WO2023066741A1

WO2023066741A1 - Phosphate-free composition and methods for their manufacture and use

Info

Publication number: WO2023066741A1
Application number: PCT/EP2022/078325
Authority: WO
Inventors: Stephan Hueffer; Thomas Weiss; Ivette Garcia Castro; Sandra Gloria KOENIG; Larissa BARTULI
Original assignee: Basf Se
Priority date: 2021-10-20
Filing date: 2022-10-12
Publication date: 2023-04-27

Abstract

Phosphate-free composition comprising (A) at least one polymer comprising (a) backbone that is based on a polyester with an average molecular weight Mn in the range of from 400 to 15,000 g that is formed from aspartic acid and polyalkylene glycol in which alkylene is selected from ethylene, 1,2-propylene and 1,2-butylene, wherein polymer (A) comprises side chains selected from (b) (poly)alkylene oxide chains on N-atoms of aspartic acid, and (c) polymerized vinyl monomers selected from vinyl-C1-C20 carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole.

Description

Phosphate-free composition and methods for their manufacture and use

The present invention is directed towards phosphate-free detergent compositions comprising

(A) at least one polymer comprising

(a) a backbone that is based on a polyester with an average molecular weight M_n in the range of from 400 to 15,000 g and that is formed from aspartic acid and polyalkylene glycol in which alkylene is selected from ethylene, 1 ,2-propylene and 1 ,2-butylene, wherein polymer (A) comprises side chains selected from

(b) (poly)alkylene oxide chains on N-atoms of aspartic acid, and

(c) polymerized vinyl monomers selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole.

Furthermore, the present invention is directed to polymers useful for such detergent compositions, and to a process for making such polymers.

Laundry detergents have to fulfil several requirements. They need to remove all sorts of soiling from laundry, for example all sorts of pigments, clay, fatty soil, and dyestuffs including dyestuff from food and drinks such as red wine, tea, coffee, and fruit including berry juices. Laundry detergents also need to exhibit a certain storage stability. Especially laundry detergents that are liquid or that contain hygroscopic ingredients often lack a good storage stability, e.g. enzymes tend to be deactivated.

Fatty soilings are still a challenge in laundering. Although numerous suggestions for removal have been made - polymers, enzymes, surfactants - solutions that work well are still of interest. It has been suggested to use a lipase to support fat removal but many builders - especially in liquid laundry detergents - do not work well with lipase.

In EP 0 648 241 , certain polymers are disclosed that are synthesized in the presence of equimolar amounts of phosphoric acid.

It was therefore an objective to provide a detergent composition that fulfils the requirements discussed above. It was further an objective to provide ingredients that fulfil the above requirements, and it was an objective to provide a process to make such ingredients and detergent compositions. Accordingly, the compositions defined at the outset have been found, hereinafter also referred to as inventive compositions or compositions according to the present invention. Inventive compositions contain at least one polymer (A) that preferably comprises several building blocks:

(a) a backbone - hereinafter also referred to as backbone (a) - that is based on a polyester with an average molecular weight M_n in the range of from 400 to 15,000 g and that is formed from aspartic acid and polyalkylene glycol in which alkylene is selected from ethylene, 1 ,2-propylene and 1 ,2-butylene, and wherein said polymer (A) comprises side chains selected from

(b) (poly)alkylene oxide chains on N-atoms of aspartic acid, hereinafter also referred to as chains (b) or side chains (b), and

Said building blocks will be described in more detail below.

Inventive compositions are phosphate-free, also referred to as “free from phosphate”. "Free from phosphate" and “phosphate-free” are used interchangeably in the context of this invention, and the terms should be understood as meaning that the content of phosphate and polyphosphate in inventive compositions range of from detection level to 1 % by weight, preferably from 10 ppm to 0.2% by weight, determined by gravimetry.

Phosphate may be added deliberately. Due to environmental concerns, though, it is preferred to not add phosphate deliberately. However, phosphate may be involuntarily be present as impurity of various ingredients.

Backbone (a) is based on a polyester that may comprise side chains. In those embodiments wherein polymer (A) does not comprise side chains, backbone (a) - and thus polymer (A) - is a polyester. Said polyester comprises aspartic acid as dicarboxylic acid component, and it comprises polyalkylene glycol as diol compound.

Aspartic acid may be selected from L-aspartic acid, D-aspartic acid, racemic aspartic acid and enantiomerically enriched mixtures of L- and D-aspartic acid, preferably those mixtures with more L- than D-aspartic acid. Enantiomerically pure L-aspartic acid and mixtures with more L- than D-aspartic acid, for example with an enantiomerical excess (ee) of at least 30%, are preferred. In other embodiments, the racemic aspartate is preferred.

Polyalkylene glycol in the context of the present invention refers to polyaddition products of alkylene oxides in which alkylene is selected from ethylene, 1 ,2-propylene and 1 ,2-butylene and combinations of at least two of the aforementioned, preferably ethylene and 1 ,2-propylene or ethylene and 1 ,2-butylene. Ethylene oxides are thus selected from ethylene oxide (“EO”), 1 ,2- propylene oxide (“PO”) and 1 ,2-butylene oxide (“BuO”) and combinations of at least two of the aforementioned. Preferably, in such polyalkylene oxide, at least 50 mol-% of the alkylene oxide is selected from ethylene oxide, more preferably at least 60 mol-%. In a particularly preferred embodiment, polyalkylene glycol is polyethylene glycol.

In one embodiment of the present invention, the average molecular weight M_n of polyalkylene glycol in backbone (a) is in the range of from 160 to 5,000 g/mol, determined by gel permeation chromatography (“GPC”).

Backbone (a) has an average molecular weight M_n in the range of from 400 to 15,000 g, preferably from 1 ,500 to 12,000 g. The average molecular weight may be determined by gel permeation chromatography (GPC), with linear polystyrene/divinylbenzene and tetrahydrofuran (“THF”) as solvent.

In one embodiment of the present invention, the polydispersity of backbone (a) M_w/M_n is in the range of from 2.0 to 6.0, preferably from 3.5 to 4.5.

In one embodiment of the present invention, the amine value of backbone (a) is in the range of from 20 to 600 mg KOH/g, determined according to ASTM D2074-07, preferably 25 to 400 mg KOH/g.

In one embodiment of the present invention, the hydroxyl value of backbone (a) is in the range of from 25 to 400 mg KOH/g, determined according to DIN 53240 (2013) , preferably 25 to 200 mg KOH/g.

Polymer (A) comprises side chains selected from

(b) (poly)alkylene oxide chains - hereinafter also referred to as side chains (b) - on N-atoms of aspartic acid, and (c) polymerized vinyl monomers - hereinafter also referred to as side chains (c) - selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole.

(Poly)alkylene oxide in side chains (b) is selected from addition polymers of ethylene oxide (“EO”), 1 ,2-propylene oxide (“PO”) or 1 ,2-butylene oxide (“BuO”) or combinations of at least two of the aforementioned. Preferably, in such (poly)alkylene oxide, at least 50 mol-% of the alkylene oxide is selected from ethylene oxide, more preferably at least 60 mol-%. In a particularly preferred embodiment, polyalkylene glycol is polyethylene glycol. Such side chains (b) are bonded to the amino group of the aspartic acid building blocks of backbone (a).

Preferably, polymer (A) bears 3 to 25 alkylene oxide groups per alkoxylated site on a nitrogen atom - thus, -N(AO)_xi - with AO being alkylene oxide selected from EO, PO, BuO and combinations, or -N[(AO)_XI]₂ with x1 being in the range of from 3 to 25.

In one embodiment of the present invention, the weight ratio of backbone (a) to side chains (b) is in the range of from 5:1 to 1 : 2.

In another embodiment of the present invention, polymer (A) bears side chains (c). Side chains (c) polymerized vinyl monomers selected from vinyl-Ci-C2o carboxylic esters and (meth)acrylic acid and N-vinyl imidazole.

Examples of vinyl-Ci-C2o carboxylic esters are vinyl formate, vinyl propionate, vinyl laurate, vinyl stearate and especially vinyl acetate. In embodiments where hydrophobic vinyl carboxylic esters are intended, such as vinyl stearate, vinyl laurate or vinyl palmitate, it is preferred to combine them with vinyl formate or even more with vinyl acetate, for example in a weight ratio of from 1 :10 to 1 :4.

Further examples of vinyl monomers are acrylic acid, methacrylic acid - as well as their respective alkali metal salts, especially the sodium salts - and N-vinyl-imidazole. Combinations of two or more of the vinyl monomers mentioned before are feasible as well.

In one embodiment of the present invention, the weight ratio of backbone to side chains (c) is in the range of from 2:3 to 10:1 , preferably 1 :1 to 5:1. Without wishing to be bound by any theory, we believe that the side chains (c) are bound to a carbon atom of the aspartic acid.

In embodiments that contain a polymer (A) with side chains (c), a polymer of the respective vinyl monomer may be contained as an impurity, for example 1 to 5 % by weight referring to polymer (A).

Polymer (A) may bear side chains (b) or side chains (c), and preferably, polymer (A) either bears side chains (b) or side chains (c).

In one embodiment of the present invention, polymers (A) that bear side chains (b) or side chains (c).

In one embodiment of the present invention, polymers (A) have a polydispersity M_w/M_n in the range of from 2.0 to 6.0, preferably from 2.5 to 5.0, more preferably from 2.5 to 4.5.

In one embodiment of the present invention, inventive compositions comprise polymer (A) in a concentration of 0.05 to 20 weight-%, preferably 0.1 to 15 weight-%, more preferably 0.5 to 5 weight-%.

Inventive compositions may comprise impurities that stem from the synthesis of polymer (A), for example, polyalkylene glycol in embodiments of polymers (A) that bear side chains (b) and polymers of vinyl monomer such as polyvinyl acetate in embodiments of polymers (A) that bear side chains (c).

In one embodiment of the present invention, inventive compositions comprise at least one enzyme. Enzymes are identified by polypeptide sequences (also called amino acid sequences herein). The polypeptide sequence specifies the three-dimensional structure including the “active site” of an enzyme which in turn determines the catalytic activity of the same. Polypeptide sequences may be identified by a SEQ ID NO. According to the World Intellectual Property Office (WIPO) Standard ST.25 (1998) the amino acids herein are represented using three-letter code with the first letter as a capital or the corresponding one letter.

Any enzyme according to the invention relates to parent enzymes and/or variant enzymes, both having enzymatic activity. Enzymes having enzymatic activity are enzymatically active or exert enzymatic conversion, meaning that enzymes act on substrates and convert these into products. The term “enzyme” herein excludes inactive variants of an enzyme. A “parent” sequence (of a parent protein or enzyme, also called “parent enzyme”) is the starting sequence for introduction of changes (e.g., by introducing one or more amino acid substitutions, insertions, deletions, or a combination thereof) to the sequence, resulting in “variants” of the parent sequences. The term parent enzyme (or parent sequence) includes wild-type enzymes (sequences) and synthetically generated sequences (enzymes) which are used as starting sequences for introduction of (further) changes.

The term “enzyme variant” or “sequence variant” or “variant enzyme” refers to an enzyme that differs from its parent enzyme in its amino acid sequence to a certain extent. If not indicated otherwise, variant enzyme “having enzymatic activity” means that this variant enzyme has the same type of enzymatic activity as the respective parent enzyme.

In describing the variants of the present invention, the nomenclature described as follows is used:

Amino acid substitutions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by the substituted amino acid. Amino acid deletions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by *. Amino acid insertions are described by providing the original amino acid of the parent enzyme followed by the number of the position within the amino acid sequence, followed by the original amino acid and the additional amino acid. For example, an insertion at position 180 of lysine next to glycine is designated as “Gly180GlyLys” or “G180GK”. In cases where a substitution and an insertion occur at the same position, this may be indicated as S99SD+S99A or in short S99AD. In cases where an amino acid residue identical to the existing amino acid residue is inserted, degeneracy in the nomenclature arises. If for example a glycine is inserted after the glycine in the above example this would be indicated by G180GG. Where different alterations can be introduced at a position, the different alterations are separated by a comma, e.g. “Arg170Tyr, Glu” represents a substitution of arginine at position 170 with tyrosine or glutamic acid. Alternatively, different alterations or optional substitutions may be indicated in brackets, e.g., Arg170[Tyr, Gly] or Arg170{Tyr, Gly}; or in short R170 [Y,G] or R170 {Y, G}; or in long R170Y, R170G.

Enzyme variants may be defined by their sequence identity when compared to a parent enzyme. Sequence identity usually is provided as “% sequence identity” or “% identity”. For calculation of sequence identities, in a first step a sequence alignment has to be produced. According to this invention, a pairwise global alignment has to be produced, meaning that two sequences have to be aligned over their complete length, which is usually produced by using a mathematical approach, called alignment algorithm. According to the invention, the alignment is generated by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453). Preferably, the program “NEEDLE” (The European Molecular Biology Open Software Suite (EMBOSS)) is used for the purposes of the current invention, with using the programs default parameter (gap open=10.0, gap extend=0.5 and matrix=EBLOSUM62).

According to this invention, the following calculation of %-identity applies: %-identity = (identical residues I length of the alignment region which is showing the respective sequence of this invention over its complete length) *100.

According to this invention, enzyme variants may be described as an amino acid sequence which is at least n% identical to the amino acid sequence of the respective parent enzyme with “n” being an integer between 10 and 100. In one embodiment, variant enzymes are at least 70%, at least 75%, at least 80%, at least 81%, at least 82%, at least 83%, at least 84%, at least

85%, at least 86%, at least 87%, at least 88%, at least 89%, at least 90%, at least 91%, at least

92%, at least 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% identical when compared to the full-length amino acid sequence of the parent enzyme, wherein the enzyme variant has enzymatic activity.

“Enzymatic activity” means the catalytic effect exerted by an enzyme, which usually is expressed as units per milligram of enzyme (specific activity) which relates to molecules of substrate transformed per minute per molecule of enzyme (molecular activity). Variant enzymes may have enzymatic activity according to the present invention when said enzyme variants exhibit at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at 10 least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, or 100% of the enzymatic activity of the respective parent enzyme.

In one embodiment, enzyme is selected from hydrolases, preferably from proteases, amylases, lipases, cellulases, and mannanases. In one embodiment of the present invention, inventive compositions comprise

(B) at least one hydrolase, hereinafter also referred to as hydrolase (B), preferably selected from lipases, hereinafter also referred to as lipase (B).

“Lipases”, “lipolytic enzyme”, “lipid esterase”, all refer to enzymes of EC class 3.1.1 (“carboxylic ester hydrolase”). Such a lipase (B) may have lipase activity (or lipolytic activity; triacylglycerol lipase, EC 3.1.1.3), cutinase activity (EC 3.1.1.74; enzymes having cutinase activity may be called cutinase herein), 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.

Commercially available lipase (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).

Suitable lipases (B) include also those that are variants of the above described lipases which have lipolytic activity. Suitable lipase variants include variants with at least 40 to 100% identity when compared to the full length polypeptide sequence of the parent enzyme as disclosed above. In one embodiment lipase variants having lipolytic activity may be at least 40%, at least

45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least

80%, at least 85%, at least 90%, at least 91%, at least 92%, at least 93%, at least 94%, at least

95%, at least 96%, at least 97%, at least 98% or at least 99% identical when compared to the full length polypeptide sequence of the parent enzyme as disclosed above.

Lipases (B) have “lipolytic activity”. The methods for determining lipolytic activity are well-known in the literature (see, e.g., Gupta et al. (2003), Biotechnol. Appl. Biochem. 37, p. 63-71). E.g. the lipase activity may be measured by ester bond hydrolysis in the substrate para-nitrophenyl palmitate (pNP-Palmitate, C:16) and releases pNP which is yellow and can be detected at 405 nm.

In one embodiment, lipase (B) is selected from fungal triacylglycerol lipase (EC class 3.1.1.3). Fungal triacylglycerol lipase may be selected from lipases of Thermomyces lanuginosa. In one embodiment, at least one Thermomyces lanuginosa lipase is selected from triacylglycerol lipase according to amino acids 1-269 of SEQ ID NO: 2 of US5869438 and variants thereof having lipolytic activity.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity which 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 when compared to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising conservative mutations only, which do not pertain the functional domain of amino acids 1- 269 of SEQ ID NO: 2 of US 5,869,438. 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.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the following amino acid substitutions when compared to amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438: T231 R and N233R. Said lipase variants may further comprise one or more of the following amino acid exchanges when compared to amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438: Q4V, V60S, A150G, L227G, P256K.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising at least the amino acid substitutions T231 R, N233R, Q4V, V60S, A150G, L227G, P256K within the polypeptide sequence of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438and 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 US 5,869,438.

Thermomyces lanuginosa lipase may be selected from variants having lipolytic activity comprising the amino acid substitutions T231 R and N233R within amino acids 1-269 of SEQ ID NO: 2 of US5869438 and 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 US 5,869,438.

Thermomyces lanuginosa lipase may be a variant of amino acids 1-269 of SEQ ID NO: 2 of US5869438 having lipolytic activity, wherein the variant of amino acids 1-269 of SEQ ID NO: 2 of US 5,869,438is characterized in containing the amino acid substitutions T231 R and N233R. Said lipase may be called Lipex herein.

In one embodiment of the present invention, a combination of at least two of the foregoing lipases (B) may be used. In one embodiment of the present invention, lipases (B) are included in inventive composition in such an amount that a finished inventive composition has a lipolytic enzyme activity in the range of from 100 to 0.005 Lll/rng, preferably 25 to 0.05 Lll/rng of the composition. A Lipase Unit (LU) is that amount of lipase which produces 1 pmol of titratable fatty acid per minute in a pH stat, under the following conditions: temperature 30° C.; pH=9.0; substrate is an emulsion of 3.3 wt. % of olive oil and 3.3% gum arabic, in the presence of 13 mmol/l Ca²⁺ and 20 mmol/l NaCI in 5 mmol/l Tris-buffer.

In one embodiment of the present invention, inventive compositions comprise (D) at least one protease (D), hereinafter also referred to as protease (D).

In one embodiment, at least one protease (D) is selected from the group of serine endopeptidases (EC 3.4.21), most preferably selected 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 catalytically active site, which forms a covalent adduct with the substrate during the catalytic reaction. A serine protease in the context of the present invention may be selected from the group consisting of chymotrypsin (e.g., EC 3.4.21.1), elastase (e.g., EC 3.4.21.36), elastase (e.g., EC 3.4.21.37 or EC 3.4.21.71), granzyme (e.g., EC 3.4.21.78 or EC 3.4.21.79), kallikrein (e.g., EC 3.4.21.34, EC 3.4.21.35, EC 3.4.21.118, or EC 3.4.21.119,) plasmin (e.g., EC 3.4.21.7), trypsin (e.g., EC 3.4.21.4), thrombin (e.g., EC 3.4.21.5), and subtilisin. Subtilisin is also known as sub- tilopeptidase, e.g., EC 3.4.21.62, the latter hereinafter also being referred to as “subtilisin”. The subtilisin related class of serine proteases shares a common amino acid sequence defining a catalytic triad which distinguishes them from the chymotrypsin related class of serine proteases. Subtilisins and chymotrypsin related serine proteases both have a catalytic triad comprising aspartate, histidine and serine.

Proteases are active proteins exerting “protease activity” or “proteolytic activity”. Proteolytic activity is related to the rate of degradation of protein by a protease or proteolytic enzyme in a defined course of time.

The 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 may 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 substrate. pNA is cleaved from the substrate molecule by proteolytic cleavage, resulting in release of yellow color of free pNA which can be quantified by measuring OD₄o5- Proteolytic activity may be provided in units per gram enzyme. For example, 1 II protease may correspond to the amount of protease which sets free 1 pmol folin-positive amino acids and peptides (as tyrosine) per minute at pH 8.0 and 37°C (casein as substrate).

Proteases of the subtilisin type (EC 3.4.21.62) may be bacterial proteases originating from a microorganism selected from Bacillus, Clostridium, Enterococcus, Geobacillus, Lactobacillus, Lactococcus, Oceanobacillus, Staphylococcus, Streptococcus, or Streptomyces protease, or a Gram-negative bacterial polypeptide such as a Campylobacter, E. coli, Flavobacterium, Fuso- bacterium, Helicobacter, llyobacter, Neisseria, Pseudomonas, Salmonella, and Ureaplasma.

In one aspect of the invention, at least one protease (D) is selected from Bacillus alcalophilus, Bacillus amyloliquefaciens, Bacillus brevis, Bacillus circulans, Bacillus clausii, Bacillus coagu- lans, Bacillus firmus, Bacillus gibsonii, Bacillus lautus, Bacillus lentus, Bacillus licheniformis, Bacillus megaterium, Bacillus pumilus, Bacillus sphaericus, Bacillus stearothermophilus, Bacillus subtilis, or Bacillus thuringiensis protease.

In one embodiment of the present invention, at least one protease (D) is selected from the following: subtilisin from Bacillus amyloliquefaciens BPN' (described by Vasantha et al. (1984) J. Bacteriol. Volume 159, p. 811-819 and JA Wells et al. (1983) in Nucleic Acids Research, Volume 11 , p. 7911-7925); subtilisin from Bacillus licheniformis (subtilisin Carlsberg; disclosed in EL Smith et al. (1968) in J. Biol Chem, Volume 243, pp. 2184-2191 , and Jacobs et al. (1985) in Nucl. Acids Res, Vol 13, p. 8913-8926); subtilisin PB92 (original sequence of the alkaline protease PB92 is described in EP 283075 A2); subtilisin 147 and/or 309 (Esperase®, Savinase®, respectively) as disclosed in WO 89/06279; subtilisin from Bacillus lentus as disclosed in WO 91/02792, such as from Bacillus lentus DSM 5483 or the variants of Bacillus lentus DSM 5483 as described in WO 95/23221 ; subtilisin from Bacillus alcalophilus (DSM 11233) disclosed in DE 10064983; subtilisin from Bacillus gibsonii (DSM 14391) as disclosed in WO 2003/054184; subtilisin from Bacillus sp. (DSM 14390) disclosed in WO 2003/056017; subtilisin from Bacillus sp. (DSM 14392) disclosed in WO 2003/055974; subtilisin from Bacillus gibsonii (DSM 14393) disclosed in WO 2003/054184; 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 application DE 102005028295.4.

Examples of useful proteases in accordance with the present invention comprise the variants described in: WO 92/19729, WO 95/23221 , WO 96/34946, WO 98/20115, WO 98/20116, WO 99/11768, WO 01/44452, WO 02/088340, WO 03/006602, WO 2004/03186, WO 2004/041979, WO 2007/006305, WO 2011/036263, WO 2011/036264, and WO 2011/072099. Suitable examples comprise especially variants of subtilisin protease derived from SEQ ID NO:22 as described in EP 1921147 (which is the sequence of mature alkaline protease from Bacillus lentus DSM 5483) with amino acid substitutions in 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), which have proteolytic activity. In one embodiment, such a protease is not mutated at positions Asp32, His64 and Ser221 (according to BPN’ numbering).

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

At least one protease (D) may be at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and is characterized by comprising one amino acid (according to (a)-(h)) or combinations according to (i) together with the amino acid 101 E, 101 D, 101 N, 101Q, 101A, 101G, or 101S (according to BPN’ numbering). In one embodiment, said protease is characterized by comprising the mutation (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. A protease having a sequence according to SEQ ID NO: 22 as described in EP 1921147 with 101 E may be called Lavergy herein.

In one embodiment, protease according to SEQ ID NO:22 as described in EP 1921147 is characterized by comprising the mutation (according to BPN’ numbering) S3T + V4I + S9R + A15T + V68A + D99S + R101S + A103S + 1104V + N218D, and by having proteolytic activity. Inventive compositions may comprise a combination of at least two proteases, preferably selected from the group of serine endopeptidases (EC 3.4.21), more preferably selected from the group of subtilisin type proteases (EC 3.4.21.62) - all as disclosed above.

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

In the context of the present invention, lipase (B) and/or protease (D) is deemed stable when its enzymatic activity “available in application” equals at least 60% when compared to the initial enzymatic activity before storage. An enzyme may be called stable within this invention if its enzymatic activity available in 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.

Subtracting a% from 100% gives the “loss of enzymatic activity during storage” when compared to the initial enzymatic activity before storage. In one embodiment, an enzyme is stable according to the invention when essentially no loss of enzymatic activity occurs during storage, i.e. loss in enzymatic activity equals 0% when compared to the initial enzymatic activity before storage. Essentially no loss of enzymatic activity within this invention may mean that the loss of enzymatic 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%.

In one embodiment of the present invention, inventive compositions comprise

(C) at least one anionic surfactant, hereinafter also being referred to as anionic surfactant (C).

Examples of anionic surfactants (C) are alkali metal and ammonium salts of Cs-Cis-alkyl sulfates, of Cs-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4- Ci2-alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of Ci2-Ci8-alkylsulfonic acids and of C -Ci8-alkylarylsulfonic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

Further examples of anionic surfactants (C) are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, and ether carboxylates. In a preferred embodiment of the present invention, anionic surfactant (C) is selected from compounds according to general formula (III)

R¹-O(CH₂CH₂O)xi-SO₃M (III) wherein

R¹ n-C -Ci8-alkyl, especially with an even number of carbon atoms, for example n-decyl, n- dodecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl, preferably Cw-Cu-alkyl, and even more preferably n-Ci₂-alkyl, x1 being a number in the range of from 1 to 5, preferably 2 to 4 and even more preferably 3.

M being selected from alkali metals, preferably potassium and even more preferably sodium.

In anionic surfactant (C), x1 may be an average number and therefore n is not necessarily a whole number, while in individual molecules according to formula (III a), x denotes a whole number.

In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of anionic surfactant (C), preferably 5 to 50 % by weight.

Inventive compositions may comprise ingredients other than the aforementioned. Examples are non-ionic surfactants, fragrances, dyestuffs, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.

Preferred inventive compositions may contain one or more non-ionic surfactants.

Preferred non-ionic 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 (APG), hydroxyalkyl mixed ethers and amine oxides. Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III a)

in which the variables are defined as follows:

R² is identical or different and selected from hydrogen and linear Ci-C -alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

R³ is selected from Cs-C22-alkyl, branched or linear, for example n-CsHi₇, n-CioH₂i, n-Ci2H₂5, n-Ci4H₂g, n-Ci6H₃3 or n-C-isHs?,

R⁴ is selected from C C -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

The variables e and f are in the range from zero to 300, where the sum of e and f is at least one, preferably in the range of from 3 to 50. Preferably, e is in the range from 1 to 100 and f is in the range from 0 to 30.

Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (III b)

in which the variables are defined as follows:

R² is identical or different and selected from hydrogen and linear Ci-Co-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl, R⁵ is selected from Ce-C₂o-alkyl, branched or linear, in particular n-CsHi₇, n-CioH₂i, n-Ci₂H₂5, n-CisH₂7, n-CisHsi, n-Ci4H₂g, n-C-ieHss, n-C-isHs?, a is a number in the range from zero to 10, preferably from 1 to 6, b is a number in the range from 1 to 80, preferably from 4 to 20, d is a number in the range from zero to 50, preferably 4 to 25.

The sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.

Compounds of the general formula (Ill a) and (III b) may be block copolymers or random copolymers, preference being given to block copolymers.

Further suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-Ci6-alkyl polyglucosides and branched C8-Ci4-alkyl polyglycosides such as compounds of general average formula (IV) are likewise suitable.

wherein:

R⁶ is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

R⁷ is -(CH₂)₂-R⁶,

G¹ is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose, y1 in the range of from 1.1 to 4, y1 being an average number,

Further examples of non-ionic surfactants are compounds of general formula (V) and (VI)

AO is selected from ethylene oxide, propylene oxide and butylene oxide, EO is ethylene oxide, CH2CH2-O,

R⁸ selected from Cs-Cis-alkyl, branched or linear, and R⁵ is defined as above.

A³O is selected from propylene oxide and butylene oxide, w is a number in the range of from 15 to 70, preferably 30 to 50, w1 and w3 are numbers in the range of from 1 to 5, and w2 is a number in the range of from 13 to 35.

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

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

Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

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

Examples of amine oxide surfactants are compounds of the general formula (VII) R9R10R11_N— >0 (VII) wherein R⁹, R¹⁰, and R¹¹ are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene Cio-C2o-alkylamido moieties. Preferably, R⁹ is selected from Cs-C2o-al- kyl or C2-C4-alkylene Cio-C2o-alkylamido and R¹⁰ and R¹¹ are both methyl.

A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.

In one embodiment of the present invention, inventive compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from non-ionic surfactants, amphoteric surfactants and amine oxide surfactants.

In a preferred embodiment, inventive solid detergent compositions for cleaners and especially those for automatic dishwashing do not contain any anionic surfactant.

Inventive compositions may contain at least one bleaching agent, also referred to as bleach. Bleaching agents may be selected from chlorine bleach and peroxide bleach, and peroxide bleach may be selected from inorganic peroxide bleach and organic peroxide bleach. Preferred are inorganic peroxide bleaches, selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate.

Examples of organic peroxide bleaches are organic percarboxylic acids, especially organic percarboxylic acids.

In inventive compositions, alkali metal percarbonates, especially sodium percarbonates, are preferably used in coated form. Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicate, sodium carbonate, and combinations of at least two of the foregoing, for example combinations of sodium carbonate and sodium sulfate.

Suitable chlorine-containing bleaches are, for example, 1 ,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate. Inventive compositions may comprise, for example, in the range from 3 to 10% by weight of chlorine-containing bleach.

Inventive compositions may comprise one or more bleach catalysts. Bleach catalysts can be selected from bleach-boosting transition metal salts or transition metal complexes such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and also cobalt-, iron-, copper- and ruthe- nium-amine complexes can also be used as bleach catalysts.

Inventive compositions may comprise one or more bleach activators, for example N-methylmor- pholinium-acetonitrile salts (“MMA salts”), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1 ,5-diacetyl-2,2-dioxohexahydro-1 ,3,5-triazine (“DADHT”) or nitrile quats (trimethylammonium acetonitrile salts).

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

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

Examples of dyestuffs 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.

Inventive compositions may contain one or more preservatives or biocides. Biocides and preservatives prevent alterations of inventive liquid detergent compositions due to attacks from microorganisms. Examples of biocides and preservatives are BTA (1 ,2,3-benzotriazole), benzalkonium chlorides, 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”), dichlorodimethylhydantoine (“DCDMH”), bromochlorodimethylhydantoine (“BCDMH”), and dibromodimethylhydantoine (“DBDMH”). Another example of biocides is 2-phe- noxyethanol, especially in combination with BIT or IPBC.

Examples particularly of interest are the following antimicrobial agents and/or preservatives: 4,4’-dichloro 2-hydroxydiphenyl ether (CAS-No. 3380-30-1), further names: 5-chloro-2-(4-chlo- rophenoxy) phenol, Diclosan, DCPP, which is commercially available as a solution of 30 wt% of 4,4’-dichloro 2-hydroxydiphenyl ether in 1 ,2 propyleneglycol under the trade name Tinosan® HP 100; and

2-Phenoxyethanol (CAS-no. 122-99-6, further names: phenoxyethanol, methylphenylglycol, Phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether, Protectol® PE);

2-bromo-2-nitropropane-1 ,3-diol (CAS-No. 52-51-7, further names: 2-bromo-2-nitro-1 ,3-pro- panediol, Bronopol®, Protectol® BN, Myacide AS);

Glutaraldehyde (CAS-No. 111-30-8, further names: 1-5-pentandial, pentane-1 , 5-dial, glutaral, glutardialdehyde, Protectol® GA, Protectol® GA 50, Myacide® GA);

Glyoxal (CAS No. 107-22-2; further names: ethandial, oxylaldehyde, 1 ,2-ethandial, Protectol® GL);

2-butyl-benzo[d]isothiazol-3-one (BBIT, CAS No. 4299-07-4); 2-methyl-2H-isothiazol-3-one (MIT, CAS No 2682-20-4); 2-octyl-2H-isothiazol-3-one (OIT, CAS No. 26530-20-1); 5-Chloro-2- methyl-2H-isothiazol-3-one (CIT, CMIT, CAS No. 26172-55-4); mixtures of 5-chloro-2-methyl- 2H- isothiazol-3-one (CMIT, EINECS 247-500-7) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (Mixture of CMIT/MIT, CAS No. 55965-84-9); 1 ,2-benzisothiazol-3(2H)-one (BIT, CAS No. 2634-33-5);

Hexa-2,4-dienoic acid (Sorbic acid, CAS No. 110-44-1) and its salts, e.g., calcium sorbate, sodium sorbate, Potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate, CAS No. 24634-61-5);

Lactic acid and its salts; especially sodium lactate, L-(+)-lactic acid (CAS No. 79-33-4);

Benzoic acid (CAS No 65-85-0, CAS No. 532-32-1) and salts of benzoic acid, e.g., sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA-benzoate, potassium benzoate;

Salicylic acid and its salts, e.g., calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, TEA salicylate; Benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate (CAS Nos 8001-54-5, 63449-41-2, 91080-29-4, 68989-01-5, 68424-85-1 , 68391-01-5, 61789-y71-7, 85409-22-9);

Didecyldimethylammonium chloride (DDAC, CAS No. 68424-95-3 and CAS No. 7173-51-5); N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine, CAS No. 2372-82-9);

Peracetic acid (CAS No. 79-21-0);

Hydrogen peroxide (CAS No. 7722-84-1);

Biocide or preservative may be added to the inventive composition in a concentration of 0.001 to 10% relative to the total weight of the composition. Preferably, inventive compositions contain 2-phenoxyethanol in a concentration of 0.1 to 2% or 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP) in a concentration of 0.005 to 0.6%.

The invention thus further pertains to a method of preserving an inventive composition against microbial contamination or growth, which method comprises addition of 2-phenoxyethanol.

The invention thus further pertains to a method of providing an antimicrobial effect on textiles after treatment with an inventive composition containing 4,4’-dichloro 2-hydroxydiphenyl ether (DCPP).

Examples of viscosity modifiers are agar-agar, carragene, tragacanth, gum arabic, alginates, pectins, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, for example polyacrylic acid cross-linked with bis-(meth)acrylamide, furthermore silicic acid, clay such as - but not limited to - montmorrilionite, zeolite, dextrin, and casein.

Hydrotropes in the context with the present invention are compounds that facilitate the dissolution of compounds that exhibit limited solubility in water. Examples of hydrotropes are organic solvents such as ethanol, isopropanol, ethylene glycol, 1 ,2-propylene glycol, and further organic solvents that are water-miscible under normal conditions without limitation. Further examples of suitable hydrotropes are the sodium salts of toluene sulfonic acid, of xylene sulfonic acid, and of cumene sulfonic acid.

Examples of polymers other than polymer (A) are especially polyacrylic acid and its respective alkali metal salts, especially its sodium salt. A suitable polymer is in particular polyacrylic acid, preferably with an average molecular weight M_w in the range from 2,000 to 40,000 g/mol. preferably 2,000 to 10,000 g/mol, in particular 3,000 to 8,000 g/mol, each partially or fully neutralized with alkali, especially with sodium. Suitable as well are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. Polyacrylic acid and its respective alkali metal salts may serve as soil anti-redeposition agents.

Further examples of polymers are polyvinylpyrrolidones (PVP). Polyvinylpyrrolidones may serve as dye transfer inhibitors.

Further examples of polymers are polyethylene terephthalates, polyoxyethylene terephthalates, and polyethylene terephthalates that are end-capped with one or two hydrophilic groups per molecule, hydrophilic groups being selected from CF^CF CF SOsNa, CH2CH(CH2-SOsNa)2, and CH₂CH(CH₂SO2Na)CH2-SO3Na.

Examples of buffers are monoethanolamine and N,N,N-triethanolamine.

Examples of defoamers are silicones.

Inventive compositions are not only good in cleaning soiled laundry with respect to organic fatty soil such as oil. Inventive liquid detergent compositions are very useful for removing non- bleachable stains such as, but not limited to stains from red wine, tea, coffee, vegetables, and various fruit juices like berry juices from laundry. They still do not leave residues on the clothes.

A further aspect of the present invention is therefore the use of inventive compositions for laundry care. Laundry care in this context includes laundry cleaning.

In another aspect, inventive compositions are useful for hard surface cleaning. A further aspect of the present invention is therefore the use of inventive compositions for hard surface cleaning.

In the context of the present invention, the term “composition for hard surface cleaning” includes cleaners for home care and for industrial or institutional applications. The term “composition for hard surface cleaning” includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, but not laundry detergent compositions. A special embodiment of compositions for hard surface cleaning are automatic dishwashing compositions. In the context of the present invention, the terms “compositions for hard surface cleaning” and “compositions for hard surface cleaners” are used interchangeably.

In the context of the present invention and unless expressly stated otherwise, percentages in the context of ingredients of laundry detergent compositions are percentages by weight and refer to the total solids content of the respective laundry detergent composition. In the context of the present invention and unless expressly stated otherwise, percentages in the context of ingredients of detergent composition for hard surface cleaners are percentages by weight and refer to the total solids content of the detergent composition for hard surface cleaning.

Inventive compositions when used for automatic dishwashing preferably contain

(E) at least one builder component selected from aminopolycarboxylic acids and preferably their alkali metal salts, in the context of the present invention also referred to as complexing agent (E) or sequestrant (E). In the context of the present invention, the terms sequestrants and chelating agents are used interchangeably.

Examples of sequestrants (E) are alkali metal salts of MGDA (methyl glycine diacetic acid), GLDA (glutamic acid diacetic acid), IDS (iminodisuccinate), EDTA, and polymers with complexing groups like, for example, polyethylenimine in which 20 to 90 mole-% of the N-atoms bear at least one CH₂COO^_ group, and their respective alkali metal salts, especially their sodium salts, for example MGDA-Nas, GLDA-Na4, or IDS-Na4.

Preferred sequestrants are those according to general formula (IX a)

[CH3-CH(COO)-N(CH₂-COO)₂]M3-X2HX2 (IX a) wherein M is selected from ammonium and alkali metal cations, same or different, for example cations of sodium, potassium, and combinations of at least two of the foregoing. Ammonium may be substituted with alkyl but non-substituted ammonium NH₄ ⁺ is preferred. Preferred examples of alkali metal cations are sodium and potassium and combinations of sodium and potassium, and even more preferred in compound according to general formula (II a) all M are the same and they are all Na; and x2 in formula (II a) is in the range of from zero to 1 .0, or (IX b)

[OOC-CH₂CH2-CH(COO)-N(CH2-COO)2]M₄-X3HX3 (IX b) wherein M is as defined above, and x3 in formula (IX b) is in the range of from zero to 2.0, preferably to 1.0, or (IX c)

[OOC-CH₂-CH(COO)]-N-CH(COO)-CH₂-COO]M₄-X4H_X4 (IX c) wherein M is as defined above, and x4 in formula (IX c) is in the range of from zero to 2.0, preferably to 1.0.

In one embodiment of the present invention, said inventive composition contains a combination of at least two of the foregoing, for example a combination of chelating agent according to general formula (IX a) and a chelating agent according to general formula (IX b).

Chelating agents according to the general formulae (IX a) and (IX b) are preferred. Even more preferred are chelating agents according to the general formula (IX a).

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

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

The enantiomeric excess of compound according to general formula (IX a) may be determined by measuring the polarization (polarimetry) or preferably by chromatography, for example by HPLC with a chiral column, for example with one or more cyclodextrins as immobilized phase or with a ligand exchange (Pirkle-brush) concept chiral stationary phase. Preferred is determination of the ee by HPLC with an immobilized optically active amine such as D-penicillamine in the presence of copper(+ll) salt. The enantiomeric excess of compound according to general formula (IX b) salts may be determined by measuring the polarization (polarimetry).

In one embodiment of the present invention, inventive compositions contain in the range of from 0.5 to 50% by weight of sequestrant (E), preferably 1 to 35% by weight, referring to the total solids content.

In order to be suitable as liquid laundry compositions, inventive compositions may be in bulk form or as unit doses, for example in the form of sachets or pouches. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.

In a preferred embodiment of the present invention, inventive compositions are liquid or gel-type at ambient temperature. In another preferred embodiment of the present invention, inventive compositions are solid at ambient temperature, for example powders or tabs.

In one embodiment of the present invention, inventive compositions are liquid or gel-type and have a pH value in the range of from 7 to 9, preferably 7.5 to 8.5. In embodiments where inventive compositions are solid, their pH value may be in the range of from 7.5 to 11 , determined after dissolving 1 g/100 ml in distilled water and at ambient temperature. In embodiments where inventive compositions are used for hard surfaces like tiles, for example bathroom tiles, their pH value may even be acidic, for example from 3 to 6.

In one embodiment of the present invention, inventive compositions are liquid or gel-type and have a total solids content in the range of from 8 to 80%, preferably 10 to 50%, determined by drying under vacuum at 80°C.

Another aspect of the present invention is related to polymers (A), hereinafter also referred to as inventive polymers (A) or simply as polymers (A). Inventive polymers (A) have been described above.

Preferably, inventive polymer (A) bears 3 to 25 alkylene oxide groups per alkoxylated site on a nitrogen atom - thus, -N(AO)_xi - with AO being alkylene oxide selected from EO, PO, BuO and combinations, or -N[(AO)_XI]2 with x1 being in the range of from 3 to 25. In one embodiment of the present invention, the weight ratio of backbone (a) to side chains (b) is in the range of from 5:1 to 1 : 2.

In another embodiment of the present invention, inventive polymer (A) bears side chains (c). Side chains (c) polymerized vinyl monomers selected from vinyl-Ci-C2o carboxylic esters and (meth)acrylic acid and N-vinyl imidazole.

In one embodiment of the present invention, in inventive polymer (A), the weight ratio of backbone to side chains (c) is in the range of from 2:3 to 10:1 , preferably 1 :1 to 5:1.

In embodiments that contain an inventive polymer (A) with side chains (c), a polymer of the respective vinyl monomer may be contained as an impurity, for example 1 to 5 % by weight referring to inventive polymer (A).

In one embodiment of the present invention, inventive polymers (A) have an average molecular weight M_n in the range of from 400 to 20,000 g, preferably 500 to 8,000 g/mol. A preferred average molecular weight M_w is in the range of from 1200 to 20,000 g/mol.

In one embodiment of the present invention, inventive polymers (A) have a polydispersity M_w/M_n in the range of from 2.0 to 6.0, preferably from 2.5 to 5.0, more preferably from 2.5 to 4.5. Inventive polymers have a phosphate content of from 1 to 100 ppm by weight. Said phosphate content may be determined by gravimetry.

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

The term "improved cleaning performance" herein may indicate that polymers (A) provide better, i.e. improved, properties in stain removal under relevant cleaning conditions, when compared to the cleaning performance of a detergent composition lacking polymer (A). In one embodiment, “improved cleaning performance” means that the cleaning performance of a detergent comprising polymer (A) and at least one enzyme, preferably at least one hydrolase (B), especially at least one lipase (B) and/or at least one protease (D), is improved when compared to the cleaning performance of a detergent comprising polymer (A) and no enzyme. In one embodiment, “improved cleaning performance” means that the cleaning performance of a detergent comprising polymer (A) and an enzyme, preferably hydrolase (B), more preferably lipase (B) and/or 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 lipase (B) and/or at least one protease (D) and no polymer (A).

The term "relevant cleaning conditions" herein refers to the conditions, particularly cleaning temperature, time, cleaning mechanics, suds concentration, type of detergent and water hardness, actually used in laundry machines, automatic dish washers or in manual cleaning processes.

Inventive polymers (A) are excellently suited as and particularly for the manufacture of inventive compositions. Inventive polymers (A) show good biodegradability according to OECD.

A further aspect of the present invention relates to a process for making inventive polymers (A), hereinafter also referred to as inventive process or inventive synthesis. The inventive process comprises step (a) and, optionally, one of the steps (P) or step (y), preferably either step (P) or step (Y).

Steps (a), (P) and (y) are described in more detail below. Steps (P) or (y), if applicable, are performed after step (a).

In step (a), aspartic acid is reacted with polyalkylene glycol and in the presence of methane sulfonic acid, thereby forming a polyester. Aspartic acid may be selected from L-aspartic acid, D-aspartic acid, racemic aspartic acid and enantiomerically enriched mixtures of L- and D-aspartic acid, preferably those mixtures with more L- than D-aspartic acid. Enantiomerically pure L-aspartic acid is preferred.

Polyalkylene glycol is selected from addition polymers of ethylene oxide (“EO”), 1 ,2-propylene oxide (“PO”) or 1 ,2-butylene oxide (“BuO”) or combinations of at least two of the aforementioned. Preferably, in such (poly)alkylene oxide, at least 50 mol-% of the alkylene oxide is selected from ethylene oxide, more preferably at least 60 mol-%. In a particularly preferred embodiment, polyalkylene glycol is polyethylene glycol.

In one embodiment of the present invention, the average molecular weight M_n of polyalkylene glycol in step (a) is in the range of from 160 to 5,000 g/mol, determined by GPC.

In one embodiment of the present invention, in step (a), the molar ratio of alcohol groups and carboxylic acid groups is in the range of from 0.7 : 1 .0 to 1.3 to 1.0, preferably from 0.9 : 1.0 to 1 .0 : 0.9, even more preferably 0.95 : 1.0 to 1 .0 : 0.95. The molar amount of alcohol groups is determined by determination of the hydroxyl value of the presentive polyalkylene glycol.

Step (a) is carried out in the presence of methanesulfonic acid. The amount of methanesulfonic acid may be in the range of 0.2 to 1 .5 mol/mol aspartic acid, preferably 0.25 to 0.6 mol/mol aspartic acid. Without wishing to be bound by any theory we assume that methanesulfonic acid is used in the first instance to protonate the amino group on the aspartic acid.

In one embodiment, methanesulfonic acid is combined with a non-oxidizing organic acid, for example formic acid, for example in a molar ratio of from 5:1 to 1 :3. In other embodiments, pure methanesulfonic acid is used as catalyst.

Step (a) may be carried out at temperatures in the range of from 100 to 180°C. In embodiments wherein the respective free acid(s) are used, temperatures in the range of from 120 to 170°C are preferred, more preferred are 130 to 160°C. Especially in embodiments wherein temperatures of 100°C or more are applied it is preferred to ramp up the temperature.

Step (a) may be performed at any pressure, for example from 10 mbar to 10 bar. Preferred are ambient pressure and pressures below, for example 10 to 500 mbar. In the course of step (a), water or an alcohol is formed, for example methanol or ethanol. It is preferred to remove such byproducts, for example by distilling them off. Suitable tools are Dean- Stark apparatuses, distillation bridges, water eliminators, and other apparatuses that may serve for removal of water or alcohols by distillation.

Step (a) may be performed in the absence or presence of a solvent. Suitable solvents are aromatic solvents like toluene, aliphatic hydrocarbons or cycloaliphatic solvents, for example n-decane, cyclohexane, n-heptane and the like. It is preferred, though, to perform step (a) in the absence of a solvent, especially when the reaction mixture is liquid at the reaction temperature.

In one embodiment of the present invention, the duration of step (a) is in the range of from 1 hour to 10 hours, preferably 90 minutes to 4 hours. Overly long reaction times may lead to decomposition of inventive polymer (A) - or backbone (a), as the case may be - and to a deeper colour which is not desirable.

The resultant backbone (a) may be worked up, for example by neutralization of the methanesulfonic acid with sodium hydroxide or an amine, for example N,N,N-triethanolamine or monoethanolamine.

The resultant backbone (a) is a polyester and may be used directly as polymer (A). However, it is preferred to perform at least one of steps (P) and (y):

(P) reacting the polyester from step (a) - also referred to as backbone (a) - with at least one C2-C4-alkylene oxide, or

(Y) reacting the polyester from step (a) with vinyl monomer selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole.

In optional step (P), backbone (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 foregoing, for examples combinations of EO and PO and combinations of EO and BuO, in each case with at least 50% mol-% of EO being more preferred. Preferred are propylene oxide and ethylene oxide, more preferred is solely EO.

In one embodiment of the present invention, the weight ratio of alkylene oxide in step (P) and backbone (a) is in the range of from 1 to 100 up to 1 to 2, preferred are 1 to 40 up to 1 to 3. In one embodiment of the present invention, in step (P) 3 to 25 molecules of alkylene oxide are reacted per N-H function.

Step (P) is preferably carried out in the presence of a catalyst, for example a base or a doublemetal cyanide.

In one embodiment of the present invention, step (P) is carried out in the presence of a base. Suitable bases such as potassium hydroxide, sodium hydroxide, sodium or potassium alkoxides such as potassium methylate (KOCH3), potassium tert-butoxide, sodium ethoxide and sodium methylate (NaOCHs), preferably from 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. Preference is given to the alkali metal hydroxides, preference being given to potassium hydroxide and sodium hydroxide, and to alkali metal alkoxides, particular preference being given to potassium t-butoxide in t-butanol, sodium n-hexanolate in n-hexanol, and to sodium methanolate in n-nonanol. Typical use amounts for the base are from 0.05 to 10% by weight, in particular from 0.5 to 2% by weight, based on the total amount of backbone (a) and C2-C4-alkylene oxide.

No phosphate is preferably used as catalyst.

In one embodiment of the present invention, step (P) is carried out in the presence of a doublemetal cyanide. Double-metal cyanides, hereinafter also referred to as double metal cyanide compounds or DMC compounds, usually comprise at least two different metals, at least one of them being selected from transition metals and the other one being selected from transition metals and alkali earth metals, and furthermore cyanide counterions. Particularly suitable catalysts for the alkoxylation are double-metal cyanide compounds which contain zinc, cobalt or iron or two thereof. Berlin blue, for example, is particularly suitable.

Preference is given to using crystalline DMC compounds. In a preferred embodiment, a crystalline DMC compound of the Zn-Co type which comprises zinc acetate as further metal salt component is used as catalyst. Such compounds crystallize in monoclinic structure and have a platelet-like habit.

In one embodiment of the present invention, the inventive synthesis is carried out in the presence of at least one double-metal cyanide selected from hexacyano cobaltates. Double-metal cyanide compounds can be used as powder, paste or suspension or be moulded to give a moulding, be introduced into mouldings, foams or the like or be applied to mouldings, foams or the like.

Preferably, a DMC catalyst used for step (P), based on backbone (a), is from 5 to 2000 ppm (i.e. mg of catalyst per kg of product), 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 mass-ppm (parts per million) of backbone (a)

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

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

In one embodiment of the present invention, step (P) is carried out once per synthesis of inventive polymer (A). In an alternative embodiment, step (y) is carried out several time, for example up to four times per synthesis of an inventive polymer (A), for example with the same or preferably with different C2-C4-alkylene oxides. It is, for example, possible to subject backbone (a) to a first alkoxylation (pi) with ethylene oxide and to subject the product from step (pi) to a second alkoxylation (P2) , for example with propylene oxide.

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

In one embodiment of the present invention, the reaction time of step (P) is generally in the range of from 0.5 to 12 hours.

Examples of suitable organic solvents for embodiment (ii) of step (P) are nonpolar and polar aprotic organic solvents. Examples of particularly suitable nonpolar aprotic solvents include aliphatic and aromatic hydrocarbons such as hexane, cyclohexane, toluene and xylene. Examples of particularly suitable polar aprotic solvents are ethers, in particular cyclic ethers such as tetrahydrofuran and 1 ,4-dioxane, furthermore N,N-dialkylamides such as dimethylformamide and dimethylacetamide, and N-alkyllactams such as N-methylpyrrolidone. It is as well possible to use mixtures of at least two of the above organic solvents. Preferred organic solvents are xylene and toluene.

In embodiment (ii), the solution obtained in the first step, before or after addition of catalyst and solvent, is dewatered before being subjected to alkylene oxide, said water removal advantageously being done by removing the water at a temperature in the range of from 120 to 180°C, preferably supported by a stream of nitrogen. The subsequent reaction with alkylene oxide may be effected as in embodiment (i). In embodiment (i), inventive polymer (A) is obtained directly in bulk and may be dissolved in water, if desired. In embodiment (ii), for work-up organic solvent is typically replaced by water. Inventive polymer (A) according to the invention may alternatively be isolated in bulk.

An - optional - step of work-up may include the deactivation of catalyst used in step (P), in the case of basic catalysts by neutralization.

In optional step (y), backbone (a) is reacted with vinyl monomer selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole. Step (y) is preferably carried out as a free-radical polymerization.

The optional step (y) may be carried out with or without a solvent. Depending on the vinyl monomers), step (y) is preferably carried out in water or, instead of water, an organic solvent or a mixture of water and one or more organic solvents such as, for example, alcohols and ketones, but also dipolar-aprotic, water-miscible solvents such as, e.g., DMSO, DMF or NMP can be used. Further suitable solvents are diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol. Preferred solvents are those that are - or may be - used as components of liquid laundry detergents.

In one embodiment of the present invention, step (y) is carried out at a temperature in the range from 60 to 120°C, preferably 65 to 100°C, very particularly preferably at 70 to 90°C.

In one embodiment of the present invention, step (y) is carried out at atmospheric pressure. In another embodiment, the process according to the invention is carried out at a pressure in the range from 1.2 to 20 bar.

In a preferred variant, backbone (a) is introduced and then vinyl monomer(s) is/are added in the presence of free-radical starter. In a particularly preferred variant, firstly backbone (a) is introduced and heated to 60 to 120°C. Then, a part vinyl monomers is added, preferably continuously, together with a free-radical starter. After the reaction with backbone (a) has subsided, further vinyl monomer(s) is/are added, preferably continuously, together with further free-radical starter.

Examples of suitable free-radical starters are: azodiisobutyronitrile (AIBN), (hydro)peroxides such as, e.g., benzoyl peroxide, tert.-butyl peroxide and peresters such as tert.butylperoxy-2- ethylhexanoate. In aqueous embodiments of step (y), particular preference is given to using sodium peroxodisulfate and tert-butyl hydroperoxide or hydrogen peroxide, which can be used in the standard commercial concentrations and preparations, e.g., as aqueous or alcoholic solutions. In another embodiment, a mixture of H2O2 with iron(ll) salts can be used. The hydrogen peroxide here is preferably used in the form of aqueous solutions. Free-radical initiators are preferably used in amounts of from 0.001 to 30 mol%, preferably from 0.1 to 25 mol% and in particular from 1 to 20 mol%, in each case based on the sum of molar amounts of vinyl monomers) and backbone (a).

In one embodiment of the present invention, the duration of step (y) is in the range of from 30 minutes to 24 hours, starting from the combination of at three components - backbone (a), at least one vinyl monomer and free-radical starter.

In one embodiment of the present invention, following completion of the addition of vinyl monomers) and free-radical starter, further free-radical starter can be added, particularly preferably in a continuous feed process. Consequently, the content of vinyl monomer(s) in inventive polymer (A) can be reduced.

In one embodiment of the present invention, after polymerization has ended, bleaching can be carried out, for example with peroxide such as H2O2.

In one embodiment of the present invention, when the polymerization is completed, residual vinyl monomer can be removed, for example by stripping with nitrogen or by steam distillation.

By carrying out the inventive process, inventive polymers (A) are obtained.

The present invention is further illustrated by working examples.

General remarks: Reactions were carried out under nitrogen atmosphere unless expressly noted otherwise. Percentages refer to % by weight unless expressly stated otherwise.

GPC was carried out with THF as mobile phase, with linear PMMA as internal standard and pol- ystyrene-1 ,3-divinylbenzene gel as stationary phase

Hydroxyl values (OH values) were determined according to DIN 53240 (2013).

Amine values were determined according to ASTM D2074-07.

The Hazen colour number was determined according to DIN ISO 6271 , ASTM D 1209, with spectrophotometric detection. (2° norm observer, normal light, layer thickness 11 mm, against distilled water). rpm: revolutions per minute. Nl: norm liter, volume determined at ambient pressure and 23°C

I. Syntheses of inventive polymers (A)

1.1 Syntheses of backbones (a), general procedure step (a)

A 2-liter flask equipped with stirrer and distillation head, or a 2-I flask as part of a rotary evaporator set-up was charged with 1 mol of polyalkylene glycol according to Table 1. An amount of 1 mol L-aspartic acid was added, followed by 0.2 to 0.4 mol of methanesulfonic acid - and additional catalyst, if applicable - according to Table 1. The resulting mixture was heated to 165°C at ambient pressure for 45 minutes. It was observed that the aspartic acid melted. Then, the pressure was reduced step-wisely, first to 600 mbar and then to 150 mbar, over 45 minutes.

Water cleaved off in the course of the polycondensation was collected in a condenser. After 2 to 3.75 hours at 150 mbar, see Table 1, the pressure was further reduced to 25 mbar and heating was continued for another 30 minutes. Then, the reaction mixed was cooled to ambient temperature, and exposed to air. ethanolamine or triethanolamine were added to adjust the pH value to 5.5, determined in a 10% by weight aqueous solution. Backbones (a) were obtained as reddish products.

Further details are summarized in Table 1.

Table 1: synthesis conditions

AO: alkylene oxide in polyalkylene oxide, EO, PO: vide supra. Percentages are mol-% MSA: methanesulfonic acid further catalyst: if applicable

Table 1 (continued): Properties of backbones

1.2 Syntheses of inventive polymers, general procedure step (P)

A 3.5-liter steel autoclave was charged with 300 g backbone (a) according to Table 2 and 4 g aqueous KOH and then heated to 100 °C. Then, 60 g of AO were dosed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, AO according to Table 2 were dosed into the autoclave within 3.5 hours. The reaction mixture was stirred at 100 °C for further 90 minutes. After that, the mixture was removed from the autoclave and residual AO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. The respective inventive polymer (A) was obtained as a yellow viscous liquid or paste.

Table 2: Synthesis conditions

1.3 Syntheses of inventive polymers, general procedure step (y)

A 2.5-I steel vessel equipped with a stainless steel anchor stirrer and two additional necks for gas inlets was charged with 600 g of backbone (a) according to Table 3 and heated to 90°C under stirring. The vinyl monomer(s) according to Table 3 were added over a period of 4 hours and 30 minutes. Simultaneously, addition of a 26 wt.-% solution of initiator tert-butylperoxy-2- ethylhexanoate in tripropylene glycol was commenced. After 5 hours 15 minutes, addition of the initiator was completed. Then, the temperature was raised to 105°C and stirring was continued for 90 minutes. Then, the temperature was raised to 115°C, and any volatile compounds were stripped off with nitrogen, 6 Nl ISh/h over 90 minutes, followed by colling down to 60°C and reduced pressure of 40 mbar. Inventive polymers (A) were obtained. Table 3: synthesis conditions

VM: vinyl monomer, VAc: vinyl acetate, VProp: vinyl propionate

VM2:if applicable Table 3 (continued): properties of inventive polymers

n.d.: not determined II. Manufacture of inventive laundry detergent compositions

The primary wash performance of inventive polymers was tested in the washing machine preparing wash solutions using 15 liter water of 14°dH hardness (2.5 mmol/L; Ca:Mg:HCOs 4:1 :8) containing 3.0 g/L of the liquid test detergent L.1 , see composition in Table 4.1 or 4.2, and 2.0% of an inventive polymer (A) according to Tables 1 to 3.

Table 3.1 : Ingredients of base mixture L.1 for a liquid detergent formulation

Table 3.2: Ingredients of base mixture L.2 for a liquid detergent formulation

Anti greying tests were also executed in a launderometer with 1-1 beakers (LP2 type from SDL Atlas, Inc.). One wash cycle (60 min.) was run at 25°C containing the wash-solution (0.25 L) together with one multi-stain monitor MSM1 and MSM2 each and a cotton ballast fabric of 2.5 g (fabric to liquor ratio of 1 :10). After the 1 cycle, the multi stain monitor was rinsed in water, followed by drying at ambient room temperature overnight. The multi-stain monitors MSM1 and MSM2 (Table 4) contain respectively 8 and 4 standardized soiled fabrics, of respectively 5.0 x 5.0 cm and 4.5x4.5 cm size and stitched on two sides to a polyester carrier.

Table 4. Multi-stain monitors for the washing machine tests

MSM1 (circular stains, 5 cm diameter):

CFT C-S-10: butterfat with colorant on cotton

CFT C-S-62: lard, colored on cotton

CFT C-S-78: soybean oil with pigment on cotton

EMPA 112: cocoa on cotton

EMPA 141/1 : lipstick on cotton

EMPA 125: soiling on cotton fabric, sensitive to surfactants as well as to lipases wfk20D: pigment and sebum-type fat on polyester/cotton mixed fabric CFT C-S-70: chocolate/mousse cream on cotton

MSM2:

CFT C-S-10: butterfat with colorant on cotton

CFT C-S-62: lard, colored on cotton

CFT C-S-61 : beef fat, colored on cotton

CFT PC-S-04: Saturated with colored olive oil on Polyester/Cotton (65/35). The total level of cleaning was evaluated using color measurements. Reflectance values of the stains on the monitors were measured using a sphere reflectance spectrometer (SF 500 type from Datacolor, USA, wavelength range 360-700nm, optical geometry d/8°) with a UV cutoff filter at 460 nm. In this case, with the aid of the CIE-Lab color space classification, the brightness L *, the value a * on the red - green color axis and the b * value on the yellow - blue color axis, were measured before and after washing and averaged for the respective stains of the monitor. The change of the color value (Delta E, AE) value, defined and calculated automatically by the evaluation color tools on the following formula,

is a measure of the achieved cleaning effect. All experiments were repeated three times to provide a representative average number.

Higher Delta E values show better cleaning. For each stain, a difference of 1 unit can be detected visually by a skilled person. A non-expert can visually detect 2 units easily. The AE values of the formulations for the 4, 8 and 11 stains of correspondingly MSM1 and MSM2 and for some selected single stains are shown in Tables 4.1 and 4.2.

able 4.1. Results of launder-O-meter test fabric monitor cleaning performance Anti-greying

able 4.2. Results of launder-O-meter test fabric monitor cleaning performance Anti-greying

ES: Polyester, BW: cotton

III. Biodegradation tests

General: the tests were carried out in accordance with the OECD Guidelines. According to the OECD guidelines a test is valid if:

1. The reference reaches 60% within 14 days.

2. The difference of the extremes of the test replicates by the end of the test is less than 20%.

3. Oxygen uptake of inoculum blank is 20 to 30 mg O2/I and must not be greater than 60 mg O2/I.

4. The pH value measured at the end of the test must be between 6 and 8.5.

Description of the test method used in the context of the present invention: Biodegradation in sewage was tested in triplicate using the OECD 301 F manometric respirometry method. OECD 301 F is an aerobic test that measures biodegradation of a sewage sample by measuring the consumption of oxygen. To a measured volume of sewage, 100 mg/L test substance, which is the nominal sole source of carbon, was added along with the inoculum (aerated sludge taken from the municipal sewage treatment plant, Mannheim, Germany). This sludge was stirred in a closed flask at a 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. Carbon dioxide evolved was absorbed in a solution of sodium hydroxide. Nitrification inhibitors were added to the flask to prevent consumption of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by a blank inoculum run in parallel) is expressed as a percentage of ThOD (theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control glucose/glutamic acid is run along with the test samples for each cabinet as reference.

Calculations:

Theoretical oxygen demand: Amount of O2 required to oxidize a compound to its final oxidation products. This is calculated using the elemental analysis data. % Biodegradation

Experimental O2 uptake x 100 and divided by the theoretical oxygen demand

The results of biodegradability tests are summarized in Tables 1 - backbones - and Table 3.

In each test, the reference had a biodegradability of more than 60%.

Claims

44 Patent claims

1. Phosphate-free detergent composition comprising

(A) at least one polymer comprising

(a) a backbone that is based on a polyester with an average molecular weight M_n in the range of from 1 ,200 to 25,000 g and that is formed from aspartic acid and polyalkylene glycol in which alkylene is selected from ethylene, 1 ,2-propylene and 1 ,2- butylene, and wherein polymer (A) comprises side chains selected from

(b) (poly)alkylene oxide chains on N-atoms of aspartic acid, and

(c) polymerized vinyl monomers selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole,

(B) at least one hydrolase.

2. Composition according to claim 1 wherein polyalkylene glycol in step (a) has an average molecular weight M_n in the range of from 160 to 5,000 g/mol, determined by GPC.

3. Composition according to claim 1 or 2 wherein the (poly)alkylene oxide side chains mainly comprise ethylene oxide units.

4. Composition according to any of the preceding claims wherein in backbone (a) at least 50 mol-% of the alkylene oxide units are ethylene oxide.

5. Composition according to any of the preceding claims wherein the molar ratio of aspartic acid and polyalkylene glycol monocarboxylic acid is in the range of from 0.95:1 to 1.05:1.

6. Composition according to claim 6 wherein said hydrolyse (B) is a lipase (B) that is selected from triacylglycerol lipases (EC 3.1.1.3).

7. Use of a composition according to any of the preceding claims for laundry care. 45

8. Polymer (A) comprising

(a) a backbone that is based on a polyester with an average molecular weight M_n in the range of from 400 to 15,000 g and that is formed from aspartic acid and polyalkylene glycol in which alkylene is selected from ethylene, 1,2-propylene and 1,2-butylene, which at least 50 mol-% of the alkylene units are CH2CH2, and wherein polymer (A) comprises side chains selected from

(b) (poly)alkylene oxide chains on N-atoms of said aspartic acid, and,

(c) polymerized vinyl monomers selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole, wherein polymer (A) has a phosphate content of from 1 to 100 ppm by weight.

9. Polymer according to claim 8 wherein in backbone (a) at least 50 mol-% of the alkylene oxide units are ethylene oxide.

10. Polymer according to claim 8 or 9 wherein polyalkylene glycol in backbone (a) has an average molecular weight M_n in the range of from 160 to 5,000 g/mol, determined by GPC.

11. Composition according to any of claims 8 to 10 wherein the (poly)alkylene oxide side chains mainly comprise ethylene oxide units.

12. Process for making polymers according to any of claims 8 to 11 comprising the steps of (a) reacting aspartic acid with polyalkylene glycol and in the presence of methane sulfonic acid, thereby forming a polyester, and, optionally,

(P) reacting the polyester from step (a) with at least one C2-C4- alkylene oxide, or

(y) with vinyl monomer selected from vinyl-Ci-C2o carboxylic esters, (meth)acrylic acid, N-vinyl pyrrolidone and N-vinyl imidazole wherein no phosphate is deliberately added in either of the steps (a) to (y).

13. Process according to claim 12 wherein, in step (a), the molar ratio of alcohol groups and carboxylic acid groups is in the range of from 0.7 : 1.0 to 1.3 to 1.0. 46

14. Method of improving the cleaning performance of a liquid detergent composition, by adding a polymer (A) according to any of claims 8 to 11 to a detergent composition that comprises at least one lipase and/or at least one protease.

15. Method of preserving a composition according to any of claims 1 to 6 against microbial contamination or microbial growth, which method comprises addition of 2-phenoxyethanol.

16. Method of providing an antimicrobial effect on textiles after treatment with a composition according to any of claims 1 to 6 containing 4,4’-dichloro 2-hydroxydiphenyl ether