Method for producing solid particles comprising at least one aminocarboxylate complexing agent

Abstract

The invention relates to a method for producing solid particles comprising at least one aminocarboxylate complexing agent.

Description

[0001] This invention relates to a method for manufacturing solid particles comprising at least one aminocarboxylate complexing agent. 。

[0002] The solid particles of the present invention are solid and may be in the form of powder or granules. Preferably, the solid particles of the present invention are free-flowing.

[0003] Granules and powders have the advantage of being essentially water-free. This means that, in the case of transportation, there is no need to transport additional water, and the cost of extra weight can be avoided.

[0004] For example, powders or granules containing typical ingredients of washing or cleaning products (e.g., for laundry or dishwashing products) are desirable for industrial users who manufacture and sell such products.

[0005] Typical components of detergent or cleaning preparations may include builders, surfactants, polymers, inorganic compounds, anionic surfactants, cationic surfactants, nonionic surfactants and / or chelating agents.

[0006] For example, many industrial users prefer to use chelating agents in granular or powder form, which may contain at least one additional compound, particularly a polymer, in addition to at least one chelating agent. Some consumers also prefer to incorporate larger quantities of additional compounds, such as polymers, into granular or powder containing at least one chelating agent.

[0007] In the art, for example in WO 2015 / 121170 A1, methods for providing granules or powders of chelating agents (and combinations with other compounds such as polymers) have been described. Generally, powders or granules containing one or more compounds can be obtained, for example, by spray drying or spray granulation.

[0008] US2023 / 0025816 A1 describes a method for manufacturing granules containing, in particular, MGDA or IDS, wherein water is removed by spray granulation in a fluidized bed, and wherein the resulting granules are subsequently treated with air or an inert gas. This disclosure does not disclose a spray drying method, nor does it disclose the crystallinity of the resulting granules.

[0009] However, solid particles (e.g., powders or granules) containing aminocarboxylate complexing agents often present problems. For example, solid particles containing aminocarboxylate complexing agents exhibit high hygroscopicity and a tendency to stain in the presence of peroxides, which, like the aminocarboxylate complexing agents themselves, are common components of cleaning agents. Both of these properties are undesirable.

[0010] Therefore, there is a need in the art to provide solid particles (e.g., powders or granules) containing aminocarboxylate complexing agents that avoid the problems mentioned above, and a need for a method for manufacturing solid particles (e.g., powders or granules) containing aminocarboxylate complexing agents, which produces solid particles with improved properties (e.g., lower hygroscopicity and / or lower tendency to become colored). Another object of the present invention is to provide a method for manufacturing solid particles, preferably free-flowing solid particles, comprising at least one aminocarboxylate complexing agent or a salt thereof with an alkali metal, which results in an increased proportion of crystalline material in the resulting solid particles.

[0011] The inventors have unexpectedly discovered that a certain spray drying method for producing solid (preferably free-flowing) particles containing at least one aminocarboxylate complexing agent (or its salt with an alkali metal) can solve the problems described above.

[0012] Therefore, one subject of the present invention is a method for producing solid, preferably free-flowing particles comprising at least one aminocarboxylate complexing agent or a salt thereof with an alkali metal, wherein the method is carried out by spray drying of a slurry comprising the aminocarboxylate complexing agent under agglomeration conditions in the presence of fine particles.

[0013] In the context of this invention, the term "free-flowing" refers to particles that do not (still) clump together after being stored under humid conditions for 24 hours. Evaluation can be performed visually.

[0014] Fine particles are defined as particles with an average diameter of up to 300 μm. To determine particle size, fine particles are classified using laboratory sieves with different sieve aperture sizes.

[0015] In the context of this invention, agglomeration conditions can refer to the following embodiments, wherein particles P1 with a particle diameter smaller than the target particle diameter P exit the spray drying equipment through the exhaust outlet on the dryer head, (ii) are removed by a cyclone separator, and (iii) are reintroduced into the drying equipment, and wherein...

[0016] Particle P1 agglomerates in the spray drying equipment when it is reintroduced to form particle P2 with an increased average particle diameter and / or weight compared to particle P1, and wherein

[0017] Particle P2 falls into a fluidized bed when it has a target particle diameter P and is optionally air-classified and optionally post-dried to obtain free-flowing particles P3.

[0018] The spray drying method of the present invention under agglomeration conditions operates in the presence of fine particles (as defined above), which typically results in higher crystallinity in the product (because the fine particles act as seed crystals), which may be desirable in some applications.

[0019] As used herein, the term "slurry" refers to its common meaning as is known to those skilled in the art.

[0020] (In other words, "slurry" refers to a mixture of solid particles distributed in an aqueous phase (which may contain dissolved compounds).)

[0021] Another subject of the invention is a solid, preferably free-flowing particulate, comprising at least one aminocarboxylate complexing agent, which is obtainable or acquireable by the method of the invention; and a detergent, preferably a dishwashing detergent, comprising the solid, preferably free-flowing particulate (preferably obtainable or acquireable by the method of the invention).

[0022] In one embodiment of the invention, the slurry comprises at least 45% by weight of an aminocarboxylate complexing agent and, optionally, seed particles of a solid aminocarboxylate complexing agent.

[0023] In another embodiment of the method of the present invention, the aminocarboxylate complexing agent is selected from a list consisting of MGDA, GLDA, EDDS, and IDS, with MGDA being preferred.

[0024] In another embodiment of the method of the present invention, the method includes the following steps:

[0025] (a) Forming an aqueous slurry comprising seed particles of a solid aminocarboxylate complexing agent, preferably at least 45% by weight of the solid aminocarboxylate complexing agent relative to the total weight of the aqueous slurry.

[0026] (b) The slurry is spray-dried in a spray dryer equipped with a fluidized bed.

[0027] Particles P1 with a diameter smaller than the target particle diameter P exit the spray drying equipment through the exhaust outlet on the dryer head, (ii) are removed by a cyclone separator, and (iii) are reintroduced into the drying equipment.

[0028] Particle P1 agglomerates in the spray drying equipment when it is reintroduced to form particle P2 with an increased average particle diameter and / or weight compared to particle P1, and wherein

[0029] Particle P2 falls into a fluidized bed when it has a target particle diameter P and is optionally air-classified and optionally post-dried to obtain free-flowing particles P3.

[0030] Alternatively, the particles P3 can be compacted into compacted aggregates.

[0031] The slurry provided in step (a) may optionally contain at least 0.1% by weight of an additional organic or inorganic compound or a mixture thereof.

[0032] In one embodiment of the invention, the slurry provided in step (a) contains at least 0.1% by weight of a (co)polymer (B), which is selected from (meth)acrylic acid and polyethyleneimine, wherein the polyethyleneimine is unsubstituted or substituted with alkoxy or CH2COOH groups that can be neutralized by alkali metals; and / or polyaspartate and / or polyepoxysuccinic acid.

[0033] In another embodiment of the invention, the slurry is preheated in step (a) before entering the spray drying apparatus in step (b). In the context of the invention, "preheating" means maintaining the slurry at a temperature of at least 50°C for a period of 2 minutes to 6 hours.

[0034] Preferably, the method of the present invention is carried out in an agglomeration-type spray drying device.

[0035] In a preferred embodiment, the method of the present invention is carried out in an agglomeration-type spray drying device with a height of at least 5 meters, preferably at least 10 meters.

[0036] The particles produced by the method of the present invention can be amorphous or crystalline.

[0037] Optionally, the particles produced by the method of the present invention may be cured. The particles of the present invention produce good results in the curing method (also known as the post-processing method) of unpublished patent application EP 22192595.1 (e.g., according to claim 1 of that application (and hereinafter dependent claims)).

[0038] In one embodiment, "maturation" refers to a method for preparing a solid, storage-stable composition comprising at least one aminocarboxylate complexing agent, the method comprising the following steps:

[0039] a) Providing an initial aminocarboxylate composition having orthorhombic aminocarboxylate solid particles in an amount of 1% to 70%, preferably 1% to 50%, and particularly 1% to 25% by weight relative to the total initial solid composition.

[0040] b) Increase the relative humidity (rH) to at least 50% and / or add at least 1% by weight of water or aqueous solution (SO) or slurry (SL), the aqueous solution or slurry having a water content of at least 10% by weight, preferably at least 30% by weight, relative to the total weight of the aqueous solution or slurry.

[0041] c) The obtained composition is kept at a temperature of 20°C to 95°C for a period of time ranging from 1 minute to 5 months.

[0042] The resulting solid composition is dried to a residual moisture content of less than 20%, thereby obtaining a solid aminocarboxylate composition with an increased orthorhombic crystal content.

[0043] In one embodiment of the invention, the slurry formed in step (a) is heated to a temperature of at least 70°C (preferably not exceeding 150°C) for a period of 10 minutes to 8 hours (preferably 2 to 4 hours) to increase the content of orthogonal MGDA in the slurry.

[0044] As mentioned above, another subject of the present invention is a solid, preferably free-flowing particle, comprising at least one aminocarboxylate complexing agent. The free-flowing particles may have a particle size of 50 to 1400 μm, preferably 100 to 1000 μm, more preferably 100 to 500 μm, and / or the particles may have a crystallinity of at least 10% as determined by X-ray diffraction, and / or an orthorhombic crystal content of at least 30% as determined by X-ray diffraction.

[0045] The solid, preferably free-flowing particles of the present invention may have a moisture content of no more than 30 wt.%, preferably less than 20 wt.%, and more preferably less than 15 wt.%.

[0046] application

[0047] Another subject of the present invention is solid particles, such as powders or granules, which are obtained or can be obtained according to the method of the present invention.

[0048] Another subject of the invention is the use of (solid) particles (e.g., powders or granules) obtained or available according to the method of the invention in laundry or dishwashing applications, preferably dishwashing applications, more preferably automatic dishwashing applications, or in industrial and institutional cleaning applications.

[0049] As an example of powders or granules obtained or available according to the method of the present invention, this document refers to a solid alkali metal salt (A) of an aminocarboxylate complexing agent.

[0050] These powders or granules of the present invention, containing, for example, MGDA, exhibit generally advantageous properties, including but not limited to excellent yellowing behavior, especially in the presence of a bleaching agent. Therefore, they are well-suited for use in the manufacture of cleaning agents containing at least one bleaching agent, which will also be referred to hereinafter as bleach. In particular, the solid compositions of the present invention are suitable for use in the manufacture of cleaning agents for fibrous or hard surfaces, wherein said cleaning agents contain at least one peroxide compound.

[0051] The solid compositions (e.g., powders) of the present invention can be readily converted into compacts and agglomerates.

[0052] Therefore, another aspect of the present invention is the use of powder or granules of a solid alkali metal salt (A) containing an aminocarboxylate complexing agent for the manufacture of a cleaning agent containing at least one bleaching agent, and particularly for the manufacture of a cleaning agent for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxide compound. Another aspect of the present invention is a method for preparing a cleaning agent by combining a solid alkali metal salt (A) containing at least one aminocarboxylate complexing agent of the present invention with at least one bleaching agent, preferably at least one peroxide compound. Another aspect of the present invention is a cleaning agent, hereinafter also referred to as the cleaning agent of the present invention. The cleaning agent of the present invention contains at least one bleaching agent and at least one solid alkali metal salt (A) containing at least one aminocarboxylate complexing agent of the present invention (e.g., powder). The cleaning agent of the present invention exhibits a reduced tendency to yellowing and therefore has an extended shelf life.

[0053] Examples of suitable peroxide compounds are sodium perborate (anhydrous or, for example, as a monohydrate or as a tetrahydrate or so-called dihydrate), sodium percarbonate (anhydrous or, for example, as a monohydrate), hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-disperoxydodecanoic acid, perbenzoic acid, peroxylauric acid, 1,9-disperoxyazelic acid, disperoxyisophthalic acid (in each case as a free acid or as an alkali metal salt, especially as a sodium salt), as well as sulfonyl peroxides and cationic peroxides.

[0054] In a preferred embodiment, the peroxide compound is selected from inorganic percarbonates, persulfates, and perborates. An example of sodium percarbonate is 2Na₂CO₃·3H₂O₂. An example of sodium perborate is (Na₂[B(OH)₂(O₂)]₂), sometimes also written as NaBO₂·O₂·3H₂O. The most preferred peroxide compound is sodium percarbonate.

[0055] The term "cleaning agent" includes compositions for washing dishes, especially manual and automatic dishes and utensils, as well as compositions for cleaning hard surfaces, such as, but not limited to, compositions for cleaning bathrooms, kitchens, floors, drains, windows, cars (including trucks), as well as open-air factory cleaning, in-situ cleaning, metal cleaning, disinfectant cleaning, farm cleaning, pressure cleaning, and also compositions for laundry detergents.

[0056] Such cleaning agents can be liquid, gel, or preferably solid at ambient temperature, with solid cleaning agents being preferred. They can be in powder form or in unit dosage form, such as tablets or sachets.

[0057] In one embodiment of the present invention, the cleaning agent of the present invention may contain...

[0058] The solid alkali metal salt (A) of the aminocarboxylic acid complexing agent of the present invention comprises, in the range of 2% to 50% by weight, and

[0059] Bleaching agent in the range of 0.5% to 15% by weight.

[0060] The percentage is based on the solids content of the corresponding cleaning agent of the present invention.

[0061] The solid alkali metal salt (A) of the aminocarboxylic acid complexing agent of the present invention is very suitable for manufacturing laundry detergents or cleaning agents.

[0062] The cleaning agent of the present invention may contain additional ingredients such as one or more surfactants, which may be selected from nonionic, amphoteric, cationic, and anionic surfactants. Other ingredients that may be included in the cleaning agent of the present invention may be selected from bleaching activators, bleaching catalysts, corrosion inhibitors, multivalent chelating agents other than chelating agent (A), enzymes, fragrances, dyes, defoamers, and detergent builders.

[0063] Particularly advantageous detergents of the present invention may contain one or more complexing agents other than MGDA or GLDA. Advantageous detergent compositions for use in detergents and advantageous laundry detergent compositions may contain one or more multivalent chelating agents (chelating agents) other than the mixtures according to the invention. Examples of multivalent chelating agents other than the mixtures according to the invention are IDS (iminodisuccinate), citrate, disodium salts of phosphonic acid derivatives such as hydroxyethane-1,1-bisphosphonic acid (“HEDP”), and polymers having complexing groups, such as those in which 20 to 90 mol% of the N atoms are accompanied by at least one CH2COO group. -The cleaning agents of the present invention contain polyethyleneimine groups, and their corresponding alkali metal salts, especially their sodium salts (e.g., IDS-Na4 and trisodium citrate), as well as phosphates such as STPP (sodium tripolyphosphate). Due to the environmental problems caused by phosphates, it is preferred that the advantageous cleaning agents of the present invention be phosphate-free. In the context of the present invention, "phosphate-free" should be understood to mean, by weight determination and relative to the corresponding cleaning agent of the present invention, that the total content of phosphates and polyphosphates is in the range of 10 ppm to 0.2% by weight.

[0064] The cleaning agent of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

[0065] Preferred nonionic surfactants are alkoxylated alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide, reaction products of sorbitol with ethylene oxide or propylene oxide, alkyl polysaccharides (APG), mixed hydroxyalkyl ethers, and amine oxides.

[0066] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds having the general formula (II).

[0067]

[0068] The variables are defined as follows:

[0069] R 1 They may be the same or different, and are selected from hydrogen and straight-chain C1-C. 10 -alkyl, preferably the same in each case and ethyl, and particularly preferably hydrogen or methyl,

[0070] R 2 C8-C selected from branches or straight chains 22 -alkyl, for example, -C8H 17 , positive-C 10 H 21 , positive-C 12 H 25 , positive-C 14 H 29 , positive-C 16 H 33 or positive -C 18 H 37 ,

[0071] R 3 Selected from C1-C 10-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodel,

[0072] m and n are in the range of 0 to 300, wherein the sum of n and m is at least 1, preferably in the range of 3 to 50. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0073] In one embodiment, the compound having general formula (II) can be a block copolymer or a random copolymer, preferably a block copolymer.

[0074] Other preferred examples of alkoxylated alcohols are, for example, compounds having the general formula (III).

[0075]

[0076] The variables are defined as follows:

[0077] R 1 They may be the same or different, and are selected from hydrogen and straight-chain C1-C0-alkyl, preferably the same in each case and ethyl, and particularly preferably hydrogen or methyl.

[0078] R 4 C6-C selected from branches or straight chains 20 -alkyl groups, especially -C8H 17 , positive-C 10 H 21 , positive-C 12 H 25 , positive-C 14 H 29 , positive-C 16 H 33 , positive-C 18 H 37 ,

[0079] a is a number in the range of 0 to 10, preferably 1 to 6.

[0080] b is a number in the range of 1 to 80, preferably 4 to 20.

[0081] d is a number in the range of 0 to 50, preferably 4 to 25.

[0082] The sum of a+b+d is preferably in the range of 5 to 100, and even more preferably in the range of 9 to 50.

[0083] Preferred examples of hydroxyalkyl mixed ethers are compounds having the general formula (IV).

[0084]

[0085] The variables are defined as follows:

[0086] R 1 are the same or different and are selected from hydrogen and linear C1-C 10 -alkyls, preferably the same in each case and being ethyl and particularly preferably hydrogen or methyl,

[0087] R 2 is selected from branched or linear C8-C 22 -alkyls, such as iso-C 11 H 23 、iso-C 13 H 27 、n-C8H 17 、n-C 10 H 21 、n-C 12 H 25 、n-C 14 H 29 、n-C 16 H 33 or n-C 18 H 37 ,

[0088] R 3 is selected from C1-C 18 -alkyls, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, i-pentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, i-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, i-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

[0089] The variables m and n are in the range from 0 to 300, where the sum of n and m is at least 1, preferably in the range from 5 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0090] The compounds having the general formulas (II) and (III) can be block copolymers or random copolymers, preferably block copolymers.

[0091] Further suitable nonionic surfactants are selected from diblock 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-C 16 -alkyl polyglucosides and branched C8-C 14-Alkyl polyglycosides, such as compounds having the average general formula (V), are also suitable.

[0092]

[0093] The variables are defined as follows:

[0094] R 5 It is a C1-C4 alkyl group, especially ethyl, n-propyl, or isopropyl.

[0095] R 6 It is -(CH2)2-R 5 ,

[0096] G 1 Selected from monosaccharides having 4 to 6 carbon atoms, especially glucose and xylose.

[0097] If y is in the range of 1.1 to 4, then y is the mean.

[0098] Other examples of nonionic surfactants are compounds having general formulas (VII) and (VIII).

[0099]

[0100] AO is selected from ethylene oxide, propylene oxide, and butane oxide.

[0101] EO stands for ethylene oxide, CH2CH2-O.

[0102] R 8 C8-C selected from branches or straight chains 18 -alkyl, and R 5 As defined above.

[0103] A 3 O is selected from propylene oxide and butane oxide.

[0104] w is a number in the range of 15 to 70, preferably 30 to 50.

[0105] w1 and w3 are numbers in the range of 1 to 5, and

[0106] w2 is a number in the range of 13 to 35.

[0107] An overview of other suitable nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19187.

[0108] A mixture of two or more different nonionic surfactants may also exist.

[0109] Other surfactants that may be present are selected from amphoteric (ampholy) surfactants and anionic surfactants and mixtures thereof.

[0110] Examples of amphoteric surfactants are those that, under the conditions of use, carry both positive and negative charges within the same molecule. A preferred example of an amphoteric surfactant is the so-called betaine-surfactant. Many examples of betaine-surfactants carry one quaternary nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauromamidopropyl betaine).

[0111] Examples of amine oxide surfactants are compounds having the general formula (IX).

[0112] R 7 R 8 R 9 N→O(IX)

[0113] Where R 7 R 8 and R 9 Each is independently selected from aliphatic, alicyclic, or C2-C4-alkylene C 10 -C 20 -alkylamide group. Preferably, R 7 Selected from C8-C 20 -alkyl or C2-C4-alkylene C 10 -C 20 -alkylamide group and R 8 and R 9 They are all methyl groups.

[0114] A particularly preferred example is lauryl dimethylamine oxide, sometimes also called laurylamine oxide. Another particularly preferred example is cocamidopropyl dimethylamine oxide, sometimes also called cocamidopropylamine oxide.

[0115] An example of a suitable anionic surfactant is C8-C. 18 Alkali metal salts and ammonium salts of alkyl sulfates, C8-C 18 -Alkali metal salts and ammonium salts of fatty alcohol polyether sulfates, ethoxylated C4-C 12 Alkali metal salts and ammonium salts of sulfated half-esters of alkylphenols (ethoxylated: 1 to 50 mol ethylene oxide / mol), C 12 -C 18 sulfonyl fatty acid alkyl esters (e.g., C 12 -C 18 Alkali metal salts and ammonium salts of sulfonated fatty acid methyl esters), in addition to C 12 -C 18 Alkali metal salts and ammonium salts of alkyl sulfonic acids and C 10 -C18 Alkali metal salts and ammonium salts of alkylaryl sulfonic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0116] Another example of a suitable anionic surfactant is soap, such as sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylic acid esters, and alkyl ether phosphate esters.

[0117] Preferably, the laundry detergent composition contains at least one anionic surfactant.

[0118] In one embodiment of the invention, the detergent of the invention used as a laundry detergent composition may contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0119] In one embodiment of the invention, the cleaning agent of the invention for cleaning hard surfaces is determined to contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0120] In a preferred embodiment, the cleaning agent of the present invention does not contain any anionic detergents.

[0121] The cleaning agent of the present invention may contain one or more bleaching catalysts. The bleaching catalyst may be selected from transition metal salts or transition metal complexes that promote bleaching, such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper complexes having nitrogen-containing tripod ligands, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, may also be used as bleaching catalysts.

[0122] The cleaning agent of the present invention may contain one or more bleaching activators, such as N-methylmorpholinium acetonitrile salt (“MMA salt”), trimethylammonium acetonitrile salt, N-acylimide such as N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”) or nitrile quaternary ammonium salt (trimethylammonium acetonitrile salt).

[0123] Other examples of suitable bleaching activators are tetraacetylethylenediamine (TAED) and tetraacetylhexanediamine.

[0124] The cleaning agents of the present invention may contain one or more corrosion inhibitors. In this case, this should be understood to include those compounds that inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, particularly benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and phenolic derivatives, such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyroglucinol.

[0125] In one embodiment of the invention, the cleaning agent of the invention contains a total of 0.1% to 1.5% corrosion inhibitor by weight.

[0126] The cleaning agent of the present invention may contain one or more builder agents selected from organic and inorganic builder agents. Examples of suitable inorganic builder agents are sodium sulfate or sodium carbonate or silicates, particularly sodium disilicate and sodium metasilicate, zeolites, succinates, especially those having the formulas α-Na₂Si₂O₅, β-Na₂Si₂O₅, and δ-Na₂Si₂O₅, as well as fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetates, tartaric acid monoacetates, oxidized starch, and polymeric builder agents, such as polycarboxylates and polyaspartic acid.

[0127] Examples of organic detergent builders are, in particular, polymers and copolymers other than (co)polymer (B), and include polymers and copolymers other than (co)polymer (B), or another (co)polymer (B). In one embodiment of the invention, the organic detergent builder is selected from polycarboxylates, such as alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, which are partially or completely neutralized by alkali.

[0128] Suitable comonomers for (meth)acrylic acid are monoene-bonded unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers, particularly polyacrylic acid, preferably have an average molecular weight M in the range of 2000 to 40,000 g / mol, more preferably 2000 to 10,000 g / mol, and particularly 3000 to 8000 g / mol. w Also suitable and in the same molecular weight range are copolymer polycarboxylates, especially those of acrylic acid and methacrylic acid, and those of acrylic acid or methacrylic acid and maleic acid and / or fumaric acid.

[0129] Alternatively, copolymers of at least one monomer with at least one hydrophilic or hydrophobic monomer listed below can be used, wherein the at least one monomer is selected from the group consisting of monoolefinic unsaturated C3-C 10 - Monocarboxylic acid or C4-C 10 -Dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid.

[0130] Suitable hydrophobic monomers are, for example, isobutylene, diisobutylene, butene, pentene, hexene, and styrene, olefins or mixtures thereof having 10 or more carbon atoms, such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docodecene, 1-tetradecene, and 1-hexadecene, C 22 -α-olefin, C 20 -C 24 Mixtures of α-olefins and polyisobutylene with an average of 12 to 100 carbon atoms per molecule.

[0131] Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxyl or alkylene oxide functional groups. Examples include: allyl alcohol, isoprene alcohol, methoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polybutylene glycol (meth)acrylate, methoxy poly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, ethoxy polybutylene glycol (meth)acrylate, and ethoxy poly(propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols may contain 3 to 50, particularly 5 to 40, and especially 10 to 30 alkylene oxide units per molecule.

[0132] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methylallylsulfonic acid, allyloxybenzenesulfonic acid, methylallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-acryloxy)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 their sodium, potassium, or ammonium salts.

[0133] The preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

[0134] Another example of a detergent builder is carboxymethyl inulin.

[0135] In addition, amphoteric polymers can also be used as detergent builders.

[0136] The cleaning agent of the present invention may contain, for example, a cleaning aid in the range of 10% to 70% by weight, preferably 10% to 50% by weight, and more preferably up to 20% by weight.

[0137] In one embodiment of the present invention, the cleaning agent according to the present invention may contain one or more co-cleaning agents.

[0138] The cleaning agent of the present invention may contain one or more defoamers, selected from, for example, silicone oil and paraffin oil.

[0139] In one embodiment of the invention, the cleaning agent of the invention comprises a total amount of defoamer ranging from 0.05% to 0.5% by weight.

[0140] The cleaning agent of the present invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectins, lactases, and peroxidases.

[0141] In one embodiment of the invention, the cleaning agent may contain, for example, up to 5% by weight, preferably 0.1% to 3% by weight, an enzyme. The enzyme may be, for example, oxidized by at least one C1-C3-carboxylic acid or C4-C... 10 - Stabilization with sodium salts of dicarboxylic acids. Formate, acetate, adipate, and succinate are preferred.

[0142] In one embodiment of the invention, the cleaning agent of the invention may contain at least one zinc salt. The zinc salt may be selected from water-soluble zinc salts and water-insoluble zinc salts. For this purpose, in the context of the invention, water-insoluble refers to those zinc salts having a solubility of 0.1 g / L or less in distilled water at 25°C. Correspondingly, zinc salts with higher solubility in water are referred to as water-soluble zinc salts in the context of the invention.

[0143] In one embodiment of the present invention, the zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2 and zinc gallate, preferably ZnCl2, ZnSO4, zinc acetate, zinc citrate, Zn(NO3)2, Zn(CH3SO3)2 and zinc gallate.

[0144] In another embodiment of the invention, the zinc salt is selected from ZnO, ZnO aqueous solution, Zn(OH)2, and ZnCO3. ZnO aqueous solution is preferred.

[0145] In one embodiment of the invention, the zinc salt is selected from zinc oxides with an average particle diameter (weight average) in the range of 10 nm to 100 μm.

[0146] The cations in zinc salts can exist in complexed forms, such as complexed with amino or aqueous ligands, and particularly in hydrated forms. For the sake of simplicity, in the context of this invention, ligands that are aqueous ligands are generally omitted.

[0147] The zinc salt may vary depending on how the pH of the mixture according to the invention is adjusted. Thus, for example, zinc acetate or ZnCl2 used to prepare the formulations according to the invention can be used, but this is converted to ZnO, Zn(OH)2, or an aqueous solution of ZnO at pH 8 or 9 in an aqueous environment, which may exist in non-complexed or complexed forms.

[0148] Zinc salts can be present in those cleaning agents of the present invention that are solid at room temperature. In such cleaning agents of the present invention, zinc salts are preferably present in particulate form, having, for example, an average diameter (number average) in the range of 10 nm to 100 μm, preferably 100 nm to 5 μm, as determined by X-ray scattering.

[0149] Zinc salts can be present in those cleaning agents of the present invention that are liquid at room temperature. In such cleaning agents of the present invention, zinc salts are preferably present in dissolved, solid, or colloidal form.

[0150] In one embodiment of the invention, the cleaning agent of the invention contains zinc salt in each case, with a total dry matter content in the range of 0.05% to 0.4% by weight based on the cleaning agent under discussion.

[0151] Here, the fraction of zinc salt is given as zinc or zinc ions. From this, the fraction of counterions can be calculated.

[0152] In one embodiment of the invention, the cleaning agent of the present invention is free of heavy metals except for zinc compounds. In the context of the present invention, this can be understood to mean that the cleaning agent of the present invention is free of those heavy metal compounds that do not act as bleaching catalysts, particularly compounds containing iron and bismuth. In the context of the present invention, "free of" in relation to heavy metal compounds should be understood to mean that the total content of heavy metal compounds that do not act as bleaching catalysts is in the range of 0 to 100 ppm, determined by a leaching method and based on dry matter content. Preferably, the cleaning agent of the present invention has a heavy metal content other than zinc of less than 0.05 ppm based on the dry matter content of the formulation under discussion. Therefore, the zinc fraction is not included.

[0153] In the context of this invention, "heavy metal" is considered to be, excluding zinc, a specific density of at least 6 g / cm³. 3 All metals. In particular, heavy metals include metals such as bismuth, iron, copper, lead, tin, nickel, cadmium, and chromium.

[0154] Preferably, the cleaning agent of the present invention contains an immeasurable fraction (e.g., less than 1 ppm) of a bismuth compound.

[0155] The cleaning agents of this invention are excellent for cleaning hard surfaces and fibers. For example, they can be used in dishwashing applications, preferably in automatic dishwashing applications.

[0156] In one embodiment of the invention, the cleaning agent of the invention comprises one or more additional ingredients such as fragrance, dye, organic solvent, buffer, disintegrant for tablets (“tabs”) and / or acid such as methanesulfonic acid.

[0157] Exemplary detergent compositions for automatic dishwashing can be formulated from the solid compositions of the present invention (e.g., granules or powders) by mixing the corresponding components according to Table F below.

[0158] Table F: Exemplary detergent compositions for automatic dishwashing

[0159]

[0160]

[0161] The laundry detergent according to the present invention can be used to wash any type of clothing and any type of fiber. The fibers can be of natural or synthetic origin, or they can be a natural mixture of natural and synthetic fibers. Examples of naturally sourced fibers are cotton and wool. Examples of synthetically sourced fibers are polyurethane fibers, such as… or Polyester or polyamide fibers. The fiber can be a single fiber or part of a textile such as knitted, woven, or nonwoven fabric.

[0162] Another aspect of the present invention is a method for preparing tablets for automatic dishwashing using a solid alkali metal salt (A) (e.g., powder or granules) of the aminocarboxylate complexing agent of the present invention, wherein the granules or powder are selected from the granules and powders of the present invention, respectively. The method is also referred to below as a granulation method according to the present invention.

[0163] The tablets of the present invention are preferably made with the aid of a machine, such as a tablet press.

[0164] The granulation method according to the invention can be carried out by mixing a solid alkali metal salt (A) (e.g., powder) of the aminocarboxylate complexing agent of the invention with at least one nonionic surfactant and optionally one or more other substances, and then compressing the mixture to give tablets. Examples of suitable nonionic surfactants and other substances (such as detergent builders, enzymes) are listed above. Particularly preferred examples of nonionic surfactants are hydroxyl mixed ethers, such as hydroxyl mixed ethers having the general formula (V).

[0165] Some aspects of the present invention are described below Work examples To illustrate.

[0166] Sample preparation

[0167] Comparison Examples

[0168] Will The M(MGDA) solution is dried in an agglomeration spray drying method using a device called an SBD (Spray Bed Dryer) available from the supplier Anhydo.

[0169] This SBD unit is a spray tower with an integrated fluidized bed. A 4 kg spray powder is introduced as initial packing. The initial packing volume is 350 Nm³. 3 Nitrogen gas (dry gas) at a rate of 25 kg / h is introduced into the top of the column around a two-component nozzle at a temperature of 200°C-210°C. The feed of liquid M (as is) is atomized through the two-component nozzle and sprayed into the dust cloud within the dryer. Exhaust gas exiting the dryer through the top / side outlet carries the dust (i.e., fine particles with an average diameter of up to 300 μm) out of the dryer. The dust is separated from the exhaust gas by a cyclone separator and reintroduced around the nozzle. The liquid is sprayed in such a manner that the dust particles are bound together, causing them to agglomerate. Overspraying generates new dust (droplets that do not impact dust particles and dry out). Sufficiently heavy agglomerates move by gravity into the internal fluidized bed and are subjected to 80 Nm of [unclear - possibly a specific process or pressure]. 3 Pre-drying with fluidized air at approximately 62°C per hour. Weirs and discharge valves maintain a dedicated fill level of 4–8 mbar differential pressure in the internal fluidized bed. The product leaving the dryer is collected as the target agglomerate.

[0170] M is commercially available from BASF SE and refers to the MGDA chelating agent.

[0171] Example 1 of the present invention

[0172] By 66.2kg Liquid M, 32.8 kg M granules and 1 kg of seed material were mixed to prepare a slurry. The slurry was mixed and heated at approximately 70°C for 3 hours.

[0173] Will The M solution is dried using an equipment called an SBD (Spray Bed Dryer) available from the supplier IHideno in an agglomeration spray drying method.

[0174] This SBD unit is a spray tower with an integrated fluidized bed. A 4 kg spray powder is introduced as initial packing. The volume is 325-340 Nm. 3Nitrogen (dry gas) at a rate of 200°C-210°C is introduced into the top of the column around a two-component nozzle. 45-50 kg / h of the Trilon gas is then introduced. The slurry is atomized through the two-component nozzle and sprayed into a dust cloud within the dryer. Exhaust gas exiting the dryer through the top / side outlet carries the dust (i.e., fine particles with an average diameter of up to 300 μm) out of the dryer. The dust is separated from the exhaust gas by a cyclone separator and reintroduced around the nozzle. The liquid is sprayed in a manner that binds the dust particles together, causing them to agglomerate. Overspraying generates new dust (droplets that do not impact dust particles and dry out). Sufficiently heavy agglomerates move by gravity into the internal fluidized bed and are subjected to 100 Nm of [unclear - possibly a specific process or pressure]. 3 Pre-drying with fluidized air at approximately 65°C-75°C per hour. Weirs and discharge valves maintain a dedicated fill level of 5-10 mbar differential pressure in the internal fluidized bed. The product leaving the dryer is collected as the target agglomerate.

[0175] Example 2 of the present invention

[0176] By using 34.79 kg of water and 3.23 kg of... CP50 pellets, 60.9kg The slurry was prepared by mixing M granules and 1.0 kg of crystal form II seed crystals. The slurry was mixed and heated at approximately 70°C for 3 hours.

[0177] The slurry thus obtained is then processed using an agglomeration-type spray drying method, as described in the first example of the invention.

[0178] CP50 is commercially available from BASF and refers to a modified polycarboxylate polymer (sodium salt).

[0179] Application testing

[0180] Percarbonate stability

[0181] The MGDA sample (10g of the MGDA sample prepared as described above together with 5g of percarbonate) was stored in a climate chamber at 35°C and 70% relative humidity in a cell culture flask with a membrane in the lid.

[0182] The b-value was measured using a Mach 5 device.

[0183] b value zero value 1 week 2 weeks 3 weeks 4 weeks Comparison Examples 3.90 4.72 11.57 11.01 9.86 Example 1 of the present invention 2.58 3.50 6.53 9.76 9.35 Example 2 of the present invention 3.32 6.41 9.22 9.92 13.03

[0184] hygroscopic

[0185] The MGDA sample (5g of the sample prepared as described above) was stored in a petri dish in a climate chamber (incubator) at 35°C and 70% relative humidity.

[0186]

[0187] Experimental data particularly demonstrate that, compared to using a solution, the agglomerated spray drying method, starting with a slurry, leads to unexpectedly improved results in the product. For example, in the presence of peroxides, the water absorption in the resulting particles of the present invention is significantly reduced, and the resulting particles of the present invention exhibit a significantly lower tendency to color.

Claims

1. A method for manufacturing solid particles, preferably free-flowing solid particles, comprising at least one aminocarboxylate complexing agent or a salt of an alkali metal thereof, wherein the method comprises spray drying of a slurry comprising an aminocarboxylate complexing agent under agglomeration conditions in the presence of fine particles with an average diameter of up to 300 μm.

2. The method of claim 1, used to manufacture solid particles comprising at least one aminocarboxylate complexing agent or a salt of an alkali metal thereof, wherein the slurry comprises at least 45% by weight of the aminocarboxylate complexing agent and optionally seed particles of the solid aminocarboxylate complexing agent.

3. The method according to claim 1 or 2, used to manufacture solid particles comprising at least one aminocarboxylate complexing agent or a salt of an alkali metal thereof, wherein the aminocarboxylate complexing agent is selected from a list consisting of MGDA, GLDA, EDDS, and IDS, preferably MGDA.

4. The method according to any one of the preceding claims, wherein, The method includes the following steps (a) Forming an aqueous slurry comprising seed particles of a solid aminocarboxylate complexing agent, preferably at least 45% by weight of the solid aminocarboxylate complexing agent relative to the total weight of the aqueous slurry. (b) The slurry is spray-dried in a spray dryer equipped with a fluidized bed. Particles P1 with a diameter smaller than the target particle diameter P exit the spray drying equipment through the exhaust outlet on the dryer head, (ii) are removed by a cyclone separator, and (iii) are reintroduced into the drying equipment. Particle P1 agglomerates in the spray drying apparatus when it is reintroduced into the apparatus to form particle P2 with an increased average particle diameter and / or weight compared to particle P1, and wherein Particle P2 falls into the fluidized bed when it has the target particle diameter P and is optionally air-classified and optionally post-dried to obtain free-flowing particles P3.

5. The method for manufacturing solid particles according to any one of the preceding claims, wherein, Particles P3 are compacted into compacted aggregates.

6. The method according to any one of the preceding claims, wherein, The slurry provided in step (a) contains at least 0.1% by weight of an additional organic or inorganic compound or a mixture thereof.

7. The method according to any one of the preceding claims, wherein, The slurry provided in step (a) contains at least 0.1% by weight of a (co)polymer (B), which is selected from (meth)acrylic acid and polyethyleneimine, wherein the polyethyleneimine is unsubstituted or substituted with alkoxy or CH2COOH groups that can be neutralized by alkali metals; and / or polyaspartate and / or polyepoxysuccinic acid.

8. The method according to any one of the preceding claims, wherein, The slurry is preheated in step (a) before entering the spray drying equipment in step (b).

9. The method according to any one of the preceding claims, wherein, This method is carried out in an agglomeration-type spray drying equipment.

10. The method according to any one of the preceding claims, wherein, The method is carried out in an agglomeration-type spray drying device with a height of at least 5 meters, preferably at least 10 meters.

11. The method according to any one of the preceding claims, wherein, The resulting particles are then cooked.

12. The method according to any one of the preceding claims, wherein, The slurry formed in step (a) is heated to a temperature of at least 70°C for a period of 10 minutes to 8 hours to increase the content of orthogonal aminocarboxylate complexing agent in the slurry.

13. A solid particle comprising at least one aminocarboxylate complexing agent, preferably a free-flowing solid particle, which can be obtained or acquired by the method according to any one of the preceding claims.

14. The solid particles comprising at least one aminocarboxylate complexing agent according to claim 13, having a particle size of 50 to 1400 μm, preferably 100 to 1000 μm, more preferably 100 to 500 μm, and / or wherein the particles have at least 10% crystallinity as determined by X-ray diffraction, and / or at least 30% orthorhombic crystal content as determined by X-ray diffraction.

15. The solid particles comprising at least one aminocarboxylate complexing agent according to claim 13 or 14, having a moisture content of not more than 30 wt.%, preferably less than 20 wt.%, more preferably less than 15 wt.%.

16. A cleaning agent, preferably a dishwashing cleaner, comprising solid particles as described in claim 13, 14 or 15.

17. The cleaning agent of claim 16, further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising an amount of the antimicrobial agent ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1% to 2% phenoxyethanol.

Images