Method for making powders or granules containing chelating agents

Abstract

The present invention relates to a method for making a powder or granules containing at least one chelating agent.

Description

[Technical Field]

[0001] The present invention relates to a method for making powders or granules containing at least one chelating agent, to powders or granules obtained or obtainable according to the method of the invention, and to the use of powders or granules obtained or obtainable according to the method of the invention in laundry applications, dishwashing applications, or industrial and institutional cleaning applications. [Background technology]

[0002] Chelating agents (hereinafter also referred to as "complexing agents") such as methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA) and their respective alkali metal salts can be used to complex Ca. 2+ and Mg 2+ As such, they are recommended and used for various purposes, such as laundry detergents, and automatic dishwashing (ADW) formulations, especially so-called phosphate-free laundry detergents and phosphate-free ADW formulations. To deliver such complexing agents, in most cases, either solids, such as granules, or aqueous solutions are applied.

[0003] Granules and powders have the advantage of being essentially water-free, which means that no water needs to be transported in the case of transportation, avoiding the cost of extra weight.

[0004] Many industrial users prefer to use chelating agents in the form of granules or powders which may contain, in addition to at least one chelating agent, at least one additional compound, in particular a polymer.

[0005] Methods for providing granules or powders of chelating agents in combination with other compounds such as polymers are described in the art, for example in WO 2015 / 121170 A1.

[0006] However, conventional methods for preparing chelating agents, such as aminocarboxylate chelating agents in solid form, are fraught with drawbacks.

[0007] For example, a significant amount of the solid product obtained from spray granulation tends to exhibit undesirable yellowing in the presence of percarbonate ("percarbonate stability test"), which is often found in cleaning products that also contain aminocarboxylate chelating agents, and exhibits an undesirable tendency to adsorb water (high hygroscopicity). Additionally, solid aminocarboxylate complexing agents can exhibit an unpleasant odor.

[0008] Furthermore, the manufacturing methods for obtaining solid products containing chelating agents such as aminocarboxylates have their own problems and drawbacks. For example, due to certain incompatibilities, it is sometimes difficult or even impossible to combine chelating agents with certain other compounds (which may be desired by customers) in a solid product, such as granules, in a one-step or one-zone spray granulation process. Another example is certain compounds, such as polymers, which, in principle, can be co-granulated with chelating agents (such as MGDA) (in a one-step / one-zone process), but not in the desired (higher) amounts. Summary of the Invention [Problem to be solved by the invention]

[0009] SUMMARY OF THE INVENTION It was therefore an object of the present invention to overcome the above-mentioned problems and drawbacks.

[0010] In particular, it is an object of the present invention to provide a method for making powders or granules containing at least one complexing agent, such as a solid alkali metal salt of an aminocarboxylate complexing agent (A), which results in a more stable product (especially a product with less tendency to yellow in the presence of percarbonate) and / or a product with lower hygroscopicity. Furthermore, it was an object of the present invention to provide a method for making powders or granules containing at least one complexing agent, which powder or granules exhibit less (unpleasant) odor.

[0011] It is a further object of the present invention to provide a method for making powders or granules containing at least one complexing agent, such as a solid alkali metal salt of an aminocarboxylate complexing agent (A), which is easy to handle and overcomes the process problems mentioned above, e.g., makes it possible to combine at least one complexing agent, such as a solid alkali metal salt of an aminocarboxylate complexing agent (A), with other compounds that are difficult to handle and / or are to some extent incompatible with the respective complexing agent.

[0012] The inventors have now unexpectedly found that the problem can be solved by dusting the surface of intermediate powders or granules with a specific additive in the process for producing chelating agent powders or granules. The respective products are significantly more stable and exhibit significantly less tendency to yellow in the presence of percarbonate. Furthermore, the products may exhibit less unpleasant odor. [Means for solving the problem]

[0013] Thus, one subject of the present invention is (a) at least one chelating agent (A), preferably selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), iminodisuccinic acid (IDS), citric acid and ethylenediaminedisuccinic acid (EDDS), their respective alkali metal salts and mixtures thereof, and (b) optionally at least one polymer (B), preferably a homopolymer or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali, preferably in an amount of up to 50% by weight (more preferably 5-30% by weight) (based on the total weight of the powder or granule). A method for producing a powder (P) or granules (G) containing The method comprises: (i) mixing at least one chelating agent (A) and, optionally, at least one homopolymer or copolymer (B) in the presence of water; (ii) removing most of the water by spray drying or spray granulation, preferably using a gas having an inlet temperature of at least 125°C, to obtain an intermediate powder (IP) or granules (IG); (iii) sprinkling at least one additive (C), preferably contained in a solution or a slurry, on the surface of the intermediate powder or granules (I) in an amount of up to 50% by weight relative to the total weight of the resulting powder (P) or granules (G), to obtain the final powder (P) or granules (G). Including, Preferably, the process is carried out in a multi-zone and / or multi-nozzle apparatus, more preferably a multi-zone and / or multi-nozzle fluid bed spray granulator. DETAILED DESCRIPTION OF THE INVENTION

[0014] The term "dusting" (as opposed to coating) in the present invention may refer to the covering of the surface of a powder or granule of the present invention, which may be partial, but preferably results in a closed surface.

[0015] Optionally, the powder (P) or granules (G) obtained may be compressed.

[0016] The method of the present invention can be a continuous process or a batch process. In this context, a "batch process" means steps (i) and (ii) followed by step (iii). In a continuous process, steps (i) to (iii) can be carried out consecutively or simultaneously.

[0017] In the present invention, a continuous process is preferred.

[0018] In one embodiment, additive (C) can also form granules, which can be recycled to the process, preferably together with so-called "fines", for example, by sieving and grinding.

[0019] In another embodiment, the additive (C) may also be identical to the homopolymer or copolymer (B).

[0020] Furthermore, the spraying step (iii) can be carried out by spray drying or spray granulation, preferably by spray granulation. The use of fluidized bed spray granulation technology for step (iii) is particularly preferred.

[0021] In one embodiment, the process is carried out in a multi-zone and / or multi-nozzle apparatus, preferably a multi-zone and / or multi-nozzle fluid bed spray granulation apparatus.

[0022] Typical reaction times are 2 minutes to 4 hours, preferably 30 minutes to 2 hours.

[0023] The pressure in such an apparatus is between 850 mbar (abs) and 1200 mbar (abs), preferably ±20 mbar above standard pressure, for example 1 mbar below standard pressure.

[0024] Bed temperature is highly product dependent. Typical bed temperatures range from 40°C to 150°C. In most cases, the inlet air temperature is 20°C to 150°C higher than the bed temperature. In one embodiment, the inlet is more than 150°C higher than the bed temperature.

[0025] Suitable nozzles are, for example, high-pressure rotary drum atomizers, rotary atomizers, three-fluid nozzles, single-fluid nozzles, single-fluid high-pressure nozzles, or two-fluid nozzles. Single-fluid and two-fluid nozzles are preferred. When a two-fluid nozzle is used, the second fluid is a compressed gas, for example, having a pressure of 1.1 to 7 bar (abs), when the first fluid is an aqueous slurry or an aqueous solution, respectively.

[0026] In one preferred embodiment of the present invention, a sieving and grinding process is used to adjust the particle size distribution, which comprises the following steps: (a) removing the powder or granules from the spray dryer or spray granulator, respectively; (b) separating fines from said powder or granules; (c) separating oversized particles (agglomerates) from said powder or granules; (d) crushing the agglomerates; (e) reintroducing the fine powder from step (b) and the comminuted agglomerates from step (d) into a spray dryer or spray granulator. Including, (f) Powders or granules having a particle size larger than that of fine powders but smaller than that of agglomerates are the target granules of the present invention.

[0027] A typical size for fines is (but is not limited to) less than 0.3 mm. A typical size for oversized particles is (but is not limited to) greater than 1.4 mm. The particle sizes of fines and oversized particles depend on the target product particle range.

[0028] In a preferred embodiment, the fines from step (b) and the crushed chunks from step (d) are introduced into zone 1.

[0029] In another embodiment, steps (ii) and (iii) are carried out in separate zones and / or nozzles of a multi-zone and / or multi-nozzle apparatus.

[0030] In one embodiment of the method of the present invention, the additive (C) is added in an amount of up to 30% by weight, preferably in the range of 3 to 25% by weight, based on the total amount of the contents (A), (B) and (C).

[0031] In a preferred embodiment, the at least one chelating agent (A) is selected from MGDA and its respective alkali metal salts, preferably the sodium salt (eg the trisodium salt).

[0032] In one embodiment, additive (C) may be selected from the list consisting of polymers (including bio-based polymers), inorganic compounds, surfactants, silicates, preferably from the list consisting of sulfopolymers, surfactants and inorganic compounds.

[0033] The polymer (B) and / or the additive (C) may be selected from copolymers of (meth)acrylic acid and a comonomer having at least one sulfonic acid group per molecule, preferably 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or polyaspartic acid.

[0034] For example, polymer (B) and / or additive (C) may be selected from bio-based and / or biodegradable polymers, such as polyaspartic acid or polyepoxysuccinic acid.

[0035] In one embodiment, polymer (B) and / or additive (C) may comprise one or more compounds selected from the group of alkoxylated polyalkyleneimines or alkoxylated polyamines, which may be referred to herein as "CP8." "CP8" also includes the structures disclosed in WO 2021 / 165468, particularly in claims 1 and pages 2-4 of WO 2021 / 165468, and structures obtained by the process described in WO 2022 / 136408 and WO 2022 / 136409, particularly in claims 1 and pages 3 of WO 2022 / 136408 and WO 2022 / 136409, respectively. The structure of the alkoxylated polyalkyleneimine or alkoxylated polyamine may be further represented by the general formula (CP8a): [ka] where the variables are defined as follows: R is the same or different, i) Straight or branched chain C2 to C 12 - an alkylene group, or ii) ether alkyl units of formula (CP8b): [ka] where the variables are defined as follows: R 10 , R 11 , R 12 represent identical or different linear or branched C2-C6-alkylene groups, and d is an integer having a value ranging from 0 to 50 or an ether alkyl unit of iii) C5-C optionally substituted with at least one C1-C3-alkyl 10 cycloalkylene group represents B represents the extension of the alkoxylated polyalkyleneimine by branching, y and z are each integers having a value ranging from 0 to 150, provided that R is a C5-C alkyl optionally substituted with at least one C1-C3 alkyl. 10 -cycloalkylene group, then both z and y are 0; E1, E2, E3, E4, E5 are hydrogen or represent identical or different residues of formula (CP8c), wherein the residue represented by formula (CP8c) is an alkyleneoxy unit defined as follows: [ka] where the variables are defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group, R 2 When z is an integer of 1 or more in the general formula (CP8b), hydrogen and / or C1 to C 22 -Alkyl and / or C7-C 22 -aralkyl, or R 2 When z is 0 in the general formula (CP8b), it is hydrogen and / or C1-C4-alkyl and / or C7-C 22 - represents aralkyl; n is an integer having a value of at least 5 to 100; Here, 20 to 100% of the total amount of E1, E2, E3, E4 and E5 in general formula (CP8a) is a residue represented by formula (CP8c).

[0036] In one embodiment, in order to tailor the alkoxylated polyalkyleneimine or alkoxylated polyamine to a particular formulation to achieve better compatibility and / or phase stability of the formulation, the nitrogen atoms present in CP8 are quaternized.

[0037] A further subject of the invention is also a powder or granule obtained or obtainable by the process of the invention.

[0038] In a preferred embodiment of the present invention, the powder or granules obtained or obtainable by the method of the present invention have a residual moisture content of 1 to 30% by weight, preferably 5 to 25% by weight.

[0039] Another subject of the present invention is the use of the powders or granules obtained or obtainable by the process of the present invention in laundry applications, dishwashing applications or industrial and institutional cleaning applications, preferably dishwashing applications, more preferably automatic dishwashing applications.

[0040] Another subject of the present invention is a cleaning agent comprising at least one powder or granule obtained or obtainable by the process of the invention, and optionally containing at least one peroxy compound, and optionally further comprising an antibacterial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antibacterial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol.

[0041] A further subject related to the present invention is a method for producing powders (P) or granules (G), generally carried out in a multizone or multinozzle drying device (A) comprising 2 to n zones (Z) and / or 2 to i nozzles (N), (i) spraying in a first zone (Z1) and / or nozzle (N1) a solution or a slurry of a single compound or a mixture of compounds; and (ii) spraying the same or different solutions or slurries of a single compound or a mixture of compounds in each of the following zones (Zn) and / or nozzles (Ni): Including, A method in which in at least one zone (Zx) or nozzle (Ny) the solution or slurry of a single compound or a mixture of compounds is different from the solution or slurry of a single compound or a mixture of compounds in the first zone (Z1) and / or nozzle (N1).

[0042] Preferably, the solution or slurry is aqueous.

[0043] In one embodiment, the method is operated continuously.

[0044] In one embodiment, the process is designed to produce powders (P) or granules (G) containing a mixture of typical ingredients of washing or cleaning formulations, where the typical ingredients of washing or cleaning formulations may be selected from the list consisting of builders, surfactants, polymers, enzymes and inorganic compounds.

[0045] Purpose The solid alkali metal salts (A) (i.e., powders or granules) of the aminocarboxylate complexing agents of the present invention exhibit overall advantageous properties, including, but not limited to, excellent yellowing behavior, especially in the presence of bleaching agents. They are therefore highly suitable for the preparation of detergents containing at least one bleaching agent, hereinafter also referred to as bleaching agents. In particular, the solid compositions of the present invention are suitable for the preparation of detergents for fabrics or hard surfaces, said detergents containing at least one peroxy compound.

[0046] The solid compositions (eg, powders) of the present invention can be readily converted into compacts and agglomerates.

[0047] Therefore, another aspect of the present invention is the use of a solid alkali metal salt of an aminocarboxylate complexing agent (A) for the preparation of a detergent containing at least one bleaching agent, particularly for the preparation of a detergent for fabrics or hard surfaces, wherein the detergent contains at least one peroxy compound. Another aspect of the present invention is a method for preparing a detergent by combining at least one solid alkali metal salt of an aminocarboxylate complexing agent (A) of the present invention with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a detergent, hereinafter also referred to as the detergent of the present invention. The detergent of the present invention contains at least one bleaching agent and at least one solid alkali metal salt of an aminocarboxylate complexing agent (A) (e.g., powder). The detergent of the present invention has a reduced tendency to yellowing and therefore has a long shelf life.

[0048] Examples of suitable peroxy compounds are sodium perborate, anhydrous or as, for example, the monohydrate or tetrahydrate or the so-called dihydrate, sodium percarbonate, anhydrous or, for example, as the monohydrate, hydrogen peroxide, in each case as the free acid or alkali metal salt, in particular the sodium salt, persulfates, organic peroxyacids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, as well as sulfonylperoxyacids and cationic peroxyacids.

[0049] In a preferred embodiment, the peroxy 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 alternatively written as NaBO2·O2·3H2O. The most preferred peroxy compound is sodium percarbonate.

[0050] The term "detergents" includes, but is not limited to, dishwashing compositions, particularly hand dishwashing compositions, automatic dishwashing and porcelain washing compositions, as well as bathroom cleaning compositions, kitchen cleaning compositions, floor cleaning compositions, pipe descaling compositions, window cleaning compositions, automobile cleaning compositions, including truck washing, and hard surface cleaning compositions such as open plant cleaning compositions, yard cleaning compositions, metal cleaning compositions, disinfectant cleaning compositions, farm cleaning compositions, pressure cleaning compositions, and also laundry detergent compositions.

[0051] Such detergents may be liquid, gel, or preferably solid at ambient temperature, with solid detergents being preferred. They may be in powder form or in unit dose form, for example as tablets or pouches.

[0052] In one embodiment of the present invention, the cleaning agent of the present invention comprises: in the range of 2 to 50% by weight of a solid alkali metal salt of an aminocarboxylate complexing agent (A) of the present invention, and It may contain bleaching agents in the range of 0.5 to 15% by weight.

[0053] Percentages are based on the solids content of each inventive cleaning agent.

[0054] The solid alkali metal salts of aminocarboxylate complexing agents (A) of the present invention are highly suitable for the preparation of laundry detergents or cleaners.

[0055] The detergents 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 which may be included in the detergents of the present invention may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestering agents other than the chelating agent (A), enzymes, fragrances, dyes, defoamers, and builders.

[0056] Particularly advantageous cleaning agents of the present invention 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 sequestering agents (chelating agents) other than the mixtures according to the present invention. Examples of sequestering agents other than the mixtures according to the present invention are IDS (iminodisuccinate), citrate, phosphonic acid derivatives, such as the disodium salt of hydroxyethane-1,1-diphosphonic acid ("HEDP"), and polymers with complexing groups, such as those in which 20 to 90 mol % of the N atoms are substituted with at least one CH2COO - These include polyethyleneimines having a group, as well as their respective alkali metal salts, in particular their sodium salts, such as IDS-Na4 (trisodium citrate), and phosphates, such as STPP (sodium tripolyphosphate). Due to the fact that phosphates pose environmental concerns, advantageous detergents of the present invention are preferably phosphate-free. "Phosphate-free" in the context of the present invention should be understood to mean that the content of phosphates and polyphosphates, determined by gravimetric method, is in the range of 10 ppm to 0.2% by weight in total, referring to the respective detergent of the present invention.

[0057] The cleaning agents of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

[0058] 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.

[0059] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, those represented by the general formula (II): [ka] where the variables are defined as follows: R1 are the same or different and are hydrogen and straight chain C1-C 10 - alkyl, preferably identical in each case and ethyl, particularly preferably hydrogen or methyl, R 2 is C8~C 22 -Alkyl, branched or linear, e.g., n-CH 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 or nC 18 H 37 is selected from R 3 is C1~C 10 - alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range of 0 to 300, and 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.

[0060] In one embodiment, the compound of general formula (II) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0061] Other preferred examples of alkoxylated alcohols include, for example, those represented by the general formula (III): [ka] where the variables are defined as follows: R 1are identical or different and selected from hydrogen and linear C1-C0-alkyl, preferably identical in each case and ethyl, particularly preferably hydrogen or methyl, R 4 is C6~C 20 Alkyl, branched or straight chain, especially n-CH 17 , nC 10 H 21 , nC 12 H 25 , nC 14 H 29 , nC 16 H 33 , nC 18 H 37 is selected from a is a number ranging from zero to 10, preferably from 1 to 6; b is a number ranging from 1 to 80, preferably from 4 to 20; d is a number ranging from 0 to 50, preferably from 4 to 25. is a compound of

[0062] The sum of a+b+d is preferably in the range of 5-100, and more preferably in the range of 9-50.

[0063] Preferred examples of hydroxyalkyl mixed ethers include those of the general formula (IV): [ka] where the variables are defined as follows: R 1 are the same or different and are hydrogen and straight chain C1-C 10 - alkyl, preferably identical in each case and ethyl, particularly preferably hydrogen or methyl, R 2 is C8~C 22 -Alkyl, branched or linear, e.g., iso-C 11 H 23 , iso-C 13 H 27 , n-C8H 17 , nC 10 H 21, nC 12 H 25 , nC 14 H 29 , nC 16 H 33 or nC 18 H 37 is selected from R 3 is C1~C 18 - selected from 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 is a compound of

[0064] The variables m and n range from 0 to 300, and 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.

[0065] The compounds of general formulae (II) and (III) can be block copolymers or random copolymers, with block copolymers being preferred.

[0066] Further suitable nonionic surfactants are selected from di- and multi-block 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-C 16 -Alkyl polyglucosides and branched chain C8-C 14 Likewise suitable are -alkyl polyglycosides, for example compounds of the average general formula (V): [ka] where the variables are defined as follows: R 5 is C1-C4-alkyl, in particular ethyl, n-propyl or isopropyl, R 6 is -(CH2)2-R 5 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, y is an average number ranging from 1.1 to 4.

[0067] Further examples of nonionic surfactants include those represented by the general formulae (VII) and (VIII): [ka] wherein AO is selected from ethylene oxide, propylene oxide, and butylene oxide; EO is ethylene oxide, CH2CH2-O, R 8 is a branched or straight chain C8-C 18 -alkyl, and R 5 is defined as above. A 3 O is selected from propylene oxide and butylene oxide; w is a number ranging from 15 to 70, preferably from 30 to 50; w1 and w3 are numbers ranging from 1 to 5, w2 is a number between 13 and 35) is a compound of

[0068] An overview of further suitable nonionic surfactants is given in EP-A 0 851 023 and DE-A 19 819 187.

[0069] Mixtures of two or more different nonionic surfactants may also be present.

[0070] Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants, and mixtures thereof.

[0071] An example of amphoteric surfactant is one that has positive and negative charges in the same molecule under the conditions of use.A preferred example of amphoteric surfactant is so-called betaine surfactant.Many examples of betaine surfactant have one quaternized nitrogen atom and one carboxylic acid group per molecule.A particularly preferred example of amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0072] Examples of amine oxide surfactants include those represented by the general formula (IX): R 7 R 8 R 9 N → O (IX) (In the formula, R 7 , R 8 and R 9 are each independently an aliphatic, alicyclic or C2-C4 alkylene C 10 ~C 20 -alkylamide moieties) Preferably, R 7 is C8~C 20 -Alkyl or C2-C4-alkylene C 10 ~C 20 -alkylamide, and R 8 and R 9 are both methyl.

[0073] A particularly preferred example is lauryl dimethylamine oxide, sometimes called lauramine oxide. A further particularly preferred example is cocamidyl propyl dimethylamine oxide, sometimes called cocamidopropyl amine oxide.

[0074] Examples of suitable anionic surfactants include C8-C 18 -Alkyl sulfate, C8-C 18 Ethoxylated C4-C fatty alcohol polyether sulfates 12-C of alkylphenol sulfuric acid half ester (ethoxylation degree: 1 to 50 mol / mol ethylene oxide) 12 ~C 18 Alkali metal and ammonium salts of sulfofatty acid alkyl esters, such as C 12 ~C 18 Sulfofatty acid methyl esters, and C 12 ~C 18 -Alkyl sulfonic acid and C 10 ~C 18 - alkali metal and ammonium salts of alkylarylsulfonic acids. The alkali metal salts of the above compounds are preferred, in particular the sodium salts.

[0075] Further examples of suitable anionic surfactants are soaps, such as the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkyl ether phosphates.

[0076] Preferably, the laundry detergent composition contains at least one anionic surfactant.

[0077] In one embodiment of the present invention, the cleaning agent of the present invention that is determined to be used as a laundry detergent composition may contain 0.1 to 60 wt % of at least one surfactant selected from anionic surfactants, amphoteric surfactants, and amine oxide surfactants.

[0078] In one embodiment of the present invention, the cleaning agent of the present invention determined to be used for cleaning hard surfaces may contain 0.1 to 60 wt % of at least one surfactant selected from anionic surfactants, amphoteric surfactants, and amine oxide surfactants.

[0079] In a preferred embodiment, the cleaning agent of the present invention does not include anionic detergents.

[0080] The detergent of the present invention may contain one or more bleaching catalysts. The bleaching catalysts may be selected from bleach-accelerating transition metal salts or transition metal complexes, such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen or -carbonyl complexes. Complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper with nitrogen-containing tripodal ligands, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, may also be used as bleaching catalysts.

[0081] The cleaning agents of the present invention may also include one or more bleach activators, such as N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quats (trimethylammonium acetonitrile salts).

[0082] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0083] The cleaning agent of the present invention may contain one or more corrosion inhibitors. In this case, this is understood to include compounds that inhibit corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and phenol derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyrogallol.

[0084] In one embodiment of the present invention, the cleaning agent of the present invention contains a corrosion inhibitor in a total amount in the range of 0.1 to 1.5 wt %.

[0085] The detergents of the invention may contain one or more builders selected from organic and inorganic builders. Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or sodium silicates, in particular sodium disilicate and sodium metasilicate, zeolites, layered silicates, in particular those of the formulae α-Na2SiO5, β-Na2SiO5, and δ-Na2SiO5, 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 such as polycarboxylates and polyaspartic acid.

[0086] Examples of organic builders are in particular other polymers and copolymers such as (co)polymer (B), including polymers and copolymers other than (co)polymer (B) or one additional (co)polymer (B). In one embodiment of the present invention, the organic builder is selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, partially or fully neutralized with alkali.

[0087] Suitable comonomers for (meth)acrylic acid are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers have, in particular, average molecular weights M in the range of 2000 to 40000 g / mol, preferably 2000 to 10000 g / mol, in particular 3000 to 8000 g / mol. w Copolymeric polycarboxylates are also suitable, especially copolymers of acrylic acid and methacrylic acid, and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid, in the same molecular weight range.

[0088] Monoethylenically unsaturated C3-C 10 Mono or C4-C 10It is also possible to use copolymers of at least one monomer selected from 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, with at least one hydrophilic or hydrophobic monomer, such as those listed below.

[0089] Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexane and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as 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 It is a mixture of α-olefins and polyisobutenes having an average of 12 to 100 carbon atoms per molecule.

[0090] Suitable hydrophilic monomers include nonionic monomers having hydroxyl functionality or alkylene oxide groups, as well as monomers having sulfonate or phosphonate groups. Examples include allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate, and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. In this case, the polyalkylene glycol may contain 3 to 50, particularly 5 to 40, and more particularly 10 to 30 alkylene oxide units per molecule.

[0091] Particularly preferred sulfonic acid group-containing monomers herein 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, methallyl sulfonic 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 the above acids, for example, their sodium, potassium, or ammonium salts.

[0092] Particularly preferred phosphonate group-containing monomers are vinylphosphonic acid and its salts.

[0093] A further example of a builder is carboxymethyl inulin.

[0094] Additionally, amphoteric polymers can also be used as builders.

[0095] The cleaning agent of the present invention may contain, for example, a builder in a total amount in the range of 10 to 70% by weight, preferably in a total amount in the range of 10 to 50% by weight, and more preferably up to 20% by weight.

[0096] In one embodiment of the invention, the cleaning agent according to the invention may comprise one or more co-builders.

[0097] The cleaning agent of the present invention may contain one or more antifoaming agents selected from, for example, silicone oils and paraffin oils.

[0098] In one embodiment of the present invention, the cleaning agent of the present invention contains a total of 0.05 to 0.5% by weight of an antifoaming agent.

[0099] The cleaning agents of the present invention may contain one or more enzymes, examples of which are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

[0100] In one embodiment of the present invention, the cleaning agent of the present invention may contain, for example, up to 5% by weight of an enzyme, preferably 0.1 to 3% by weight. The enzyme may, for example, be a C1-C3 carboxylic acid or a C4-C 10 -can be stabilized with sodium salts of dicarboxylic acids, with formates, acetates, adipates and succinates being preferred.

[0101] 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 and water-insoluble zinc salts. In this context, water-insoluble zinc salts are used in the context of the present invention to refer to zinc salts having a solubility of 0.1 g / l or less in distilled water at 25°C. Therefore, zinc salts with higher water solubility are referred to as water-soluble zinc salts in the context of the present invention.

[0102] In one embodiment of the 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.

[0103] In another embodiment of the invention, the zinc salt is selected from ZnO, aqueous ZnO, Zn(OH)2, and ZnCO3. Aqueous ZnO is preferred.

[0104] In one embodiment of the present invention, the zinc salt is selected from zinc oxide having an average particle size (weight average) in the range of 10 nm to 100 μm.

[0105] The cations in zinc salts can be present in complexed form, for example complexed with ammonium or water ligands, and in particular in hydrated form. For simplicity of notation, in the context of the present invention, the ligands are generally omitted when they are water ligands.

[0106] Depending on how the pH value of the mixture according to the invention is adjusted, the zinc salt may vary. Thus, for example, it is possible to use zinc acetate or ZnCl to prepare the formulation according to the invention, which in an aqueous environment at a pH of 8 or 9 will convert to ZnO, Zn(OH) or an aqueous ZnO solution, which may be present in uncomplexed or complexed form.

[0107] The zinc salt may be present in the cleaning agent of the present invention that is solid at room temperature, and in such a cleaning agent of the present invention, the zinc salt is preferably present in the form of particles having an average diameter (number average) in the range of, for example, 10 nm to 100 μm, preferably 100 nm to 5 μm, as determined, for example, by X-ray scattering.

[0108] The zinc salt may be present in cleaning agents of the present invention that are liquid at room temperature, and in such cleaning agents of the present invention the zinc salt is preferably present in dissolved or solid or colloidal form.

[0109] In one embodiment of the present invention, the cleaning agent of the present invention contains zinc salts in a range of 0.05 to 0.4% by weight in total, each based on the dry content of the cleaning agent.

[0110] Here, the fraction of zinc salt is given as zinc or zinc ion, from which it is possible to calculate the proportion of counter ions.

[0111] In one embodiment of the present invention, the detergent of the present invention is free of heavy metals other than zinc compounds. In the context of the present invention, this can be understood to mean that the detergent of the present invention is free of heavy metal compounds that do not act as bleach catalysts, in particular iron and bismuth compounds. In the context of the present invention, "free" in relation to heavy metal compounds should be understood to mean that the content of heavy metal compounds that do not act as bleach catalysts is in the range of 0 to 100 ppm in total, based on the dry content, as determined by the leaching method. Preferably, the detergent of the present invention has a heavy metal content, excluding zinc, of less than 0.05 ppm, based on the dry content of the formulation. Therefore, the zinc fraction is free.

[0112] In the context of the present invention, "heavy metals" are defined as metals with a concentration of at least 6 g / cm, excluding zinc. 3 Heavy metals are considered to be all metals having a specific density of 1000 .mu.m. In particular, heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium, and chromium.

[0113] Preferably, the cleaning agents of the present invention do not contain any measurable fraction of bismuth compounds, for example less than 1 ppm.

[0114] The detergents of the present invention are excellent for cleaning hard surfaces and fabrics, for example, they can be used in dishwashing applications, preferably automatic dishwashing applications.

[0115] In one embodiment of the 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 methylsulfonic acid.

[0116] From the solid compositions of the present invention, e.g., granules or powders, an exemplary detergent composition for an automatic dishwashing detergent can be formulated by mixing the respective ingredients according to Table F below.

[0117] [Table 1]

[0118] The laundry detergent according to the present invention is useful for washing all types of laundry and all types of fibers. The fibers may be of natural or synthetic origin, or a mixture of natural and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples of fibers of synthetic origin are polyurethane fibers such as Spandex® or Lycra®, polyester fibers, or polyamide fibers. The fibers may be single fibers or part of a textile product such as knitwear, woven fabrics, or nonwoven fabrics.

[0119] Another aspect of the present invention is a process for preparing tablets for automatic dishwashing from a solid alkali metal salt (A) of an aminocarboxylate complexing agent of the present invention, e.g., a powder or granules, said granules or powder being selected from the granules of the present invention and the powders of the present invention, respectively, said process being hereinafter also referred to as the pelletizing process according to the present invention.

[0120] The tablets of the present invention are preferably made using a machine, such as a tablet press.

[0121] The pelleting method according to the present invention can be carried out by mixing the solid alkali metal salt (A) of the aminocarboxylate complexing agent of the present invention, for example, powder, with at least one nonionic surfactant and optionally one or more additional substances, and then compressing the mixture to obtain tablets. Examples of suitable nonionic surfactants and additional substances such as builders, enzymes, etc. are listed above. Particularly preferred examples of nonionic surfactants are hydroxy mixed ethers, such as the hydroxy mixed ethers of general formula (V):

[0122] Some aspects of the methods of the present invention are illustrated by the following non-limiting examples. [Example]

[0123] Comparative Example 1: In a stirred tank, a concentrated Trilon® M max (MGDA) solution at 70°C was mixed with a Nuclesil® (silicate) 10 solution to obtain a Nuclesil® concentration of 4.5% based on the active ingredient content. Thus, 195.937 kg of Trilon® M max liquid was heated to 70°C in a stirred tank. 33.515 kg of Trilon® M SG was then added and dissolved. A clear solution was obtained. 10.575 kg of Nuclesil® 10 was then added to this concentrated, clear solution. Immediately after adding the Nuclesil® 10, lumps of gel that could not be dissolved in the liquid were observed. These lumps clogged the nozzle, and the experiment was stopped.

[0124] Comparative Example 2: In a stirred tank, 190.427 kg of Trilon® M solution was heated to 70°C. Then, 32.573 kg of Trilon® M SG and 16.405 kg of Sokalan® CP50 (polycarboxylate, modified, sodium salt) were added. A clear solution was obtained. In a second tank, 12.6 kg of Sokalan® CP50 solution and 7.4 kg of Nuclesil® 10 solution were mixed. The aim was to obtain a mixture of both liquids before the nozzle and co-granulate them. Immediately after mixing the Sokalan® CP50 and Nuclesil® 10, lumps of gel that could not be dissolved in the liquid were observed. These lumps clogged the nozzle, and the experiment was stopped.

[0125] Example 1: Preparation of spray solutions SL1a and SL1b: A concentrated Trilon® M solution was prepared by heating 204.95 kg of Trilon® M liquid to 70° C. and adding 35.05 kg of Trilon® M max SG. A clear solution SL1a was obtained.

[0126] The Nuclesil® 10 solution was spray solution SL1b but was kept separate from SL1a.

[0127] In this Example 1, a rectangular multi-zone granulator with an internal filter having four zones, commercially available as "Procell PilotSystem with GF25 inserts," was used. Zone 1 is at the front end of the granulator, where the crushed overs are returned, and Zone 4 is at the back end of the granulator, where the discharge to the screening and crushing circuit is located.

[0128] In contrast to Counter Example 1, the liquids in Example 1 were not mixed, so SL1a and SL1b were sprayed into separate zones of a multi-zone granulator. The granulator was charged with 40 kg of Trilon® M SG as the initial charge. A 1100-1200 Nm granule was sprayed into the granulator at a temperature of 180-200°C so that fluidization of the Trilon® M SG granules could be observed. 3 Fluidizing gas was introduced through the bottom plate at 24.25 kg / h each of SL1a in zones 1 and 2, spraying the fluidized granules in each zone. In zone 3, 2.24 kg / h of SL1b was sprayed onto the fluidized particles. Zone 4 was used as a cooling chamber without any feed. To maintain a constant bed level, the granules were continuously discharged and placed on a sieve. This sieving generated three fractions: fines with a particle size of less than 250 μm, a fine fraction with a particle size of 250-1200 μm, and coarse particles with a particle size of more than 1200 μm. The coarse particles were continuously milled and returned to zone 1 of the granulator together with the fines. Granulation was carried out without interruption.

[0129] Example 2: Preparation of spray solutions SL2a, SL2b and SL2c: SL2a: 190.9 kg of Trilon® M max liquid was heated to 70° C. Then 32.7 kg of Trilon® max granules and 16.4 kg of Sokalan® CP50 liquid were added. A clear solution was obtained. SL2b: Sokalan® CP50 solution heated to 50°C. SL2c: Nuclesil® 10 solution.

[0130] The spray solutions were kept separate.

[0131] The granulation of Example 2 was carried out in the same manner as described in Example 1. This time, 24.2 kg / hour of SL2a was sprayed into zones 1 and 2, respectively. In zone 3, 10.4 kg / hour of SL2b was sprayed. In zone 4, 2.6 kg / hour of SL2c was sprayed. Granulation was carried out continuously for 2 hours.

[0132] The examples show that by using the method of the present invention, the process can be carried out smoothly as desired, even when several compounds that may be incompatible with each other are used, whereas the comparative examples, in which the method of the present invention was not utilized, caused serious problems in the process and therefore had to be discontinued.

Claims

1. (a) at least one chelating agent (A), preferably selected from methylglycine diacetate (MGDA), glutamic acid diacetate (GLDA), iminodisuccinic acid (IDS), citric acid, and ethylenediaminedisuccinic acid (EDDS), their respective alkali metal salts, and mixtures thereof; and (b) optionally at least one polymer (B), preferably a homopolymer or copolymer of (meth)acrylic acid, partially or fully neutralized with alkali. A method for producing a powder (P) or granules (G) containing The method comprises: (i) mixing said at least one chelating agent (A) and, optionally, said at least one homopolymer or copolymer (B) in the presence of water; (ii) removing most of the water by spray drying or spray granulation, preferably using a gas having an inlet temperature of at least 125°C, to obtain an intermediate powder (IP) or granules (IG); and (iii) sprinkling at least one additive (C), preferably contained in a solution or a slurry, on the surface of the intermediate powder or granules (I) in an amount of up to 50% by weight relative to the total weight of the resulting powder (P) or granules (G), to obtain the final powder (P) or granules (G). Including, The process is carried out in a multi-zone and / or multi-nozzle apparatus, preferably a multi-zone and / or multi-nozzle fluidized bed spray granulation apparatus.

2. The method of claim 1 , wherein the method is continuous.

3. The method of claim 1 , wherein the method is a batch process.

4. The method according to any one of claims 1 to 3, wherein the spraying step (iii) is carried out by spray drying or spray granulation, preferably spray granulation, more preferably fluidized bed spray granulation.

5. 5. The method of any one of claims 1 to 4, wherein step (ii) and spraying step (iii) are carried out in separate zones and / or nozzles of a multi-zone and / or multi-nozzle apparatus.

6. The method according to any one of claims 1 to 5, wherein the additive (C) is added in an amount of up to 30% by weight, preferably in the range of 3 to 25% by weight, based on the total content of (A), (B) and (C).

7. 7. The method according to any one of claims 1 to 6, wherein the at least one chelating agent is selected from methylglycine diacetic acid (MGDA) and its respective alkali metal salts, preferably the sodium salt.

8. 8. The method according to any one of claims 1 to 7, wherein the additive (C) is selected from the list consisting of polymers, inorganic compounds, surfactants, silicates, preferably from the list consisting of sulfopolymers, surfactants and inorganic compounds.

9. 9. The method according to claim 1, wherein the polymer (B) and / or the additive (C) are selected from copolymers of (meth)acrylic acid and a comonomer having at least one sulfonic acid group per molecule, preferably 2-acrylamido-2-methylpropanesulfonic acid (AMPS), or polyaspartic acid or polyepoxysuccinic acid.

10. A powder or granule obtained or obtainable according to the method of any one of claims 1 to 9.

11. 11. Powder or granules according to claim 10, having a residual moisture content in the range of 1 to 30% by weight, preferably 5 to 25% by weight.

12. 10. Use of a powder or granule obtained or obtainable according to the method of any one of claims 1 to 9 in laundry or dishwashing applications, preferably dishwashing applications, more preferably automatic dishwashing applications, or industrial and institutional cleaning applications.

13. 12. A cleaning agent comprising at least one powder or granule according to claim 10 or 11, and optionally at least one peroxy compound, and optionally further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% phenoxyethanol.

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