Process for making a powder or granule

Abstract

The present invention deals with a process for making a powder or granule containing (A) at least one aminocarboxylate chelating agent, and (B) at least one amphoteric surfactant, and, optionally, (C) at least one polymer, wherein the powder or granule contains in the range of from 70 to 99.5 % by weight of aminocarboxylate chelating agent (A), in the range of from 0.5 to 10 % by weight amphoteric surfactant, and in the range of from 0 to 29.5 % by weight polymer (C), percentages referring to the actives content of said powder or granule, said process comprising the steps of (a) mixing the at least one chelating agent (A), the at least one amphoteric surfactant (B) and, optionally, at least one polymer (C) in the presence of water, (b) removing most of said water by spray-drying or spray-granulation, wherein the resulting powder or granule has a residual moisture content in the range of from 0.1 to 20 % by weight, as determined by Karl-Fischer-titration.

Description

[0001] Process for making a powder or granule

[0002] The present invention deals with a process for making a powder or granule containing

[0003] (A) at least one aminocarboxylate chelating agent, and

[0004] (B) at least one amphoteric surfactant, and, optionally

[0005] (C) at least one polymer,

[0006] wherein the powder or granule contains in the range of from 70 to 99.5 % by weight of aminocarboxylate chelating agent (A), in the range of from 0.5 to 10 % by weight amphoteric surfactant, and in the range of from 0 to 29.5 % by weight polymer (C), percentages referring to the actives content of said powder or granule, said process comprising the steps of

[0007] (a) mixing the at least one chelating agent (A), the at least one amphoteric surfactant (B) and, optionally, at least one polymer (C) in the presence of water,

[0008] (b) removing most of said water by spray-drying or spray-granulation, wherein the resulting powder or granule has a residual moisture content in the range of from 0.1 to 20 % by weight, as determined by Karl-Fischer-titration.

[0009] Chelating agents of the aminocarboxylate type such as methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their respective alkali metal salts are useful sequestrants for alkaline earth metal ions such as Ca2+and Mg2+. A lot of aminocarboxylates show good biodegradability and are thus environmentally friendly. For that reason, they are recommended and used for various purposes such as laundry detergents and for automatic dishwashing (ADW) formulations, in particular for so-called phosphate-free laundry detergents and phosphate-free ADW formulations.

[0010] Depending on the type of product - liquid home care and fabric care products versus solid home care and fabric care products - and the manufacturing process of solid home care and fabric care products care product manufacturers may either prefer to handle solutions of aminocarboxylates or solid arminocarboxylates, for example joint spray drying or solid mixing. Powders and granules of aminocarboxylates may be shipped economically due to their high active ingredient content that goes along with low water content. Therefore, convenient processes for providing granules are still of great commercial interest.

[0011] WO 2024 / 126730 A1 describes a free flowing particulate composition comprising at least 50 wt% of one or more amphoteric surfactants and at least 0.1 wt% of one or more chelating agents. A process to manufacture the particulate composition by spray-drying is also mentioned. The use of polymers in the particulate composition is not described. US 2017 / 058239 A1 discloses a process for making a powder or granule containing at least one chelating agent and at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali.

[0012] WO 2021 / 115851 A1 also describes a process for making a granule containing at least one chelating agent and, optionally, at least one homo- or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali.

[0013] Said two publications do not specifically mention the use of amphoteric surfactants.

[0014] Commonly ADW formulations contain up to 40% of MGDA builder and are packaged in single unit doses, in brief also "SUD”. The space in these SUD is limited and thus a higher bulk density is desired, because a higher bulk density allows for more active product per volume unit in these SUDs.

[0015] Thus, an increase of the bulk density of said powders or granules is desirable, since a higher bulk density leads to a lowered need for packaging materials and thus decreased energy consumption in transporting the products.

[0016] In an attempt to increase the bulk density, WO 2020 / 064379 discloses a process for making a powder or granule containing a chelating agent (e. g. MGDA) and an alkali metal salt of a 010 to 020 fatty acid, which involves spraygranulating or spray-drying a mixture of the chelating agent and alkali metal salt of 010 to 020 fatty acid, i. e. an ionic surfactant, with relatively long C chains. The additional use of polymers in the granulation process is not mentioned. However, the disclosed processes (and the resulting products) still leave room for improvement. For example, the sodium oleate used in the process mentioned above does not form an solution, but an emulsion; fast stirring is required to keep the sodium oleate emulsified.

[0017] Furthermore, in general, when using surfactants, foaming (creation of foam) has to be considered. In some processes, generation of foam is undesirable.

[0018] Besides, regarding the solid product containing (inter alia) aminocarboxylate chelating agent, the hygroscopicity is an important characteristic, since it influences the storage stability of the powder or granule containing aminocarboxylate chelating agent.

[0019] It was therefore an objective of the present invention to provide a process that yields powders or granules of chelating agents, preferably with an increased bulk density. It was also an objective of the present invention to provide powders or granules of chelating agents, preferably with an increased bulk density. Furthermore, it was an objective of the present invention to provide a process that yields powders or granules of chelating agents, preferably with a reduced content of overs. Another objective of the present invention was to provide a convenient process that yields powders or granules of chelating agents, preferably with a low or reduced hygroscopicity.

[0020] The inventors have now surprisingly found that a process for making a powder or granule comprising at least one aminocarboxylate chelating agent and at least one amphoteric surfactant works well and is suited to obtain powders or granules containing aminocarboxylate chelating agents, mostly with a high bulk density and / or a reduced amount of overs and / or a low hygroscopicity. Furthermore, the inventors have surprisingly found that the inventive process for making a powder or granule comprising at least one aminocarboxylate chelating agent is convenient to handle, and, surprisingly, avoids undesired foam creation in the drying (e.g. granulation) process even though amphoteric surfactants are used.

[0021] Thus, one object of the present invention is a process for making a powder or granule, preferably with high bulk density and / or low amount of overs and / or low hygroscopicity, containing

[0022] (A) at least one aminocarboxylate chelating agent, and

[0023] (B) at least one amphoteric surfactant, and, optionally

[0024] (C) at least one polymer, optionally selected from homo- or copolymers of (meth)acrylic acid,

[0025] said process comprising the steps of

[0026] (a) mixing the at least one chelating agent (A), the at least one amphoteric surfactant (B) and, optionally, at least one polymer (C) in the presence of water,

[0027] (b) removing most of said water by spray-drying or spray-granulation, preferably using a gas with an inlet temperature of at least 125° C, more preferably at least 140° C, wherein the resulting powder or granule has a residual moisture content in the range of from 0.1 to 20 % by weight, as determined by Karl-Fischer-titration.

[0028] The term "overs” refers to, in other words, "lumps” that may be formed in the drying (e. g. spray granulation) process In embodiments of the inventive process wherein granules are desired, said lumps (also referred to as "overs”, as mentioned above) to be separated off are particles that have a minimum particle diameter of 1,500 pm, for example, 1,500 pm to 2 mm or even more. In a preferred embodiment, lumps are particles that have a minimum particle diameter of 1,250 pm or more, even more preferably 900 pm to 2 mm.

[0029] In embodiments wherein powders are desired, said lumps or overs have a minimum particle diameter of 250 pm or more, for example 250 to 1,000 pm.

[0030] Overs or lumps may be removed, e.g., with the help of a discharge screw or a rotary valve, usually together with desired product, and then classified.

[0031] The bulk density may be determined in accordance with ISO 697 (2ndedition 1981-03-01).

[0032] Hygroscopicity may be determined in accordance with the following procedure: about 5 g of the respective sample is placed on a Petri dish, and the weight is determined. The Petri dish with the sample is put in a conditioning cabinet with 38°C and 78% relative humidity. The weight is determined again after 1 hour, 3 hours, 6 hours, 24 hours, 48 hours, etc

[0033] The term "granule” in the context of the present invention refers to particulate materials that are solids at ambient temperature and that preferably have an average particle diameter (D50) in the range of from 0.1 mm to 2 mm, preferably 0.4 mm to 1.25 mm, even more preferably 400 pm to 1 mm. The average particle diameter of inventive granules can be determined, e.g., by optical or preferably by sieving methods. Sieves employed may have a mesh in the range of from 60 to 3,000 m.

[0034] In one embodiment of the present invention, granules made according to the present invention have a broad particle diameter distribution. In another embodiment of the present invention, granules made according to the present invention have a narrow particle diameter distribution. The particle diameter distribution can be adjusted, if desired, by multiple sieving steps.

[0035] Granules made by the inventive process may contain residual moisture, moisture referring to water including water of crystallization and adsorbed water. The amount of water may be in the range of from 0.1 to 20% by weight or from 1.0 to 20% by weight, preferably 1 to 15% by weight, referring to the total solids content of the respective granule, and may be determined by Karl-Fischer-titration or by drying at 160 to 200°C to constant weight with infrared light. Particles of granules made by the inventive process have a regular shape; they have smooth surfaces, no sharp edges, reducing the generation of fines while moving

[0036] Regarding the inventive process, step (a) can be performed at ambient temperature. In other embodiments, step (a) is being performed at 20° C or at elevated temperature, for example at a temperature in the range of from 25 to 90°C, preferably 60 to 75°C.

[0037] In one embodiment of the present invention, the total solids content of the solution or slurry formed as result of step (a) is in the range of from 20 to 75%, preferably 35 to 50%.

[0038] In step (b), most of the water is removed from the aqueous solution or slurry provided in step (a) by spray granulation in a fluidized bed.

[0039] The aqueous slurry or aqueous solution according to step (a) may have a temperature in the range of from 15 to 95°C, preferably 20 to 90°C and even more preferably 50 to 90°C.

[0040] In step (b), said aqueous slurry or aqueous solution is introduced into a spray granulator. In the context of the present invention, a spray granulator usually contains a fluidized bed, in the context of the present invention it is a fluidized bed of chelating agent (A), or of granule made according to the present invention. Such fluidized bed of chelating agent (A) is preferably in the form of chelating agent in crystalline form, for example at least 66% crystalline form, determined by X-Ray diffraction. In one embodiment of the present invention, the fluidized bed may have a temperature in the range of from 75 to 150°C, preferably 80 to 110°C.

[0041] Spraying is being performed through one or more nozzles per spray granulator. Suitable nozzles are, for example, high-pressure rotary drum atomizers, rotary atomizers, three-fluid nozzles, single-fluid nozzles, three-fluid nozzles and two-fluid nozzles, single-fluid nozzles and two-fluid nozzles and three-fluid nozzles being preferred. The first fluid is the aqueous slurry or aqueous solution or emulsion, respectively, the second fluid is compressed hot gas, also referred to as hot gas inlet stream, for example with a pressure of 1.1 to 7 bar. The hot gas inlet stream may have a temperature in the range of from at least 125°C to 250°C, preferably 150 to 250°C, even more preferably 160 to 220°C.

[0042] In step (b), the aqueous slurry or aqueous solution of complexing agent (A) and / or surfactant (B) and, optionally, (co)polymer (C) is introduced in the form of droplets into said fluidized bed. In one embodiment of the present invention, the droplets formed during the spray-granulating have an average diameter in the range of from 10 to 500 m, preferably from 20 to 180 pm, even more preferably from 30 to 100 pm.

[0043] In one embodiment of the present invention, the off-gas departing the spray granulator may have a temperature in the range of from 40 to 140°C, preferably 80 to 110°C but in any way colder than the hot gas stream. Preferably, the temperature of the off-gas departing the drying vessel and the temperature of the solid product present in the drying vessel are identical.

[0044] In one embodiment of the present invention, the pressure in the spray tower or spray granulator in step (b) is normal pressure ± 100 mbar, preferably normal pressure ± 20 mbar, for example one mbar less than normal pressure.

[0045] In one embodiment of the present invention, especially in a process for making an inventive granule, the average residence time of chelating agent (A) in step (b) is in the range of from 2 minutes to 4 hours, preferably from 30 minutes to 2 hours.

[0046] In embodiments wherein an aged slurry is used, such aging may take in the range of from 2 hours to 24 hours at the temperature preferably higher than ambient temperature.

[0047] In the course of step (b), most of the water is removed in a fluidized bed. Most of the water shall mean that a residual moisture content of 0.1 to 20% by weight may remain, referring to the granule. In embodiments that start off from a solution, about 51 to 75% by weight of the water present in the aqueous solution is removed in step (b).

[0048] A granule is obtained, hereinafter also referred to as "resultant particulate residue” or "granule from step (b)”. Said granule from step (b) has the appearance of a granule that may have a bulk density in the range of from 700 to 950 g / l, preferably more than 750 g / l. Particles of granule from step (b) may show some degree of irregularity in shape.

[0049] At the end of step (b), the granule from step (b) is removed from the spray granulator. Said granule has been at least partially formed in the course of step (b) of the inventive process. Said removal may be performed through one or more openings in the spray tower or spray granulator. Preferably, such one or more openings are at the bottom of the respective spray tower or spray granulator. Granules are removed including fines and lumps. In a further optional step (c), the granule from step (b) may be treated with air or an inert gas or a combination of the foregoing in a vessel of which at least one part rotates around a horizontal axis. Examples of inert gases are nitrogen and rare gases such as, but not limited to argon. Mixtures of air and inert gases are feasible as well. Preferably, such air or inert gas is "dry”. In this context, dry is meant to understand less than 5 g H2O per kg of gas.

[0050] The at least one aminocarboxylate chelating agent (A) may be selected from MGDA, GLDA, IDS, EDDS and their respective alkali metal salts, preferably sodium and / or potassium salts. Preferred is MGDA and its alkali metal salts, particularly MGDA trisodium salt.

[0051] The aminocarboxylate agent (A) may also be only partially neutralized. For example, in a preferred embodiment of the present invention, the aminocarboxylate agent (A) is selected from MGDA and the MGDA contains 0.940 to 0.995 molar equivalent counterions, preferably sodium ions, per acidic group.

[0052] The at least one amphoteric surfactant (B) may be selected from amphoteric surfactants bearing an alkyl chain with has eight to fourteen carbon atoms.

[0053] In a preferred embodiment, the at least one amphoteric surfactant (B) is selected from acylamidopropylbetaines, particularly cocamidopropylbetaine.

[0054] In a further preferred embodiment, the at least one amphoteric surfactant (B) is selected from sodium salts of amphoacetates with a linear C10 to C14 alkyl chain, preferably sodium lauroamphoacetate.

[0055] In another embodiment of the inventive process, the at least one amphoteric surfactant (B) is selected from reaction products of an amino acid or a salt thereof with a monooxirane compound.

[0056] Said reaction product of an amino acid or a salt thereof the reaction product may comprise a compound of the formula (I)

[0057] 3

[0058] R2 )y_COOX

[0059] O I H R I. 1 R

[0060]

[0061] (I)

[0062] x is 0, 1, 2 or 3 and y is 0 or 1.

[0063] R1is selected from the group consisting of hydrogen, Ci-10-alkyl, which is optionally substituted by COOX, C2-io-alkeny I and Ce-12-aryl, which is unsubstituted or substituted by 1 or 2 substituents Ra; R2is selected from the group consisting of hydrogen, Ci-io-alkyl group which is optionally substituted by one of the following groups:

[0064] guanidino, carboxamide, hydroxyl, carboxyl, sulfhydryl, imidazolyl, amino, Ci-C4-alkylsulfanyl, Ce-12-aryl, in particular phenyl, which is optionally substituted by 1 or 2 substituents Rb, or hetaryl, such as imidazolyl or indolyl, and a radical CH2-S-CH2-CH(OH)-R3;

[0065] R1and R2together with CH-(CH2)X-N may alternatively form a 5 or 6-membered saturated or partially unsaturated ring which may have a further heteroatom selected from 0, N and S, where the 5 or 6- membered saturated or partially unsaturated ring may carry 1 or 2 C1-6 alkyl substituents. R3is selected from the group consisting of Ci.2o-alkyl, C2.2o-alkenyl, Ce-i2-ary I and CHRX-O-Ry;

[0066] Rxis selected from the group consisting of hydrogen and Ci-4-alkyl;

[0067] Ry is selected from the group consisting of hydrogen, Ci.2o-alkyl, C2.2o-alkenyl, where Ci.2o-alkyl and C2.2o-alkenyl are unsubstituted or substituted by 1 or 2 substituents Rc, Ce-i2-aryl, which is unsubstituted or substituted by 1 or 2 substituents Rd;

[0068] X is selected from the group consisting of hydrogen and alkali metal ions, and

[0069] where

[0070] Ra, Rb, Rdindependently of each other are selected from OH, Ci-4-alkyl,

[0071] O-Ci-4-alkyl and C(0)0-Ci-4-alkyl; and

[0072] Rcis selected from OH, =0, O-Ci-4-alkyl, 0-C(0)-Ci-4-alkyl and

[0073] C(O)O-Ci-4-alkyl.

[0074] In another embodiment of the inventive process, the at least one amphoteric surfactant (B) is selected from compounds of the formula (la),

[0075]

[0076] wherein

[0077] x is 0, 1, 2 or 3 and y is 0 or 1;

[0078] R1and R2together with CH-(CH2)X-N form a 5 or 6-membered saturated or partially unsaturated ring which may have a further heteroatom selected from 0, N and S, where the 5 or 6-membered saturated or partially unsaturated ring may carry 1 or 2 Ci-6-alkyl substituents.

[0079] R4is selected from the group consisting of hydrogen and Ci-4-alkyl;

[0080] R5is selected from the group consisting of hydrogen, Ci-2o-alkyl, C2.2o-alkenyl, where Ci-2o-alkyl and C2.2o- alkenyl are unsubstituted or substituted by 1 or 2 substituents Rc, Ce-i2-aryl, which is unsubstituted or substituted by 1 or 2 substituents Rd; where

[0081] Rcis selected from OH, =0, O-Ci-C4-alkyl, 0-C(0)-Ci-4-alkyl and C(0)0-Ci-4-alkyl;

[0082] Rdis selected from OH, Ci-4-alkyl, O-Ci-4-alkyl and C(0)0-Ci-4-alkyl

[0083] X is selected from the group consisting of hydrogen and alkali metal ions. Said formula (la) mentioned above may be represented by the following formulae (la-1) - (la-7): 5

[0084]

[0085]

[0086] (la-7)

[0087] wherein R4, R5and X are same as defined in the formula (la).

[0088] The at least one polymer (C) may be selected from homo- or copolymers of (meth)acrylic acid, partially or fully neutralized with alkali.

[0089] Polymer (C) may be selected from homopolymers (C) of (meth)acrylic acid and of copolymers (C) of (meth)acrylic acid, preferably of acrylic acid, partially or fully neutralized with alkali. In the context of the present invention, copolymers (C) are those in which at least 50 mol-% of the comonomers are (meth)acrylic acid, preferably at least 75 mol-%, even more preferably 80 to 99 mol-%.

[0090] Suitable comonomers for copolymers (C) are ethy lenically unsaturated compounds, such as styrene, isobutene, ethylene, o-olefins such as propylene, 1 -butylene, 1 -hexene, and ethylenically unsaturated dicarboxylic acids and their alkali metal salty and anhydrides such as but not limited to maleic acid, fumaric acid, itaconic acid disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride. Further examples of suitable comonomers are Ci-C4-alkyl esters of (meth)acrylic acid, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate.

[0091] In one embodiment of the present invention, polymer (C) is selected from copolymers of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule. Comonomers bearing at least one sulfonic acid group per molecule may be incorporated into polymer (B) as free acid or least partially neutralized with alkali.

[0092] Particularly preferred sulfonic-acid-group-containing comonomers are 1 -acrylamido-1 -propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 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 the sodium salts, potassium salts or ammonium salts thereof.

[0093] Copolymers (C) may be selected from random copolymers, alternating copolymers, block copolymers and graft copolymers, alternating copolymers and especially random copolymers being preferred.

[0094] Useful copolymers (C) are, for example, random copolymers of acrylic acid and methacrylic acid, random copolymers of acrylic acid and maleic anhydride, ternary random copolymers of acrylic acid, methacrylic acid and maleic anhydride, random or block copolymers of acrylic acid and styrene, random copolymers of acrylic acid and methyl acrylate. More preferred are homopolymers of methacrylic acid. Even more preferred are homopolymers of acrylic acid.

[0095] Polymer (C) may constitute straight-chain or branched molecules. Branching in this context will be when at least one repeating unit of such polymer (C) is not part of the main chain but forms a branch or part of a branch. Preferably, polymer (C) is not cross-linked.

[0096] In one embodiment of the present invention, polymer (C) has an average molecular weight Mwin the range of from 1,200 to 30,000 g / mol, preferably from 2,500 to 15,000 g / mol and even more preferably from 3,000 to 10,000 g / mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.

[0097] In one embodiment of the present invention, polymer (C) is at least partially neutralized with alkali, for example with lithium or potassium or sodium or combinations of at least two of the forgoing, especially with sodium. For example, in the range of from 10 to 100 mol-% of the carboxyl groups of polymer (B) may be neutralized with alkali, especially with sodium.

[0098] In one embodiment of the present invention, polymer (C) is selected from per-sodium salts of polyacrylic acid, thus, polyacrylic acid, fully neutralized with sodium.

[0099] In one embodiment of the present invention, polymer (C) is selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer bearing at least one sulfonic acid group per molecule, both polymers being fully neutralized with alkali.

[0100] In one embodiment of the present invention, polymer (C) is selected from per-sodium salts of polyacrylic acid with an average molecular weight Mwin the range of from 1,200 to 30,000 g / mol, preferably from 2,500 to 15,000 g / mol and even more preferably from 3,000 to 10,000 g / mol, determined by gel permeation chromatography (GPC) and referring to the respective free acid.

[0101] The at least one polymer (C) may also be selected from other types of suitable polymers. "Suitable” in this context means that the polymers may be co-granulated or co-spray dried with the other mandatory ingredients of the present invention.

[0102] For example, polymer (C) may be selected from polyaspartic acid. Polymer (C) may also be selected from the polymers described in unpublished patent application no. EP 24222051.5 (e. g. in claim 5 or claim 6).

[0103] In a preferred embodiment of the inventive process, the powder or granule contains in the range of from 70 to 99.5 % by weight of aminocarboxylate chelating agent (A), in the range of from 0.5 to 10 % by weight amphoteric surfactant, and in the range of from 0 to 29.5 % by weight polymer (C), percentages referring to the actives content of said powder or granule. The amphoteric surfactant is, more preferably, contained in a weight percentage of from 2.0 to 6.0.

[0104] The inventive process involves, in one embodiment, spray-granulation, preferably fluidized bed spray granulation, preferably with a bed temperature in the range of from 80° C to 150° C, preferably 80 to 110° C.

[0105] In one embodiment, a gas with an inlet temperature of at least 125° C, more preferably at least 140° C, is used. In one embodiment, a gas with an inlet temperature of at most 350° C is used in the inventive process.

[0106] Another object of the present invention is also a powder or granule containing at least one aminocarboxylate chelating agent (A), at least one amphoteric surfactant (B), and, optionally, at least one polymer (C), optionally selected from homo- or copolymers of (meth)acrylic acid, preferably obtained or obtainable by the inventive process (as described above and in the appended claims).

[0107] Still another object of the present invention is the use of an inventive powder or granule, and of a powder or granule obtained or obtainable by the inventive process, for detergent applications, preferably dishwashing detergent applications. Particularly preferred are automatic dishwashing (ADW) applications.

[0108] Applications

[0109] Another aspect of the present invention is the use of an inventive granule for detergent applications, e. g. for the manufacture of a cleaning agent that may contain at least one bleaching agent, and in particular for the manufacture of cleaning agent for fibers or hard surfaces, wherein said cleaning agent contains at least one peroxy compound. Another aspect of the present invention is a process for making at a cleaning agent by combining at least one inventive granule with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, hereinafter also being referred to as inventive cleaning agent.

[0110] Inventive cleaning agents may contain at least one bleaching agent and at least one inventive granule. Inventive cleaning agents show a reduced tendency for yellowing and therefore have an extended shelve-life.

[0111] Examples of suitable peroxy compounds are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-o-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1 ,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid or as alkali metal salt, in particular as sodium salt, also sulfonylperoxy acids and cationic peroxy acids.

[0112] In a preferred embodiment, peroxy compound is selected from inorganic percarbonates, persulfates and perborates. Examples of sodium percarbonates are 2 Na2CO3'3 H2O2. Examples of sodium perborate are (Na2[B(OH)2(O2)]2), sometimes written as NaBC^C^SfW instead. Most preferred peroxy compound is sodium percarbonate. The term "cleaning agents” includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, and in addition, laundry detergent compositions.

[0113] Such cleaning agents may be liquids, gels or preferably solids at ambient temperature, solids cleaning agents being preferred. They may be in the form of a powder or granule or in the form of a unit dose, for example as a tablet.

[0114] In one embodiment of the present invention, inventive cleaning agents may contain

[0115] in the range of from 2 to 50 % by weight of inventive granule,

[0116] in the range of from 0.5 to 15 % by weight of bleach.

[0117] Percentages are based on the solids content of the respective inventive cleaning agent.

[0118] Inventive cleaning agents may contain further ingredients such as one or more surfactants that may be selected from non-ionic, zwitterionic, cationic, and anionic surfactants. Other ingredients that may be contained in inventive cleaning agents may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestering agents other than chelating agent (A), enzymes, fragrances, dyestuffs, antifoams, and builders.

[0119] Particularly advantageous inventive cleaning agents may contain one or more complexing agents other than MGDA or GLDA. Advantageous detergent compositions for cleaners and advantageous laundry detergent compositions may contain one or more sequestrant (chelating agent) other than a mixture according to the present invention. Examples for sequestrants other than a mixture according to the present invention are citrate, phosphonic acid derivatives, for example the disodium salt of hydroxyethane-1 , 1 -diphosphonic acid (“HEDP”), and polymers with complexing groups like, for example, polyethylenimine in which 20 to 90 mole-% of the N-atoms bear at least one CH2COO- group, and their respective alkali metal salts, especially their sodium salts, for example IDS-Na4, and trisodium citrate, and phosphates such as STPP (sodium tripolyphosphate). Due to the fact that phosphates raise environmental concerns, it is preferred that advantageous inventive cleaning agents are free from phosphate. "Free from phosphate" should be understood in the context of the present invention, as meaning that the content of phosphate and polyphosphate is in sum in the range from 10 ppm to 0.2% by weight, determined by gravimetric methods and referring to the respective inventive cleaning agent.

[0120] Inventive cleaning agents may contain one or more surfactant, preferably one or more non-ionic surfactant.

[0121] Preferred non-ionic surfactants are alkoxylated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides. Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (I)

[0122] R1

[0123]

[0124] (I)

[0125] in which the variables are defined as follows:

[0126] R1is identical or different and selected from hydrogen and linear Ci-Cio-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0127] R2is selected from C8-C22-alkyl, branched or linear, for example n-CsHiz, n-C H2i , n-Ci2H25, n-Cufe, n-C Hss or n-CisHsz,

[0128] R3is selected from Ci-C -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl or isodecyl,

[0129] m and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 3 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0130] In one embodiment, compounds of the general formula (I) may be block copolymers or random copolymers, preference being given to block copolymers.

[0131] Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (II)

[0132] R1R1

[0133]

[0134] (II)

[0135] in which the variables are defined as follows:

[0136] R1is identical or different and selected from hydrogen and linear Ci-Co-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl,

[0137] R4is selected from C6-C2o-alkyl, branched or linear, in particular n-CsHiz, n-C H2i , n-Ci2H25, n-Cufe, n-C Hss, n-CisHsz, a is a number in the range from zero to 10, preferably from 1 to 6,

[0138] b is a number in the range from 1 to 80, preferably from 4 to 20,

[0139] d is a number in the range from zero to 50, preferably 4 to 25.

[0140] The sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.

[0141] Preferred examples for hydroxyalkyl mixed ethers are compounds of the general formula (III)

[0142] OH

[0143] 1

[0144] R

[0145]

[0146] in which the variables are defined as follows:

[0147] R1is identical or different and selected from hydrogen and linear Ci-Cio-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0148] R2is selected from C8-C22-alkyl, branched or linear, for example Iso-CnFh, Iso-C F , n-CsH , n-CioH2i, n- C12H25, n-CuFfe, n-CieH33 or n-CisHsz,

[0149] R3is selected from Ci-Ci8-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.

[0150] The variables m and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 5 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0151] Compounds of the general formula (II) and (III) may be block copolymers or random copolymers, preference being given to block copolymers.

[0152] Further suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-Ci6-alkyl polyglucosides and branched Cs-Cu-alkyl polyglycosides such as compounds of general average formula (IV) are likewise suitable.

[0153]

[0154] wherein the variables are defined as follows:

[0155] R5is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

[0156] R6is -(CH2)2-R5,

[0157] G1is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose,

[0158] x in the range of from 1.1 to 4, x being an average number.

[0159] An overview of suitable further nonionic surfactants can be found in EP-A 0851 023 and in DE-A 198 19 187.

[0160] Mixtures of two or more different nonionic surfactants may also be present.

[0161] Other surfactants that may be present in the inventive cleaning agent (detergent) are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

[0162] Notwhithstanding the above explanations, examples of amphoteric surfactants are also those that bear a positive and a negative charge in the same molecule under use conditions. Preferred examples of amphoteric surfactants are so-called betaine-surfactants. Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).

[0163] Examples of amine oxide surfactants are compounds of the general formula (V)

[0164] R7R8R9N^O (V)

[0165] wherein R7, R8and R9are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene Cio-C2o-alkylamido moieties. Preferably, R7is selected from C8-C2o-alkyl or C2-C4-alkylene Cio-C2o-alkylamido and R8and R9are both methyl.

[0166] A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.

[0167] Examples of suitable anionic surfactants are alkali metal and ammonium salts of Cs-Cis-alky I sulfates, of Cs-Cis-fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-C 12-alky Iphenols (ethoxylation: 1 to 50 mol of ethylene oxide / mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of C12-C1 s-alky Isulfonic acids and of Cio-Cis-alky lary Isulfonic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

[0168] Further examples for suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearoic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.

[0169] In one embodiment of the present invention, inventive cleaning agents that are determined to be used as laundry detergent compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0170] In one embodiment of the present invention, inventive cleaning agents that are determined to be used 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.

[0171] Inventive cleaning agents may comprise one or more bleach catalysts. Bleach catalysts can be selected from bleachboosting 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.

[0172] Inventive cleaning agents may comprise one or more bleach activators, for example 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).

[0173] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0174] Inventive cleaning agents may 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.

[0175] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor. Inventive cleaning agents may comprise one or more builders, selected from organic and inorganic builders.

[0176] Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, in particular those of the formula o-Na2Si2O5, p-Na2Si2O5, and 5-Na2Si2O5, also fatty acid sulfonates, a-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.

[0177] Examples of organic builders are especially polymers and copolymers. In one embodiment of the present invention, organic builders are selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, partially or completely neutralized with alkali.

[0178] Suitable comonomers for (meth)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 an average molecular weight Mwin the range from 2000 to 40000 g / mol, preferably 3,000 to 10,000 g / mol.

[0179] It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated Ca-Cio-mono- or C4-Cio-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 hydrophilic or hydrophobic monomer as listed below.

[0180] Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with 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, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

[0181] Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic 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)acry-late, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here may comprise 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

[0182] Particularly preferred sulfonic-acid-group-containing monomers here are 1-acrylamido-1-pro-panesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methyl-propanesulfonic acid, 3-methacrylamido-2-hydroxypropane-sulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyl-oxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-pro-pene-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.

[0183] Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

[0184] Moreover, amphoteric polymers can also be used as builders.

[0185] Inventive cleaning agents may comprise, for example, in the range from in total 10 to 50% by weight, preferably up to 20% by weight, of builder.

[0186] In one embodiment of the present invention, inventive cleaning agents according to the invention may comprise one or more cobuilders.

[0187] Inventive cleaning agents may comprise one or more antifoams, selected for example from silicone oils and paraffin oils.

[0188] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.05 to 0.5% by weight of antifoam.

[0189] Inventive cleaning agents may comprise one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

[0190] In one embodiment of the present invention, inventive cleaning agents may comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight. Said enzyme may be stabilized, for example with the sodium salt of at least one Ci-Ca-carboxylic acid or C4-Cio-dicarboxylic acid. Preferred are formates, acetates, adipates, and succinates.

[0191] In one embodiment of the present invention, inventive cleaning agents may comprise at least one zinc salt. Zinc salts can be selected from water-soluble and water-insoluble zinc salts. In this connection, within the context of the present invention, water-insoluble is used to refer to those zinc salts which, in distilled water at 25°C, have a solubility of 0.1 g / l or less. Zinc salts which have a higher solubility in water are accordingly referred to within the context of the present invention as water-soluble zinc salts.

[0192] In one embodiment of the present invention, zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCh, ZnSC>4, zinc acetate, zinc citrate, Zn(NOa)2, Zn(CH3SO3)2 and zinc gallate, preferably ZnCl2, ZnSC>4, zinc acetate, zinc citrate, Zn(NOa)2, Zn(CH3SO3)2 and zinc gallate.

[0193] In another embodiment of the present invention, zinc salt is selected from ZnO, ZnOaq, Zn(OH)2 and ZnCOs. Preference is given to ZnOaq. In one embodiment of the present invention, zinc salt is selected from zinc oxides with an average particle diameter (weight-average) in the range from 10 nm to 100 m.

[0194] The cation in zinc salt can be present in complexed form, for example complexed with ammonia ligands or water ligands, and in particular be present in hydrated form. To simplify the notation, within the context of the present invention, ligands are generally omitted if they are water ligands.

[0195] Depending on how the pH of mixture according to the invention is adjusted, zinc salt can change. Thus, it is for example possible to use zinc acetate or ZnCh for preparing formulation according to the invention, but this converts at a pH of 8 or 9 in an aqueous environment to ZnO, Zn(OH)2 or ZnOaq, which can be present in non-complexed or in complexed form.

[0196] Zinc salt may be present in those inventive cleaning agents that are solid at room temperature. In such inventive cleaning agents zinc salts are preferably present in the form of particles which have for example an average diameter (number-average) in the range from 10 nm to 100 pm, preferably 100 nm to 5 pm, determined for example by X-ray scattering.

[0197] Zinc salt may be present in those inventive cleaning agents that are liquid at room temperature. In such inventive cleaning agents zinc salts are preferably present in dissolved or in solid or in colloidal form.

[0198] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.05 to 0.4% by weight of zinc salt, based in each case on the solids content of the cleaning agent in question.

[0199] Here, the fraction of zinc salt is given as zinc or zinc ions. From this, it is possible to calculate the counterion fraction.

[0200] In one embodiment of the present invention, inventive cleaning agents are free from heavy metals apart from zinc compounds. Within the context of the present, this may be understood as meaning that inventive cleaning agents are free from those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and of bismuth. Within the context of the present invention, "free from" in connection with heavy metal compounds is to be understood as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in sum in the range from 0 to 100 ppm, determined by the leach method and based on the solids content. Preferably, inventive cleaning agents has, apart from zinc, a heavy metal content below 0.05 ppm, based on the solids content of the formulation in question. The fraction of zinc is thus not included.

[0201] Within the context of the present invention, "heavy metals" are deemed to be all metals with a specific density of at least 6 g / cm3with the exception of zinc. In particular, the heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium. Preferably, inventive cleaning agents comprise no measurable fractions of bismuth compounds, i.e. for example less than 1 ppm.

[0202] Inventive cleaning agents are excellent for cleaning hard surfaces and fibres.

[0203] The present invention is further illustrated by (non-limiting, illustrative) working examples.

[0204] Some aspects of the invention are also visualized in the appended figures 1 and 2.

[0205] A. Foaming tests were performed with amphoteric surfactant.

[0206] Test 1: Mixture 100g Water + 3.5g amphoteric surfactant

[0207] 5 s manual shaking in bottle

[0208] Mixture foams strongly (see attached Figure 1)

[0209] Test 2: Mixture 100g MGDA and + 3.5g amphoteric surfactant

[0210] 5 s manual shaking in bottle

[0211] Surprisingly, mixture also shows some foam formation, but much less than in water (see attached Figure 2)

[0212] Test 3: Co-Granulation MGDA + 3.25% amphoteric surfactant

[0213] Percentages are given with respect to content of active substances.

[0214] Experimental setup laboratory:

[0215] Plant details

[0216] o ProCell LabSystem with Vario 3 insert

[0217] o Zig-zag sifter at particle outlet

[0218] o Manual sieving of extracted particles >250pim and <1000pm

[0219] o Grinding of particles / ” overs” > 1000pm and recycle with fines (<250pim) to granulator Process parameters (standard granulation parameters for Trilon M)

[0220] o Bed temperature: 100°C + / - 2°C

[0221] o Gas temperature (inlet): 165°C + / - 5°C

[0222] o Gas volume flow (exit): 200m3 / h @ ~160°C

[0223] o Spray rate (feed): 7000g / h @70°C Preparation

[0224] o Stirring and preheating of MGDA in a vessel. Amphoteric surfactant is added slowly to stirred vessel. Amphoteric surfactant is fully solved in mixture.

[0225] During the granulation experiment, surprisingly, no foam formation was observed.

[0226] B. Co granulation with amphoteric surfactant

[0227] Experimental setup laboratory:

[0228] - Plant details of ProCell LabSystem with Vario 3 insert

[0229] o Zig-zag sifter at particle outlet

[0230] o Manual sieving of extracted particles >250pm and <1000pm

[0231] o Grinding of particles / ” overs” >1000pm and recycle with fines (<250pm) to granulator

[0232] - Process parameters (fluidized bed spray granulation) o Bed temperature: 100°C + / - 2°C

[0233] o Gas temperature (inlet): 165°C + / - 5°C

[0234] o Gas volume flow (exit): 200m3 / h @ ~160°C

[0235] o Spray rate (feed): 7000g / h @70°C

[0236] - Preparation of Premixing of MGDA, amphoteric surfactant (and optionally polymer) in a vessel at 40°C, slowly stirred for several hours until all granules are dissolved

[0237] Granules containing MGDA (and optionally polymer) were obtained.

Claims

Patent Claims1. Process for making a powder or granule containing(A) at least one aminocarboxylate chelating agent, and(B) at least one amphoteric surfactant, and, optionally,(C) at least one polymer,wherein the powder or granule contains in the range of from 70 to 99.5 % by weight of aminocarboxylate chelating agent (A), in the range of from 0.5 to 10 % by weight amphoteric surfactant, and in the range of from 0 to 29.5 % by weight polymer (C), percentages referring to the actives content of said powder or granule, said process comprising the steps of(a) mixing the at least one chelating agent (A), the at least one amphoteric surfactant (B) and, optionally, at least one polymer (C) in the presence of water,(b) removing most of said water by spray-drying or spray-granulation, preferably using a gas with an inlet temperature of at least 125° C, more preferably at least 140° C, wherein the resulting powder or granule has a residual moisture content in the range of from 0.1 to 20 % by weight, as determined by Karl-Fischer-titration.

2. Process according to claim 1, wherein the at least one aminocarboxylate chelating agent (A) is selected from MGDA, GLDA, IDS, EDDS and their respective alkali metal salts, preferably sodium and / or potassium salts, wherein the aminocarboxylate chelating agent (A) may be fully neutralized or only partially neutralized.

3. Process according to claims 1 or 2, wherein the at least one aminocarboxylate chelating agent (A) is selected from MGDA and its alkali metal salts, preferably MGDA trisodium salt.

4. Process according to any one of the preceding claims, wherein the at least one amphoteric surfactant (B) bears an alkyl chain which has eight to fourteen carbon atoms.

5. Process according to any one of the preceding claims, wherein the at least one amphoteric surfactant (B) is selected from sodium salts of amphoacetates with a linear C10 to C14 alkyl chain, preferably sodium lauroamphoacetate, and acylamidopropylbetaines, preferably cocamidopropylbetaine .

6. Process according to any one of the preceding claims 1 to 3, wherein the at least one amphoteric surfactant (B) is selected from reaction products of an amino acid or a salt thereof with a monooxirane compound.

7. Process according to any one of the preceding claims 1 to 3, wherein the at least one amphoteric surfactant (B) is selected from compounds of the formula (la),whereinx is 0, 1, 2 or 3 and y is 0 or 1;R1and R2together with CH-(CH2)X-N form a 5 or 6-membered saturated or partially unsaturated ring which may have a further heteroatom selected from 0, N and S, where the 5 or 6-membered saturated or partially unsaturated ring may carry 1 or 2 Ci-6-alkyl substituents;R4is selected from the group consisting of hydrogen and Ci-4-alkyl;R5is selected from the group consisting of hydrogen, Ci-20-alkyl, C2-2o-alkenylJwhere Ci-20-alkyl and C2-20- alkenyl are unsubsituted or substituted by 1 or 2 substituents Rc, Ce-12-aryl, which is unsubstituted or substituted by 1 or 2 substituents Rd; whereRcis selected from OH, =0, O-Ci-C4-alkyl, O-C(O)-Ci-4-alkyl and C(O)O-Ci-4-alkyl;Rdis selected from OH, Ci-4-alkyl, O-Ci-4-alkyl and C(O)O-Ci-4-alkyl, X is selected from the group consisting of hydrogen and alkali metal ions.

8. Process according to any one of the preceding claims, wherein the at least one polymer (0) is selected from the group consisting of homo- or copolymers of (meth)acrylic acid, partially or fully neutralized with alkali, and polyaspartic acid.

9. Process according to any one of the preceding claims, wherein the powder or granule contains in the range of from 70 to 99.5 % by weight of aminocarboxylate chelating agent (A), in the range of from 2 to 6 % by weight amphoteric surfactant, and in the range of from 0 to 29.5 % by weight polymer (C), percentages referring to the actives content of said powder or granule.

10. Process according to any one of the preceding claims, wherein the process involves spray-granulation, preferably fluidized bed spray granulation, preferably with a bed temperature in the range of from 80° C to 150° C.

11. Process according to any one of the preceding claims, wherein the resulting powder or granule has a residual moisture content in the range of from 1 to 20 % by weight.

12. Powder or granule containing at least one aminocarboxylate chelating agent (A), at least one amphoteric surfactant (B), and, optionally, at least one polymer (C), preferably obtained or obtainable by the process according to any one of claims 1 to 11.

13. Powder or granule according to claim 12, having a residual moisture content in the range of from 1 to 20 % by weight.

14. Use of a powder or granule according to claim 12 or 13, or obtained or obtainable by the process according to any one of claims 1 to 11, for detergent applications, preferably dishwashing detergent applications.

Images