WO2025223955A1

WO2025223955A1 - Method for producing polyaspartic acid, polyaspartic acid and its use

Info

Publication number: WO2025223955A1
Application number: PCT/EP2025/060478
Authority: WO
Inventors: Christian Schade; Marcel WALASCHEK; Swati DE; Roland Ettl
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2024-04-25
Filing date: 2025-04-16
Publication date: 2025-10-30
Anticipated expiration: 2026-10-25

Abstract

The present invention relates to a method for producing polyaspartic acid (PAA) including a step of treating the polyaspartic acid with at least one agent having oxidizing properties, to polyaspartic acid obtainable in such a manner, a polyaspartic acid of low colour and odour exhibiting a high stability against colouration, and also to the use of such polyaspartic acids.

Description

Method for producing polyaspartic acid, polyaspartic acid and its use

Due to the climate change, one of the most important targets of the detergent and cleaning (D&C) industry today is to significantly lower the CO2 emission per wash, by improving e.g. cold water conditions by improving the cleaning efficiency at low temperatures of below 40, 30 or 20 or even colder, to lower the amounts of chemicals employed per wash, increasing the weight-efficiency of the cleaning technologies, reducing the amount of water per wash, introducing bio-derived components etc. Hence, one important target of the D&C industry is the need to improve the sustainability of the cleaning formulations by improving efficiency, especially also at lower temperatures, needing less water (especially also in the laundry and dish wash formulations) and to avoid the accumulation of non-degradable compounds in the ecosystem. Such reduction in CO2-emision or the desire to improve the “footprint” of any product is of high and even further rising interest in the industry and with the consumers, be it in terms of its origin like being from natural or renewable resources, or - all compared to previous products - its production in terms of production efficiency and thus reduced usage of energy, its efficiency in usage such as reduced amounts for the same performance or higher performance at the same amount levels used, its persistence in the natural environment upon and/or after its usage such as bio-degradation.

As a result of these trends, there is a strong need for new biodegradable cleaning additives that provide at least comparable cleaning properties and a reduction in the CO2-footprint by being bioderived, bio-degradable or even both. The materials should preferably exhibit good primary cleaning activity, soil removal for oily/fatty and particulate stains and/or should lead to improved white-ness maintenance, thus minimizing also the amount of suspended and emulsified oily/fatty and particulate soil from redepositing on the surfaces of the textiles or hard surfaces, etc.

Hence, one need resides in the provision of compounds being bio-degradable and still having at least the same performance as already known but not bio-degradable compounds, such biodegradation as measured under de-fined conditions within 28 days as to be required by many users especially in the field of detergents, and as being a future requirement by applicable legislation in several countries and regions of the world.

The preparation of polyaspartic acid and salts thereof is generally known since many years. For example, PAA may be produced by acid-catalyzed thermal polycondensation of aspartic acid to polyaspartimide and subsequent alkaline hydrolysis of the polyaspartimide. The acidic catalysts used are, for example, mineral acids such as phosphoric acid, phosphorous acid, sulfuric acid and sulfurous acid. It is also possible to use organic acids such as methanesulfonic acid or amidosulfonic acid. Phosphoric acid has proven to be particularly suitable as a moderately strong and non-oxidative acid. Methanesulfonic acid (MSA) is also a suitable catalyst due to its non- oxidative effect. Preferably, acids such as phosphoric acid serve not only as catalyst but also as solvent. The advantage of a well-controlled polycondensation, when phosphoric acid is catalyst and solvent at the same time, is set against the disadvantage of a necessary product purification. The acid has to be removed by washing and, for reasons of cost, should be laboriously recovered. The alternative would be the use of only small amounts of catalyst. If, however, only small amounts of the acidic catalyst (1 to 25 mol%, based on the amount of aspartic acid used) are used, this results during the condensation in highly viscous to very hard condensation phases which tend to become caked, which in stirring apparatuses or kneaders can no longer be stirred or kneaded. The consequence is that either the condensation has to be stopped or at least interrupted in order to break up again and to comminute baked solid polycondensate. Only then can the polycondensation be continued.

For instance, US 5457176 A describes the thermal polycondensation of aspartic acid using catalytic amounts of phosphoric acid or methanesulfonic acid. In both examples, the polycondensation is interrupted, the solid intermediate laboriously isolated and comminuted and the comminuted intermediate is fed back to the reaction vessel to complete the condensation.

A similar process is described in DE 4023463 A1 , where phosphoric acid is used as catalyst in the condensation of aspartic acid and the resulting reaction product has to be mechanically comminuted in a second stage.

The use of PAA in various applications as addition to or a partial or complete replacement for polycarboxylate-polymers, and here especially for the poor to non-biodegradable polycacrylic acids is also well documented:

Polymers of carboxyl group containing monomers and obtainable by radical polymerization have been an important constituent of phosphate-containing and phosphate-free automatic dishwashing detergents (ADW) for many years. As a result of their soil-dispersing and filminhibiting effect, they make for example a considerable contribution to the cleaning and clear rinse performance of the machine dishwashing detergents. Homopolymers and copolymers of acrylic acid are often used for this purpose.

A disadvantage of these polymers of carboxyl group containing monomers obtainable by radical polymerization is that they are not biodegradable under aerobic conditions, as prevail e.g. in a communal sewage plant.

On account of increasing environmental awareness, the demand for biodegradable polymeric alternatives to the polycarboxylates based on acrylic acid is therefore growing. However, commercially available biodegradable polymers such as, for example, polyaspartic acid or carboxymethylated inulin have only gained acceptance in commercial terms with difficulty. The reasons are manifold: inadequate effect in the specific application, excessively high costs on account of complex production processes and/or expensive feed materials.

Polyaspartic acid-polymers are well known for such applications, and are especially suitable as they exhibit a very high biodegradation and can be derived from natural sources.

Thus, polyaspartic acid-polymers are exceptionally well-suited for applications from which such polymers will be at least partially get in contact with nature or will be even partially or fully released or even brought onto the environment. Hence, their use in cleaning compositions, agrochemical compositions and the like is highly desirable due to their ready biodegradation.

Thus, many publications on their use are know; an arbitrary selection is shown hereinafter:

WO 2011/001170 describes cleaning compositions for machine dishwashing, comprising polyaspartic acid, a liquid nonionic surfactant and at least one solid nonionic surfactant. WO 2015/036325 describes the use of modified polyaspartic acids in dishwashing detergents, in particular as dispersants, film inhibitors and spot inhibitors. The invention also relates to dishwashing detergent compositions containing modified polyaspartic acids.

WO 2015/197378 claims dishwashing detergents with low film formation on glass containing

(A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA), and salts thereof,

(B) at least one graft copolymer composed of

(a) at least one graft base selected from monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of

(b) at least one ethylenically unsaturated mono- or dicarboxylic acid and

(c) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, and

(C) at least one inorganic peroxide compound selected from sodium peroxodisulfate, sodium perborate and sodium percarbonate.

WO 2015/197379 claims dishwashing detergents with low film formation on glass containing

(A) at least one compound selected from methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA) and salts thereof,

(B) at least one graft copolymer composed of

(a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of

(b) at least one ethylenically unsaturated mono- or dicarboxylic acid and

(c) at least one compound of the general formula (I), where the variables are defined as follows:

R1 is selected from methyl and hydrogen,

A1 is selected from C2-C4-alkylene,

R2 are identical or different and selected from C1-C4- alkyl,

X- is selected from halide, mono-01 -C4-alkyl sulfate and sulfate.

EP3788125 discloses the combined use of

(a1) at least one of polyaspartic acid or modified polyaspartic acid or salts thereof, wherein the modified polyaspartic acid is obtainable by polycondensation of

(i) 50 to 99 mol% of aspartic acid and

(ii) 1 to 50 mol% of at least one carboxyl-containing compound different from aspartic acid and subsequent hydrolysis of the co-condensates with the addition of a base, and

(a2) at least one graft copolymer composed of

(a21) at least one graft base selected from oligosaccharides and polysaccharides, and side chains obtainable by grafting on of

(a22) at least one ethylenically unsaturated mono- or dicarboxylic acid and

(a23) at least one ethylenically unsaturated N-containing monomer with a permanent cationic charge, wherein the weight ratio of (a1) : (a2) is from 20 : 1 to 1 : 12 as film inhibiting additives in dishwashing detergent formulations, preferably in automatic dishwashing detergent formulations.

Due to the process of production, which usually involves a high and prolonged exposure to high temperatures, the resulting polymers suffer from that process in that they typically exhibit an intense colouring and odour.

Such coloured, odorous polymers however are not desired for incorporation into many applications, and especially not into cleaning compositions, as they would colour the products with their typically brown colour and thus destroy the “clean and fresh” appearance such compositions shall have to be appealable to the consumers.

Thus, many attempts have been published to reduce the colour or the odour:

EP725099A1 discloses a method for decolouring or for preventing or inhibiting colouring of a water-soluble polyamino acid or salt prepd. by thermal polymerisation, comprises: (i) adding a sulphite or hydrogen sulphite; the method is said to effectively prevent colouring during storage of polyamino acids prepd. by thermal polymerisation. Sulphite is used as 0.05-10 wt.% based on the polyamino acid (salt); the water-soluble polyamino acid is polyaspartic acid; and the sulphite is Li, Na, K or ammonium sulphite or Na or K hydrogen sulphite. The polymers are to be used in cosmetic, toiletry and detergent compsitions.

The treatment however is done at very high pH in a sodium hydroxide-solution; a step of treating the polymer under oxidizing conditions is not present.

JP09003201 A discloses a method comprising the decolouring of a water-soluble polyaspartic acid or its salt with peroxodisulphate, peroxoborate, dithionite, sulphurous acid hydrogen salt, disulphite and/or an organic peroxide and/or an organic peroxide. The amount of the decolouring agent is 0.001-0.2 pts. wt. based on pt. wt. of a water-soluble polyaspartic acid. Thermally produced polysuccinic acid imide was hydrolysed, the solution thereof was adjusted to a pH value of 9-10 to give an aq. solution of sodium polyaspartate, which was heated to 55 degree C with then dropwise addition of an aq. solution of 10 wt. % sodium peroxodisulphate, and then further reacted at 55 degree C for 1 hour to decolorize the sodium polyaspartate, the 30 wt.%aq. solution having a colour tone of 9 by a Gardner colour difference meter.

JP09003202 A claims the sodium polyaspartate resulting from JP09003201 A.

No stabilization step is disclosed. The colour obtained is an improvement over the produced polysuccinnimid but not sufficient for many applications.

US5496922 A discloses a process for producing polyaspartic acid salt by first producing polysuccinimide by thermal condensation of 1- aspartic acid in the presence of 15 wt% ofphosphoric acid catalyst and drying at 250 °C over 2,5 hours to a resulting polysuccinimide being dark red brown in colour. It was finely ground and then hydrolysed in concentrated NaOH- solution having a pH of close to 10, the aq. solution being clear but dark red brown in colour, whereas another sample was treated with a 30.2 wt% hydrogen peroxide in water over 24 hours at ambient room temperature, the resulting polysuccinimide particles being said to be very light tan in colour .

No similar treatment of polyaspartic acid salt is disclosed.

US5610264 A discloses process for production of a polyaspartate salt comprising also a method of purifying poly-succinimide from remaining sodium bisulphite (which was used for the polymerization reaction), thereafter hydrolyzing to polyaspartic acid salt and adding hydrogen peroxide to the solution of the salt of polyaspartic acid to reduce colour.

However, such treatment is not very long lasting, as the colour will darken again readily after such treatment.

WO1 994003526 A1 discloses a method for decolourising polymers of aspartic acid prepared by thermal condensation or for decolourising amine copolymers of aspartic acid prepared by thermal condensation, comprising reacting an aq. solution of the polymer or copolymer with a decolourising agent, selected from hypochlorite, chlorine, chlorine dioxide, hydrogenperoxide , a peroxydicarbonate or ozone. For example, a 30% aq. solution of sodium polyaspartate at pH 10 was treated with a 5.25 % soln, of sodium hypochlorite; the colour thereby changing from a light tan to a “straw coloured liquid”.

CN 108085689 A discloses a method of decolorization polyaspartic acid using hydrogen peroxide in methanolic solution.

Methanol solutions are not suitable for commercial-scale production as the toxic methanol has to be removed completely, thus being too expensive and dangerous.

CN 109679092 discloses a method of decolorization polyaspartic acid using activated carbon, silica, aluminum sulfate as decolorizing agent.

Such process involves the handling and filtering of large amounts of suspensions, with the viscosity increasing with higher polymer content; hence such process is not suitable for large- scale production due to cost.

JP11147953 A discloses a method of decolorization polyaspartic acid using activated carbon, as decolorizing agent.

EP 737704 A1 discloses a method of decolorization using activated hydrogen for treating nitrogen-containing polymers with succinyl repeat units. Polyaspartic acids are not treated. It thus does not disclose the decolorization of polyaspartartic acid or their salts.

JP11147954 A discloses a process of decolorization of polysuccinimid and therafter hydrolyzing the polysuccinimide to polyaspartic acid. Polyaspartic acids are not treated. It thus does not disclose the decolorization of polyaspartartic acid or their salts.

Hence, many disclosures have already discussed the colour problem of polyaspartic acid salts, which stems from their production process, as they are produced from aspartic acid under very high temperature conditions of typically 200 to 250 °C for at least some hours. Colour formation is the natural result of such harsh reaction conditions.

As a consequence, the need to lower the colour has been pursued in various ways.

However, no disclosure has so far focused on the lowering of the colour, the lowering of the odour and - at the same time - on ways how to stabilize such low colour and odour over prolonged storage.

Thus, there was still the need of providing polyaspartic acid and their salts having a low colour, preferably also a low odour, and at the same time an improved stability of odour and colour over prolonged time of storage.

Hence, this present invention relates to i) a method for producing polyaspartic acid and their salts, such method including a step of treating the polyaspartic acid (salt) with at least one agent having oxidizing properties under low pH-conditions, ii) polyaspartic acid and their salts obtainable by such method, iii) a polyaspartic acid (salt) of low colour and odour exhibiting a high stability against colouration, and iv) the use of such polyaspartic acid (salt) in various applications, especially in cleaning compositions, paper industry, agricultural formulations.

This technical object has been achieved by the present invention as described herein and defined in the claims.

Definitions

Throughout this specification and the claims which follow, unless the context requires otherwise, the word “comprise”, and variations such as “comprises” and “comprising”, will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integer or step. When used herein the term “comprising” can be substituted with the term “containing” or “including” or sometimes when used herein with the term “having”.

When used herein, “consisting of" excludes any element, step, or ingredient not specified in the claim element. When used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim.

In each instance herein any of the terms "comprising", "consisting essentially of" and "consisting of" may be replaced with either of the other two terms. “Comprising” may be replaced in a preferred embodiment with "consisting essentially of" and both may be replaced by "consisting of' in an even more preferred embodiment.

The compositions of the present disclosure can “comprise” (i.e. contain other ingredients), “consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or “consist of” (i.e. contain only the mentioned ingredients and in addition may contain only impurities not avoidable in an technical environment, preferably only the ingredients) the components of the present disclosure. Similarly, the terms “substantially free of....” or“ substantially free from...” or “(containing/comprising) essentially no....” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1 %, or even less than 0.1%, or even more less than 0.01%, or even 0%, by weight of the composition.

Generally, as used herein, the term “obtainable by” means that corresponding products do not necessarily have to be produced (i.e. obtained) by the corresponding method or process described in the respective specific context, but also products are comprised which exhibit all features of a product produced (obtained) by said corresponding method or process, wherein said products were actually not produced (obtained) by such method or process. However, the term “obtainable by” also comprises the more limiting term “obtained by”, i.e. products which were actually produced (obtained) by a method or process described in the respective specific context.

All such terms not specifically defined have their ordinary meaning as known in the field of polymer chemistry.

As used herein, the articles “a” and “an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms “include(s)” and “including” are meant to be non-limiting, and thus encompass more than the specific item mentioned after those words.

The term “about” as used herein encompasses the exact number “X” mentioned as e.g. “about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations. Of course if the value X given itself is already “100%” (such as for purity etc.) then the term “about” clearly can and thus does only mean deviations thereof which are smaller than “100”.

The term "free of water" means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.

All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under the atmospheric pressure.

In all embodiments of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.

The phrase “fabric care composition” is meant to include compositions and formulations designed for treating fabric. Such compositions include but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein and detailed herein below when describing the compositions. Such compositions may be used as a pre-laundering treatment, a post- laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, and as further detailed herein below when describing the use and application of the inventive and compositions comprising such COMPOUND.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

Throughout this description, the term “inventive compound” and “compound of this (present) invention” may be used instead of the polyacrylic acids, their salts, solutions thereof(i.e. the BSPAA-S) or solids thereof (i.e. the PSPAA-P) - each of which have been defined according to the invention, and whichever applies to the respective context where this term is used -, meaning those compounds being disclosed herein as invention, defined by their structure and/or their process to produce and/or obtainable by the process defined herein.

Description of the invention

The definitions and their preferences given within the “Definition”-section before are included as part of this invention as described herein below.

The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” (or “preferably” etc.) options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

Process

This present invention encompasses a method for producing polyaspartic acid (PAA), comprising the following steps:

(A) preparing a treated polyaspartic acid polymer solution (PAA-S), with

(a) providing a polyaspartic acid polymer in aqueous solution,

- the polyaspartic acid polymer having a degree of neutralization of from 0 to 100%, - the counterion of the hydrolyzed carboxylic acid units in the PAA being selected from the group of sodium, potassium, ammonium, preferably sodium; the solution comprising water as solvent, preferably being essentially water;

(b) adjusting the pH of the PAA-S to a value of from 1 to at most 7, preferably at most 6, more preferably at most 5,5, and preferably from 3, more preferably from 4, and most preferably from 4,5, using preferably an acid selected from the group comprising sulfuric acid, hydrochloric acid, citric acid, gluconic acid, glucoronic acid, ethylenediamine-N,N’-disuccinic acid, preferably sulfuric acid or citric acid, more preferably using only citric acid;

(c) contacting the pH-adjusted PAA-S with a first agent having oxidizing properties (FA), such FA preferably being selected from the group of hydrogen peroxide, peroxodisulfate, active oxygen, ozone, preferably hydrogen peroxide, peroxodisulfate, more preferably hydrogen peroxide; such contacting with FA taking place in solution, such solution comprising water and optionally organic solvents miscible with water, preferably essentially water, such as plain water; at elevated temperature of at least 30 °C, preferably at least 35, more preferably at least 40, even more preferably at least 45, and most preferably at about 50°C, such as at 50°C, and of at most 95°C, preferably not more than 80 °C, even more preferably not more than 70°C, and most preferably not more than 60 °C; for a duration of from 10 minutes to 100 hours, preferably at least 30 minutes, more preferably at least 1 hour, even more preferably at least 2 hours, and most preferably at least 3 hours, and preferably at most 30 hours, even more preferably at most 15 hours, such as 3,5 to 12 hours and including 4 and 10 hours; to obtain a treated PAA-S;

(B) and thereafter optionally cooling the treated PAA-S to a temperature of not more than 50 °C, preferably not more than 40°C, and most preferably not more than 30 °C; after step (B) optionally adding one or more additives, such additives being selected from preservatives, stabilizers, biocides, preferably preservatives, stabilizers, biocides, more preferably preservatives such as sodium benzoate;

(C) and thereafter optionally adding a second agent having oxidation-inhibiting properties (SE) to the - optionally cooled - treated PAA-S from step (A) or the cooled treated PAA-S from optional step (B); such SE being preferably selected from the group comprising SE being preferably selected from the group comprising copper(ll)chloride, bisulfites such as alkali and preferably sodium bisulfite, hypophosphite salts such as alkali and preferably sodium hypophosphite; such SE being added to such PAA-S from the previous step, and then mixing the obtained PAA-S comprising SE until a uniform distribution of SE can be reasonably considered to be achieved, such as mixing for from 10 minutes to up to 2 hours, such mixing time depending on the size and geometry of the tank the addition is performed in, or by adding such SE inline into a tubing wherein the PAA-S is transported, optionally using a static mixing element for mixing in; to obtain a bleached and stabilized polyaspartic acid polymer solution (BSPAA-S); after step (C)/ before step (D) optionally further adding one or more additives, such additives being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate;

(D) and optionally further subjecting the BSPAA-S to a means of concentration or drying to obtain a concentrated or dried BSPAA-P.

As a result, of course, the BSPAA-S and the BSPAA-P also contain amounts of the SE in case SE has been added during the process. Depending on the treatment of the BSPAA after the addition of the SE, the amount of the SE may be reduced compared to the amount per PAA actually added during the process, as such SE - depending on its chemical nature - may decompose or react with e.g. oxygen or simply alone at elevated temperatures. In such case, the typical decomposition products of such SE will be contained unless such decomposition product is to be partially or to a large(r) extent removed by a following treatment such as drying or concentrating.

“Polyaspartic acid (salt)” is meant to include polyaspartic acid-homo- and copolymers and their respective salts, the co-polymers additionally comprising at least 50 weight% of aspartic acid- moieties in such polymer (PAA).

The polyaspartic acid-co-polymers comprise additional moieties which are derived from acids co- polymerizable with the aspartic acid-moiety (or the succinimide when this is used as starting material) during the production of the PAA. How that is done is also well-known, for example from WO 2017/042112. For example, it is possible to use additionally a carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and/or an amino acid (except aspartic acid). Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. Typically, in that preparation of polyaspartic acid, polybasic carboxylic acids and anhydrides thereof may be used, e.g. oxalic acid, adipic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, aconitic acid, succinic acid, succinic anhydride, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C26 alkylsuccinic acids (e.g. octylsuccinic acid), C2-C26 alkenylsuccinic acids (e.g. octenylsuccinic acid), 1 ,2,3-propanetricarboxylic acid, 1 , 1 ,3,3- propanetetracarboxylic acid, 1 ,1 ,2,2-ethanetetracarboxylic acid, 1 ,2,3,4-butanetetracarboxylic acid, 1 ,2,2,3-propanetetracarboxylic acid, 1 ,3,3,5-pentanetetracarboxylic acid, trimellitic acid or trimellitic anhydride. It is also possible to use polybasic hydroxycarboxylic acids, for example citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid. Amino acids used may include, inter alia, aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprolactam), uncharged amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxy amino acids (e.g. hydroxyproline, serine, threonine), iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid - a this has to be present anyway in the PAA-copolymer. Preferred carboxyl- containing compounds for PAA-co-polymers in thei present invention butane-1 , 2, 3, 4- tetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably butane-1 ,2, 3, 4-tetracarboxylic acid, citric acid, glycine and glutamic acid. The carboxyl-groups may be partially, fully or not neutralized, thus such polymers may comprise carboxylic acid-groups and carboxylate-groups depending on the degree of neutralization. How to achieve neutralization is well-known in the art; any suitable method can be employed for that.

The aspartic acid to be used for the PAA of the invention can be both L- and D-aspartic acid and DL-aspartic acid. Preference is given to using L-aspartic acid.

The degree of neutralization can be measured using the standard methods known in the art, such as potentiometric titration of the acid number according to ASTM D664. .

The pH can be measured in the typical way known in the art, such as DIN 19268.

The “first agent”/ “FA” is an agent which has to impart oxidizing properties at pH-Values of 7 and below. It is preferably also water-soluble to assure a good compatibility in the reaction mixture (without the need for adding a compatibilizer, such as medium-chain alcohols such as isopropanol and the like) and thus can provide efficient reaction to lower the colour of the “polyaspartic acid polymer solution” (“PAA-S”).

Such FA preferably is selected from the group of hydrogen peroxide, peroxodisulfate, active oxygen, ozone, preferably hydrogen peroxide, peroxodisulfate, more preferably hydrogen peroxide.

The “second agent” I “SE” is an agent which imparts oxidation-inhibition properties to the PAA-S. This SE is key in achieving the long-term stability of the PAA-S, i.e. the “bleached and stabilized polyaspartic acid polymer solution (BSPAA-S)”.

Such SE preferably is selected from the group comprising bisulfites such as alkali and preferably sodium bisulfite, hypophosphite salts such as alkali and preferably sodium hypophosphite.

A “uniform distribution” is a known definition in the field of chemical engineering and especially reactor- and mixing-technology; such distribution depends on the size and geometry of the apparatuses employed, e.g. the size and volume and aspect ratio of a vessel, a tube or a tube reactor etc. a distribution is “uniform” when at least 80, preferably at least 85, more preferably at least 90, even more preferably at least 95 and most preferably at least 97% of all increments of a reaction volume show the same concentration of all reactants can be reasonably considered to be achieved. How such distribution is calculated and - if desired or needed - also measured depends on the apparatuses employed; the methods and instruments for such however are generally known but need to be adjusted to the actual reactants being desired to measure.

The reaction can be in principle performed in any apparatus suitable for the desired reaction and the to be applied temperature and duration of the reaction, such as a simple vessel or a tube reactor.

Mixing therein can be achieved by any typical known means for mixing, such as any type of stirrer (which preferably is suitable for the volume to be mixed and the viscosity of the reaction mixture) or any installation such as baffles or static mixers or static mixing elements.

Such BSPAA-S can be optionally submitted to a means of concentration or drying to obtain a concentrated BSPAA-S or dried “bleached and stabilized polyaspartic acid polymer powder” (BSPAA-P). “Powder” however also includes any solid state of such PAA-polymer, e.g. powder, granules, granulates, agglomerates, “foams”, or any other solid particle appearance of the PAA- polymer.

In a preferred embodiment, the PAA-S is neutralized to more than 5%, preferably to more than 10, more preferably to more than 25 %, even more preferably more than 50%, even more preferably to more than 75%, such as 80%, 90%, 95 or about 100%.

For many applications the PAA is employed in aqueous medium and medium to higher pH, and thus it is suitable to already neutralize the PAA to a useful degree before providing it to the user. Depending on the use, the degree of neutralization can be chosen as desired to any value. How this is done is well-known in the art.

Upon neutralization a counterion is typically introduced, such as sodium, potassium, but also ammonium, calcium, lithium may be used, or even strontium or barium. This present invention is not limited to the type of counterion; any suitable ion that can be either introduced upon neutralisation or that can be exchanged by way of ion-exchange is included in this present invention. However, for most applications potassium and especially sodium are the ions of choice. That depends, however, on the application, thus the compatibility in and with formulations and substrates, into which the PAA or with which the PAA will get into contact in the application.

In a preferred embodiment, the PAA-S is obtained from the polycondensation of aspartic acid and optional neutralization of the polyaspartic acid polymer with a base, or from the polycondensation of succinimide followed by hydrolysis with a base and optional neutralization of the resulting polyaspartic acid polymer with an acid.

In a preferred embodiment, the PAA is a copolymer comprising aspartic acid-units and units derived from other carboxylic acid-monomer(s) which are polymerizable with aspartic acid or succinimide, which - in case of succinimide as comprised monomer - thereafter is subjected to hydrolysis with a base and thereafter optional neutralization with an acid, such other carboxylic acid-monomer(s) being preferably selected from the group comprising polybasic carboxylic acids and anhydrides thereof may be used, e.g. oxalic acid, adipic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, aconitic acid, succinic acid, succinic anhydride, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C26 alkylsuccinic acids (e.g. octylsuccinic acid), C2-C26 alkenylsuccinic acids (e.g. octenylsuccinic acid), 1 ,2,3- propanetricarboxylic acid, 1 ,1 ,3,3-propanetetracarboxylic acid, 1 ,1 ,2,2-ethanetetracarboxylic acid, 1 ,2,3,4-butanetetracarboxylic acid, 1 ,2,2,3-propanetetracarboxylic acid, 1 ,3,3,5- pentanetetracarboxylic acid, trimellitic acid or trimellitic anhydride. It is also possible to use polybasic hydroxycarboxylic acids, for example citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid. Amino acids used may include, inter alia, aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprolactam), uncharged amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxy amino acids (e.g. hydroxyproline, serine, threonine), iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid - a this has to be present anyway in the PAA-copolymer. Preferred carboxyl-containing compounds for PAA-co-polymers in theis present invention butane-1 ,2,3,4-tetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably butane-1 ,2,3,4-tetracarboxylic acid, citric acid, glycine and glutamic acid.

In a preferred embodiment, step (C) is performed.

In another preferred embodiment, step (B) is performed.

In another, more preferred embodiment, step (B) and step (C) are performed.

In another, preferred embodiment, step (D) is performed, preferably for step (D) a means of removing solvent is employed, selected from the group consisting of: spray-drying, granulation, spray-granulation, paddle-drying, vacuum-drying, freeze-drying, agglomeration, sprayagglomeration, fluidized bed-drying, preferably pray-drying, spray-granulation, most preferably spray-granulation.

In another, more preferred embodiment, step (B), step (C) and step (D) are performed, with step (B), (C) and (D) as defined and described before.

Subsequently, the salts of polyaspartic acid-polymer may be acidifed in order to obtain the corresponding acid form with a degree of neutralization of zero or about zero. This can be done after step I and before step (D) in a further, optional step. How to achieve this is known in the art; any typical method can in principle be employed.

Also, neutralization is possible; this as well can be done - instead of acidification - after step I and before step (D) in a further, optional step. How to achieve this is known in the art; any typical method can in principle be employed.

In a preferred embodiment of any of the embodiments for the process as disclosed before, in a further step i), after step (B) one or more additive is added, such additive(s) being selected from preservatives, stabilizers, biocides, preferably preservatives, stabilizers, biocides, more preferably preservatives such as sodium benzoate;

In a preferred embodiment of any of the embodiments for the process as disclosed before, in a further step ii), after step (C) or - if step (C) is not employed but step (D) is employed - before step (D), or - if neither step (C) nor step (D) is employed - a further additive is added after the step i) (step i) = adding an additive after step (B)). one or more additive is being added, such additive(s) being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate.

In an alternative preferred embodiment of any of the embodiments for the process as disclosed before, in step i) one or more additive is added, such additive(s) being selected from preservatives, stabilizers, biocides, preferably preservatives, stabilizers, biocides, more preferably preservatives such as sodium benzoate, and in step ii) one or more additive - preferably an additive different to the additive(s) in step i) - is being added, such additive(s) being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate. The process to prepare BSPAA-S is preferably comprising a step of adding at least one additive instep i) and/or step ii), such additive being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate, most preferably sodium benzoate, the preservative being in a range of from 0,04 to 1 ,5, more preferably from 0,1 to 1 , even more preferably from 0,3 to 0,8, and any number in between and any range in between, such as lower limits of 0,05, 0,15, 0,2, 0,25, 0,35, 0,4, 0,5, and as upper limits such as 1 ,4, 1 ,3, 1 ,2, 1 ,1 , 0,9, 0,85, 0,75, 0,7, 0,65, 0,6, all such numbers in weight percent of preservative based on 100 weight percent of BSPAA-S.

The process to prepare BSPAA-P is preferably comprising a step of adding at least one additive in step i) and/or step ii), such additive being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate, most preferably sodium benzoate, the preservative being in a range of from 0,1 to 3, more preferably from 0,4 to 2,5, even more preferably from 0,7 to 1 ,75, and any number in between and any range in between, such as lower limits of 0,0,2, 0,3, 0,5, 0,6, 0,8, 0,9, 1 ,0, 1 ,1 , 1 ,2, 1 ,3, 1 ,4, 1 ,5, and upper limits such as 2,9, 2,8, 2,7, 2,6, 2,4, 2,3, 2,2, 2,1 2,0, 1 ,9, 1 ,8, 1 ,7, 1 ,6, all such numbers in weight percent of preservative based on 100 weight percent of BSPAA-P.

Most preferably, however, BSPAA-P does not contain a preservative, stabilizer, biocide and/or antioxidant.

The process is further defined in the claims hereinafter.

PAA-Polymer

By the method described herein above and throughout this description, a “bleached and stabilized polyaspartic acid polymer solution” (BSPAA-S) is obtainable, preferably obtained, and can thereafter concentrated or even dried, with the PAA, PAA-S, BSPAA-S and BSPAA-P and the measures, apparatuses, ingredients, reactants, and solvents etc, being the ones described herein, each individually in their broadest definition and any of the preferred and more preferred etc. embodiments, and in any combination thereof.

In view of the viscosities to be handled, a concentration of the polyaspartic acid polymer in BSPAA-S is preferably being present at a concentration from 20 to 80, more preferably 25 to 70, even more preferably 30 to 60, most preferably 35 to 45 weight percent of polymer in BSPAA-S, such as any value in between the upper and lower limits given, such as 21 , 22, 23, 24, 26, 27, 28, 29, 31 , 32, 33, 34, 36, 27, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 51 , 52, 53, 54, 56, 57, 58, 59, 61 , 62, 63, 64, 66, 67, 68, 69, 71 , 72, 73, 74, 75, 76, 77, 78, 79.

In a preferred embodiment, the BSPAA-S is further dried to a BSPAA-P, the methods to dry are those as described before, with the preferred, more preferred etc embodiments thereof applying here as well.

In a preferred embodiment, the BSPAA-S or - if dried to BSPAA-P then also the BSPAA-P - contains one or more additive, such additive(s) being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate.

The preservative in BSPAA-S is preferably present in a range of from 0,04 to 1 ,5, more preferably from 0,1 to 1 , even more preferably from 0,3 to 0,8, and any number in between and any range in between, such as lower limits of 0,05, 0,15, 0,2, 0,25, 0,35, 0,4, 0,5, and as upper limits such as 1 ,4, 1 ,3, 1 ,2, 1 ,1 , 0,9, 0,85, 0,75, 0,7, 0,65, 0,6, all such numbers in weight percent of preservative based on 100 weight percent of BSPAA-S.

In a preferred embodiment, BSPAA-S contains at least one additive, such additive most preferably being sodium benzoate, in the same amounts and ranges given immediately before for the preservative.

The preservative in BSPAA-P is preferably present in a range of from 0, 1 to 3, more preferably from 0,4 to 2,5, even more preferably from 0,7 to 1 ,75, and any number in between and any range in between, such as lower limits of 0,0,2, 0,3, 0,5, 0,6, 0,8, 0,9, 1 ,0, 1 ,1 , 1 ,2, 1 ,3, 1 ,4, 1 ,5, and upper limits such as 2,9, 2,8, 2,7, 2,6, 2,4, 2,3, 2,2, 2,1 2,0, 1 ,9, 1 ,8, 1 ,7, 1 ,6, all such numbers in weight percent of preservative based on 100 weight percent of BSPAA-P.

In a preferred embodiment, BSPAA-P does not contain any preservatives, stabilizers, biocides, antioxidants.

In an alternative preferred embodiment, BSPAA-P does contain at least one of preservatives, stabilizers, biocides, antioxidants, more preferably a preservative, most preferably sodium benzoate, in the same amounts and ranges given immediately before for the preservative.

The BSPAA-S and the BSPAA-P are further defined in the claims hereinafter.

A great advantage of the measures disclosed herein leading to the BSPAA-S and BSPAA-P are the long-term stability of those polymers upon storage; this means, that the colour, and preferably also in addition the odour, of those polymers do not significantly, preferably do not essentially change over time for the periods observed.

“No significant change” here means that the change of the colour value is less than 30 percent, preferably less than 20 percent, more preferably less than 10 percent, of the original colour value that had been measured directly after obtaining the polymer from the process steps.

“No essential change” here means that the change of the colour value is less than 5 percent, preferably less than 3 percent, and more preferably the change is within the error margin of the measurement of the original colour value that had been measured directly after obtaining the polymer from the process steps.

The same applies similarly for the odour; however, the odour cannot be measured in values as it depends on the perception of a person. Thus, odour stability has to be assessed by a panel of experienced people comparing certain freshly produced and stored samples of the PAA- polymers. As this testing and comparing is not an easy task - although manageable but costly -, the odour stability is only an optional feature within this invention.

The present Invention can provide PAA-polymers having a colour value of not more than 40, preferably not more than 20, more preferably not more than 15, with such values being the iodine- colour number, which can be measured in a known way, using Lico 150 or similar model. A further advantage of the polyaspartic acids (BSPAA-S and BSPAA-P) prepared or defined in accordance with the invention is that they are biodegradable under aerobic conditions in contrast to other polymers which are typically used in such compositions and which have been prepared by free-radical polymerization of carboxyl-containing monomers, i.e. such as the polyacrylic acidtype homo- and co-polymers, which in principle can serve the same purpose but are not biodegradable to any useful extent.

The polyaspartic acids (BSPAA-S and BSPAA-P) to be prepared in accordance with the invention may have different weight-average molecular weights, preferably 1000 to 100 000 g/mol, more preferably 1500 to 50 000 g/mol and especially 2000 to 20 000 g/mol.

The molecular masses Mw specified in the context of the present invention can be calculated, inter alia, with the aid of a calibration curve, which can be generated using narrowly distributed sodium polyacrylate standards from Polymer Standard Service having molecular weights of M = 1250 g/mol to M = 130 500 g/mol, as is known to those skilled in the art and as is described herein. In addition, Na-acrylate having a molecular weight of M = 96 and a PEG standard with M = 620, which is synonymous with Na-PAA M = 150, can be used, inter alia, for the calibration.

The polyaspartic acids (BSPAA-S and BSPAA-P) prepared with this present invention still inherit their, inter alia, very good scale-inhibiting and dispersing effect, and specifically with respect to both inorganic and organic deposits. In particular, they inhibit deposits of calcium carbonate and magnesium carbonate and calcium phosphates and phosphonates and magnesium phosphates and phosphonates. In addition, they prevent deposits which originate from the soil constituents of a rinse liquor, for example, fat, protein and starch deposits.

Uses and Compositions

The polyaspartic acids prepared or defined according to the invention (i.e. the polyaspartic acid polymer or their salts either in solution or as solids, and including any mixture thereof, are used, for example, in cleaning compositions, detergent compositions and dishwashing compositions, particularly but not exclusively in dishwashing detergents for automatic dishwashing.

The polyaspartic acids to be used or which are produced/preparable according to the invention, may be used as an aqueous solution or in solid form e.g. in powder form or granulated form. As is known to those skilled in the art, the powder or granulated form of a polymer may be obtained, for example, by spray-drying, spray granulation, fluidized bed spray granulation, spouted bed granulation, drum drying or freeze-drying of the aqueous solution of the polyaspartic acids or salts thereof.

However, as already disclosed above, part of the invention comprises also the process for producing polyaspartic acid comprising a process step of subjecting the BSPAA-S to a means of concentration or drying to obtain a concentrated or dried BSPAA-P.

The present invention therefore also relates to the use of the polyaspartic acid preparable or as defined according to the invention as scale inhibitors or dispersants.

The polyaspartic acids can be used here both as additive in cleaning agents, dishwashing agents (particularly machine dishwashing agents) or detergents and also as scale inhibitors or dispersants in water-conducting systems as shown and described here. Specifically, the invention encompasses the use of the polyaspartic acid and/or their salt, either as a solution or as a solid, in a composition suitable for cleaning such as soft and hard surfaces and/or fabric for avoiding or reducing scale-formation in water-conducting systems, such systems including washing machines, tubes for water transport or storage, water purification, water treatment, cooling systems using water as coolant, and desalination of water.

Moreover, the use as specified before preferably is within a composition that is a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product, cosmetic or personal care product.

More preferably, the use as specified before, is in composition that is a cleaning composition and/or in fabric and home care product, preferably a dish wash detergent formulation, more preferably in an automatic dish wash detergent composition.

Within such compositions, the polyaspartic acid and/or their salt, either as a solution or as a solid, is preferably used as scale inhibitor and/or dispersant.

Further preferred uses are a in cleaning compositions, specifically in combination with, as partial or full replacement of polycarboxylate-polymers, and here especially for replacing the poor to non- biodegradable polycacrylic acids.

In particular preferred uses are in phosphate-free and phosphonate-free automatic dishwashing detergent formulations.

Further encompassed by this invention is a composition comprising at least one bleached and stabilized polyaspartic acid polymer solution (BSPAA-S), or of a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) - both as defined herein - or their mixture.

Preferably, the composition comprises at least one bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) as defined herein before in the various embodiments, or a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) as defined herein before in the various embodiments, or their mixture. More preferably, such composition is a cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic or personal care product, preferably a fabric detergent formulation or a dish wash detergent formulation, more preferably a dish wash detergent composition, even more preferably being an automatic dish wash detergent composition, wherein the at least one BSPAA-S and/or at least one BSPAA-P is present in the composition at a concentration of from about 0.1 % to about 50%, preferably from about 0,25% to 25%, more preferably from about 0.5% to about 20%, and even more preferably from about 0.5% to about 15%, and most preferably in amounts of up to 10%, 8%, 5%, or even 3%, each in weight % in relation to the total weight of such composition, optionally further comprising from about 1% to about 70% by weight of a surfactant system, optionally in addition comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types; and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system; optionally further comprising an antimicrobial agent selected from the group consisting of 2- phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol, whereas in case of an automated dish washing-composition such phenoxyethanol preferably is not comprised in such composition; optionally further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition, whereas in case of an automated dish washing-compositions such 4,4’-dichoro 2- hydroxydiphenylether preferably is not comprised in such composition.

Even more preferably, such composition comprises at least one bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) as defined herein before in the various embodiments, or a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) as defined herein before in the various embodiments, or their mixture, the composition being a cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic or personal care product, preferably a fabric detergent formulation or a dish wash detergent formulation, more preferably a dish wash detergent composition, even more preferably being an automatic dish wash detergent composition, wherein the at least one BSPAA-S and/or at least one BSPAA-P is present in the composition at a concentration of from about 0.1 % to about 20%, preferably from about 0,25% to 15%, more preferably from about 0.5% to about 10%, and even more preferably from about 0.5% to about 5%, and most preferably in amounts of up to 3%, each in weight % in relation to the total weight of such composition, optionally further comprising from about 1% to about 70% by weight of a surfactant system, optionally in addition comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types; and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system; optionally further comprising an antimicrobial agent selected from the group consisting of 2- phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol, whereas in case of an ADW-compositions such phenoxyethanol preferably is not comprised in such composition; optionally further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition, whereas in case of an ADW-compositions such 4,4’-dichoro 2-hydroxydiphenylether preferably is not comprised in such composition.

In a preferred embodiment of the embodiments before, it is a cleaning composition and/or fabric and home care product and/or industrial and institutional cleaning product, comprising at least one inventive compound obtained by a process of the invention or defined according to the invention. In particular, it is a cleaning composition for improved cleaning performance, especially improved primary washing, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

In a preferred embodiment of the embodiments before, the cleaning composition of the present invention is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.

In an alternative preferred embodiment of the embodiments before, the cleaning composition of the present invention is a liquid or solid (e.g. powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably a liquid manual dish wash detergent composition. Such compositions are known to a person of skill in the art.

In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass. One - preferred - example is a detergent formulation for washing dishes and cutlery, i.e. a “hand dish detergent”. Another example is a spray cleaner, which is typically to be sprayed on a hard surface and then wiped away thereby removing soil and grease etc.

In one embodiment of the present invention, the inventive compound(s) obtained by a process of the invention or defined according to the invention is a component of a cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.

In one embodiment it is also preferred in the present invention that the cleaning composition comprises (besides at least one inventive compound obtained by a process of the invention) additionally at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from lipases.

Even more preferably, the cleaning compositions of the present invention comprising at least one inventive compound obtained by a process of the invention and optionally further comprising at least one surfactant or a surfactant system - as detailed before - are those for improved cleaning performance within laundry and manual dish wash applications, even more specifically, for improved cleaning performance (such actions as detailed before) such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of optionally further comprising at least one enzyme, preferably selected from one or more optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases, pectate lyases, cutinases, DNases, xylanases, oxicoreductases, dispersins, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from lipases.

In one embodiment, the inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment the inventive compound(s) obtained by a process of the invention may be utilized in cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

In a further embodiment, the inventive compound(s) obtained by a process of the invention may be utilized in the cleaning compositions or fabric and home care product, preferably a laundry cleaning composition, a laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising C8-C18 linear or branched alkyl ethersulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In one embodiment of the present invention, the inventive compound(s) obtained by a process of the invention is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant.

In a further embodiment, this invention also encompasses a composition comprising at least one inventive compound obtained by a process of the invention, further comprises an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2- phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.

In a further embodiment, this invention also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising inventive compound(s) obtained by a process of the invention in the amounts detailed before as described herein before, such composition further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

In a further embodiment, this invention also encompasses a composition, specifically a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation or solid automatic dish washing formulation, more preferably a laundry detergent formulation, comprising inventive compound(s) obtained by a process of the invention and in the amounts as detailed before, such composition being preferably a detergent composition, such composition further comprising an antimicrobial agent as disclosed hereinafter, preferably selected from the group consisting of 2- phenoxyethanol, more preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; even more preferably comprising 0.1 to 2% of phenoxyethanol.

Even more preferably, the compositions or products of the present invention as detailed herein before comprising at least one inventive compound or obtainable by or obtained by a process of the invention and in the amounts as specified in the previous paragraph, optionally further comprising at least one surfactant or a surfactant system in amounts from about 1% to about 70% by weight of the composition or product, are preferably those for primary cleaning (i.e. removal of stains) and more preferably within laundry applications, and may additionally comprise at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types.

The cleaning compositions of the invention comprise a surfactant system in an amount sufficient to provide desired cleaning properties. In some embodiments, the cleaning composition comprises, by weight of the composition, from about 1 % to about 70% of a surfactant system. In other embodiments, the liquid cleaning composition comprises, by weight of the composition, from about 2% to about 60% of the surfactant system. In further embodiments, the cleaning composition comprises, by weight of the composition, from about 5% to about 30% of the surfactant system. In embodiments for for a liquid hand dishwashing or spray detergent cleaning composition such composition comprises preferably from from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system, more preferably of an anionic surfactant. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

The present invention further relates to the use of polyaspartic acids preparable according to the invention as washing power enhancers, graying inhibitors and encrustation inhibitors in detergent compositions and cleaning compositions (e.g. as additives for detergents and cleaning agents for textiles, washing aids, laundry after-treatment agents).

Further encompassed are a method of preserving a composition according to the invention as defined herein before against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol to the composition which is an aqueous composition comprising water as solvent.

Further encompassed is also a method of laundering fabric or of cleaning hard surfaces, which method comprises treating a fabric or a hard surface with a composition according to the invention as defined herein before, wherein the composition comprises 4,4’-dichloro 2- hydroxydiphenylether, preferably comprising 4,4’-dichloro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1 %, more preferably 0.01 to 0.6%, each by weight of the composition.

As has been found in the context of the present invention, the polyaspartic acid produced or preparable in accordance with the method according to the invention described here is very well- suited as calcium carbonate scale inhibitor. The present invention therefore further comprises the use of polyaspartic acids produced or preparable according to the invention or compositions comprising these as scale inhibitors, preferably as calcium carbonate scale inhibitors.

Further encompassed by this invention is a method of reducing or avoiding scale-formation in water-conducting or water-containing systems, such systems including washing machines such as those for dish or fabric, tubes for water transport or storage, water purification, water treatment, cooling systems using water or aqueous mixtures as coolant, and desalination of water, by adding an effective amount of at least bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) as defined by this invention, and/or of a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) as defined by this invention, or their mixture, to the water-containing fluid contained or transported inside such water-conducting or water-containing system.

The invention further relates to the use of polyaspartic acids of the invention or mixtures thereof as scale inhibitors or dispersants in water-conducting systems. Water-conducting systems in which polyaspartic acids preparable by the method of the invention can be used are in principle all systems which come into contact permanently or periodically with water such as seawater, brackish water, river water, urban or industrial wastewater or industrial process water such as cooling water, and in which scale formation can occur.

Water-conducting systems in which the polymers of the invention can be used are, in particular, seawater desalination plants, brackish water desalination plants, cooling water systems and boiler feed water systems, boilers, heaters, continuous-flow heaters, hot water tanks, cooling towers, cooling water circuits and other industrial process water. The desalination plants may be thermal in nature or based on membrane processes such as reverse osmosis or electrodialysis.

In general, the polymers of the invention are added to the water-conducting systems in amounts of 0.1 mg/l to 100 mg/l. The optimal dosage is determined by the requirements of the respective application or according to the operating conditions of the relevant process. For instance, in thermal seawater desalination, the polymers are preferably used at concentrations of 0.5 mg/l to 10 mg/l. Polymer concentrations of up to 100 mg/l are used in industrial cooling circuits or boiler feed water systems. Water analyses are often carried out in order to determine the proportion of scale-forming salts and thus the optimal dosage.

Formulations may also be added to the water-conducting systems which may comprise, in addition to the polymers of the invention and depending on requirements, inter alia, phosphonates, polyphosphates, zinc salts, molybdate salts, organic corrosion inhibitors such as benzotriazole, tolyltriazole, benzimidazole or ethynyl carbinol alkoxylates, biocides, complexing agents and/or surfactants. Examples of phosphonates are 1-hydroxyethane-1 ,1-diphosphonic acid (HEDP), 2-phosphonobutane-1 ,2,4-tricarboxylic acid (PBTC), aminotrimethylenephosphonic acid (ATMP) diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and ethylenediamine tetra(methylene phosphonic acid) (EDTMP), which are used in each case in acid form or in the form of sodium salts thereof.

The inventive compound(s) as directly obtained from the inventive process can be used advantageously in cleaning compositions.

They may be used as at least one inventive compound, or mixtures of more than one inventive compound.

Hence, another subject matter of the present invention is the use of the above-mentioned inventive compound(s) in cleaning compositions, specifically as prepared by the process defined herein.

The inventive compound(s) can be added to cleaning compositions.

The inventive compound(s) are present in general in said formulations at a concentration of from about 0.5% to about 50%, preferably from about 1 % to 20%, more preferably from about 1 % to about 15%, and even more preferably from about 2% to about 12%, each in weight % in relation to the total weight of such composition/product, optionally further comprising from about 1% to about 70% by weight of a surfactant system, wherein - specifically - for a liquid hand dishwashing or spray detergent cleaning composition such composition comprising from 0.1 % to 50%, preferably from 1% to 35%, more preferably from 3% to 30%, by weight of the total composition, of a surfactant system, and such surfactant system preferably comprising from 60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant.

The phrase "cleaning composition" as used herein includes compositions and formulations and products designed for cleaning soiled material. Such compositions, formulations and products include those designed for cleaning soiled material or soiled surfaces of any kind.

Compositions for “industrial and institutional cleaning” includes such cleaning compositions being designed for use in industrial and institutional cleaning, such as those for use of cleaning soiled material or surfaces of any kind, such as hard surface cleaners for surfaces of any kind, including tiles, carpets, PVC-surfaces, wooden surfaces, metal surfaces, lacquered surfaces.

“Compositions for Fabric and Home Care” include cleaning compositions including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agent or composition, laundry rinse additive, wash additive, post-rinse fabric treatment, ironing aid, dish washing compositions, hard surface cleaning compositions, unit dose formulation, delayed delivery formulation, detergent contained on or in a porous substrate or nonwoven sheet, and other suitable forms that may be apparent to one skilled in the art in view of the teachings herein. Such compositions may be used as a prelaundering treatment, a post-laundering treatment, or may be added during the rinse or wash cycle of the laundering operation, preferably during the wash cycle of the laundering or dish washing operation.

The cleaning compositions of the invention may be in any form, namely, in the form of a liquid; a solid such as a powder, granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion; types delivered in dual- or multi-compartment containers; single-phase or multi-phase unit dose; a spray or foam detergent; premoistened wipes (i.e., the cleaning composition in combination with a nonwoven material such as that discussed in US 6,121 ,165, Mackey, et al.); dry wipes (i.e., the cleaning composition in combination with a nonwoven materials, such as that discussed in US 5,980,931 , Fowler, et al.) activated with water by a user or consumer; and other homogeneous, non-homogeneous or single-phase or multiphase cleaning product forms.

The liquid cleaning compositions of the present invention preferably have a viscosity of from 50 to 10000 mPa*s; liquid manual dish wash cleaning compositions (also liquid manual “dish wash compositions”) have a viscosity of preferably from 100 to 10000 mPa*s, more preferably from 200 to 5000 mPa*s and most preferably from 500 to 3000 mPa*s at 20 1/s and 20°C; liquid laundry cleaning compositions have a viscosity of preferably from 50 to 3000 mPa*s, more preferably from 100 to 1500 mPa*s and most preferably from 200 to 1000 mPa*s at 20 1/s and 20°C.

The cleaning compositions and formulations of the invention may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as “adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.

Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes.

Liquid cleaning compositions additionally may comprise - and preferably do comprise at least one of - rheology control/modifying agents, emollients, humectants, skin rejuvenating actives, and solvents.

Solid compositions additionally may comprise - and preferably do comprise at least one of - fillers, bleaches, bleach activators and catalytic materials.

Suitable examples of such cleaning adjuncts and levels of use are found in WO 99/05242, U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above or below.

The surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

The cleaning compositions of the invention typically comprise a surfactant system in an amount sufficient to provide desired cleaning properties.

The liquid cleaning compositions of the present invention may have any suitable pH-value. Preferably the pH of the composition is adjusted to between 4 and 14. More preferably the composition has a pH of from 6 to 13, even more preferably from 6 to 10, most preferably from 7 to 9. The pH of the composition can be adjusted using pH modifying ingredients known in the art and is measured as a 10% product concentration in demineralized water at 25°C. For example, NaOH may be used and the actual weight% of NaOH may be varied and trimmed up to the desired pH such as pH 8.0. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

The selection of the additional surfactants and further ingredients in these embodiments may be dependent upon the application and the desired benefit.

All such cleaning compositions, their ingredients including (adjunct) cleaning additives, their general compositions and more specific compositions are known, as for example illustrated in the publications WO 2022/136409 and WO 2022/136408, wherein in any of the before prior art documents the polyaspartic acid and/or their salt within the general compositions and also each individualized specific cleaning composition disclosed in the beforementioned publications may be replaced partially or completely by the inventive polyaspartic acid and/or their salt of this present invention. In those beforementioned documents, also various types of formulations for cleaning compositions are disclosed; all such composition types - the general compositions and also each individualized specific cleaning composition - can be equally applied also to those cleaning compositions contemplated herein.

Hence, the present invention also encompasses any and all of such disclosed compositions of the before-mentioned prior art-disclosures but further comprising at least one of the inventive inventive polyaspartic acid and/or their salt in addition to or as a replacement for any already ins such prior art-composition contained polyaspartic acid and/or their salt or any such compound, which can be replaced by such inventive polyaspartic acid and/or their salt - such replacements in principle known to a person of skill in the art or readily obvious in view of the present invention - , with the content of the inventive polyaspartic acid and/or their salt being present in said formulations at a concentration of generally from about 0.5% to about 50%, preferably from about 1 % to 20%, more preferably from about 1% to about 15%, and even more preferably from about 2% to about 12%, each in weight % in relation to the total weight of such composition/product.

General description of cleaning compositions, formulations and their ingredients

Cleaning compositions such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, are known to a person skilled in the art. Any composition etc. known to a person skilled in the art, in connection with the respective use, can be employed within the context of the present invention by including at least one inventive compound, preferably at least one such inventive compound in amounts suitable for expressing a certain property within such a composition, especially when such a composition is used in its area of use. Cleaning additives

Suitable adjunct cleaning additives include builders, cobuilders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, dispersants such as polymeric dispersing agents, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, and perfumes. Alls such adjuncts are detailed and exemplified further below in the following chapters.

Hence, the cleaning compositions of the invention such as fabric and home care products, and formulations for industrial and institutional cleaning, more specifically such as laundry and manual dish wash detergents, preferably additionally comprise a surfactant system and, more preferably, also further adjuncts, as the one described above and below in more detail. The surfactant system may be composed from one surfactant or from a combination of surfactants selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a surfactant system for detergents encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

The cleaning compositions of the invention preferably comprise a surfactant system in an amount sufficient to provide desired cleaning properties. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, non-ionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

Laundry compositions

“Laundry composition” may be any composition, formulation or product which is intended for use in laundry including laundry care, laundry cleaning etc.; hence this term will be used in the following denoting any composition, formulation or product. In laundry compositions, anionic surfactants contribute usually by far the largest share of surfactants within such formulation. Hence, preferably, the inventive cleaning compositions for use in laundry comprise at least one anionic surfactant and optionally further surfactants selected from any of the surfactant classes described herein, preferably from non-ionic surfactants and/or amphoteric surfactants and/or zwitterionic surfactants and/or cationic surfactants.

Cleaning compositions may - and preferably do - also contain anionic surfactants - which may be employed also in combinations of more than one other surfactant.

Nonlimiting examples of anionic surfactants - which may be employed also in combinations of more than one surfactant - useful herein include C9-C20 linear alkylbenzenesulfonates (LAS), C10-C20 primary, branched chain and random alkyl sulfates (AS); C10-C18 secondary (2,3) alkyl sulfates; C10-C18 alkyl alkoxy sulfates (AExS) wherein x is from 1 to 30; C10-C18 alkyl alkoxy carboxylates comprising 1 to 5 ethoxy units; mid-chain branched alkyl sulfates as discussed in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as discussed in US 6,008,181 and US 6,020,303; modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO 99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefin sulfonate (AOS).

Preferred examples of suitable anionic surfactants are alkali metal and ammonium salts of C8- C12-alkyl sulfates, of C12-C18-fatty alcohol ether sulfates, of C12-C18-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-C12-alkylphenols (ethoxylation: 3 to 50 mol of ethylene oxide/mol), of C12-C18-alkylsulfonic acids, of C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, of C10-C18-alkylarylsulfonic acids, preferably of n-C10-C18-alkylbenzene sulfonic acids, of C10-C18 alkyl alkoxy carboxylates and of soaps such as for example C8-C24-carboxylic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts. In one embodiment of the present invention, anionic surfactants are selected from n-C10-C18- alkylbenzene sulfonic acids and from fatty alcohol polyether sulfates, which, within the context of the present invention, are in particular sulfuric acid half-esters of ethoxylated C12-C18- alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol), preferably of n-C12-C18-alkanols. In one embodiment of the present invention, also alcohol polyether sulfates derived from branched (i.e., synthetic) C11-C18-alkanols (ethoxylation: 1 to 50 mol of ethylene oxide/mol) may be employed.

Preferably, the alkoxylation group of both types of alkoxylated alkyl sulfates, based on C12- C18-fatty alcohols or based on branched (i.e., synthetic) C11-C18-alcohols, is an ethoxylation group and an average ethoxylation degree of any of the alkoxylated alkyl sulfates is 1 to 5, preferably 1 to 3.

Preferably, the laundry detergent formulation of the present invention comprises from at least 1 wt. % to 50 wt. %, preferably in the range from greater than or equal to about 2 wt. % to equal to or less than about 30 wt. %, more preferably in the range from greater than or equal to 3 wt. % to less than or equal to 25 wt. %, and most preferably in the range from greater than or equal to 5 wt. % to less than or equal to 25 wt. % of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.

In a preferred embodiment of the present invention, anionic surfactants are selected from C10- C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10- C18 alkylsulfates. Cleaning compositions may also contain non-ionic surfactants - which may be employed also in combinations of more than one other surfactant.

Non-limiting examples of non-ionic surfactants - which may be employed also in combinations of more than one other surfactant - include: C8-C18 alkyl ethoxylates, such as, NEODOL® non- ionic surfactants from Shell; ethylenoxide/propylenoxide block alkoxylates as PLURONIC® from BASF; C14-C22 mid-chain branched alkyl alkoxylates, BAEx, wherein x is from 1 to 30, as discussed in US 6,153,577, US 6,020,303 and US 6,093,856; alkylpolysaccharides as discussed in U.S. 4,565,647 Llenado, issued January 26, 1986; specifically alkylpolyglycosides as discussed in US 4,483,780 and US 4,483,779; polyhydroxy fatty acid amides as discussed in US 5,332,528; and ether capped poly(oxyalkylated) alcohol surfactants as discussed in US 6,482,994 and WO 01/42408.

Preferred examples of non-ionic surfactants are in particular alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, furthermore alkylphenol ethoxylates, alkyl glycosides, polyhydroxy fatty acid amides (glucamides). Examples of (additional) amphoteric surfactants are so-called amine oxides.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (A)

[ formula (A)] in which the variables are defined as follows:

R1 is selected from linear C1 -C10-alkyl , preferably ethyl and particularly preferably methyl, R2 is selected from C8-C22-alkyl, for example n-C8H17, n-C10H21 , n-C12H25, n-C14H29, n- C16H33 or n-C18H37,

R3 is selected from C1 -C10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secbutyl, 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, m and n are in the range from zero to 300, where the sum of n and m is at least one. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

Here, compounds of the general formula (A) may be block copolymers or random copolymers, preference being given to block copolymers.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (B)

[formula (B)] in which the variables are defined as follows:

R1 is identical or different and selected from linear C1-C4-alkyl, preferably identical in each case and ethyl and particularly preferably methyl,

R4is selected from C6-C20-alkyl, in particular n-C8H17, n-C10H21 , n-C12H25, n-C14H29, n- C16H33, n-C18H37, a is a number in the range from zero to 6, preferably 1 to 6, b is a number in the range from zero to 20, preferably 4 to 20, d is a number in the range from 4 to 25.

Preferably, at least one of a and b is greater than zero.

Here, compounds of the general formula (B) may be block copolymers or random copolymers, preference being given to block copolymers.

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. Alkylphenol ethoxylates or alkyl polyglycosides or polyhydroxy fatty acid amides (glucamides) are likewise suitable. An overview of suitable further non-ionic surfactants can be found in EP A 0 851 023 and in DE-A 198 19 187.

Mixtures of two or more different non-ionic surfactants may of course also be present. In a preferred embodiment of the present invention, non-ionic surfactants are selected from C12/14 and C16/18 fatty alkoholalkoxylates, C13/15 oxoalkoholalkoxylates, C13- alkoholalkoxylates, and 2-propylheptylalkoholalkoxylates, each of them with 3 - 15 ethoxy units, preferably 5-10 ethoxy units, or with 1-3 propoxy- and 2-15 ethoxy units.

Cleaning compositions may also contain amphoteric surfactants - which may be employed also in combinations of more than one other surfactant.

Non-limiting examples of amphoteric surfactants - which may be employed also in combinations of more than one other surfactant - include: water-soluble amine oxides containing one alkyl moiety of from about 8 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl moieties and hydroxyalkyl moieties containing from about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl moieties and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms. See WO 01/32816, US 4,681 ,704, and US 4,133,779. Suitable surfactants include thus so-called amine oxides, such as lauryl dimethyl amine oxide (“lauramine oxide”).

Preferred examples of amphoteric surfactants are amine oxides. Preferred amine oxides are alkyl dimethyl amine oxides or alkyl amido propyl dimethyl amine oxides, more preferably alkyl dimethyl amine oxides and especially coco dimethyl amino oxides. Amine oxides may have a linear or mid-branched alkyl moiety. Typical linear amine oxides include water-soluble amine oxides containing one R1 = C8-18 alkyl moiety and two R2 and R3 moieties selected from the group consisting of C1-C3 alkyl groups and C1-C3 hydroxyalkyl groups. Preferably, the amine oxide is characterized by the formula

R1-N(R2)(R3)-O wherein R1 is a C8-18 alkyl and R2 and R3 are selected from the group consisting of methyl, ethyl, propyl, isopropyl, 2-hydroxethyl, 2-hydroxypropyl and 3-hydroxy propyl. The linear amine oxide surfactants in particular may include linear C10-C18 alkyl dimethyl amine oxides and linear C8-C12 alkoxy ethyl dihydroxy ethyl amine oxides. Preferred amine oxides include linear C10, linear C10-C12, and linear C12-C14 alkyl dimethyl amine oxides. As used herein "midbranched" means that the amine oxide has one alkyl moiety having n1 carbon atoms with one alkyl branch on the alkyl moiety having n2 carbon atoms. The alkyl branch is located on the alpha carbon from the nitrogen on the alkyl moiety. This type of branching for the amine oxide is also known in the art as an internal amine oxide. The total sum of n1 and n2 is from 10 to 24 carbon atoms, preferably from 12 to 20, and more preferably from 10 to 16. The number of carbon atoms for the one alkyl moiety (n1) should be approximately the same number of carbon atoms as the one alkyl branch (n2) such that the one alkyl moiety and the one alkyl branch are symmetric. As used herein "symmetric" means that (n1-n2) is less than or equal to 5, preferably 4, most preferably from 0 to 4 carbon atoms in at least 50 wt. %, more preferably at least 75 wt. % to 100 wt. % of the mid-branched amine oxides for use herein. The amine oxide further comprises two moieties, independently selected from a C1-C3 alkyl, a C1-C3 hydroxyalkyl group, or a polyethylene oxide group containing an average of from about 1 to about 3 ethylene oxide groups. Preferably the two moieties are selected from a C1-C3 alkyl, more preferably both are selected as a C1 alkyl.

In a preferred embodiment of the present invention, amphoteric surfactants are selected from C8-C18 alkyl-dimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.

Certain amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N- lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium). Hence, such amphoteric surfactants arte preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.

Cleaning compositions may also contain zwitterionic surfactants - which may be employed also in combinations of more than one other surfactant.

Suitable zwitterionic surfactants include betaines, such as alkyl betaines, alkylamidobetaine, amidazoliniumbetaine, sulfobetaine (INCI Sultaines) as well as the phosphobetaines. Examples of suitable betaines and sulfobetaines are the following (designated in accordance with INCI): Almond amidopropyl of betaines, Apricotamidopropyl betaines, Avocadamidopropyl of betaines, Babassuamidopropyl of betaines, Behenamidopropyl betaines, Behenyl of betaines, Canol amidopropyl betaines, Capryl/Capramidopropyl betaines, Carnitine, Cetyl of betaines, Cocamidoethyl of betaines, Cocamidopropyl betaines, Cocamidopropyl Hydroxysultaine, Coco betaines, Coco Hydroxysultaine, Coco/Oleam idopropyl betaines, Coco Sultaine, Decyl of betaines, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl of PG-betaines, Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow of betaines, Isostearamid-'opropyl betaines, Lauramidopropyl betaines, Lauryl of betaines, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl betaines, Minkamidopropyl of betaines, Myristamidopropyl betaines, Myristyl of betaines, Oleamidopropyl betaines, Oleamidopropyl Hydroxysultaine, Oleyl of betaines, Olivamidopropyl of betaines, Palmamidopropyl betaines, Palmitamidopropyl betaines, Palmitoyl Carnitine, Palm Kernelamidopropyl betaines, Polytetrafluoroethylene Acetoxypropyl of betaines, Ricinoleam idopropyl betaines, Sesamidopropyl betaines, Soyamidopropyl betaines, Stearamidopropyl betaines, Stearyl of betaines, Tallowamidopropyl betaines, Tallowamidopropyl Hydroxysultaine, Tallow of betaines, Tallow Dihydroxyethyl of betaines, Undecylenamidopropyl betaines and Wheat Germamidopropyl betaines.

Preferred betaines are, for example, C12-C18-alkylbetaines and sulfobetaines. The zwitterionic surfactant preferably is a betaine surfactant, more preferable a Cocoamidopropylbetaine surfactant.

Non-limiting examples of cationic surfactants - which may be employed also in combinations of more than one other surfactant - include: the quaternary ammonium surfactants, which can have up to 26 carbon atoms include: alkoxylated quaternary ammonium (AQA) surfactants as discussed in US 6,136,769; dimethyl hydroxyethyl quaternary ammonium as discussed in US 6,004,922; dimethyl hydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants as discussed in WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; cationic ester surfactants as discussed in US patents Nos. 4,228,042, 4,239,660 4,260,529 and US 6,022,844; and amino surfactants as discussed in US 6,221 ,825 and WO 00/47708, specifically amido propyldimethyl amine (APA).

Compositions according to the invention may comprise at least one builder. In the context of the present invention, no distinction will be made between builders and such components elsewhere called “co-builders”. Examples of builders are complexing agents, hereinafter also referred to as complexing agents, ion exchange compounds, and precipitating agents. Builders are selected from citrate, phosphates, silicates, carbonates, phosphonates, amino carboxylates and polycarboxylates.

In the context of the present invention, the term citrate includes the mono- and the dialkali metal salts and in particular the mono- and preferably the trisodium salt of citric acid, ammonium or substituted ammonium salts of citric acid as well as citric acid. Citrate can be used as the anhydrous compound or as the hydrate, for example as sodium citrate dihydrate. Quantities of citrate are calculated referring to anhydrous trisodium citrate.

The term phosphate includes sodium metaphosphate, sodium orthophosphate, sodium hydrogenphosphate, sodium pyrophosphate and polyphosphates such as sodium tripolyphosphate. Preferably, however, the composition according to the invention is free from phosphates and polyphosphates, with hydrogenphosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate (“phosphate-free”). In connection with phosphates and polyphosphates, “free from” should be understood within the context of the present invention as meaning that the content of phosphate and polyphosphate is in total in the range from 10 ppm to 0.2% by weight of the respective composition, determined by gravimetry.

The term carbonates includes alkali metal carbonates and alkali metal hydrogen carbonates, preferred are the sodium salts. Particularly preferred is Na2CO3.

Examples of phosphonates are hydroxyalkanephosphonates and aminoalkane-'phosphonates. Among the hydroxyalkanephosphonates, the 1-hydroxyethane-1,1 -diphosphonate (HEDP) is of particular importance as builder. It is preferably used as sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Suitable aminoalkanephosphonates are preferably ethylene diamine-^,tetra-^,methylene-^,phosphonate (EDTMP), diethylenetriaminepenta-'methylene-'phosphonate (DTPMP), and also their higher homologues. They are preferably used in the form of the neutrally reacting sodium salts, e.g. as hexasodium salt of EDTMP or as hepta- and octa-sodium salts of DTPMP.

Examples of amino carboxylates and polycarboxylates are nitrilotriacetates, ethylene diamine tetraacetate, diethylene triamine pentaacetate, triethylene tetraamine hexaacetate, propylene diamines tetraacetic acid, ethanol-diglycines, methylglycine diacetate, and glutamine diacetate. The term amino carboxylates and polycarboxylates also include their respective non-substituted or substituted ammonium salts and the alkali metal salts such as the sodium salts, in particular of the respective fully neutralized compound. Silicates in the context of the present invention include in particular sodium disilicate and sodium metasilicate, alumosilicates such as for example zeolites and sheet silicates, in particular those of the formula a-Na2Si2O5, p-Na2Si2O5, and 5-Na2Si2O5.

Compositions according to the invention may contain one or more builder selected from materials not being mentioned above. Examples of builders are a-hydroxypropionic acid and oxidized starch.

In one embodiment of the present invention, builder is selected from polycarboxylates. The term “polycarboxylates” includes non-polymeric polycarboxylates such as succinic acid, C2-C16-alkyl disuccinates, C2-C16-alkenyl disuccinates, ethylene diamine N,N’-disuccinic acid, tartaric acid diacetate, alkali metal malonates, tartaric acid monoacetate, propanetricarboxylic acid, butanetetracarboxylic acid and cyclopentanetetracarboxylic acid.

Oligomeric or polymeric polycarboxylates are for example polyaspartic acid or in particular alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers.

Suitable co-monomers are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has a weight-average molecular weight Mw in the range from 2000 to 40 000 g/mol, preferably 2000 to 10 000 g/mol, in particular 3000 to 8000 g/mol. Further suitable copolymeric polycarboxylates are in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and/or fumaric acid. It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated C3-C10-mono- or C4-C10-dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilically or hydrophobically modified co-monomer as listed below.

Suitable hydrophobic co-monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with ten or more carbon atoms or mixtures thereof, such as, for example, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1 -octadecene, 1-eicosene, 1- docosene, 1-tetracosene and 1-hexacosene, C22-a-olefin, a mixture of C20-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

Suitable hydrophilic co-monomers are monomers with sulfonate or phosphonate groups, and also non-ionic monomers with hydroxyl function or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here can comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido-1- propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2- methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3- methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2- propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.

Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

Moreover, amphoteric polymers can also be used as builders.

Compositions according to the invention can comprise, for example, in the range from in total 0.1 to 70% by weight, preferably 10 to 50% by weight, preferably up to 20% by weight, of builder(s), especially in the case of solid formulations. Liquid formulations according to the invention preferably comprise in the range of from 0.1 to 8% by weight of builder.

Formulations according to the invention can comprise one or more alkali carriers. Alkali carriers ensure, for example, a pH of at least 9 if an alkaline pH is desired. Of suitability are, for example, the alkali metal carbonates, the alkali metal hydrogen carbonates, and alkali metal metasilicates mentioned above, and, additionally, alkali metal hydroxides. A preferred alkali metal is in each case potassium, particular preference being given to sodium. In one embodiment of the present invention, a pH >7 is adjusted by using amines, preferably alkanolamines, more preferably triethanolamine.

In one embodiment of the present invention, the laundry formulation or composition according to the invention comprises additionally at least one enzyme.

Useful enzymes are, for example, one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types.

In one embodiment, the composition according to the present invention comprises additionally at least one enzyme.

Preferably, the at least one enzyme is a detergent enzyme.

In one embodiment, the enzyme is classified as an oxidoreductase (EC 1), a transferase (EC 2), a hydrolase (EC 3), a lyase (EC 4), an isomerase (EC 5), or a ligase (EC 6) (the EC-numbering is according to Enzyme Nomenclature, Recommendations (1992) of the Nomenclature Committee of the International Union of Biochemistry and Molecular Biology including its supplements published 1993-1999). Preferably, the enzyme is a hydrolase (EC 3).

In a preferred embodiment, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, hemicellulases, phospholipases, esterases, pectinases, lactases, peroxidases, xylanases, cutinases, pectate lyases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, nucleases, DNase, phosphodiesterases, phytases, carbohydrases, galactanases, xanthanases, xyloglucanases, oxidoreductase, perhydrolases, aminopeptidase, asparaginase, carbohydrase, carboxypeptidase, catalase, chitinase, cyclodextrin glycosyltransferase, alphagalactosidase, beta-galactosidase, glucoamylase, alpha-glucosidase, beta-glucosidase, invertase, ribonuclease, transglutaminase, and dispersins, and combinations of at least two of the foregoing types. More preferably, the enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, mannanases, xylanases, DNases, dispersins, pectinases, oxidoreductases, and cutinases, and combinations of at least two of the foregoing types. Most preferably, the enzyme is a protease, preferably, a serine protease, more preferably, a subtilisin protease. Such enzyme(s) can be incorporated into the composition at levels sufficient to provide an effective amount for achieving a beneficial effect, preferably for primary washing effects and/or secondary washing effects, like antigreying or antipilling effects (e.g., in case of cellulases). Preferably, the enzyme is present in the composition at levels from about 0.00001 % to about 5%, preferably from about 0.00001 % to about 2%, more preferably from about 0.0001% to about 1 %, or even more preferably from about 0.001 % to about 0.5% enzyme protein by weight of the composition.

Preferably, the enzyme-containing composition further comprises an enzyme stabilizing system. Preferably, the enzyme-containing composition described herein comprises from about 0.001% to about 10%, from about 0.005% to about 8%, or from about 0.01 % to about 6%, by weight of the composition, of an enzyme stabilizing system. The enzyme stabilizing system can be any stabilizing system which is compatible with the enzyme.

Preferably, the enzyme stabilizing system comprises at least one compound selected from the group consisting of polyols (preferably, 1 ,3-propanediol, ethylene glycol, glycerol, 1 ,2- propanediol, or sorbitol), salts (preferably, CaCI2, MgCI2, or NaCI), short chain (preferably, C1- C6) carboxylic acids (preferably, formic acid, formate (preferably, sodium formate), acetic acid, acetate, or lactate), borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4- FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. Preferably, the enzyme stabilizing system comprises a combination of at least two of the compounds selected from the group consisting of salts, polyols, and short chain carboxylic acids and preferably one or more of the compounds selected from the group consisting of borate, boric acid, boronic acids (preferably, 4-formyl phenylboronic acid (4-FPBA)), peptide aldehydes, peptide acetals, and peptide aldehyde hydrosulfite adducts. In particular, if proteases are present in the composition, protease inhibitors may be added, preferably selected from borate, boric acid, boronic acids (preferably, 4-FPBA), peptide aldehydes (preferably, peptide aldehydes like Z-VAL-H or Z-GAY-H), peptide acetals, and peptide aldehyde hydrosulfite adducts.

Compositions according to the invention may comprise one or more bleaching agent (bleaches). Preferred bleaches are selected from sodium perborate, anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, and sodium persulfate, where the term “persulfate” in each case includes the salt of the peracid H2SO5 and also the peroxodisulfate.

In this connection, the alkali metal salts can in each case also be alkali metal hydrogen carbonate, alkali metal hydrogen perborate and alkali metal hydrogen persulfate. However, the dialkali metal salts are preferred in each case.

Formulations according to the invention can comprise one or more bleach catalysts. Bleach catalysts can be selected from oxaziridinium-based bleach catalysts, 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 ruthenium-amine complexes can also be used as bleach catalysts.

Formulations according to the invention can comprise one or more bleach activators, for example tetraacetyl ethylene diamine, tetraacetylmethylene diamine, tetra^_,acetylglycoluril, tetraacetylhexylene diamine, acylated phenolsulfonates such as for example n-nonanoyl- or isononanoyloxybenzene sulfonates, N-methylmorpholinium-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).

Formulations according to the invention can comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, formulations according to the invention comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.

Besides such “typical” corrosion inhibitors, also amphoteric surfactants can promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N- lauryl-beta-iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium).

Formulations according to the invention may also comprise further cleaning polymers and/or soil release polymers.

The additional cleaning polymers may include, without limitation, “multifunctional polyethylene imines” (for example BASF’s Sokalan® HP20) and/or “multifunctional diamines” (for example BASF’s Sokalan® HP96), and also those disclosed and claimed in WO2021/254828, WO2022/136408A1 , WO2022/136409A1, WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and WO2023/117494. Such multifunctional polyethylene imines are typically ethoxylated polyethylene imines with a weight-average molecular weight Mw in the range from 3000 to 250000, preferably 5000 to 200000, more preferably 8000 to 100000, more preferably 8000 to 50000, more preferably 10000 to 30000, and most preferably 10000 to 20000 g/mol. Suitable multifunctional polyethylene imines have 80 wt. % to 99 wt. %, preferably 85 wt. % to 99 wt. %, more preferably 90 wt. % to 98 wt. %, most preferably 93 wt. % to 97 wt. % or 94 wt. % to 96 wt. % ethylene oxide side chains, based on the total weight of the materials. Ethoxylated polyethylene imines are typically based on a polyethylene imine core and a polyethylene oxide shell. Suitable polyethylene imine core molecules are polyethylene imines with a weight-average molecular weight Mw in the range of 500 to 5000 g/mol. Preferably employed is a molecular weight from 500 to 1000 g/mol, even more preferred is a Mw of 600 to 800 g/mol. The ethoxylated polymer then has on average 5 to 50, preferably 10 to 35 and even more preferably 20 to 35 ethylene oxide (EO) units per NH-functional group.

Suitable multifunctional diamines are typically ethoxylated C2 to C12 alkylene diamines, preferably hexamethylene diamine, which are further quaternized and optionally sulfated. Typical multifunctional diamines have a weight-average molecular weight Mw in the range from 2000 to 10000, more preferably 3000 to 8000, and most preferably 4000 to 6000 g/mol. In a preferred embodiment of the invention, ethoxylated hexamethylene diamine, furthermore quaternized and sulfated, may be employed, which contains on average 10 to 50, preferably 15 to 40 and even more preferably 20 to 30 ethylene oxide (EO) groups per NH-functional group, and which preferably bears two cationic ammonium groups and two anionic sulfate groups. In a preferred embodiment of the present invention, the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional diamine to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents. The multifunctional polyethylene imines or multifunctional diamines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt. %, preferably from 0.1 to 10 wt. % and more preferably from 0.25 to 5 wt. % and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.

In a preferred embodiment of the present invention, the cleaning compositions may contain at least one multifunctional polyethylene imine and/or at least one multifunctional di- and/or oligoamine, specifically any of the claimed polymers from WO2021/254828, WO2022/136408A1 , WO2022/136409A1, WO2021/165468, W02023/021103, W02023/021104, W02023/021105 and/or WO2023/117494, to improve the cleaning performance, such as preferably improve the stain removal ability, especially the primary detergency of particulate stains on polyester fabrics of laundry detergents. The multifunctional polyethylene imines or multifunctional di- or oligomines or mixtures thereof according to the descriptions above may be added to the laundry detergents and cleaning compositions in amounts of generally from 0.05 to 15 wt%, preferably from 0.1 to 10 wt% and more preferably from 0.25 to 5 wt% and even as low as up to 2 wt.%, based on the particular overall composition, including other components and water and/or solvents.

Thus, one aspect of the present invention is a laundry detergent composition, in particular a liquid laundry detergent, comprising (i) at least one inventive compound and (ii) at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof.

In one embodiment of the present invention, the ratio of the at least one inventive compound and (ii) the at least one compound selected from multifunctional polyethylene imines and multifunctional diamines and mixtures thereof, is from 10:1 to 1 :10, preferably from 5:1 to 1:5 and more preferably from 3:1 to 1 :3.

Cleaning compositions, fabric and home care products and specifically the laundry formulations comprising the inventive compound may also comprise at least one antimicrobial agent (named also “preservative”).

An antimicrobial agent is a chemical compound that kills microorganisms or inhibits their growth or reproduction. Microorganisms can be bacteria, yeasts or molds. A preservative is an antimicrobial agent which may be added to aqueous products and compositions to maintain the original performance, characteristics and integrity of the products and compositions by killing contaminating microorganisms or inhibiting their growth.

The composition/formulation may contain one or more antimicrobial agents and/or preservatives as listed in patent WO2021/115912 A1 (“Formulations comprising a hydrophobically modified polyethyleneimine and one or more enzymes”) on pages 35 to 39.

Especially of interest for the cleaning compositions and fabric and home care products and specifically in the laundry formulations are any of the following antimicrobial agents and/or preservatives: 4,4’-dichloro 2-hydroxydiphenyl ether (further names: 5-chloro-2-(4-chlorophenoxy) phenol, Diclosan, DCPP), Tinosan® HP 100 (commercial product of BASF SE containing 30% of the antimicrobial active 4,4’-dichoro 2-hydroxydiphenylether); 2-Phenoxyethanol (further names: Phenoxyethanol, Methylphenylglycol, Phenoxetyethanol, ethylene glycol phenyl ether, Ethylene glycol monophenyl ether, 2-(phenoxy) ethanol, 2-phenoxy-1-ethanol); 2-bromo-2-nitropropane-

1.3-diol (further names: 2-bromo-2-nitro-1,3-propanediol, Bronopol); Glutaraldehyde (further names: 1-5-pentandial, pentane-1, 5-dial, glutaral, glutar-dialdehyde); Glyoxal (further names: ethandial, oxylaldehyde, 1,2-ethandial); 2-butyl-benzo[d]isothiazol-3-one (“BBIT”); 2-methyl-2H- isothiazol-3-one (“MIT””); 2-octyl-2H-isothiazol-3-one (“OIT”); 5-Chloro-2-methyl-2H-isothiazol-3- one (“GIT” or“CMIT”); Mixture of 5-chloro-2-methyl-2H- isothiazol-3-one (“CMIT”) and 2-methyl- 2H-isothiazol-3-one (“MIT”) (Mixture of CMIT/MIT); 1 ,2-benzisothiazol-3(2H)-one (“BIT”); Hexa-

2.4-dienoic acid (trivial name “sorbic acid”) and its salts, e.g., calcium sorb-ate, sodium sorbate; potassium (E,E)-hexa-2,4-dienoate (Potassium Sorbate); Lactic acid and its salts; L-(+)-lactic acid; especially sodium lactate; Benzoic acid and salts of benzoic acid, e.g., sodium benzoate, ammonium benzo-ate, 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; Didecyldimethylammonium chloride (“DDAC”); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine ("Diamine"); Peracetic acid; Hydrogen peroxide.

At least one such antimicrobial agent 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, the composition contains 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 also encompasses a method of preserving an aqueous composition according to the invention against microbial contamination or growth, which method comprises addition of at least one antimicrobial agent or preservative, preferably 2-phenoxyethanol.

The invention also encompasses a method of providing an antimicrobial effect on textiles after treatment with a solid laundry detergent (e.g. powders, granulates, capsules, tablets, bars etc.), a liquid laundry detergent, a softener or an after-rinse containing 4,4’-dichloro 2- hydroxydiphenyl ether (DCPP).

Formulations according to the invention may also comprise water and/or additional organic solvents, e.g., ethanol or propylene glycol.

Further optional ingredients may be but are not limited to viscosity modifiers, cationic surfactants, foam boosting or foam reducing agents, perfumes, dyes, optical brighteners, and dye transfer inhibiting agents.

Dish wash compositions

Another aspect of the present invention is also a dish wash composition, comprising at least one inventive compound(s) as described above.

Thus, an aspect of the present invention is also the use of the inventive compound(s) as described above, in dish wash applications, such as manual or automated dish wash applications. Dish wash compositions according to the invention can be in the form of a liquid, semi-liquid, cream, lotion, gel, or solid composition, solid embodiments encompassing, for example, powders and tablets. Liquid compositions are typically preferred for manual dish wash applications, whereas solid formulations and pouch formulations (where the pouches may contain also solids in addition to liquid ingredients) are typically preferred for automated dish washing compositions; however, in some areas of the world also liquid automated dish wash compositions are used and are thus of course also encompassed by the term “dish wash composition”.

The dish wash compositions are intended for direct or indirect application onto dishware and metal and glass surfaces, such as drinking and other glasses, beakers, dish and cooking ware like pots and pans, and cutlery such as forks, spoons, knives and the like.

The inventive method of cleaning dishware, metal and/or glass surfaces comprises the step of applying the dish wash cleaning composition, preferably in liquid form, onto the surface, either directly or by means of a cleaning implement, i.e. , in neat form. The composition is applied directly onto the surface to be treated and/or onto a cleaning device or implement such as a dish cloth, a sponge or a dish brush and the like without undergoing major dilution (immediately) prior to the application. The cleaning device or implement is preferably wet before or after the composition is delivered to it. In the method of the invention, the composition can also be applied in diluted form.

Both neat and dilute application give rise to superior cleaning performance, i.e. the formulations of the invention containing at least one inventive compound(s)exhibit excellent degreasing properties. The effort of removing fat and/or oily soils from the dishware, metal and/or glass surfaces is decreased due to the presence of the inventive compound(s), even when the level of surfactant used is lower than in conventional compositions.

Preferably the composition is formulated to provide superior grease cleaning (degreasing) properties, long-lasting suds and/or improved viscosity control at decreased temperature exposures; preferably at least two, more preferably all three properties are present in the inventive dish wash composition. Optional - preferably present - further benefits of the inventive manual dish wash composition include soil removal, shine, and/or hand care; more preferably at least two and most preferably all three further benefits are present in the inventive dish wash composition.

In one embodiment of the present invention, the inventive compound(s) is one component of a manual dish wash formulation that additionally comprises at least one surfactant, preferably at least one anionic surfactant.

In another embodiment of the present invention, the inventive compound(s)is one component of a manual dish wash formulation that additionally comprises at least one anionic surfactant and at least one other surfactant, preferably selected from amphoteric surfactants and/or zwitterionic surfactants. In a preferred embodiment of the present invention, the manual dish wash formulations contain at least one amphoteric surfactant, preferably an amine oxide, or at least one zwitterionic surfactant, preferably a betaine, or mixtures thereof, to aid in the foaming, detergency, and/or mildness of the detergent composition. Examples of suitable anionic surfactants are already mentioned above for laundry compositions. Preferred anionic surfactants for dish wash compositions are selected from C10-C15 linear alkylbenzenesulfonates, C10-C18 alkylethersulfates with 1-5 ethoxy units and C10-C18 alkylsulfates.

Preferably, the manual dish wash detergent formulation of the present invention comprises from at least 1 wt% to 50 wt%, preferably in the range from greater than or equal to about 3 wt% to equal to or less than about 35 wt%, more preferably in the range from greater than or equal to 5 wt% to less than or equal to 30 wt%, and most preferably in the range from greater than or equal to 5 wt% to less than or equal to 20 wt% of one or more anionic surfactants as described above, based on the particular overall composition, including other components and water and/or solvents.

Dish wash compositions according to the invention may comprise at least one amphoteric surfactant.

Examples of suitable amphoteric surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred amphoteric surfactants for dish wash compositions are selected from C8-C18 alkyldimethyl aminoxides and C8-C18 alkyl-di(hydroxyethyl)aminoxide.

The manual dish wash detergent composition of the invention preferably comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of an amphoteric surfactant, preferably an amine oxide surfactant. Preferably the composition of the invention comprises a mixture of the anionic surfactants and alkyl dimethyl amine oxides in a weight ratio of less than about 10:1 , more preferably less than about 8:1, more preferably from about 5:1 to about 2:1.

Addition of the amphoteric surfactant provides good foaming properties in the dish wash composition.

In this chapter on Dish Wash it needs to be emphasized again that certain amphoteric surfactants can - besides their typical action as surfactant - promote corrosion inhibition, such as compounds having one or two carboxylic groups and one or more amine groups, and optionally further containing also amide-groups and/or hydroxy-groups; such compounds for example being N-(2-carboxyethyl)-N-dodecyl-beta-alaninate (also named N-lauryl-beta- iminodipropionate metal salt, cocoamphodiacetate di-metal salt, cocoamphoacetate metal salt (the metal typically being sodium). Hence, such amphoteric surfactants are preferred when corrosion inhibition is of importance, such as in cleaning applications which typically have a high pH, e.g. automatic dish washing.

Dish wash compositions according to the invention may comprise at least one zwitterionic surfactant.

Examples of suitable zwitterionic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred zwitterionic surfactants for dish wash compositions are selected from betaine surfactants, more preferable from Cocoamidopropylbetaine surfactants.

In a preferred embodiment of the present invention, the zwitterionic surfactant is Cocamidopropylbetaine. The manual dish wash detergent composition of the invention optionally comprises from 1 wt% to 15 wt%, preferably from 2 wt% to 12 wt%, more preferably from 3 wt% to 10 wt% of the composition of a zwitterionic surfactant, preferably a betaine surfactant.

Dish wash compositions according to the invention may comprise at least one cationic surfactant.

Examples of suitable cationic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Cationic surfactants, when present in the composition, are present in an effective amount, more preferably from 0.1 wt% to 5 wt%, preferably 0.2 wt% to 2 wt% of the composition.

Dish wash compositions according to the invention may comprise at least one non-ionic surfactant.

Examples of suitable non-ionic surfactants for dish wash compositions are already mentioned above for laundry compositions.

Preferred non-ionic surfactants are the condensation products of Guerbet alcohols with from 2 to 18 moles, preferably 2 to 15, more preferably 5-12 of ethylene oxide per mole of alcohol. Other preferred non-ionic surfactants for use herein include fatty alcohol polyglycol ethers, alkylpolyglucosides and fatty acid glucamides.

The manual hand dish detergent composition of the present invention may comprise from 0.1 wt% to 10 wt%, preferably from 0.3 wt% to 5 wt%, more preferably from 0.4 wt% to 2 wt% of the composition, of a linear or branched C10 alkoxylated non-ionic surfactant having an average degree of alkoxylation of from 2 to 6, preferably from 3 to 5. Preferably, the linear or branched C10 alkoxylated non-ionic surfactant is a branched C10 ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 2 to 6, preferably of from 3 to 5. Preferably, the composition comprises from 60 wt% to 100 wt%, preferably from 80 wt% to 100 wt%, more preferably 100 wt% of the total linear or branched C10 alkoxylated non-ionic surfactant of the branched C10 ethoxylated non-ionic surfactant. The linear or branched C10 alkoxylated non- ionic surfactant preferably is a 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5. A suitable 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of 4 is Lutensol® XP40, commercially available from BASF SE, Ludwigshafen, Germany. The use of a 2-propylheptyl ethoxylated non- ionic surfactant having an average degree of ethoxylation of from 3 to 5 leads to improved foam levels and long-lasting suds.

Thus, one aspect of the present invention is a manual dish wash detergent composition, in particular a liquid manual dish wash detergent composition, comprising (i) at least one inventive compound, and (ii) at least one further 2-propylheptyl ethoxylated non-ionic surfactant having an average degree of ethoxylation of from 3 to 5.

Dish wash compositions according to the invention may comprise at least one hydrotrope in an effective amount, to ensure the compatibility of the liquid manual dish wash detergent compositions with water.

Suitable hydrotropes for use herein include anionic hydrotropes, particularly sodium, potassium, and ammonium xylene sulfonate, sodium, potassium and ammonium toluene sulfonate, sodium, potassium, and ammonium cumene sulfonate, and mixtures thereof, and related compounds, as disclosed in U.S. Patent 3,915,903. The liquid manual dish wash detergent compositions of the present invention typically comprise from 0.1 wt% to 15 wt% of the total liquid detergent composition of a hydrotrope, or mixtures thereof, preferably from 1 wt% to 10 wt%, most preferably from 2 wt% to 5 wt% of the total liquid manual dish wash composition.

Dish wash compositions according to the invention may comprise at least one complexing agent, which may be selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, methylglycinediacetic acid, glutamic acid diacetic acid, iminodisuccinic acid, hydroxyiminodisuccinic acid, ethylenediaminedisuccinic acid, aspartic acid diacetic acid, and also salts thereof in each case. Preferred complexing agents are methylglycinediacetic acid and glutamic acid diacetic acid and salts thereof. Particularly preferred complexing agents are methylglycinediacetic acid and salts thereof, especially the mono-, di- and trisodium, - potassium, -lithium and -ammonium salts. The salts of methylglycinediacetic acid may be in racemic form, meaning that D- and L-enantiomers are present in an equimolar mixture, or one enantiomer, e.g. the L-enantiomer, may be present in excess. Preference is given to 3 to 50% by weight complexing agents according to the invention.

Dish wash compositions according to the invention may comprise at least one builder and/or cobuilder; they may be selected from, in particular, water-soluble or water-insoluble substances of which the main task consists of binding calcium and magnesium ions. These may be low molecular weight carboxylic acids and also salts thereof such as alkali metal citrates, in particular anhydrous trisodium citrate or trisodium citrate dihydrate, alkali metal succinates, alkali metal malonates, fatty acid sulfonates, oxydisuccinate, alkyl or alkenyl disuccinates, gluconic acids, oxadi acetates, carboxymethyloxysuccinates, tartrate monosuccinate, tartrate disuccinate, tartrate monoacetate, tartrate diacetate and a-hydroxypropionic acid.

A further substance class with cobuilder properties which may be present in the cleaning compositions of the invention is that of the phosphonates. These are in particular hydroxyalkanephosphonates or aminoalkanephosphonates. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1 ,1 -diphosphonate (HEDP) is of particular significance as cobuilder. It is preferably used in the form of sodium salt, the disodium salt giving a neutral reaction and the tetrasodium salt an alkaline reaction (pH 9). Suitable aminoalkanephosphonates are preferably ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and the higher homologs thereof. They are preferably used in the form of the neutral reacting sodium salts, for example as the hexasodium salt of EDTMP or as heptasodium and octasodium salts of DTPMP. The builder used in this case is from the class of the phosphonates, preferably HEDP. Aminoalkanephosphonates additionally have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use aminoalkanephosphonates, particularly DTPMP, or mixtures of the phosphonates mentioned, particularly if the compositions also comprise bleach. Silicates may be used, inter alia, as builders. Crystalline sheet silicates having the general formula NaMSixO2x+1 yH2O may be present, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, particularly preferred values for x being 2, 3 or 4, and y is a number from 0 to 33, preferably 0 to 20. In addition, amorphous sodium silicates having an SiO2: Na2O ratio of 1 to 3.5, preferably 1 .6 to 3 and in particular 2 to 2.8 may be used. Furthermore, in the context of the dishwashing composition according to the invention, builders and/or co-builders used may be carbonates and hydrogen carbonates, among which the alkali metal salts, particularly sodium salts, are preferred.

Furthermore, the cobuilders used may be homopolymers and copolymers of acrylic acid or methacrylic acid preferably having a weight-average molar mass of 2000 to 50 000 g/mol. Suitable comonomers are in particular monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and also anhydrides thereof such as maleic anhydride. Also suitable are comonomers containing sulfonic acid groups such as 2-acrylamido- 2-methylpropanesulfonic acid, allylsulfonic acid and methanesulfonic acid. Hydrophobic comonomers are also suitable, for example isobutene, diisobutene, styrene, alpha-olefins with 10 or more carbon atoms. Hydrophilic monomers having hydroxyl functions or alkylene oxide groups may also be used as comonomers. Examples include: allyl alcohol and isoprenol and also alkoxylates thereof and methoxypolyethylene glycol (meth)acrylate. Preferably however, those homopolymers and copolymers of acrylic acid or methacrylic acid may be completely replaced by the polyaspartic acid polymers and their salts of the present invention.

Preferred amounts of builders and/or cobuilders in the context of the dishwashing composition of the invention are 5 to 80 wt%, more preferably 10 to 75 wt%, 15 to 70 wt% or 15 to 65 wt%.

Dish wash compositions according to the invention may comprise at least one organic solvent. Examples of organic solvents are C4-C14 ethers and diethers, glycols, alkoxylated glycols, C6- C16 glycol ethers, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branched alcohols, alkoxylated aliphatic branched alcohols, alkoxylated linear C1-C5 alcohols, linear CIGS alcohols, amines, C8-C14 alkyl and cycloalkyl hydrocarbons and halohydrocarbons, and mixtures thereof.

When present, the liquid dish wash compositions will contain from 0.01 wt% to 20 wt%, preferably from 0.5 wt% to 15 wt%, more preferably from 1 wt% to 10 wt%, most preferably from 1 wt% to 5 wt% of the liquid detergent composition of a solvent. These solvents may be used in conjunction with an aqueous liquid carrier, such as water, or they may be used without any aqueous liquid carrier being present. At higher solvent systems, the absolute values of the viscosity may drop but there is a local maximum point in the viscosity profile.

The dish wash compositions herein may further comprise from 30 wt% to 90 wt% of an aqueous liquid carrier, comprising water, in which the other essential and optional ingredients are dissolved, dispersed or suspended. More preferably the compositions of the present invention comprise from 45 wt% to 85 wt%, even more preferably from 60 wt% to 80 wt% of the aqueous liquid carrier. The aqueous liquid carrier, however, may contain other materials which are liquid, or which dissolve in the liquid carrier, at room temperature (25 °C) and which may also serve some other function besides that of an inert filler.

Dish wash compositions according to the invention may comprise at least one electrolyte. Suitable electrolytes are preferably selected from inorganic salts, even more preferably selected from monovalent salts, most preferably sodium chloride.

The liquid manual dish wash compositions according to the invention may comprise from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 2 wt% of the composition of an electrolyte.

Manual dish wash formulations comprising the inventive compound(s) may also comprise at least one antimicrobial agent. Examples of suitable antimicrobial agents for dish wash compositions are already mentioned above for laundry compositions.

The antimicrobial agent may be added to the inventive hand dish wash composition in a concentration of 0.0001 wt% to 10 wt% relative to the total weight of composition. Preferably, the formulation contains 2-phenoxyethanol in a concentration of 0.01 wt% to 5 wt%, more preferably 0.1 wt% to 2 wt% and/or 4,4’-dichloro 2-hydroxydiphenyl ether in a concentration of 0.001 wt% to 1 wt%, more preferably 0.002 wt% to 0.6 wt% (in all cases relative to the total weight of the composition).

Further additional ingredients are such as but not limited to conditioning polymers, cleaning polymers, surface modifying polymers, soil flocculating polymers, rheology modifying polymers, enzymes, structurants, builders, chelating agents, cyclic diamines, emollients, humectants, skin rejuvenating actives, carboxylic acids, scrubbing particles, bleach and bleach activators, perfumes, malodor control agents, pigments, dyes, opacifiers, beads, pearlescent particles, microcapsules, antibacterial agents, pH adjusters including NaOH and alkanolamines such as mono-ethanolamines and buffering means.

General cleaning compositions and formulations for Laundry and Dish Wash

The disclosed liquid formulations in this chapter may and preferably do comprise 0 to 2 % 2- phenoxyethanol, preferably about 1 %, in addition to all other mentioned ingredients.

The disclosed liquid formulations in this chapter may and preferably do comprise 0-0,2% 4,4’- dichoro 2-hydroxydiphenylether, preferably about 0,15 %, in addition to all other mentioned ingredients.

The bleach-free solid laundry compositions may comprise 0-0,2% 4,4’-dichoro 2- hydroxydiphenylethe, preferably about 0,15 %, in addition to all other mentioned ingredients. The disclosed formulations in this chapter may and preferably do comprise one or more enzymes selected from those disclosed herein above, more preferably a protease and/or an amylase, wherein even more preferably the protease is a protease with at least 90% sequence identity to SEQ ID NO: 22 of EP1921147B1 and having the amino acid substitution R101E (according to BPN’ numbering) and wherein the amylase is an amylase with at least 90% sequence identity to SEQ ID NO: 54 of WO2021032881 A1 , such enzyme(s) preferably being present in the formulations at levels from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5% enzyme protein by weight of the composition.

The tables in this chapter show general cleaning compositions of certain types, which correspond to typical compositions correlating with typical washing conditions as typically employed in various regions and countries of the world. The at least one inventive compound may be added to such formulation(s) in suitable amounts as outlined herein.

When no inventive compound is added, a shown formulation is a “comparative formulation”; when the amount chosen is in the general range as disclosed herein and specifically within ranges disclosed herein as preferred amounts for the various ingredients and the inventive compound, the formulation is a formulation according to the invention. Ingredients (other than the inventive compound) listed with amounts including “zero%” in the mentioned range may be present but not necessarily have to be present, in both the inventive and the comparative formulations. Hence, each number encompassed by a given range is meant to be included in the formulations shown in this chapter, and all variations and permutations possible are likewise meant to be included.

In a preferred embodiment the inventive compound is used in a laundry detergent.

Liquid laundry detergents according to the present invention are preferably composed of: 0,1 - 50 % of at least one inventive compound 1 - 50% of surfactants

0,1 - 40 % of builders, cobuilders and/or chelating agents

0,1 - 50 % other adjuncts water to add up 100 %.

Preferred liquid laundry detergents according to the present invention are composed of: 0,5 - 20 % of at least one inventive compound

5 - 40 % of anionic surfactants selected from C10-C15- LAS and C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units

1.5 - 10 % of nonioic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units

2 - 20 % of soluble organic builders/ cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxy-di- and hydroxytricaboxylic acids, aminopolycarboxylates and polycarboxylic acids

0,05 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylenglycol, or propylenglyclol

0,1 - 20 % other adjuncts water to add up to 100%.

Solid laundry detergents (like e.g. powders, granules or tablets) according to the present invention are preferably composed of:

1 - 50 % of at least one inventive compound 1 - 50% of surfactants

0,1 - 80 % of builders, cobuilders and/or chelating agents

0 - 50% of fillers

0 - 40% of bleach actives

0,1 - 30 % of other adjuncts and/or water wherein the sum of the ingredients adds up 100 %.

Preferred solid laundry detergents according to the present invention are composed of: 1 - 20 % of at least one inventive compound

5 - 30 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkylsulfates and C10- C18 alkyl ethersulfates containing 1-5 ethoxy-units

1.5 - 7,5 % of non-ionic surfactants selected from C10-C18-alkyl ethoxylates containing 3 - 10 ethoxy-units

20 - 80 % of inorganic builders and fillers selected from sodium carbonate, sodium bicarbonate, zeolites, soluble silicates, sodium sulfate 0,5 - 15 % of cobuilders selected from C10-C18 fatty acids, di- and tricarboxylic acids, hydroxydi- and hydroxytricarboxylic acids, aminopolycarboxylates and polycarboxylic acids 0,1 - 5 % of an enzyme system containing at least one enzyme suitable for detergent use and preferably also an enzyme stabilizing system

0,5 - 30 % of bleach actives

0,1 - 20 % other adjuncts water to ad up to 100%

In a preferred embodiment at least one compound according to the present invention is used in a manual dish wash detergent.

Liquid manual dish wash detergents according to the present invention are composed of: 1 - 50 % of at least one inventive compound

1 - 90% of surfactants

0,1 - 50 % of other adjuncts water to add up 100 %.

Preferred liquid manual dish wash detergents according to the present invention are composed of:

1 - 20 % of at least one inventive compound

1 - 35 % of a surfactant system:

60% to 90%, more preferably from 70% to 80% by weight of the surfactant system of an anionic surfactant;

0.5% to 15% - by weight of the surfactant system - of a co-surfactant, preferably selected from the group consisting of an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof; 1% to 10% - by weight of the surfactant system - of a non-ionic surfactant;

0 - 5 % of an enzyme, preferably also including an enzyme stabilizing system;

0,5 - 20 % of mono- or diols selected from ethanol, isopropanol, ethylene glycol, or propylene glycol;

0,1 - 20 % other adjuncts; water to add up to 100%.

Alternative preferred liquid manual dish wash detergents according to the present invention are composed of:

1 - 15 % of at least one inventive compound

5 - 80 % of anionic surfactants selected from C10-C15- LAS, C10-C18 alkyl ethersulfates containing 1-5 ethoxy-units, and C10-C18 alkylsulfate

2 - 10 % of Cocamidopropylbetaine

0 - 10 % of Lauramine oxide

0 - 2 % of a non-ionic surfactant, preferably a C10-Guerbet alcohol alkoxylate

0 - 5 % of an enzyme, preferably Amylase, and preferably also an enzyme stabilizing system

0,1 - 20 % other adjuncts water to add up to 100% A preferred dishwashing composition according to the invention comprises

(a) 1-20% by weight, preferably 1-15% by weight, particularly preferably 2-12% by weight of the polyaspartic acid prepared or preparable in accordance with the invention and described herein throughout the description, examples and claims;

(b) 0-50% by weight complexing agents;

(c) 0.1 -80% by weight builders and/or co-builders;

(d) 0.1 -20% by weight non-ionic surfactants;

(e) 0-30% by weight bleach, bleach activators and bleach catalysts;

(f) 0-8% by weight enzymes; and

(g) 0-50% by weight additives.

It is clear that the total amount of all ingredients within the herein disclosed formulations have to add up to “100” percent by weight of the total formulation.

In the following tables:

“Inventive Compound(s)” = at least one inventive compound as described in this present invention, i.e. at least one (and thus also including a mixture of more than one) polyaspartic acid prepared or preparable in accordance with the invention and described herein throughout the description, examples and claims;

General formula for laundry detergent compositions according to the invention: (numbers: wt.%)

Liquid laundry frame formulations according to the invention:

Liquid laundry frame formulations according to the invention - continued: Laundry powder frame formulations according to the invention:

Laundry powder frame formulations according to the invention - continued:

Further typical liquid detergent formulations LD1 , LD2 and LD3 are shown in the following three tables: (numbers: wt.% active)

Liquid detergent 1- LD1 “excellent” detergent;

Liquid detergent 2- LD2 “medium” performance detergent Liquid detergent 3- LD3 “medium” performance “biobased” detergent All previous three tables on LD1, LD2, LD3: *”graft polymer” = (poly ethylene glycol of Mn 6000 g/mol as graft base, grafted with 40 weigth % vinyl acetate (based on total polymer weight; produced following general disclosure of W02007138054A1)

Liquid manual dish wash frame formulations according to the invention:

It is preferred, that within the respective laundry detergent, cleaning composition and/or fabric and home care product, the at least one compound as described in this invention is present at a concentration of from about 0.1% to about 50%, preferably from about 0,5% to 20%, more preferably from about 1% to about 15%, and even more preferably from about 2% to about 12%, each in weight % in relation to the total weight of such composition/product, and all numbers in between, and including all ranges resulting from selecting any of the lower limits mentioned and including further 0.6, 0.7, 0.8, 0.9, 1 , 1.5, 2, 2.5, 3, 3.5, 4, 4.5, and so on, and combing with any of the upper limits mentioned and including any value in between 50 and 20, and 19, 18, 17, 16, 14, 13, 12, 11 , 9.5, 9, 8.5, 8, 7.5, 7, 6.5 and 6.

Specifically for a liquid hand dishwashing or spray detergent composition, in one embodiment the at least one compound as described in this invention is present at a concentration of from about between 0.1 and 50%, preferably between 1% and 30%, by weight of the detergent composition. The specific embodiments as described throughout this disclosure are encompassed by the present invention as part of this invention; the various further options being disclosed in this present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” options of a specific embodiment may be individually and independently (unless such independent selection is not possible by virtue of the nature of that feature or if such independent selection is explicitly excluded) selected and then combined within any of the other embodiments (where other such options and preferences can be also selected individually and independently), with each and any and all such possible combinations being included as part of this invention as individual embodiments.

The following examples serve to illustrate the present invention and must not be understood as a restriction thereon.

Examples

Exemplary synthesis procedures for a polyaspartic acid to be used as starting material in the present invention:

Polycondensation of L-aspartic acid in the presence of 5 mol% methanesulfonic acid in a glass reactor

133.1 g of L-aspartic acid, 30 g of water and 4.81 g of methanesulfonic acid (100%) were initially charged in a 2 I capacity glass reactor equipped with stirrer and temperature sensor. The reaction mixture was heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen with simultaneous removal of water by distillation. After 15 minutes, a highly viscous paste formed which could no longer be stirred. Within a further 15 minutes, the reaction product had solidified to a solid mass. The reactor was cooled to room temperature. The caked reaction mixture was removed from the reactor with a spatula and comminuted to a powder using a pestle and mortar. The comminuted reaction mixture was again placed in the reactor, heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen and polycondensed at this temperature for a further 5.5 hours with simultaneous removal of water by distillation. In order to prepare the aqueous sodium salt solution of the polyaspartic acid, 100 g of the cooled reaction product were dispersed in 100 g of water, the mixture was heated to 70°C and sufficient 50% aqueous sodium hydroxide solution was added at this temperature that the pH was in the range of 7 to 9. The powder dispersed in water dissolved gradually and a clear aqueous sodium salt solution of polyaspartic acid was obtained. The weight-average molecular weight Mw was 7700 g/mol.

Polycondensation of L-aspartic acid under reflux cooling in the presence of 5 mol% methanesulfonic acid in a 0.7 L LIST Discotherm B reactor

266.2 g of L-aspartic acid, 10 g of water and 13.7 g of methanesulfonic acid (70% in water) were initially charged in a 0.7 I LIST Discotherm B reactor. The reactor contents were heated under reflux cooling at a temperature of 170 to 180°C for 2 h while stirring at 20 revolutions per minute. The degree of conversion of L-aspartic acid after this step was 9.5% (measured as described below). The reaction mixture was then heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen and polycondensed at this temperature for 5 h with simultaneous removal of water by distillation. Caking of the reaction mixture and thus standstill of the apparatus did not occur. Manual comminution with the aid of a spatula or mortar was not required. Hydrolysis of the resulting end product to give the aqueous sodium salt solution of polyaspartic acid was carried out as described in C1. The weightaverage molecular weight Mw was 7680 g/mol.

266.2 g of L-aspartic acid, 20 g of water and 13.7 g of methanesulfonic acid (70% in water) were initially charged in a 0.7 I LIST Discotherm B reactor. The reactor contents were heated under reflux cooling at a temperature of 170 to 180°C for 1 h while stirring at 20 revolutions per minute. The degree of conversion of L-aspartic acid after this step was 2.0% (measured as described below). The reaction mixture was then heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen and polycondensed at this temperature for 5 h with simultaneous removal of water by distillation. Caking of the reaction mixture and thus standstill of the apparatus did not occur. Manual comminution with the aid of a spatula or mortar was not required. Hydrolysis of the resulting end product to give the aqueous sodium salt solution of polyaspartic acid was carried out as described in C1. The weightaverage molecular weight Mw was 7530 g/mol.

Polycondensation of L-aspartic acid under reflux cooling in the presence of 8 mol% phosphoric acid in a glass reactor

266.2 g of L-aspartic acid, 10 g of water and 18.5 g of phosphoric acid (85% in water) were initially charged in a 2 I capacity glass reactor equipped with stirrer and temperature sensor. The reactor contents were heated under reflux cooling at a temperature of 170 to 180°C for 2 h while stirring at 20 revolutions per minute. The degree of conversion of L-aspartic acid after this step was 3.7% (measured as described below). The reaction mixture was then heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen and polycondensed at this temperature for 4.5 h with simultaneous removal of water by distillation. Caking of the reaction mixture and thus standstill of the apparatus did not occur. Manual comminution with the aid of a spatula or mortar was not required. Hydrolysis of the resulting end product to give the aqueous sodium salt solution of polyaspartic acid was carried out as described in C1. The weight-average molecular weight Mw was 9780 g/mol.

Polycondensation of L-aspartic acid under reflux cooling in the presence of 5 mol% methanesulfonic acid in a glass reactor

266.2 g of L-aspartic acid and 9.61 g of methanesulfonic acid (100%) were initially charged in a 2 I capacity glass reactor equipped with stirrer and temperature sensor. The reactor contents were heated under reflux cooling at a temperature of 170 to 180°C for 1.5 h while stirring at 20 revolutions per minute. The degree of conversion of L-aspartic acid after this step was 5.2% (measured as described below). The reaction mixture was then heated to the condensation temperature of 210°C to 220°C with stirring under a gentle stream of nitrogen and polycondensed at this temperature for 6 h with simultaneous removal of water by distillation. Caking of the reaction mixture and thus standstill of the apparatus did not occur. Manual comminution with the aid of a spatula or mortar was not required. Hydrolysis of the resulting end product to give the aqueous sodium salt solution of polyaspartic acid was carried out as described in C1. The weight-average molecular weight Mw was 8300 g/mol.

Determination of the molecular weight (Mw and Mn)

The weight-average or number-average molecular weight (Mw and Mn) of the examples was determined by GPC (gel permeation chromatography) under the following conditions:

To determine the molecular weight, a small amount of the polyaspartimide formed after the polycondensation step was taken and washed repeatedly with water in order to remove the methanesulfonic acid used. The washed powder was then hydrolyzed as described with aqueous sodium hydroxide solution (i.e. the washed powder was dispersed in water, the mixture was heated to 70°C and sufficient 50% aqueous sodium hydroxide solution was added at this temperature so that the pH was in the range of 7-9. The powder dispersed in water dissolved gradually and a clear aqueous sodium salt solution of polyaspartic acid was obtained). Sample solutions were filtered through Sartorius Minisart RC 25 (0.2 pm). Calibration was performed using narrowly distributed Na-PAA standards from Polymer Standard Service with molecular weights of M = 1250 g/mol to M = 130 500 g/mol. In addition, Na-acrylate having a molecular weight of M = 96 and a PEG standard with M = 620, which is synonymous with Na- PAA M = 150, was used. The values outside of this elution range were extrapolated. The evaluation limit was 122 g/mol.

Materials and Methods

Materials

A sodium poyaspartate solution with a molar mass of Mw 5010 g/mol and solid content of 40% was used. The material was produced via thermal condensation of aspartic acid, followed by hydrolysis of the intermediate polysuccinimide by aqueous NaOH - following the procedure as disclosed in WO2015036292, comparative example 2. The solution had a dark brown color (iodine color number 86) and a pH value of 8,2.

Iodine Color Value

The color value is determined by using the Lico 150 Colorimeter from Hach Industries. For this analysis undiluted samples are used. Preprogrammed Method of Iodine Color Value according to DIN 6162 is used.

Examples

Comparative example 1

To 250 g of the polyaspartate solution were added 12,5g of 50 w.-% aqueous H2O2 solution at 50°C under stirring. The solution was maintained at this temperature for 4 hours.

Comparative Example 2

To 250 g of the polyaspartate solution were added 12,5g of 50 w.-% aqueous H2O2 solution at 50°C under stirring. The solution was maintained at this temperature for 4 hours. Afterwards, sodium bisulfite was added to obtain a solution containing 6000 ppm. Comparative Example 3To 250 g of the polyaspartate solution were added 12,5g of 50 w.-% aqueous H2O2 solution at 50°C under stirring. The solution was maintained at this temperature for 4 hours. Afterwards, sodium hypophosphite was added to obtain a solution containing 2000 ppm.

Example 1: Bleaching at low pH-value

To 250 g of polyaspartate solution were added 12,5g of 50 w.-% aqueous H2O2 solution at 50°C at a pH value of 6, adjusted via addition of H2SO4, under stirring. The solution was maintained at this temperature for 4 hours. We obtained a material with an Iodine Color Value of 12,4. After 130 days a color number of 4 was determined.

Example 2: Bleaching at very low pH-value and Addition of Hydrogenchloride

The polyaspartate solution was treated in the same manner as in comparative example 1. Afterwards, the pH value of the solution was adjusted with HCI-solution to a pH value of 4,1. The solution was stored at 23°C for 180 days. The iodine color number of the solution was measured to be 12.5. The iodine color number of the comparative sample, stored under the same conditions, was 18.9.

Storage of materials at 23°C and 40°C

The solutions have been stored at 23°C and 40°C. The iodine color number was determined at certain intervals.

Examples 3 to 6 In a similar manner as Example 1 , polyaspartate solution was adjusted to pH 5.5 with citric acid.

To this solution 50 w.-% aqueous H2O2 solution was added at different temperatures and stirred for 0 to 96 hours. Afterwards, the color number was determined.

Examples 7 to 12 (example 9 being comparative)

In a similar manner as Example 1 , 250 g of polyaspartate solution were adjusted to the pH value as shown in the Table by addition of acid. To this solution, 12,5 g of 50 w.-% aqueous H2O2 solution were added and stirred at 50°C for 4 hours. Afterwards, the samples were stored at 40°C. The color number was determined after 14 and 40 days.

As a rule observed, a higher pH during the bleaching means a faster decomposition of H2O2 (see increase in color pH 5 vs pH 6 -> pH 7 even worse); moreover, a test at higher pH would also reduce the overall storage stability as seen in the original bleached data (see comparative examples ).

Example 13

In a similar manner as Example 1 , 250 g of polyaspartate solution were adjusted to the pH value 5 by addition of citric acid. To this solution, 10 g of 50 w.-% aqueous H2O2 solution were added and stirred at 90°C for 8 hours. Afterwards, the samples were stored at 40°C. The color number was determined after 8 days to be 9,0 and after 49 days to be 10,3.

Examples 14 - 20 In a similar manner as Example 1 , 250 g of polyaspartate solution were adjusted to the pH value shown by addition of citric acid. To this solution, 12,5 g of 50 w.-% aqueous H2O2 solution were added and stirred at 50°C for 4 hours. Afterwards, the samples were stored at 40°C.

Examples 14 - 20 (Example 17 = comparative)

Experiment 17 shows the increase in colour when the pH approaches 7 at storage of 40°C: the results are by far worse than when bleaching is performed at a lower pH-value.

Without wishing to be bound by the following summary, it seems that the lower the temperature the longer the bleaching takes to reach an acceptable (i.e. superior to current state-of-the-art- procedures) final colour value, whereas increasing the temperature speeds up the process but also shortens the window of operation for stopping the reaction, as treating the polymer for a too long period also starts to deteriorate again the colour, i.e. leads again to a darkening of the colour.

The optimum time of treatment at the optimum temperature for a given set-up can be easily found out starting from the values and the rules given herein.

Drying

Drying for commercial bleached product at commercial scale-operation has been done via spray granulation. Samples were dried immediately after production and stored as solids for 10 days or 16 months, then dissolved in water and tested immediately (examples 21 and 22). Examples 22 and 23 show, that storage as a powder when the powder is prepared immediately after production is satisfactory.

However, storage of untreated solutions yields poor results in terms of colour (and also odour).

However, the present invention shows that also solutions can be stored for extended periods of time when prepared according to the present process.

Of course, drying of the solutions certainly can improve the stability even further although such improvement can be only small when compared to prior art. However, as the storage of the solution is improved, the timing of the drying is no longer essential - thus the invention anyway showing a significant improvement.

Upon storing of solutions, the addition of a preservative is typically of relevance: (to avoid bacterial etc degradation or contamination upon storage and handling of such solutions)

To the solutions a preservative such as sodium benzoate may be added. Those preserved solutions may be dried.

The amount of preservative(s) generally and specifically to be used is as disclosed in the description and the claims of this invention.

Example 22

To a solution of 250 g of polyaspartate solution 1 ,25 g of sodium benzoate were added and the pH value adjusted to pH = 5,4 by addition of citric acid. To this solution, 10,0 g of 50 w.-% aqueous H2O2 solution were added and stirred at 90°C for 5 hours. We determined a color value of 6,6. Afterwards, the samples were stored at 40°C. After 35 days, a color value of 6,5 was determined.

To several other examples (examples 3, 4, 7, 10, 11 , 12, 13, 14, 16, 18, 20) of solutions as prepared herein sodium benzoate has been added in various ranges, such as the amounts of preservative as disclosed in the description of this invention, i.e. in amounts of at least one of the following amounts 0,3, 0,4, 0,5, 0,6, 0,7 and 0,8 weight percent of preservative (based on 100 weight percent of polyaspartic acid polymer solution as obtained; the solution typically had a polymer content of from about 35 to 45 weight percent of polyaspartic acid polymer).

The results did not deviate from the original data by more than “0,2” in colour value from the results shown herein, i.e. thus the addition of the preservative does not show an influence on colour number.

An amount of 0,3 to 0,8 wt.% turned to be out fully satisfactory, with the best range being about 0,4 to 0,6 wt.%.

Claims

1 . Method for producing polyaspartic acid (PAA), comprising the following steps:

(A) preparing a treated polyaspartic acid polymer solution (PAA-S), with

(a) providing a polyaspartic acid polymer in aqueous solution,

- the polyaspartic acid polymer having a degree of neutralization of from 0 to 100%,

- the counterion of the hydrolyzed carboxylic acid units in the PAA being selected from the group of sodium, potassium, ammonium, preferably sodium;

- the solution comprising water as solvent, preferably being essentially water;

(b) adjusting the pH of the PAA-S to a value of from 1 to at most 6,5, preferably at most 6, more preferably at most 5,5, and preferably from 3, more preferably from 4, and most preferably from 4,5, using preferably an acid selected from the group comprising sulfuric acid, hydrochloric acid, citric acid, gluconic acid, glucoronic acid, ethylenediamine-N,N’-disuccinic acid, preferably sulfuric acid or citric acid, more preferably using only citric acid;

(C) and thereafter optionally adding a second agent having oxidation-inhibiting properties (SE) to the - optionally cooled - treated PAA-S from step (A) or the cooled treated PAA-S from optional step (B) or from the step after adding additive(s); such SE being preferably selected from the group comprising copper(ll)chloride, bisulfites such as alkali and preferably sodium bisulfite, hypophosphite salts such as alkali and preferably sodium hypophosphite; such SE being added to such PAA-S from the previous step, and then mixing the obtained PAA-S comprising SE until a uniform distribution of SE can be reasonably considered to be achieved, such as mixing for from 10 minutes to up to 2 hours, such mixing time depending on the size and geometry of the tank the addition is performed in, or by adding such SE inline into a tubing wherein the PAA-S is transported, optionally using a static mixing element for mixing in; to obtain a bleached and stabilized polyaspartic acid polymer solution (BSPAA-S); after step (C)/before step (D) optionally further adding one or more additives, such additives being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate, such additive preferably different from the additive optionally added after step (B);

2. Method according to claim 1 , wherein the PAA-S is neutralized to more than 5%, preferably to more than 10, more preferably to more than 25 %, even more preferably more than 50%, even more preferably to more than 75%, such as 80%, 90%, 95 or about 100%.

3. Method according to any o claims 1 or 2, wherein the PAA-S is obtained from the polycondensation of aspartic acid and optional neutralization of the polyaspartic acid polymer with a base, or from the polycondensation of succinimide followed by hydrolysis with a base and optional neutralization of the resulting polyaspartic acid polymer with an acid.

4. Method according to any of claims 1 to 2, wherein the PAA is a copolymer comprising aspartic acid-units and units derived from other carboxylic acid-monomer(s) which are polymerizable with aspartic acid or succinimide, which - in case of succinimide as comprised monomer - thereafter is subjected to hydrolysis with a base and thereafter optional neutralization with an acid, such other carboxylic acid-monomer(s) being preferably selected from the group comprising polybasic carboxylic acids and anhydrides thereof, e.g. oxalic acid, adipic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, aconitic acid, succinic acid, succinic anhydride, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C26 alkylsuccinic acids (e.g. octylsuccinic acid), C2- C26 alkenylsuccinic acids (e.g. octenylsuccinic acid), 1,2,3-propanetricarboxylic acid, 1 ,1 ,3,3-propanetetracarboxylic acid, 1 ,1,2,2-ethanetetracarboxylic acid, 1 , 2,3,4- butanetetracarboxylic acid, 1 ,2,2,3-propanetetracarboxylic acid, 1 , 3,3,5- pentanetetracarboxylic acid, trimellitic acid or trimellitic anhydride, and/or the group of polybasic hydroxycarboxylic acids, such as citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid; and/or the group of amino acids such as aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprolactam), uncharged amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxy amino acids (e.g. hydroxyproline, serine, threonine), iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranilic acid, tryptophan, tyrosine, histidine), but not including aspartic acid; preferably carboxyl- containing compounds such as butane-1 ,2,3,4-tetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, and particularly preferably butane-1,2,3,4-tetracarboxylic acid, citric acid, glycine and glutamic acid.

5. Method according to any of claims 1 to 4, wherein at least one of i) to iii) applies: i) step (B) is performed, ii) (C) is performed, iii) step (D) is performed.

6. Method according to any of claims 1 to 5, wherein at least one additive is added according to the following steps i) or ii), with i) after step (B), ii) after step (C) or - if step (C) is not employed but step (D) is employed - before step (D), or - if neither step (C) nor step (D) is employed - a further additive is added after the step i).

7. Method according to any of claims 1 to 6, wherein step (D) is performed, preferably for step (D) a means of removing solvent is employed, selected from the group consisting of spray-drying, granulation, spray-granulation, paddle-drying, vacuum-drying, freeze-drying, agglomeration, spray-agglomeration, fluidized bed-drying, preferably pray-drying, spraygranulation, most preferably spray-granulation.

8. Bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) obtainable by, preferably obtained by, a process according to any of claims 1 to 6, more preferably containing at least one additive, such additive being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate, most preferably sodium benzoate, the preservative being in a range of from 0,04 to 1 ,5 weight percent of preservative based on 100 weight percent of BSPAA-S.

9. Bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) obtainable by, preferably obtained by, a process according to claim 7, wherein step (D) is employed, more preferably containing at least one additive, such additive being selected from flowing agents, preservatives, stabilizers, colorants, perfume, biocides, antioxidants, preferably preservatives, stabilizers, biocides, antioxidants, more preferably preservatives such as sodium benzoate, most preferably sodium benzoate, the preservative being in a range of from 0,1 to 3 weight percent of preservative based on 100 weight percent of BSPAA-P, and most preferably not containing preservatives, stabilizers, biocides and antioxidants.

10. Use of a bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) according to claim 8, or of a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) according to claim 9, or their mixture.

11. The use according to claim 10 in a composition suitable for cleaning of soft and hard surfaces and/or fabric, and/or for avoiding or reducing scale-formation in water-conducting systems, such systems including washing machines, tubes for water transport or storage, water purification, water treatment, cooling systems using water as coolant, and desalination of water.

12. The use according to claim 11 , wherein the composition is a fabric and home care product, a cleaning composition, an industrial and institutional cleaning product, cosmetic or personal care product.

13. The use according to claim 12 in cleaning compositions and/or in fabric and home care products, preferably within a dish wash detergent formulation, more preferably in an automatic dish wash detergent composition.

14. The use according to any of claims 10 to 13 as scale inhibitor and/or dispersant.

15. Composition comprising at least one bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) according to claim 8, or a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) according to claim 9, or their mixture.

16. Composition according to claim 15 being a cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic or personal care product, preferably a fabric detergent formulation or a dish wash detergent formulation, more preferably a dish wash detergent composition, even more preferably being an automatic dish wash detergent composition, wherein the at least one BSPAA-S and/or at least one BSPAA-P is present in the composition at a concentration of from about 0.1% to about 50%, preferably from about 0,25% to 25%, more preferably from about 0.5% to about 20%, and even more preferably from about 0.5% to about 15%, and most preferably in amounts of up to 10%, 8%, 5%, or even 3%, each in weight % in relation to the total weight of such composition, optionally further comprising from about 1% to about 70% by weight of a surfactant system, optionally in addition comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types; and in case an enzyme is comprised preferably also containing at least one enzyme-stabilizing system; optionally further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol, whereas in case of an automated dish washing-composition such phenoxyethanol preferably is not comprised in such composition; optionally further comprising 4,4’-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition, whereas in case of an automated dish washing-compositions such 4,4’- dichoro 2-hydroxydiphenylether preferably is not comprised in such composition.

17. Method of reducing or avoiding scale-formation in water-conducting or water-containing systems, such systems including washing machines such as for dish or fabric, tubes for water transport or storage, water purification, water treatment, cooling systems using water as coolant, and desalination of water, by adding an effective amount of at least one bleached and stabilized polyaspartic acid polymer solution (BSPAA-S) according to claim 8, or of a bleached and stabilized polyaspartic acid polymer powder (BSPAA-P) according to claim 9, or their mixture, to the water-containing fluid treated, contained or transported inside such water-conducting or water-containing system.