Process for preparing solid composition comprising at least one aminocarboxylate complexing agent

Abstract

The present invention relates to a process for preparing a solid storage-stable composition comprising at least one aminocarboxylate complexing agent.

Description

[0001] The present invention relates to a process for preparing a solid, preferably storage-stable composition comprising at least one aminocarboxylate complexing agent, the process comprising the following steps:

[0002] a) providing an initial aminocarboxylate composition having an amount of solid aminocarboxylate particles of orthorhombic system in an amount of 0.1% and 50% by weight, preferably 1% to 25% by weight, relative to the total initial solid composition,

[0003] b) increasing the relative humidity (rH) to at least 50% and / or adding at least 1% by weight of water or an aqueous solution (SO) or slurry (SL) having a water content of at least 10% by weight, preferably at least 30% by weight, relative to the total weight of the aqueous solution or slurry,

[0004] c) maintaining the obtained composition at a temperature ranging from 20° C. to 95° C. for a period ranging from 1 minute to 5 months,

[0005] d) optionally drying the resulting solid composition, preferably to a residual moisture content of less than 20%, preferably to obtain a solid aminocarboxylate composition having an increased orthorhombic crystalline content.

[0006] Complexing agents such as methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their corresponding alkali metal salts are alkaline earth metal ions such as Ca 2+ and Mg 2+ Therefore, they are recommended and used in various applications such as laundry detergents and automatic dishwashing (ADW) formulations, in particular so-called phosphate-free laundry detergents and phosphate-free ADW formulations. For the transportation of such complexing agents, in most cases solids such as pellets or aqueous solutions are used.

[0007] Solid compositions (such as pellets and powders) have the advantage of being substantially free of water. This means that in the case of transportation, water does not have to be transported and the cost of additional weight can be avoided. (The term "solid" has its usual meaning, i.e., refers to the state of a compound or composition at room temperature, i.e., at 20°C).

[0008] In the art, methods for providing granules or powders of chelating agents (also in combination with other compounds like polymers) have been described, for example, in WO 2015 / 121170 A1. In addition, EP 0 845 456 A2 describes a method for preparing a crystalline solid consisting essentially of certain glycine-N, N-diacetic acid derivatives, which is carried out by adjusting the water content of the initial material containing the glycine-N, N-diacetic acid derivative to a range of 10% to 30% by weight and then inducing crystallization. In the example, MGDA powder and MGDA solution are mixed and heated, and then a crystalline solid is produced. However, there is no mention of crystallinity, and in particular no indication of the content of orthorhombic crystals. It is said that the solids produced by these examples are storage-stable; however, there is no (verifiable) experimental evidence to support this statement.

[0009] However, solid compositions containing aminocarboxylate complexing agents often encounter problems when stored for extended periods of time.

[0010] For example, many powders and granules show problems with yellowing (discoloration), especially when in contact with non-chlorine-containing bleaching agents such as, but not limited to, inorganic peroxides, which are often used in detergent formulations, such as dishwashing detergent formulations (e.g., ADW formulations), together with complexing agents like MGDA. Examples of inorganic peroxides are sodium perborate, sodium persulfate, and especially sodium percarbonate.

[0011] In order to limit such yellowing, many additives have been tried. However, most of them either deteriorate the activity of the bleaching agent or significantly slow down the dissolution of the complexing agent, both of which are undesirable effects.

[0012] One way known in the art to improve the storage stability of, for example, MGDA is to increase the crystallinity of the complexing agent and to increase the amount of MGDA in the orthorhombic form. There are some solidification processes that provide MGDA with a relatively high content of orthorhombic form, such as EP 2 257 522 B1; however, most of these processes (such as evaporative crystallization or drying processes starting from a slurry) are not economically attractive or do not provide sufficiently pure orthorhombic products.

[0013] It is therefore an object of the present invention to avoid the above mentioned problems. In particular, it is an object of the present invention to provide storage stable solid compositions containing aminocarboxylate complexing agents. It is also an object to provide solid compositions containing aminocarboxylate complexing agents which show a reduced tendency to yellowing when in contact with non-chlorine containing bleaching agents such as but not limited to inorganic peroxides.

[0014] Furthermore, it was an object of the present invention to provide solid compositions containing aminocarboxylate complexing agents which have an increased content of complexing agent, in particular MGDA, in the orthorhombic crystal form.

[0015] A further object is to provide a process for the preparation of storage-stable solid compositions containing aminocarboxylate complexing agents. Another object of the present invention is to provide a process for the preparation of solid compositions containing aminocarboxylate complexing agents, which solid compositions show a reduced tendency to yellowing when in contact with chlorine-free bleaching agents. Furthermore, an object of the present invention is to provide a process for the preparation of solid compositions containing aminocarboxylate complexing agents, which solid compositions have an increased content of complexing agents in the orthorhombic form, in particular MGDA.

[0016] Surprisingly, it was found that the method defined in the appended claims (as well as in the present description) can overcome the above mentioned disadvantages and problems.

[0017] In particular, it was found that the process of the invention - involving a step of increasing the relative humidity and / or adding water - leads to a solid composition showing improved yellowing and storage stability.

[0018] Furthermore, it has been found that the process of the present invention can facilitate achieving increased levels of aminocarboxylate complexing agents (eg, MGDA) in the orthorhombic crystalline form.

[0019] The process according to the invention for preparing a solid, preferably storage-stable composition comprising at least one aminocarboxylate complexing agent comprises the following steps:

[0020] a) providing an initial aminocarboxylate composition having an amount of solid aminocarboxylate particles of orthorhombic system in an amount of 0.1% and 50% by weight, preferably 1% to 25% by weight, relative to the total initial solid composition,

[0021] b) increasing the relative humidity (rH) to at least 50% and / or adding at least 1% by weight of water or an aqueous solution (SO) or slurry (SL) having a water content of at least 10% by weight, preferably at least 30% by weight, relative to the total weight of the aqueous solution or slurry,

[0022] c) keeping the obtained composition at a temperature ranging from 20° C. to 95° C. for a period ranging from 1 minute to 5 months, preferably from 2 minutes to 1 month,

[0023] Optionally, d) drying the obtained solid composition, preferably to a residual moisture content of less than 20%, preferably to obtain a solid aminocarboxylate composition having an increased orthorhombic crystalline content.

[0024] Another object of the present invention is a solid, preferably storage-stable composition comprising at least one aminocarboxylate complexing agent, which composition is obtainable or obtained by the process according to the process of the invention.

[0025] A further object of the present invention is the use of a solid, preferably storage-stable composition comprising at least one aminocarboxylate complexing agent obtainable or obtained by the process according to the invention for the production of detergent or cleaning formulations, preferably dishwashing detergent formulations, more preferably automatic dishwashing detergent formulations.

[0026] In one embodiment of the process according to the invention, water is added by setting the relative humidity in the range of 50 to 90%, preferably 60 to 85%, and / or by adding at least 1 % by weight, preferably 2 to 10 % by weight, of water or an aqueous solution (SO) or a slurry (SL), optionally by spraying the water or the aqueous solution (SO) or the slurry (SL) onto the initial solid composition.

[0027] In another embodiment of the method of the present invention, the solid composition is maintained at a temperature of 30°C to 95°C for a period of time of 30 minutes to 1 month, preferably at 30°C to 70°C for a period of time of 30 minutes to 2 weeks, preferably 30 minutes to 48 hours.

[0028] In the process of the invention, the drying may be carried out at a temperature in the range of 40° to 240°C, preferably 60° to 150°C, more preferably 60° to 120°C, and / or the drying is carried out until a residual moisture content of less than 18% by weight relative to the total weight of the solid composition is reached.

[0029] In another embodiment of the method of the present invention, the initial composition is prepared by adding 0.1% and 50% by weight of an orthogonal aminocarboxylate to a composition that does not contain an orthogonal aminocarboxylate, or by drying a slurry or solution of an aminocarboxylate composition having a solid content of 0.1% and 70% by weight. The drying can be carried out, for example, by spray drying or spray granulation.

[0030] The solids content can be determined by Karl-Fischer titration (for the water content), Fe titration (for the content of chelating agent such as MGDA) and residual content calculation (for the content of optional polymer).

[0031] The discoloration (in this case yellowing) of the stored mixtures was determined by measuring the b value in the CIELAB color space (Mach 5 measuring device).

[0032] In the process according to the invention, providing the solid particles (step a)) and adding water (step b)) can be carried out simultaneously or successively.

[0033] In an embodiment of the process of the invention, the solid particles (step a)) are in the form of powders, granules, crystals, compacts, flakes, or agglomerates.

[0034] The process according to the invention can be carried out at least partially in a mixer, belt dryer, kneader, fluidized bed dryer, paddle dryer and / or cone dryer.

[0035] The aminocarboxylate complexing agent can be selected from methylglycine diacetic acid (MGDA), (N,N)-dicarboxymethylglutamic acid (GLDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS) and their corresponding alkaline salts, preferably the sodium salt, more preferably the sodium salt of MGDA.

[0036] The initial solid composition may further comprise up to 40% by weight, preferably up to 30% by weight, of at least one organic or inorganic compound or a mixture thereof, relative to the total weight of the initial solid composition.

[0037] In an embodiment of the inventive process, the aqueous solution (SO) or slurry (SL) further comprises up to 40% by weight, preferably up to 30% by weight, of at least one organic or inorganic compound or a mixture thereof, relative to the total weight of the aqueous solution (SO) or slurry (SL).

[0038] The initial solid composition and / or the aqueous solution (SO) or slurry (SL) may also comprise at least one compound selected from the list consisting of polymers (preferably sulfonated polymers), antioxidants, surfactants, colorants, pigments, additional complexing agents, organic and inorganic acids, and salts thereof.

[0039] The initial solid composition may contain at least one polymer, such as a homopolymer and / or a copolymer. The polymer may be selected from homopolymers and copolymers of (meth)acrylic acid.

[0040] The initial solid composition may contain at least one antioxidant.

[0041] The initial solid composition may contain at least one surfactant, which may be selected from nonionic, zwitterionic, cationic and anionic surfactants.

[0042] The initial solid composition may contain at least one colorant.

[0043] The initial solid composition may contain at least one pigment.

[0044] The initial solid composition may contain one or more complexing agents other than MGDA or GLDA, such as IDS, citrate, EDDS and / or phosphonic acid derivatives.

[0045] The initial solid composition may contain at least one organic acid (or a salt thereof) having a molecular weight of less than 500 g / mol, such as formic acid, acetic acid and / or citric acid.

[0046] In the context of the present invention, the term "storage-stable" solid composition refers to a solid composition (comprising at least one aminocarboxylate complexing agent) in combination with a bleaching agent (e.g. percarbonate) which shows improved yellowing or no yellowing when stored at elevated temperatures (e.g. 35° C.) and elevated humidity (e.g. 75% rH). Yellowing is determined by the change in the b value (CIELAB color space, Mach 5 measuring device).

[0047] The solid compositions of the present invention (e.g., powders and granules) exhibit generally advantageous properties, including, but not limited to, excellent yellowing behavior, especially in the presence of bleaching agents. Therefore, they are very suitable for use in the manufacture of cleaning agents containing at least one bleaching agent, such cleaning agents also being referred to hereinafter as bleach. In particular, the solid compositions of the present invention are suitable for use in the manufacture of cleaning agents for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxy compound.

[0048] The solid compositions of the invention (eg powders or granules) can be easily converted into compacts and agglomerates.

[0049] Therefore, another aspect of the present invention is the use of a solid composition for the manufacture of a cleaning agent containing at least one bleaching agent, and in particular for the manufacture of a cleaning agent for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxy compound. Another aspect of the present invention is a method for manufacturing a cleaning agent by combining at least one solid composition of the present invention with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, also referred to as the cleaning agent of the present invention hereinafter. The cleaning agent of the present invention contains at least one bleaching agent and at least one solid composition of the present invention (e.g., granules or powder). The cleaning agent of the present invention shows a reduced tendency to yellowing and therefore has an extended shelf life.

[0050] Examples of suitable peroxy compounds are 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), hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid (in each case as the free acid or as an alkali metal salt, in particular as the sodium salt), and also sulfonylperoxyacids and cationic peroxyacids.

[0051] In a preferred embodiment, the peroxygen compound is selected from inorganic percarbonates, persulfates and perborates. An example of sodium percarbonate is 2Na2CO3·3H2O2. An example of sodium perborate is (Na2[B(OH)2(O2)]2), sometimes also written as NaBO2·O2·3H2O. The most preferred peroxygen compound is sodium percarbonate.

[0052] The term "cleaner" includes compositions for dishwashing, especially manual dishwashing and automatic dishwashing and warewashing, and compositions for hard surface cleaning, such as but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, car cleaning (including truck cleaning), further open plant cleaning, cleaning in place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, and also laundry detergent compositions.

[0053] Such detergents may be liquid, gel or preferably solid at ambient temperature, solid detergents being preferred. They may be in powder form or in unit dosage form, for example as tablets or sachets.

[0054] In one embodiment of the present invention, the cleaning agent of the present invention may contain

[0055] The solid composition of the present invention in the range of 2% to 50% by weight and

[0056] In the range of 0.5% to 15% by weight bleaching agent.

[0057] The percentages are based on the solids content of the respective cleaning agents according to the invention.

[0058] The solid composition of the present invention is very suitable for the manufacture of laundry detergents or cleaning agents.

[0059] The cleaning agent of the present invention may contain additional ingredients such as one or more surfactants, which may be selected from nonionic, zwitterionic, cationic and anionic surfactants. Other ingredients that may be included in the cleaning agent of the present invention may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestrants other than chelating agent (A), enzymes, perfumes, dyes, defoamers and builders.

[0060] Particularly advantageous cleaning agents according to the invention may contain one or more complexing agents in addition to MGDA or GLDA. Advantageous detergent compositions for cleaning agents and advantageous laundry detergent compositions may contain one or more sequestrants (chelants) in addition to the mixtures according to the invention. Examples of sequestrants in addition to the mixtures according to the invention are IDS (iminodisuccinates), citrates, phosphonic acid derivatives such as the disodium salt of hydroxyethane-1,1-diphosphonic acid ("HEDP"), and polymers having complexing groups such as, for example, polymers in which 20 to 90 mol-% of the N atoms carry at least one CH2COO - The invention also contains polyethyleneimines of the group, and the corresponding alkali metal salts thereof, in particular the sodium salts thereof (e.g. IDS-Na4 and trisodium citrate), and phosphates such as STPP (sodium tripolyphosphate). Due to the fact that phosphates cause environmental problems, it is preferred that the cleaning agents according to the invention are phosphate-free. In the context of the present invention, "phosphate-free" is understood to mean that the sum of the contents of phosphates and polyphosphates, determined by the gravimetric method and relative to the corresponding cleaning agent according to the invention, is in the range of 10 ppm to 0.2% by weight.

[0061] The cleaning agent of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

[0062] Preferred nonionic surfactants are alkoxylated alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APGs), hydroxyalkyl mixed ethers and amine oxides.

[0063] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds such as those having the general formula (II)

[0064]

[0065] The variables are defined as follows:

[0066] R 1 are the same or different and are selected from hydrogen and straight chain C1-C 10 - alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0067] R 2 Selected from branched or straight chain C8-C 22 -alkyl, such as n-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C16 H 33 Or positive-C 18 H 37 ,

[0068] R 3 Selected from C1-C 10 - alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

[0069] m and n are in the range of 0 to 300, wherein the sum of n and m is at least 1, preferably in the range of 3 to 50. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0070] In one embodiment, the compound having the general formula (II) may be a block copolymer or a random copolymer, preferably a block copolymer.

[0071] Other preferred examples of alkoxylated alcohols are compounds such as those having the general formula (III)

[0072]

[0073] The variables are defined as follows:

[0074] R 1 are identical or different and are selected from hydrogen and straight-chain C1-C0-alkyl, are preferably identical in each case and are ethyl and particularly preferably hydrogen or methyl,

[0075] R 4 Selected from branched or straight chain C6-C 20 -alkyl, especially n-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C 16 H 33 , Positive-C 18 H 37 ,

[0076] a is a number in the range of 0 to 10, preferably 1 to 6,

[0077] b is a number in the range of 1 to 80, preferably 4 to 20,

[0078] d is a number in the range of 0-50, preferably 4-25.

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

[0080] Preferred examples of hydroxyalkyl mixed ethers are compounds having the general formula (IV)

[0081]

[0082] The variables are defined as follows:

[0083] R 1 are the same or different and are selected from hydrogen and straight chain C1-C 10 - alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0084] R 2 Selected from branched or straight chain C8-C 22 -alkyl, such as iso-C 11 H 23 , Iso-C 13 H 27 、positive-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C 16 H 33 Or positive-C 18 H 37 ,

[0085] R 3 Selected from C1-C 18 -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

[0086] The variables m and n are in the range of 0 to 300, wherein the sum of n and m is at least 1, preferably in the range of 5 to 50. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0087] The compounds having the general formulae (II) and (III) may be block copolymers or random copolymers, preferably block copolymers.

[0088] Other suitable nonionic surfactants are selected from diblock and multiblock copolymers composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-C 16 -Alkyl polyglucosides and branched C8-C 14 -Alkyl polyglycosides such as compounds having the average general formula (V) are likewise suitable.

[0089]

[0090] The variables are defined as follows:

[0091] R 5 is C1-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

[0092] R 6 Yes -(CH2)2-R 5 ,

[0093] G 1 is chosen from monosaccharides having 4 to 6 carbon atoms, in particular from glucose and xylose,

[0094] y is in the range of 1.1 to 4, y is the average.

[0095] Further examples of nonionic surfactants are compounds of the general formula (VII) and (VIII)

[0096]

[0097] AO is selected from ethylene oxide, propylene oxide and butylene oxide,

[0098] EO is ethylene oxide, CH2CH2-O,

[0099] R 8 Selected from branched or straight chain C8-C 18 -alkyl, and R 5 As defined above.

[0100] A 3 O is selected from propylene oxide and butylene oxide,

[0101] w is a number in the range of 15 to 70, preferably 30 to 50,

[0102] w1 and w3 are numbers in the range of 1 to 5, and

[0103] w2 is a number in the range of 13 to 35.

[0104] An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19187.

[0105] Mixtures of two or more different nonionic surfactants may also be present.

[0106] Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

[0107] Examples of amphoteric surfactants are those which carry a positive charge and a negative charge in the same molecule under the conditions of use. Preferred examples of amphoteric surfactants are so-called betaine surfactants. Many examples of betaine surfactants carry one quaternary nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0108] Examples of amine oxide surfactants are compounds having the general formula (IX)

[0109] R 7 R 8 R 9 N→O(IX)

[0110] Where R 7 , R 8 and R 9 independently selected from aliphatic, alicyclic or C2-C4-alkylene 10 -C 20 -alkylamide moiety. Preferably, R 7 Selected from C8-C 20 -alkyl or C2-C4-alkylene C 10 -C 20 -alkylamide and R 8 and R 9 They are all methyl.

[0111] A particularly preferred example is lauryl dimethylamine oxide, sometimes also referred to as lauryl amine oxide.Another particularly preferred example is cocamidopropyl dimethylamine oxide, sometimes also referred to as cocamidopropylamine oxide.

[0112] Examples of suitable anionic surfactants are C8-C 18 -Alkali metal and ammonium salts of alkyl sulfates, C8-C 18 -Alkali metal salts and ammonium salts of fatty alcohol polyether sulfates, ethoxylated C4-C 12 -Alkali metal and ammonium salts of sulfuric acid half esters of alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide / mol), C 12 -C18 Sulfonic fatty acid alkyl esters (such as C 12 -C 18 Alkali metal salts and ammonium salts of sulfo fatty acid methyl esters), in addition C 12 -C 18 -Alkali metal and ammonium salts of alkylsulfonic acids and C 10 -C 18 - Alkali metal salts and ammonium salts of alkylarylsulfonic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0113] Further examples of suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates and alkyl ether phosphates.

[0114] Preferably, the laundry detergent composition contains at least one anionic surfactant.

[0115] In one embodiment of the present invention, the cleaning agent of the present invention intended for use as a laundry detergent composition may contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0116] In one embodiment of the present invention, the cleaning agent of the present invention intended for hard surface cleaning may contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0117] In a preferred embodiment, the cleaners of the present invention do not contain any anionic detergents.

[0118] Cleaning agents of the present invention may contain one or more bleaching catalysts. The bleaching catalyst may be selected from transition metal salts or transition metal complexes that promote bleaching, 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-type ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleaching catalysts.

[0119] The cleaning agents of the present invention may contain one or more bleach activators, for example N-methyl-morpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acyl-imides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or quaternary ammonium nitrile salts (trimethylammonium acetonitrile salts).

[0120] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexanediamine.

[0121] The cleaning agent of the invention may contain one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and phenol derivatives, such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0122] In one embodiment of the present invention, the cleaner of the present invention comprises a total of 0.1% to 1.5% by weight of corrosion inhibitor.

[0123] Cleaning agents according to the invention may comprise one or more builders selected from organic and inorganic builders. Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, in particular those of formula α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5, also fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartrate diacetate, tartrate monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.

[0124] Examples of organic builders are in particular polymers and copolymers other than (co)polymer (B), and include polymers and copolymers other than (co)polymer (B), or a further (co)polymer (B). In one embodiment of the invention, the organic builder is selected from polycarboxylates, such as alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, which are partially or completely neutralized with a base.

[0125] Suitable comonomers of (meth)acrylic acid are monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers are in particular polyacrylic acids, which preferably have an average molecular weight M in the range of 2000 to 40 000 g / mol, preferably 2000 to 10 000 g / mol, in particular 3000 to 8000 g / mol. w Also suitable and in the same molecular weight range are copolymer polycarboxylates, in particular those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

[0126] You can also use at least one to free

[0127] Monoethylenically unsaturated C3-C 10 -monocarboxylic acid or C4-C 10- Copolymers of monomers of the group consisting of dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, and at least one hydrophilic or hydrophobic monomer as listed below.

[0128] Suitable hydrophobic monomers are, for example, isobutylene, diisobutylene, butene, pentene, hexene and styrene, olefins having 10 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, C 22 -α-olefins, C 20 -C 24 - mixtures of α-olefins and polyisobutylenes having an average of 12 to 100 carbon atoms per molecule.

[0129] Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl functions or alkyleneoxy groups. By way of example, mention may be made of: allyl alcohol, prenyl alcohol, 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. The polyalkylene glycols here may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkyleneoxy units per molecule.

[0130] Particularly preferred monomers containing sulfonic acid groups 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 the salts of the acids, such as the sodium, potassium or ammonium salts thereof.

[0131] Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

[0132] A further example of a builder is carboxymethylinulin.

[0133] Furthermore, amphoteric polymers can also be used as builders.

[0134] The detergents of the invention may contain, for example, in the range of 10 to 70% by weight in total, preferably 10 to 50% by weight in total, more preferably up to 20% by weight of builder.

[0135] In one embodiment of the present invention, the inventive cleaning agent according to the present invention may comprise one or more co-builders.

[0136] The cleaning agent of the present invention may contain one or more defoaming agents selected from, for example, silicone oil and paraffin oil.

[0137] In one embodiment of the present invention, the cleaning agent of the present invention comprises a total of 0.05% to 0.5% by weight of defoaming agent.

[0138] The cleaning agents of the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

[0139] In one embodiment of the invention, the cleaning agent of the invention may contain, for example, up to 5% by weight, preferably 0.1% to 3% by weight, of an enzyme. The enzyme may, for example, be reacted with at least one C1-C3-carboxylic acid or a C4-C 10 - Stabilization with sodium salts of dicarboxylic acids. Preferred are formates, acetates, adipates, and succinates.

[0140] In one embodiment of the present invention, the cleaning agent of the present invention may comprise at least one zinc salt. The zinc salt may be selected from water-soluble zinc salts and water-insoluble zinc salts. In this connection, in the context of the present invention, water-insoluble is used to refer to those zinc salts having a solubility of 0.1 g / l or less in distilled water at 25° C. Correspondingly, zinc salts having a higher solubility in water are referred to as water-soluble zinc salts in the context of the present invention.

[0141] In one embodiment of the present invention, the zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2 and zinc gallate, preferably ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2 and zinc gallate.

[0142] In another embodiment of the present invention, the zinc salt is selected from ZnO, ZnO aqueous solution, Zn(OH)2 and ZnCO3. ZnO aqueous solution is preferred.

[0143] In one embodiment of the present invention, the zinc salt is selected from zinc oxides having an average particle size (weight average) ranging from 10 nm to 100 μm.

[0144] The cations in the zinc salt may be present in complexed form, for example with ammonia ligands or water ligands, and in particular in hydrated form. To simplify notation, within the context of the present invention, ligands are generally omitted if they are water ligands.

[0145] Depending on how the pH of the mixture according to the invention is adjusted, the zinc salt may change. Thus, for example, zinc acetate or ZnCl2 can be used for the preparation of the formulation according to the invention, but this is converted into ZnO, Zn(OH)2 or aqueous ZnO solutions at a pH of 8 or 9 in an aqueous environment, which may be present in uncomplexed or complexed form.

[0146] The zinc salt may be present in those cleaning agents according to the invention which are solid at room temperature. In such cleaning agents according to the invention, the zinc salt is preferably present in the form of particles which have, for example, an average diameter (number average), determined, for example, by X-ray scattering, in the range of 10 nm to 100 μm, preferably 100 nm to 5 μm.

[0147] The zinc salt may be present in those cleaning agents according to the invention which are liquid at room temperature. In such cleaning agents according to the invention, the zinc salt is preferably present in dissolved or solid or colloidal form.

[0148] In one embodiment of the invention, the inventive cleaning agent comprises in total in the range from 0.05 to 0.4% by weight of zinc salt, based in each case on the dry matter content of the cleaning agent in question.

[0149] Here, the fraction of zinc salt is given as zinc or zinc ion. From this, the counterion fraction can be calculated.

[0150] In one embodiment of the present invention, the cleaning agent of the present invention is free of heavy metals other than zinc compounds. In the context of the present invention, this is understood to mean that the cleaning agent of the present invention is free of those heavy metal compounds that do not act as bleaching catalysts, in particular free of iron and bismuth compounds. In the context of the present invention, "free" in relation to heavy metal compounds is understood to mean that the content of heavy metal compounds that do not act as bleaching catalysts is in the range of 0 to 100 ppm in total, which is determined by a leaching method and is based on the dry matter content. Preferably, the cleaning agent of the present invention has a heavy metal content other than zinc of less than 0.05 ppm based on the dry matter content of the formulation in question. The zinc fraction is therefore not included.

[0151] In the context of the present invention, "heavy metals" are considered to be metals other than zinc, having a specific density of at least 6 g / cm 3Heavy metals are in particular metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

[0152] Preferably, the cleaning agents of the present invention contain unmeasurable fractions (eg, less than 1 ppm) of bismuth compounds.

[0153] The cleaning agents of the present invention are excellent for cleaning hard surfaces and fibers. For example, they can be used in dishwashing applications, preferably automatic dishwashing applications.

[0154] In one embodiment of the present invention, the cleaning agent of the present invention comprises one or more additional ingredients such as fragrances, dyes, organic solvents, buffers, disintegrants for tablets ("tabs"), and / or acids such as methanesulfonic acid.

[0155] Exemplary detergent compositions for automatic dishwashing detergents can be formulated from the solid compositions (eg, granules or powders) of the present invention by mixing the corresponding components according to Table F below.

[0156] Table F: Exemplary Detergent Compositions for Automatic Dishwashing

[0157]

[0158] The laundry detergent according to the invention can be used for washing any type of laundry and any type of fiber. The fibers may be of natural or synthetic origin, or they may be a natural mixture of natural fibers and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples of fibers of synthetic origin are polyurethane fibers such as or Polyester fiber, or polyamide fiber. The fiber can be a single fiber or a part of a textile such as a knitted fabric, a woven fabric, or a nonwoven fabric.

[0159] Another aspect of the present invention is a process for making an automatic dishwashing tablet from a solid composition of the present invention, such as a powder or granules, wherein the granules or powders are selected from the group consisting of granules of the present invention and powders of the present invention, respectively. The process is also referred to hereinafter as a granulation process according to the present invention.

[0160] The tablets of the invention are preferably produced with the aid of a machine, such as a tablet press.

[0161] Granulation method according to the present invention can be carried out by making solid composition of the present invention (for example pellet or powder) mix with at least one nonionic surfactant and optionally one or more other materials and then compressing the mixture to provide tablet.The example of suitable nonionic surfactant and other material (such as builder, enzyme) is listed above.The particularly preferred example of nonionic surfactant is hydroxy mixed ether, for example has the hydroxy mixed ether of general formula (V).

[0162] The present invention is further illustrated by the following non-limiting working examples.

[0163] Working Example

[0164] 1. Recrystallization experiment

[0165] 1.1 Sample:

[0166] (M.1) MGDA sodium salt agglomerates

[0167] (M.2) MGDA sodium salt amorphous powder

[0168] (M.3)MGDA sodium salt orthogonal powder

[0169] (M.4) A mixture of MGDA sodium salt amorphous powder and MGDA sodium salt orthorhombic powder; (M.4) is a mixture of 50% by weight of (M.2) and 50% by weight of (M.3). 10 g of each product was placed in a ceramic dish and then ground together.

[0170] 1.2 Composition of the sample:

[0171] (C.1) Percentage of monoclinic alkali metal salt of MGDA

[0172] (C.2) Percentage of orthorhombic alkali metal salt of MGDA

[0173] (C.3) Percentage of crystalline salt of MGDA

[0174] (C.4) Percentage of amorphous salt of MGDA

[0175] (W.1) Percentage of monoclinic alkali metal salt of MGDA in the whole sample

[0176] (W.2) Percentage of orthorhombic alkali metal salt of MGDA in the whole sample

[0177] The percentages of (C.1), (C.2), (C.3) and (C.4) were determined by X-ray diffraction (Table 1). (The measurement and evaluation methods are described below.)

[0178] Table 1: Measurement results of sample composition before recrystallization

[0179]

[0180] The data of the ratio of (C.1) to (C.2) refer to (C.3). Based on the measured data, the ratio of (C.1) to (C.2) in the whole sample was calculated by formula (1) (results in Table 2).

[0181]

[0182] Table 2: Calculated data of sample composition before recrystallization

[0183]

[0184] 1.3 Recrystallization experiment

[0185] 15 g of each sample or each mixture was placed in a petri dish with a diameter of 100 mm. The petri dish was not closed to allow exchange with the surrounding atmosphere. The petri dish was stored in a climate chamber at 35° C. and 70% humidity for 2 hours. Afterwards, the X-ray diffraction was determined (Table 3).

[0186] Table 3: Measurement results of sample composition after recrystallization

[0187]

[0188] Based on the measured data, the ratio of (C.1) to (C.2) in the entire sample was calculated by formula (1) (results in Table 4).

[0189] Table 4: Calculated data of sample composition after recrystallization

[0190]

[0191] These experiments clearly show that, surprisingly, when the method of the invention is used, the crystallinity and / or the content of orthorhombic MGDA salt in the samples increases. All samples showed excellent results in the storage test after recrystallization.

[0192] Recrystallization Experiment Pilot Facility Test

[0193] All samples were produced by spray drying and agglomerates were formed. Before further processing, one sample was taken (V.1; V.3; V.5). Afterwards, the sample was divided into two parts.

[0194] The second portion was added to the mixer. Briefly, 7% distilled water at 70°C was then sprayed onto the sample while the sample was continuously stirred. After the required amount of water had been added, the mixture was stirred for an additional 3 minutes. The mixture was then compacted with 20 kN and milled to <1 mm (V.2; V.4; V.6).

[0195] 2.1 Sample

[0196] (V.1) MGDA sodium salt agglomerates

[0197] (V.2) Agglomerates of MGDA sodium salt after recrystallization

[0198] (V.3) MGDA sodium salt agglomerates

[0199] (V.4) Agglomerates of MGDA sodium salt after recrystallization

[0200] (V.5) MGDA sodium salt (94%) + sulfonated acrylic acid polymer (6%) agglomerate

[0201] (V.6) Agglomerates of MGDA sodium salt (94%) + sulfonated acrylic acid polymer (6%) after recrystallization

[0202] 2.2 Composition of samples:

[0203] (C.1) Percentage of monoclinic alkali metal salt of MGDA

[0204] (C.2) Percentage of orthorhombic alkali metal salt of MGDA

[0205] (C.3) Percentage of crystalline salt of MGDA

[0206] (C.4) Percentage of amorphous salt of MGDA

[0207] (W.1) Percentage of monoclinic alkali metal salt of MGDA in the whole sample

[0208] (W.2) Percentage of orthorhombic alkali metal salt of MGDA in the whole sample

[0209] The percentages of (C1), (C2), (C3) and (C4) were determined by X-ray diffraction (Table 1).

[0210] Table 5: Measurement results of sample composition

[0211]

[0212]

[0213] The data of the ratio of (C.1) to (C.2) refer to (C.3). Based on the measured data, the ratio of (C.1) to (C.2) in the whole sample was calculated by formula (1) (results in Table 2).

[0214] Table 6: Calculated data of sample composition

[0215]

[0216] 1. Testing

[0217] 3.1 Samples:

[0218] (B.1) Base granules of monoclinic alkali metal salt of MGDA commercially available from BASF

[0219] (V.1) MGDA sodium salt agglomerates

[0220] (V.2) Agglomerates of MGDA sodium salt after recrystallization

[0221] (V.3) MGDA sodium salt agglomerates

[0222] (V.4) Agglomerates of MGDA sodium salt after recrystallization

[0223] (V.5) MGDA sodium salt (94%) + sulfonated polymer (6%) agglomerate

[0224] (V.6) Agglomerates of MGDA sodium salt (94%) + sulfonated polymer (6%) after recrystallization

[0225] 3.3 Discoloration in ADW formulation as tablets

[0226] 1.88 g of the sample was mixed with 12.53 g of a typical ADW formulation and compressed into tablets with 100 kN. The tablets were then packed in LD-PE bags. The tablets were stored in a climate chamber at 35°C and 70% humidity for 9 weeks.

[0227] The discoloration (in this case yellowing) of the stored mixtures was determined by measuring the b-value in the CIELAB color space (Mach 5 measurement).

[0228] Color change test:

[0229] (D.1): Starting value

[0230] (D.2): Color change after 9 weeks of storage (difference from previous measurement)

[0231] (D.3): Total discoloration

[0232] The results are summarized in Table 7.

[0233] Table 7: Color change behavior

[0234]

[0235] Humidity Experiments on Crystallization Mixtures

[0236] Humidity XRD experiments were performed using the Anton Paar CHC plus low temperature and humidity chamber installed on a Bruker D8 Advance. Using a primary Johansson type monochromator, data were collected using Cu Ka1 radiation. In order to ensure high temporal resolution, a detector (Lynxeye, Bruker AXS) was set in a fixed position to detect an angle range of 7.5 ° to 9 ° (2θ). Humidity and temperature were set, and the first data were collected when these set points were reached. Each experiment was performed for ten hours of data collection.

[0237] These samples were prepared by taking pure phase samples of the monoclinic form (Form I) and the orthorhombic form (Form II) and preparing them for XRD via slight manual grinding. The samples were then carefully homogenized by shaking the weighed portion in a closed sample bottle for 30 seconds. The mixture was then filled into a sample holder and flattened using a glass plate.

[0238] Using TOPAS 6 1 All fitting procedures were performed. The data were analyzed using two distinct reflections that distinguished the monoclinic form (Form I) of Na3-MGDA at about 8.13° (2θ) and the orthorhombic form (Form II) at about 8.27° (2θ). The separation of the two modeled reflections was limited to 0.139° (2θ). The grain size broadening was refined using the Voigt model and fixed to 106nm determined using the integral width method. These intensities were related to the corrected scattering factors determined using the standard Rietveld method. No correction for preferred orientation was applied. This resulted in a reflection intensity ratio of 2.305 for Form I:Form II. The resulting volume fraction was then determined using the following equation:

[0239]

[0240] Where I1 is the intensity of the first reflection associated with Form I, and I2 is the intensity of the second reflection associated with Form II. Form II is complementary:

[0241]

[0242] Figures 1 to 7

[0243] This data clearly shows the beneficial effect of high humidity in the conversion to the orthorhombic structure.

[0244] Humidity experiments on crystalline / amorphous mixtures

[0245] To confirm that the amorphous material recrystallized into the orthorhombic form (Form II), the internal standard method was used. 2Amorphous content was estimated. 10 mass % corundum was added to the sample, and the relative intensity of corundum relative to Form II was then used to analyze recrystallization. Data collection was changed to an angular range of 23° to 26° (2θ). Here, two reflections were fitted to the data. The first reflection at approximately 23.6° (2θ) was associated with Form II, while the reflection at 25.4° (2θ) was associated with corundum. The temperature and humidity were set, and the data was collected for the same time as the crystallized sample. The initial intensity ratio was used to calibrate the 50% Form II volume fraction. In subsequent data sets, the following ratios were used to determine the Form II fraction:

[0246]

[0247] Among them I iII is the intensity of the first reflection of the first data set associated with Form II, and I iCor is the intensity of the second reflection of the first data set associated with the corundum standard.

[0248] Quantification by XRD -

[0249] The diffractometer was used with Cu-Kα radiation in a Bruker D8 Advance Bragg-Brentano diffractometer. XRD data were collected. The angular range was set to 2°-80° (2θ) with a step size of 0.02° (2θ). The incident divergent beam slit was set to 0.1°. A Lynxeye detector with an opening angle of 3° was used. The data collection time was optimized to ensure a maximum peak height of more than 50'000 counts / step. The data were then analyzed using a Rietveld model containing the crystal structures of the orthorhombic and monoclinic forms of Na3-MGDA-dihydrate. The instrumental contribution to line broadening was calculated using the fundamental parameter method 1，2 To calculate, just as the method in the software TOPAS 6 1 A third order polynomial and a 1 / X function were used to model the background. The mass percentage values ​​were as reported within the TOPAS user interface.

[0250] References:

[0251] 1.TOPAS 6 Technical Reference. Bruker AXS GmbH: 2017.

[0252] 2. Dinnebier, R.E.; Billinge, S.J., Powder diffraction: theory and practice. Royal society of chemistry: 2008.

[0253] Figure 8

[0254] This data again clearly shows the beneficial effect of high humidity in the conversion to the orthorhombic structure.

Claims

1. A method for preparing a solid, storage-stable composition comprising at least one aminocarboxylate complexing agent, the method comprising the following steps: a) providing an initial aminocarboxylate composition having an amount of solid aminocarboxylate particles of orthorhombic system in an amount of 1% to 25% by weight relative to the total initial solid composition, b) increasing the relative humidity (rH) to at least 50% and / or adding at least 1% by weight of water or an aqueous solution (SO) or slurry (SL) having a water content of at least 10% by weight, preferably at least 30% by weight, relative to the total weight of the aqueous solution or slurry, c) keeping the obtained composition at a temperature ranging from 20° C. to 95° C. for a period ranging from 1 minute to 5 months, d) drying the obtained solid composition to a residual moisture content of less than 20%, thereby obtaining a solid aminocarboxylate composition having an increased orthorhombic crystalline content.

2. The method according to claim 1, wherein: Water is added by setting the relative humidity in the range of 50 to 90%, preferably 60 to 85%, and / or by adding at least 1% by weight, preferably 2 to 10% by weight, of water or an aqueous solution (SO) or a slurry (SL), optionally by spraying the water or aqueous solution (SO) or a slurry (SL) onto the initial solid composition.

3. The method according to claim 1 or 2, wherein: The solid composition is maintained at a temperature of 30°C to 95°C for a period of 2 minutes to 1 month, preferably at 30°C to 70°C for a period of 3 minutes to 2 weeks.

4. A method according to any one of the preceding claims, wherein: The drying is carried out at a temperature ranging from 40° to 240°C, preferably from 60° to 150°C, more preferably from 60° to 120°C, and / or the drying is carried out until a residual moisture content of less than 18% by weight relative to the total weight of the solid composition is reached.

5. A method according to any one of the preceding claims, wherein: The initial composition is prepared by adding 0.1% and 50% by weight of an orthogonal aminocarboxylate to a composition containing no orthogonal aminocarboxylate, or by spray drying or spray granulating a slurry or solution containing 0.1% and 70% by weight of an aminocarboxylate composition in solid content.

6. A method according to any one of the preceding claims, wherein: Providing the solid particles (step a) and adding water (step b) are performed simultaneously or sequentially.

7. A method according to any one of the preceding claims, wherein: These solid particles (step a) are in the form of powders, granules, crystals, compacts, flakes, or agglomerates.

8. A method according to any one of the preceding claims, wherein: The process is carried out at least partially in a mixer, a belt dryer, a kneader, a fluidized bed dryer, a paddle dryer and / or a cone dryer.

9. A method according to any one of the preceding claims, wherein: The aminocarboxylate complexing agent is selected from methylglycine diacetic acid (MGDA), (N,N)-dicarboxymethylglutamic acid (GLDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), ethylenediamine disuccinic acid (EDDS) and their corresponding alkaline salts, preferably sodium salt, more preferably sodium salt of MGDA.

10. A method according to any one of the preceding claims, wherein: The initial solid composition further comprises up to 40% by weight, preferably up to 30% by weight, of at least one organic or inorganic compound or a mixture thereof, relative to the total weight of the initial solid composition.

11. A method according to any one of the preceding claims, wherein: The aqueous solution (SO) or slurry (SL) further comprises up to 40% by weight, preferably up to 30% by weight, of at least one organic or inorganic compound or a mixture thereof, relative to the total weight of the aqueous solution (SO) or slurry (SL).

12. A method according to any one of the preceding claims, wherein: The initial solid composition and / or the aqueous solution (SO) or slurry (SL) comprises at least one compound selected from the list consisting of polymers, preferably sulfonated polymers, antioxidants, surfactants, colorants, pigments, further complexing agents, organic and inorganic acids, and salts thereof.

13. A solid, storage-stable composition comprising at least one aminocarboxylate complexing agent, obtainable or obtained by a process according to any one of claims 1 to 12.

14. Use of a solid, storage-stable composition comprising at least one aminocarboxylate complexing agent obtainable or obtained by the process according to any one of claims 1 to 12 for the manufacture of a detergent or cleaning formulation, preferably a dishwashing detergent formulation, more preferably an automatic dishwashing detergent formulation.

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