of anionic surfactants (D) include C8 to C 18 -Alkyl sulfate, C8~C 18 -Ethoxylated C4-C fatty alcohol polyether sulfates 12 - Sulfuric acid half ester of alkylphenol (ethoxylation degree: 1 to 50 mol / mol ethylene oxide), C 12 ~C 18 Alkali metal and ammonium salts of 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 - the alkali metal and ammonium salts of alkylarylsulfonic acids. The alkali metal salts of the abovementioned compounds are preferred, and the sodium salts are particularly preferred.

[0101] Further examples of anionic surfactants (D) are soaps, such as the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkyl ether phosphates.

[0102] In a preferred embodiment of the present invention, the anionic surfactant (D) is represented by the general formula (III) R 1 -O(CH2CH2O) x1 -SO3M (III) (In the formula, R 1 is especially for nC with an even number of carbon atoms 10 ~C 18 -alkyl, such as n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl, preferably C 10 ~C 14 -alkyl, and even more preferably nC12 -alkyl, x1 is a number ranging from 1 to 5, preferably 2 to 4, and even more preferably 3; M is selected from alkali metals, preferably potassium, and even more preferably sodium. The compound is selected from the compounds according to the formula:

[0103] In the anionic surfactant (D), x1 may be an average number, so that n is not necessarily an integer, but in the individual molecules according to formula (IIIa), x represents an integer.

[0104] In one embodiment of the present invention, the composition of the present invention may contain 0.1 to 60% by weight, preferably 5 to 50% by weight, of an anionic surfactant (D).

[0105] The compositions of the present invention may contain ingredients other than those previously mentioned, examples being non-ionic surfactants, fragrances, dyes, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.

[0106] Preferred compositions of the present invention may contain one or more non-ionic surfactants.

[0107] Preferred nonionic surfactants are alkoxylated alcohols, di- 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.

[0108] 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 2are 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 C8~C 22 -Alkyl, branched or linear, 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; The variables e and f range from 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.

[0109] In one embodiment, the compound of general formula (II) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0110] Other preferred examples of alkoxylated alcohols include those represented by the general formula (IIIb): [ka] where the variables are defined as follows: R 2are identical or different and selected from hydrogen and linear C1-C0 alkyl, preferably are identical in each case and are ethyl, particularly preferably are hydrogen or methyl, R 5 is C6~C 20 -Alkyl, branched or linear, 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. It is a compound of the formula:

[0111] The sum of a+b+d is preferably in the range of 5-100, and even more preferably in the range of 9-50.

[0112] The compounds of general formulae (IIIa) and (IIIb) may be block or random copolymers, with block copolymers being preferred.

[0113] Further suitable non-ionic surfactants are selected from di- 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 formula (IV) [ka] (In the formula, 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, y1 ranges from 1.1 to 4, and y1 is the average number).

[0114] Further examples of non-ionic surfactants include those represented by the general formulas (V) and (VI): [ka] (AO is selected from ethylene oxide, propylene oxide and butylene oxide; EO is ethylene oxide, CH2CH2-O; R 8 is a branched or linear C8-C 18 -alkyl; R 5 is defined as 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 between 13 and 35) It is a compound of the formula:

[0115] Surveys of further suitable nonionic surfactants are given in EP-A 0 851 023 and DE-A 198 19 187.

[0116] Mixtures of two or more different nonionic surfactants selected from the aforementioned nonionic surfactants may also be present.

[0117] Other surfactants which may be present may be selected from amphoteric (zwitterionic) surfactants and anionic surfactants, and mixtures thereof.

[0118] An example of an amphoteric surfactant is a surfactant that has positive and negative charges in the same molecule under the conditions of use.A preferred example of an amphoteric surfactant is the so-called betaine surfactant.Many examples of betaine surfactants have one quaternary nitrogen atom and one carboxylic acid group per molecule.A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0119] Examples of amine oxide surfactants include those represented by the general formula (VII): R 9 R 10 R 11 N → O (VII) (In the formula, R 9 , R 10 and R 11 are each independently an aliphatic, alicyclic or C2-C4 alkylene C 10 ~C 20 -alkylamide moieties) Preferably, R 9 is C8~C 20 -Alkyl or C2-C4-alkylene C 10 ~C 20 -alkylamide; R 10 and R 11 are both methyl.

[0120] A particularly preferred example is lauryl dimethylamine oxide, sometimes called lauramine oxide. A still more particularly preferred example is cocamidyl propyl dimethylamine oxide, sometimes called cocamidopropylamine oxide.

[0121] 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.

[0122] The composition of the present invention may contain at least one bleaching agent, also called bleach. The bleaching agent may be selected from chlorine bleaches and peroxide bleaches, and the peroxide bleaches may be selected from inorganic peroxide bleaches and organic peroxide bleaches. Inorganic peroxide bleaches selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates are preferred.

[0123] Examples of organic peroxide bleaching agents are organic percarboxylic acids, especially organic percarboxylic acids.

[0124] In the composition of the present invention, the alkali metal percarbonates, especially sodium percarbonate, are preferably used in the form of a coating. Such coatings can be organic or inorganic. Examples include glycerol, sodium sulfate, silicates, sodium carbonate, and combinations of at least two of the above, such as sodium carbonate and sodium sulfate.

[0125] 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.

[0126] The composition of the present invention may contain a chlorine-containing bleaching agent, for example in the range of 3 to 10% by weight.

[0127] The composition of the present invention may contain one or more bleach catalysts. The bleach catalysts may be selected from bleach-boosting transition metal salts or transition metal complexes, such as manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. In addition to the complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper with nitrogen-containing tripod ligands, cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleach catalysts.

[0128] The compositions of the present invention may also include one or more bleach activators, such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quats (trimethylammonium acetonitrile salts).

[0129] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0130] Examples of fragrances are benzyl salicylate, 2-(4-tert-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0131] 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.

[0132] The composition of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid laundry detergent composition of the present invention due to attack from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), benzoic acid, sorbic acid, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH") and dibromodimethylhydantoin ("DBDMH").

[0133] Examples of viscosity modifiers are agar, carrageenan, tragacanth, gum arabic, alginates, pectin, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, such as polyacrylic acid crosslinked with bis(meth)acrylamide, as well as silicic acid, clays (including but not limited to montmorillonite, zeolite, dextrin, and casein).

[0134] A hydrotrope in the context of the present invention is a compound that promotes the dissolution of compounds that have limited solubility in water. Examples of hydrotropes are, but are not limited to, organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and other organic solvents that are miscible with water under normal conditions. Further examples of suitable hydrotropes are the sodium salts of toluenesulfonic acid, xylenesulfonic acid, and cumenesulfonic acid.

[0135] Examples of polymers other than the polymer (B) are especially polyacrylic acids and the respective alkali metal salts thereof, especially the sodium salts thereof. Suitable polymers are especially polyacrylic acids, preferably having average molecular weights M in the range from 2,000 to 40,000 g / mol, preferably from 2,000 to 10,000 g / mol, in particular from 3,000 to 8,000 g / mol. w Each is partially or completely neutralized with an alkali, especially sodium. Copolymeric polycarboxylates 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 respective alkali metal salts can function as soil redeposition inhibitors.

[0136] A further example of a polymer is polyvinylpyrrolidone (PVP), which can function as a dye transfer inhibitor.

[0137] 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.

[0138] Examples of buffers are monoethanolamine and N,N,N-triethanolamine.

[0139] An example of a defoamer is silicone.

[0140] The composition of the present invention is not only good for cleaning soiled laundry against organic fat stains such as oil.The liquid detergent composition of the present invention is very useful for removing non-bleachable stains such as, but not limited to, stains from red wine, tea, coffee, various fruit juices such as vegetable and berry juice from laundry.In addition, the composition of the present invention does not leave any residue on woven fabrics.

[0141] A further aspect of the present invention is therefore the use of the inventive composition for laundry care. Laundry care in this context includes laundry cleaning. In the context of the present invention, the expressions "liquid laundry detergent composition" and "liquid laundry composition" can be used synonymously.

[0142] In another aspect, the compositions of the invention are useful for cleaning hard surfaces. A further aspect of the invention is therefore the use of the compositions of the invention in cleaning hard surfaces.

[0143] In the context of the present invention, the term "hard surface cleaning compositions" includes cleaners for home care and industrial or institutional applications. The term "hard surface cleaning compositions" includes hard surface cleaning compositions such as dishwashing compositions, especially hand dishwashing compositions, automatic dishwashing and ceramic cleaning compositions, bathroom cleaning compositions, kitchen cleaning compositions, floor cleaning compositions, plumbing descaling compositions, window cleaning compositions, automobile cleaning compositions including truck cleaning, as well as open plant cleaning compositions, yard cleaning compositions, metal cleaning compositions, germicidal cleaning compositions, farm cleaning compositions, and pressure cleaning compositions, but does not include laundry detergent compositions. A specific embodiment of the hard surface cleaning composition is an automatic dishwashing composition.

[0144] In the context of the present invention, the terms "hard surface cleaning composition" and "hard surface cleaner composition" are used synonymously.

[0145] In the context of the present invention, unless otherwise specified, percentages of ingredients of laundry detergent compositions are percent by weight and refer to the total solids content of the respective laundry detergent composition. In the context of the present invention, unless otherwise specified, percentages of ingredients of detergent compositions for hard surface cleaners are percent by weight and refer to the total solids content of the detergent compositions for hard surface cleaning.

[0146] The compositions of the present invention when used in automatic dishwashing preferably comprise (E) At least one builder component selected from aminopolycarboxylic acids and preferably their alkali metal salts, which in the context of the present invention is also called a complexing agent (E) or a sequestering agent (E). In the context of the present invention, the terms "sequestering agent" and "chelating agent" are used synonymously.

[0147] Examples of the sequestering agent (E) include alkali metal salts of MGDA (methylglycine diacetate), alkali metal salts of GLDA (glutamic acid diacetate), alkali metal salts of IDS (iminodisuccinic acid), alkali metal salts of EDTA, and alkali metal salts of iminodisuccinic acid having 20 to 90 mol % of N atoms in at least one CH2COO - Polymers having complexing groups, such as polyethyleneimine, and their respective alkali metal salts, in particular their sodium salts, for example MGDA-Na3, GLDA-Na4, or IDS-Na4.

[0148] Preferred sequestering agents are those of the general formula (IXa) [CH3-CH(COO)-N(CH2-COO)2]M 3-x2 H x2 (IXa) (wherein M is the same or different and is selected from ammonium and alkali metal cations, such as sodium cations, potassium cations, and combinations of at least two of the foregoing. 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 preferred in the compounds according to general formula (IIa) are all M the same and all Na; In formula (IIa), x2 is in the range of 0 to 1.0. or (IXb) [OOC-CH2CH2-CH(COO)-N(CH2-COO)2]M 4-x3 H x3 (IXb) (wherein M is as defined above, and x3 in formula (IXb) is in the range of 0 to 2.0, preferably up to 1.0), or (IXc) [OOC-CH2-CH(COO)]-N-CH(COO)-CH2-COO]M 4-x4 H x4 (IXc) (In the formula, M is as defined above, and x4 in formula (IXc) is in the range of 0 to 2.0, preferably up to 1.0.) This is due to.

[0149] In one embodiment of the invention, the composition of the invention comprises a combination of at least two of the foregoing, for example a combination of a chelating agent according to general formula (IXa) and a chelating agent according to general formula (IXb).

[0150] The chelating agents according to the general formulae (IXa) and (IXb) are preferred. The chelating agents according to the general formula (IXa) are even more preferred.

[0151] In one embodiment of the present invention, the compound according to general formula (IXa) is selected from the ammonium or alkali metal salts of racemic MGDA and the ammonium and alkali metal salts of a mixture of L- and D-enantiomers according to formula (IXa), said mixture predominantly containing the respective L-isomer with an enantiomeric excess (ee) in the range of 5-99%, preferably 5-95%, more preferably 10-75% and even more preferably 10-66%.

[0152] In one embodiment of the invention, the compound according to general formula (IXb) is selected from at least one alkali metal salt of a mixture of the L-enantiomer and the D-enantiomer according to formula (IXb), said mixture containing 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%.

[0153] The enantiomeric excess of the compound according to general formula (IXa) can be determined by measuring polarized light (polarimetry) or preferably by chromatography, for example by HPLC with a chiral column, for example using one or more cyclodextrins as stationary phase or using a chiral stationary phase of the ligand exchange (Pirkle-brush) concept. Determination of the ee (enantiomeric excess) by HPLC is preferred, using immobilized optically active amines such as D-penicillamine in the presence of copper(+II) salts. The enantiomeric excess of the compound according to general formula (IXb) salt can be determined by measuring polarized light (polarimetry).

[0154] Due to environmental concerns related to the use of phosphates, it is preferred that the advantageous composition is phosphate-free. "Phosphate-free" is to be understood in the context of the present invention to mean that the content of phosphates and polyphosphates ranges from the gravimetrically determined detection level to 1% by weight in total, preferably from 10 ppm to 0.2% by weight.

[0155] In one embodiment of the present invention, the composition of the present invention contains a sequestering agent (E) in an amount of 0.5 to 50% by weight, preferably 1 to 35% by weight, based on the total solid content.

[0156] 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 in the form of a sachet or pouch. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.

[0157] In a preferred embodiment of the present invention, the liquid laundry compositions of the present invention are in liquid or gel form at ambient temperature.

[0158] In one embodiment of the invention, the compositions of the invention are in liquid or gel form and have a pH value ranging from 7 to 9, preferably from 7.5 to 8.5. In embodiments where the compositions of the invention are used for hard surfaces such as tiles, for example bathroom tiles, their pH value may be more acidic, for example from 3 to 6.

[0159] 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%, measured after drying under vacuum at 80° C.

[0160] In one embodiment of the present invention, the compositions of the present invention are liquid at ambient temperature and have a dynamic viscosity in the range of 400 to 1200 mPa·s, determined at 20° C. according to Anton Paar in a rotational viscometer.

[0161] The composition of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent composition of the present invention due to attack from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), 2-butyl-benzo[d]isothiazol-3-one (BBIT), 2-octyl-2H-isothiazol-3-one (OIT); Benzoic acid, sorbic acid and their 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").

[0162] Of particular interest are the following antimicrobial and / or antiseptic agents: 4,4'-dichloro 2-hydroxydiphenyl ether, further name: 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP (commercially available as a 30% by weight solution of 4,4'-dichloro 2-hydroxydiphenyl ether in 1,2-propylene glycol); 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-pentanedial, pentane-1,5-dial, glutaral, glutaric dialdehyde, glyoxal (further names: ethanedial, oxylaldehyde, 1,2-ethanedial); Mixtures of 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (CMIT / MIT mixtures); (E,E)-potassium 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.

[0163] 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.

[0164] 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%.

[0165] Thus, the present invention further relates to a method for protecting an aqueous composition of the present invention from bacterial contamination or growth, the method comprising the addition of 2-phenoxyethanol.

[0166] Thus, the present invention relates to a method of imparting antimicrobial benefit to fabrics after treatment with a liquid laundry detergent of the present invention containing 4,4'-dichloro 2-hydroxydiphenyl ether (DCPP).

[0167] In one aspect, the present invention provides a method for improving the cleaning performance of a liquid laundry detergent composition, comprising: (A) a combination of compounds comprising: (α) triethanolamine, and (β) Citric acid or mono- or diammonium salts of citric acid, where ammonium is selected from alkylammonium and alkanolammonium. The present invention relates to a method of

[0168] The addition can be done by separate addition or by adding a combination of compound (α) and compound (β).

[0169] The liquid laundry detergent composition further comprises at least one polymer (B).

[0170] The hydrolase (C) and polymer (B) are described in more detail (see above).

[0171] In one embodiment of the invention, the liquid laundry detergent composition is phosphate-free.

[0172] The term "improved cleaning performance" as used herein may indicate that the combination (A) provides better, i.e. improved, properties in removing soils under relevant washing conditions when compared to the cleaning performance of a detergent composition not containing a polymer (B) and optionally a hydrolase (C). In particular, however, the addition of the combination (A), with or without a hydrolase (C), leads to an improvement in the shelf life of the polymer (B).

[0173] In one embodiment, "improved cleaning performance" means that the cleaning performance of a detergent comprising polymer (B) without or together with at least one hydrolase (C), in particular together with at least one lipase (C) and / or at least one protease (C), is improved when compared to the cleaning performance of a detergent comprising polymer (B) but not combination (A).

[0174] In this specification, the term "relevant washing conditions" refers to the conditions actually used in a washing machine, automatic dishwasher or manual washing process, in particular the washing temperature, time, washing equipment, foam concentration, detergent type and water hardness.

[0175] Preferably, the liquid laundry detergent composition is an aqueous composition.

[0176] In one embodiment of the invention, the liquid detergent composition has a pH value in the range of 7.5 to 8.5.

[0177] In one embodiment of the invention, the liquid detergent composition has a sodium content of less than 2.0% by weight, preferably less than 0.5% by weight, more preferably between 0.001 and 0.4% by weight, based on the total solids content of the composition. The total solids content may be determined by removing water and solvent at a pressure of 40-100 mbar and a temperature of 60-80° C. until constant weight is reached.

[0178] Compound (α) and compound (β) are described in more detail above.

[0179] In one embodiment of the present invention, the total molar ratio of N-CH2CH2-OH groups of compound (α) to carboxylic acid groups from compound (β) ranges from 1:10 to 10:1.

[0180] The present invention is further illustrated by examples. EXAMPLES

[0181] Synthesis of MCDA×2EO(α.3) A 2 liter autoclave equipped with a propeller stirrer was charged with 512 g of methylcyclohexyldiamine and 80 g of water, then evacuated and purged with nitrogen three times. The autoclave was then heated to 125° C. An amount of 355 g of ethylene oxide was added within 2.5 hours under stirring and reacted at 130° C. for another 45 minutes. The mixture so obtained was cooled to 90° C. and the volatile components were removed under reduced pressure. A highly viscous brownish liquid was obtained in an amount of 895 g (α.3).

[0182] Synthesis of N4 amine x 2PO(α.4) A 2 liter autoclave equipped with a propeller stirrer was charged with 356 g of N4-amine (N,N'-bis(3-aminopropyl)ethylenediamine) and 55 g of water, then evacuated and purged with nitrogen three times. The autoclave was then heated to 125°C. A quantity of 230 g of propylene oxide ("PO") was added within 2 hours with stirring and reacted at 130°C for another 90 minutes. The mixture so obtained was cooled to 90°C and the volatile components were removed under reduced pressure. A quantity of 682 g of a highly viscous brownish liquid was obtained (α.4).

[0183] I. Preparation of Combination (A) I.1 Manufacturing of the Combination (A.1) A 2 liter glass vessel equipped with stirrer and funnel was charged with 550 g (3.7 moles) of triethanolamine (α.1). 260 g of water was added. Within 15 minutes, 210 g of citric acid (β.1) monohydrate (1.0 mole) was added via the funnel. The pH of the resulting clear liquid, combination (A.1), was 7.6. Molar ratio of N-CH2CH2-OH groups to COOH groups: 1.2:1.

[0184] I.2 Manufacturing of the combination (A.2) A 2 liter glass vessel equipped with stirrer and funnel was charged with 150 g (1.0 mol) of triethanolamine (α.1) and 159 g (2.6 mol) of ethanolamine (α.2). 260 g of water was added. Within 15 minutes, 225 g of citric acid monohydrate (β.1) (1.07 mol) was added via the funnel. The pH value of the resulting clear liquid, combination (A.2), was 7.5. Molar ratio of N-CH2CH2OH groups to COOH groups: 1.1:1.

[0185] I.3 Manufacturing of the combination (A.3) A 2 liter glass vessel equipped with stirrer and funnel was charged with 300 g (2.0 moles) of triethanolamine (α.1). 260 g of water and 190 g of MCDA as a mixture of isomers were added. Within 20 minutes, 265 g of citric acid monohydrate (β.1) (1.26 moles) were added via the funnel. The pH value of the resulting clear liquid, combination (A.3), was 7.25. N-CH2CH(X 1 ) Molar ratio of OH groups to COOH groups: 1.9:1.

[0186] I.4 Manufacturing of the combination (A.4) A 2 liter glass vessel equipped with stirrer and funnel was charged with 300 g (2.0 moles) of triethanolamine (α.1) and 320 g (1.5 moles) (α.3). 260 g of water was added. Within 30 minutes, 265 g of citric acid monohydrate (β.1) (1.26 moles) was added via the funnel. The pH of the resulting clear liquid, combination (A.4), was 7.1. Molar ratio of N-CH2CH2OH groups to COOH groups: 1.3:1.

[0187] I.5 Manufacturing of the combination (A.5) A 2 liter glass vessel equipped with stirrer and funnel was charged with 300 g (2.0 mol) of triethanolamine (α.1) and 320 g (1.1 mol) (α.4). 145 g of water was added. Within 30 minutes, 265 g of citric acid monohydrate (β.1) (1.26 mol) was added via the funnel. The pH value of the resulting clear liquid combination (A.5) was 7.35. N-CH2CHX 1 Molar ratio of OH groups to COOH groups: 1.1:1.

[0188] II. Preparation of Polymer (B) II.1 Preparation of polymer (B1)

[0189] [Table 1]

[0190] [Table 2]

[0191] II.1.1 Synthesis of polymer (B1.1) A 250 ml flask equipped with a stirrer, Dean-Stark apparatus, nitrogen inlet and internal thermometer was charged with the backbone (a.1) and citric acid in a 1:1 molar ratio. An amount of 0.15 g of Ti(IV) tetraisobutyrate was added. The reaction mixture was then heated to 160° C. (internal temperature). Water was distilled off. Stirring at 160° C. was continued under nitrogen for 4 hours. Then, polyethylene glycol oxide (M n 200 g / mol, molar ratio monoacid:diacid 2:7) was added and heating and water removal was continued for 1.5 hours. The resulting polymer (B1.1) was collected as a solid material. GPC in HFIP:M n 5600 g / mol, M w 21,600 g / mol.

[0192] II.1.2 Synthesis of polymer (B1.2) A 250 ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and internal thermometer was charged with the backbone molecule (a.2) (0.69 mol) and 0.2 g of Ti(IV) tetraisobutyrate. Then, monomethyl ether oxide of polyethylene glycol (85:15 molar ratio of COOH groups to OH groups) was added. The reaction mixture was then heated to 160° C. (internal temperature). Water was distilled off. Stirring at 160° C. was continued under nitrogen for 4.5 hours, and heating and water removal were continued for 1.5 hours. The resulting polymer (B1.2) was collected as a paste. GPC in HFIP:M n 5,300 g / mol, M w 14,160 g / mol.

[0193] Polymers (B3.1), (B3.2) and (B3.3) correspond to polymers (A1.2), (A.3.1) and (A.4.1), respectively, of WO 2022 / 008416.

[0194] III. Preparation and Stability Testing of the Compositions of the Present Invention Percentages are by weight unless otherwise indicated.

[0195] III.1 Storage Test and IR Detection The formulations of the invention were prepared by mixing 85 g of LLF.1 or LLF.2, respectively, "15% gap" in Table 3, with 5 g of the respective polymer (B) and 5-8 g of combinations (A.1)-(A.5) shown in Table 5, then filling with water to 100 g.

[0196] The ester bonds of the polymer were analyzed by infrared spectroscopy ("IR") and the 1730-1760 cm -1 CO peak at 1240 cm -1 The COC control band frequency was detected at 100%. The band intensity was set as 100% at the pre-storage time point and compared with the intensity after storage at various time points.

[0197] After storage at 50° C. for 3 weeks (simulating approximately 4-6 months at 20° C.), the IR spectra were measured again and a decrease in the strength of the ester bonds correlated with the degradation of polymer (B).

[0198] For comparison, similar experiments were carried out in water, in LLF.1 and in LLF.2, but without the combination (A).

[0199] [Table 3]

[0200] [Table 4]

[0201] III.2 Storage test and molecular weight detection General protocol: Polymer (B) was diluted with water to obtain a 20% aqueous solution. The pH value was adjusted to 8.0-8.3 with combination (A) and the resulting solution was stored at 50°C for 3 weeks. The degree of degradation over storage was confirmed by GPC analysis. In a comparative experiment, polymer (B) was diluted with water to obtain a 20% aqueous solution by weight, but without the addition of combination (A). The pH value was adjusted to 8.0 with either citric acid or ethanolamine.

[0202] [Table 5]

Claims

1. 1. A liquid laundry composition comprising: (A) at least one combination comprising: (α) triethanolamine, (β) citrate, and (B) at least one water-soluble polymer having at least two ester groups per molecule; 1. A liquid laundry composition comprising:

2. 10. The liquid laundry composition of claim 1, wherein the polymer (B) has a biodegradability of at least 40% as determined by OECD 301F manometric respirometry.

3. A liquid laundry composition according to claim 1 or 2, further comprising an enzyme selected from hydrolases (C).

4. A liquid laundry composition according to any one of claims 1 to 3, wherein such composition has a pH value in the range of from 7.5 to 8.

5.

5. A liquid laundry composition according to any one of claims 1 to 4, wherein the total molar ratio of amino groups in compound (α) to carboxylic acid groups from compound (β) is in the range of 1:10 to 10:

1.

6. 6. A liquid laundry composition according to claim 1, comprising 2 to 20% by weight of compound (α) and compound (β) based on the total solid content.

7. A liquid laundry composition according to any preceding claim, wherein the composition has a sodium ion content of less than 2.0% by weight based on total solids.

8. The combination (A) has a boiling point at ambient pressure of 180° C. or more, and ２ CH(X １ )-OH group (X １ is hydrogen and C １ ~C ２ 8. The liquid laundry composition of claim 1, further comprising a (γ) aliphatic or cycloaliphatic amine having no alkyl radicals (selected from aryl, ...

9. The polymer (C) is (d) a core having 1 to 3 moieties of general formula (I) 【Chemistry 1】 where the variables are defined as follows: Z ３ are different or identical, C ２ ~C １２ -Alkylene and C ３ ~C １２ -cycloalkylene, wherein said C ２ ~C １２ -Alkylene or C ３ ~C １２ Each cycloalkylene is unsubstituted or has one or more O—C １ ~C ４ - may be substituted with an alkyl group, ３ ~C １２ -cycloalkylene may have 1 to 3 methyl groups; A ３ are different or identical, C １ ~C １２ -Alkylene, C ６ -arylene, and C ３ ~C １２ -cycloalkylene, where C ２ ~C １２ -Alkylene and C ３ ~C １２ -Cycloalkylene is unsubstituted or has one or more O-C １ ~C ４ - may be substituted with an alkyl group or an OH group, ３ ~C １２ -cycloalkylene may have 1 to 3 methyl groups; or based on citric acid, X １ is selected from hydrogen, methyl, ethyl, and combinations of at least two of the foregoing; n ranges from 1 to 100); (e) Polyalkylene oxide chain A liquid laundry composition according to any one of claims 1 to 8, wherein the polymer is selected from polymers having the formula:

10. Use of a liquid laundry composition according to any one of claims 1 to 9 for laundry care.

11. 1. A method for improving the cleaning performance of a liquid laundry detergent composition, comprising: (α) triethanolamine and (β) Citric acid or a mono- or diammonium salt of citric acid (ammonium is selected from alkylammonium and alkanolammonium). by adding a chemical combination (A) comprising:

12. N-CH of compound (α) ２ CH ２ 12. The process of claim 11, wherein the total molar ratio of -OH groups to carboxylic acid groups from compound (β) ranges from 1:10 to 10:

1.

13. 13. The method of claim 11 or 12, wherein the sodium content of the detergent composition is less than 2.0% by weight, based on the total solids of the composition.

14. The combination (A) has a boiling point at ambient pressure of 180° C. or more, and ２ CH(X １ 14. The method according to claim 10, further comprising a (γ) aliphatic or cycloaliphatic amine having no —OH group.

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