Process for producing granules containing at least one chelating agent and / or at least one polymer.

Abstract

The present invention relates to a process for producing granules with increased bulk density containing at least one chelating agent and / or at least one polymer.

Description

[Technical Field]

[0001] The present invention relates to a process for producing granules comprising at least one chelating agent and / or at least one polymer. [Background technology]

[0002] Chelating agents such as methylglycine diacetic acid (MGDA), and their respective alkali metal salts, are Ca 2+ and Mg 2+ These are useful metal ion chelating agents for alkaline earth metal ions. Therefore, they are recommended and used in a variety of applications, particularly in laundry detergents and automatic dishwasher (ADW) formulations, especially so-called phosphate-free laundry detergents and phosphate-free ADW formulations. When transporting such chelating agents, they are almost always transported in solid form, such as powder or granules, or in aqueous solution form.

[0003] Depending on the type of product – liquid home care and textile care products versus solid home care and textile care products – and the manufacturing process of solid home care and textile care products, care product manufacturers may prefer to handle either a solution or solid aminocarboxylate, for example, by joint spray drying or solid mixing. Aminocarboxylate powders and granules can be transported economically due to their high active ingredient content in addition to their low water content. Therefore, convenient processes for providing granules remain of great commercial interest.

[0004] Typically, ADW formulations contain up to 40% MGDA builder, are packaged in single-dose units, and are also packaged in "SUDs." The space within these SUDs is limited, and therefore, higher bulk density is desirable, as it allows for more active product per unit volume within these SUDs. Furthermore, granules and / or polymers containing chelating agents such as MGDA typically contain a certain amount of so-called "fine powder," which is undesirable for ADW formulation manufacturers. Fine powder can also pose environmental and health risks to employees working with polymers containing MGDA and / or fine powder. In relation to the present invention, the term "fine powder" refers to particles having a particle size (diameter) of less than 300 μm.

[0005] International Publication No. 2023 / 105006A1 discloses a granular additive for detergent compositions, which comprises at least one builder and at least one cationic polymer.

[0006] European Patent No. 0520582B1 describes a process for producing a free-flowing, spray-dried particulate detergent composition containing zeolite and optionally citric acid. This document does not refer to the use of chelating agents such as MGDA or IDS.

[0007] International Publication No. 2021 / 115851 discloses a process for producing granules containing at least one chelating agent and optionally at least one polymer by spray granulation, followed by a post-processing step.

[0008] However, the bulk density of the resulting granules still has room for improvement. [Overview of the project] [Problems that the invention aims to solve]

[0009] Therefore, an object of the present invention was to provide a process that yields chelating agent and / or polymer granules with high or increased bulk density and reduced amount of fine powder. [Means for solving the problem]

[0010] Accordingly, the process described herein was discovered and is hereafter referred to as the process of the present invention or the process according to the present invention.

[0011] Therefore, the present invention relates to a process for producing granules that have a high bulk density and preferably contain less fine powder, wherein these granules are (A) at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), and / or at least one polymer (PA), and optionally, (B) comprising at least one homo- or copolymer selected from a list of polyaspartates having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol, and a homo- or copolymer of (meth)acrylic acid partially or completely neutralized with alkali, The aforementioned process is (a) A step of providing an aqueous solution or slurry containing a chelating agent (A) and / or a polymer (PA), and, where applicable, a (co)polymer (B), (b) A step of removing most of the aforementioned water by spray granulation in a fluidized bed, thereby obtaining granules, (c) A step of treating the granules obtained from step (b) with air or an inert gas in a container in which at least a portion rotates about a horizontal or vertical axis, wherein the container is selected from a high-speed mixer, a paddle mixer, a plow shear mixer, a free-fall mixer, a mixer having an additional chopper unit to enhance mixing and mixing, wherein the container further comprises an aqueous composition (AC) containing at least one surfactant (S), wherein the surfactant (S) preferably generates at least 100 ml of foam when measured according to EN 14371:20004 (0.1 g / l, 25°C, atmospheric pressure, and after 10 minutes in water), wherein the surfactant (S) is preferably selected from a list consisting of a nonionic surfactant (S1), anionic surfactant (S2), amphoteric surfactant (S3) and mixtures thereof. Includes.

[0012] The feature in the process of the present invention that the container "further comprises an aqueous composition (AC) containing at least one surfactant (S)" includes any potential process variations for its effect.

[0013] Specifically, this includes, but is not limited to, alternative methods in which (i) both the granules obtained from step (b) and the aqueous composition (AC) are filled into a container and then the process is started, or (ii) the aqueous composition (AC) is pre-filled into a container and then the granules obtained from step (b) are introduced into the container and the process is started, or (iii) the granules obtained from step (b) are pre-filled into a container and then the aqueous composition (AC) is gradually introduced during the process, preferably through a foam-generating nozzle.

[0014] In a preferred embodiment, the granules obtained from step (b) are pre-filled into a container, and then the aqueous composition (AC) is gradually introduced during processing, preferably through a foam-generating nozzle. The foam-generating nozzle generates foam by mixing two flows, for example, air in one flow and a liquid (containing a surfactant) in the other flow, which is schematically shown in Figures 3 and 4 below.

[0015] Preferably, the aqueous composition (AC) contains 0.01 to 10.00% by weight of surfactant S, preferably 0.10 to 3.00% by weight, and more preferably 0.20 to 2% by weight of surfactant S.

[0016] The process of the present invention is a process for producing granules. In relation to the present invention, the term "granules" refers to particulate material that is solid at ambient temperature and has an average particle size (D50) in the range of preferably 0.1 mm to 2 mm, preferably 0.4 mm to 1.25 mm, and more preferably 400 μm to 1 mm. The average particle size of the granules of the present invention can be determined, for example, optically or preferably by a sieving method. The mesh range of the sieve used may be 60 to 3,000 μm.

[0017] In one embodiment of the present invention, the granules produced according to the present invention have a broad particle size distribution. In another embodiment of the present invention, the granules produced according to the present invention have a narrow particle size distribution. The particle size distribution can be adjusted by a series of sieving steps as needed.

[0018] The granules produced by the process of the present invention may contain residual moisture, moisture including crystallized water, and adsorbed water. The amount of water may be in the range of 0.1 to 20% by weight, preferably 1 to 15% by weight, based on the total solid content of each granule, and can be determined by Karl Fischer titration or by drying at 160 to 200°C using infrared light until a constant weight is reached.

[0019] The granular particles produced by the process of the present invention have a regular shape, a smooth surface, and no sharp edges, thereby reducing the generation of fine powder during transport.

[0020] The granular particles produced by the process of the present invention comprise at least one chelating agent and / or polymer (PA), hereinafter also referred to as chelating agent (A). Chelating agent (A) is selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS).

[0021] Alkali metal salts of MGDA are given by general formula (Ia) [CH3-CH(COO)-N(CH2-COO)2]M 3-x H x (Ia) (In the formula, M is selected from the same or different alkali metal cations, such as lithium, sodium, potassium, rubidium, cesium cations, and at least two of the aforementioned combinations.) The compounds are selected from those containing alkali metal cations. Preferred examples of alkali metal cations are sodium and potassium, as well as combinations of sodium and potassium.

[0022] In equation (Ia), x is in the range of 0 to 1.0, preferably 0 to 0.5. In a particularly preferred embodiment, x is zero.

[0023] Alkali metal salts IDS are given by the general formula (Ib) [HN-(CH(COO)-CH2COO)2]M 4-x H x (I C) (In the formula, M is selected from the same or different alkali metal cations defined above.) In equation (Ib), x is in the range of 0 to 2.0, preferably 0 to 0.5. A compound is selected from those obtained by [the specified agent]. In a particularly preferred embodiment, x is zero.

[0024] In one embodiment of the present invention, the alkali metal salt of MGDA is selected from lithium salt, potassium salt, and preferably sodium salt of MGDA. MGDA can be partially or preferably completely neutralized with the respective alkali. In a preferred embodiment, the average 2.7 to 3 COOH groups of MGDA are neutralized with an alkali metal, preferably sodium. In a particularly preferred embodiment, the chelating agent (A) is the trisodium salt of MGDA.

[0025] MGDA and the respective alkali metal salts thereof are selected from racemic mixtures, the D-isomer and the L-isomer, and mixtures of the D-isomer and the L-isomer other than racemic mixtures. Preferably, MGDA and the respective alkali metal salts thereof are selected from racemic mixtures and mixtures comprising the L-isomer in the range of 55 to 85 mol%, with the remainder being the D-isomer. Mixtures comprising the L-isomer in the range of 60 to 80 mol%, with the remainder being the D-isomer, are particularly preferred. Other particularly preferred embodiments are racemic mixtures.

[0026] IDS and the respective alkali metal salts thereof are selected from various mixtures of stereoisomers, for example D,D-IDS, L,L-IDS and D,L-IDS, and combinations thereof. Optically inactive mixtures are preferred because they are cheaper to produce.

[0027] In any case, a small amount of the chelating agent (A) may have cations other than alkali metals. Accordingly, small amounts, such as 0.01 to 5 mol% of the total amount of MGDA or IDS, respectively, may contain Mg 2+ or Ca 2+ alkaline earth metal cations, or Fe 2+ or Fe 3+ cations.

[0028] In one embodiment of the present invention, the alkali metal salt of the chelating agent (A) may comprise one or more impurities that may result from the synthesis of the respective chelating agent (A). In the case of MGDA and its alkali metal salts, such impurities may be selected from propionic acid, lactic acid, alanine, nitrilotriacetic acid (NTA) and the like, and the respective alkali metal salts thereof. In the case of IDS, such impurities may be selected from maleic acid, maleic acid / fumaric acid monoamide, and racemic asparagine. Such impurities are usually present in small amounts. The term "small amount" in this context refers to a total of 0.1 to 5% by weight, preferably up to 2.5% by weight, based on the alkali metal salt of the chelating agent (A). In the context of the present invention, such small amounts are ignored when determining the composition of the granules produced according to the process of the present invention.

[0029] In a special embodiment of the present invention, a combination of at least two different alkali metal salts of chelating agents, for example, sodium salts of MGDA and ISD in a weight ratio of 1:1 to 5:1, is used. In other embodiments, only one alkali metal salt of a chelating agent, in particular the sodium metal salt of MGDA, is used.

[0030] The granular particles produced by the process of the present invention are polymer (PA) and optionally, (B) At least one homo- or copolymer (PB) of (meth)acrylic acid (hereinafter also referred to as "polymer (B)"), partially or completely neutralized with an alkali. It may further include. A homopolymer polymer (B) is also called "homopolymer (B)", and a copolymer polymer (B) is also called "copolymer (B)".

[0031] The polymer (PA) and / or (PB) can also be selected from polyaspartates having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol.

[0032] The polymer (PA) and / or (PB) may also be selected from graft copolymers comprising a polymer P which can be obtained by grafting a polymer P onto a graft substrate, comprising at least one graft substrate selected from nonionic mono-, di-, oligo-, and polysaccharides, and an ethylenically unsaturated monomer M, wherein monomer M comprises at least one monomer b1 selected from monoethylenically unsaturated mono- and dicarboxylic acids, and at least one monomer b2 selected from ethylenically unsaturated monomers having a permanent cationic charge.

[0033] Polyaspartic acid is well known as a biodegradable, dispersible, and scale-inhibiting polymer. Three main methods have been developed for the industrial production of polyaspartic acid and its sodium salts: (1) Thermoplastic polycondensation of aspartic acid and subsequent alkaline hydrolysis of the intermediate polyscinimide, (2) Thermopolycondensation of aspartic acid in the presence of an acid catalyst such as phosphoric acid, sulfuric acid or methanesulfonic acid, followed by alkaline hydrolysis of the intermediate polyscinimide. (3) Polymerization of maleic anhydride in the presence of ammonia or an ammonium salt, followed by alkaline hydrolysis of the intermediate polyscinimide.

[0034] Regardless of the synthesis route, the intermediate polyscinimide must be hydrolyzed, for example, with sodium hydroxide, to obtain an aqueous solution of polyaspartate. Polyaspartic acid is obtained by acidifying the polyaspartate solution with a mineral acid such as hydrochloric acid or sulfuric acid.

[0035] Modified polyaspartic acid that can be used in accordance with the present invention is: (i) 50-99 mol%, preferably 60-95 mol%, particularly preferably 80-95 mol%, of aspartic acid, (ii) Polycondensation of at least one carboxyl group-containing compound in an amount of 1 to 50 mol%, preferably 5 to 40 mol%, and particularly preferably 5 to 20 mol%, It can also be prepared by hydrolysis of the co-condensate by the subsequent addition of a base, such as a sodium hydroxide solution, where (ii) is not aspartic acid.

[0036] The carboxyl-containing compound (ii) used in connection with the preparation of polyaspartic acid used according to the present invention may, in particular, be a carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (other than aspartic acid). Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. In this regard, polybasic carboxylic acids can thus be used in the preparation of polyaspartic acid used according to the present invention, for example, oxalic acid, adipic acid, fumaric acid, maleic acid, itaconic acid, aconitic acid, succinic acid, malonic acid, suberic acid, azelaic acid, diglycolic acid, glutaric acid, C1-C 26Alkyl succinic acid (e.g., octyl succinic acid), C2-C 26 Alkenyl succinic acid (e.g., octenyl succinic acid), 1,2,3-propanetricarboxylic acid, 1,1,3,3-propanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,3-propanetetracarboxylic acid, or 1,3,3,5-pentanetetracarboxylic acid may be used. Furthermore, in connection therewith, polybasic hydroxycarboxylic acids, such as citric acid, isocitric acid, mucinic acid, tartaric acid, tartonic acid, or malic acid may also be used. In connection with this, amino acids that can be used include, among others, aminocarboxylic acids (e.g., glutamic acid, cysteine), basic diaminocarboxylic acids (e.g., lysine, arginine, histidine, aminocaprolactam), neutral amino acids (e.g., glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isosparagine, glutamine, isoglutamine), aminosulfonic acids (e.g., taurine), hydroxyamino acids (e.g., hydroxyproline, serine, threonine), iminocarboxylic acids (e.g., proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g., anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid. In connection with the preparation of modified polyaspartic acid used according to the present invention, preferred carboxyl-containing compounds (ii) are 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid, and glutaric acid, and particularly preferred are 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, and glutamic acid.

[0037] The molecular weight (Mw) of modified polyaspartic acid can be easily adjusted by changing the reaction conditions. Molecular weights from 1,000 g / mol to 100,000 g / mol can be achieved by simply adjusting process parameters (temperature, catalyst, reaction time).

[0038] The preferred molecular weight of the (modified) polyaspartic acid used in accordance with the present invention is in the range of 1,000 g / mol to 20,000 g / mol, preferably 1,500 to 15,000 g / mol, and particularly preferably 2,000 to 10,000 g / mol.

[0039] The aspartic acid (i) used in connection with the preparation of (modified) polyaspartic acid used according to the present invention may be L- or D- and DL-aspartic acid. L-aspartic acid is preferred.

[0040] The polymer (PA) and / or (PB) may be selected from a homopolymer of (meth)acrylic acid and a copolymer (B) of (meth)acrylic acid, preferably acrylic acid, that has been partially or completely neutralized with an alkali. In relation to the present invention, the copolymer is one in which at least 50 mol%, preferably at least 75 mol%, and more preferably 80-99 mol%, of the comonomer is (meth)acrylic acid.

[0041] Suitable comonomers for copolymers (PA) and / or (PB) are ethylenically unsaturated compounds such as styrene, isobutene, and ethylene; α-olefins such as propylene, 1-butylene, and 1-hexene; and ethylenically unsaturated dicarboxylic acids and their alkali metal salts, as well as anhydrides, for example, but not limited to, maleic acid, fumaric acid, itaconic acid, disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride. Further examples of suitable comonomers are C1-C4 alkyl esters of (meth)acrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, and n-butyl acrylate.

[0042] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are selected from copolymers of (meth)acrylic acid and a comonomer having at least one sulfonic acid group per molecule. The comonomer having at least one sulfonic acid group per molecule may be incorporated into the (co)polymer (B) as a free acid, or may be at least partially neutralized with an alkali. Particularly preferred sulfonic acid group-containing comonomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of the aforementioned acids, such as sodium salts, potassium salts, or ammonium salts thereof.

[0043] The copolymer (PA) and / or (PB) can be selected from random copolymers, alternating copolymers, block copolymers and graft copolymers, with alternating copolymers and particularly random copolymers being preferred.

[0044] Useful copolymers (PA) and / or (PB) include, for example, random copolymers of acrylic acid and methacrylic acid, random copolymers of acrylic acid and maleic anhydride, ternary random copolymers of acrylic acid, methacrylic acid, and maleic anhydride, random or block copolymers of acrylic acid and styrene, and random copolymers of acrylic acid and methyl acrylate. Homopolymers of methacrylic acid are more preferred. Homopolymers of acrylic acid are even more preferred.

[0045] The (co)polymer (PA) and / or (PB) may constitute linear or branched molecules. In this regard, branching is when at least one repeating unit of such (co)polymer (B) is not part of the main chain but forms a branch or part of a branch. Preferably, the (co)polymer (B) is not crosslinked.

[0046] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are determined by gel permeation chromatography (GPC) and have an average molecular weight M in the range of 1,200 to 30,000 g / mol, preferably 2,500 to 20,000 g / mol, and more preferably 5,000 to 18,500 g / mol, based on the respective free acid. w It holds.

[0047] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are at least partially neutralized with an alkali, for example, lithium, potassium, or sodium, or a combination of at least two of the aforementioned, particularly sodium. For example, the (co)polymer (B) may be neutralized with an alkali, particularly sodium, in the range of 10 to 100 mol% of the carboxyl groups.

[0048] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are selected from the persodium salt of polyacrylic acid, i.e., polyacrylic acid completely neutralized with sodium.

[0049] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are selected from a combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer having at least one sulfonic acid group per molecule, and both polymers are completely neutralized with alkali.

[0050] In one embodiment of the present invention, the (co)polymer (PA) and / or (PB) are determined by gel permeation chromatography (GPC) and have an average molecular weight M in the range of 1,200 to 30,000 g / mol, preferably 2,500 to 20,000 g / mol, and more preferably 5,000 to 18,500 g / mol, based on the respective free acid. w It is selected from persodium salts of polyacrylic acid having the following properties.

[0051] In embodiments where a (co)polymer (PA) and / or (PB) is present, the weight ratio of (A):(B) is in the range of 2:1 to 1,000:1, preferably in the range of 7.5:1 to 1,000:1, and more preferably in the range of 40:1 to 100:1. At this weight ratio, impurities in the chelating agent (A) resulting from the synthesis described above are negligible.

[0052] surfactant Generally, the surfactant (S) that can be used in the process of the present invention is selected from foam-generating surfactants, i.e., surfactants that form sustainable foam in the presence of water.

[0053] In particular, when the surfactant (S) is measured according to EN 14371:2004 after being circulated in demineralized water for 10 minutes at 0.1 g / l, 25°C, and atmospheric pressure, it preferably generates at least 100 ml of foam, more preferably at least 200 ml of foam, and even more preferably at least 300 ml of foam.

[0054] The surfactant (S) in the aqueous composition (AC) is preferably selected from a list consisting of nonionic surfactants (S1), anionic surfactants (S2), amphoteric surfactants (S3), and mixtures thereof.

[0055] In one embodiment of the present invention, the nonionic surfactant (S1) can be selected from alkyl polyglycosides (APG) and / or alkoxylates (and mixtures thereof).

[0056] In one embodiment of the present invention, the nonionic surfactant (S1) can be selected from 2-propylheptanol-based ethoxylates ethoxylated with 5 to 20 ethylene oxide units.

[0057] In another embodiment of the present invention, the anionic surfactant (S2) can be selected from sodium lauryl sulfate (SLS) or sodium laureth sulfate having 1 to 5 EO units (or a mixture thereof).

[0058] In one embodiment of the present invention, the amphoteric surfactant (S3) is selected from compounds of the general formula (AMS2a), (AMS2b), or (AMS2c), which may be referred to as betaine and / or sulfobetaine (AMS2): [ka]

[0059] The variables in the general formulas (AMS2a), (AMS2b), and (AMS2c) are defined as follows:

[0060] R 11 C7-C is either linear (linear, n-) or branched. 22 Alkyl and linear (linear, n-) or branched C7-C 22 Selected from Alkenil.

[0061] R 12 Each of these is independently selected from linear (linear, n-)C1-C4 alkyl groups.

[0062] R 13 This is selected from C1-C5-alkyl and hydroxy C1-C5-alkyl, for example, 2-hydroxypropyl.

[0063] A - The compound is selected from carboxylates and sulfonates.

[0064] The integer r in the general formulas (AMS2a), (AMS2b), and (AMS2c) is in the range of 2 to 6.

[0065] Preferably, the amphoteric surfactant (S3) is selected from acylamidopropyl betaine, more preferably cocamidopropyl betaine.

[0066] In a preferred embodiment of the process of the present invention, the surfactant (S) is selected from a list consisting of C8-C10 alkyl polyglucosides with a degree of polymerization of 1.2-1.8, C8-C14 alkyl polyglucosides with a degree of polymerization of 1.2-1.8, C16-C18 ethoxylates having 25 EO units, ethoxylates of 2-propylheptanol and C16-C18 alcohols having 7 EO units, ethoxylate of 2-propylheptanol having 7 EO units, sulfated C12-C14 ethoxylates having 2 EO units, cocamidopropyl betaine, and mixtures thereof.

[0067] In one embodiment, the aqueous composition (AC) comprises at least one nonionic surfactant (S1) and at least one anionic surfactant (S2).

[0068] In one embodiment, the aqueous composition (AC) comprises at least one nonionic surfactant (S1) and at least one amphoteric surfactant (S3). In a further embodiment, the aqueous composition (AC) comprises at least one anionic surfactant (S2) and at least one amphoteric surfactant (S3).

[0069] In another embodiment, the aqueous composition (AC) comprises at least one nonionic surfactant (S1), at least one anionic surfactant (S2), and at least one amphoteric surfactant (S3).

[0070] In one embodiment, the aqueous composition (AC) comprises at least one nonionic surfactant (S1) and at least one anionic surfactant (S2) in a molar ratio of 10:1 to 1:10.

[0071] In one embodiment, the aqueous composition contains at least one nonionic surfactant (S1) and at least one amphoteric surfactant (S3) in a molar ratio of 10:1 to 1:10.

[0072] In further embodiments, the aqueous composition (AC) comprises at least one anionic surfactant (S2) and at least one amphoteric surfactant (S3) in a molar ratio of 10:1 to 1:10. [Brief explanation of the drawing]

[0073] [Figure 1] Figure 1 shows particles obtained from a comparative process (without using the aqueous surfactant composition of the present invention), including undesirable fine particles. [Figure 2] Figure 2 shows the particles obtained from the process of the present invention. [Figure 3] Figure 3 schematically shows a mixer equipped with a foam generating device. [Figure 4] Figure 4 is a (diagrammatic) depiction of the foam nozzle. [Modes for carrying out the invention]

[0074] The process of the present invention will be described in detail below.

[0075] Step (a) provides an aqueous solution or aqueous slurry of a chelating agent (A) and / or a polymer (PA), and, where applicable, a (co)polymer (PB). Such aqueous solutions or slurries can be produced by processes known to themselves. For example, aqueous solutions of alkali metal salts of chelating agent (A) can be obtained from their synthesis. Such solutions can be further concentrated by the addition of a solid chelating agent (A) or by evaporation of water. The (co)polymer (PA) and / or (PB) can be added as solids or as aqueous solutions, as required.

[0076] Step (a) can be carried out at ambient temperature. In other embodiments, step (a) is carried out at 20°C or a higher temperature, for example, in the range of 25°C to 90°C, preferably 60°C to 75°C.

[0077] The water used in step (a) may be present in an amount sufficient to dissolve both the chelating agent (A) and the (co)polymer (PA) and / or (PB). However, it is also possible to use a smaller amount of water to mix the chelating agent (A) and the (co)polymer (PA) and / or (PB) so that a slurry is formed. A solution is preferred.

[0078] In one embodiment of the present invention, the total solid content of the solution or slurry formed as a result of step (a) is in the range of 20 to 75%, preferably 35 to 50%.

[0079] In step (b), most of the water is removed from the aqueous solution or slurry provided in step (a) by spray granulation in a fluidized bed.

[0080] The aqueous slurry or aqueous solution obtained in step (a) may have a temperature in the range of 15 to 95°C, preferably 20 to 90°C, and more preferably 50 to 90°C.

[0081] In step (b), the aforementioned aqueous slurry or aqueous solution is introduced into a spray granulator. In relation to the present invention, the spray granulator typically includes a fluidized bed, which in relation to the present invention is a fluidized bed of the chelating agent (A) or granules produced according to the present invention. Such a fluidized bed of the chelating agent (A) is preferably in the form of a crystalline form determined by X-ray diffraction, for example, a chelating agent in the form of at least 66% crystalline form. In one embodiment of the present invention, the temperature of the fluidized bed may be in the range of 75 to 150°C, preferably 80 to 110°C.

[0082] Spraying is performed through one or more nozzles per spray granulator. Suitable nozzles include, for example, high-pressure rotary drum atomizers, rotary atomizers, three-fluid nozzles, single-fluid nozzles, three-fluid nozzles, and two-fluid nozzles, with single-fluid nozzles, two-fluid nozzles, and three-fluid nozzles being preferred. The first fluid is an aqueous slurry, aqueous solution, or emulsion, and the second fluid is a compressed hot gas, also called a hot gas inlet stream, having a pressure of, for example, 1.1 to 7 bar. The hot gas inlet stream may have a temperature in the range of at least 125°C to 250°C, preferably 150°C to 250°C, and more preferably 160°C to 220°C.

[0083] In step (b), an aqueous slurry or aqueous solution of the complexing agent (A) and / or polymer (PA), and optionally the (co)polymer (B), is introduced into the aforementioned fluidized bed in the form of droplets. In one embodiment of the present invention, the droplets formed during spray granulation have an average diameter in the range of 10 to 500 μm, preferably 20 to 180 μm, and more preferably 30 to 100 μm.

[0084] In one embodiment of the present invention, the off-gas exiting the spray granulator may have a temperature in the range of 40°C to 140°C, preferably 80°C to 110°C, but is lower than the high-temperature gas stream in any way. Preferably, the temperature of the off-gas exiting the drying container is the same as the temperature of the solid product present in the drying container.

[0085] In one embodiment of the present invention, the pressure inside the spray tower or spray granulator in step (b) is the standard pressure ± 100 millibars, preferably the standard pressure ± 20 millibars, and is, for example, 1 millibar lower than the standard pressure.

[0086] In one embodiment of the present invention, in particular, in the process for producing the granules of the present invention, the average residence time of the chelating agent (A) in step (b) is in the range of 2 minutes to 4 hours, preferably 30 minutes to 2 hours.

[0087] In embodiments where aged slurry is used, such aging may preferably be carried out at a temperature higher than the ambient temperature for a range of 2 to 24 hours.

[0088] In step (b), most of the water is removed in the fluidized bed. This means that a residual water content of 0.1 to 20% by weight may remain, based on the granules. In embodiments starting from a solution, about 51 to about 75% by weight of water present in the aqueous solution is removed in step (b).

[0089] Hereinafter, granules are obtained, which will also be referred to as "obtained particulate residue" or "granules from step (b)". The aforementioned granules from step (b) have a granular appearance and may have a bulk density in the range of 700 to 950 g / l, preferably greater than 750 g / l. The particles of the granules from step (b) may exhibit a certain degree of irregularity in shape.

[0090] At the end of step (b), the granules from step (b) are removed from the spray granulator. The aforementioned granules were at least partially formed during step (b) of the process of the present invention. The aforementioned removal may be performed through one or more openings in the spray tower or spray granulator. Preferably, one or more such openings are located at the bottom of each spray tower or spray granulator. Granules containing fine powder and lumps are removed.

[0091] In step (c), the granules from step (b) are treated with air, an inert gas, or a combination thereof in a container in which at least a portion rotates about a horizontal axis. Examples of inert gases include nitrogen and, but not limited to, rare gases such as argon. Mixtures of air and inert gas are also possible. Preferably, such air or inert gas is "dry." In this context, dry should be understood as containing less than 5 g of H2O per kg of gas.

[0092] As described above, step (c) is carried out in a container, such as a mixing member or mixer, in which at least a portion rotates about a horizontal axis. Preferably, the mixing member rotates about a horizontal axis, while the rest of the reactor does not rotate.

[0093] Various embodiments of reactor design are possible to carry out step (c) of the process of the present invention. Step (c) of the process of the present invention can be carried out in a forced mixer. Examples of forced mixers are paddle mixers and plow shear mixers.

[0094] A preferred mixer for process step (c) may be selected from a list consisting of paddle mixers, plowshaar mixers and central mixers (e.g., from Eirich). It is also possible to perform process (c) using a so-called free-fall mixer.

[0095] A free-fall mixer utilizes gravity to move particles, while a forced mixer operates with a moving mixing member, particularly a rotating mixing member installed in a mixing chamber. In relation to the present invention, the mixing chamber is the inside of the reactor. Examples of forced mixers are plow shear mixers, paddle mixers, and shovel mixers. Plow shear mixers are preferred. A preferred plow shear mixer is installed horizontally, where horizontal refers to the axis around which the mixing member rotates. Preferably, the process of the present invention is carried out, for example, in a shovel mixing tool, paddle mixing tool, blade mixing tool, and more preferably a plow shear mixer, according to the principles of hurling and whirling.

[0096] In one embodiment of the present invention, the process of the present invention is carried out in a free-fall mixer, which uses gravity to achieve mixing. In a preferred embodiment, step (c) of the process of the present invention is carried out in a drum or pipe-shaped container that rotates about its horizontal axis. In a more preferred embodiment, step (c) of the process of the present invention is carried out in a rotating container having baffles.

[0097] In one embodiment of the present invention, the container or at least a part thereof rotates at a speed in the range of 5 to 200 times per minute, preferably 5 to 60 times per minute.

[0098] In one embodiment of the present invention, step (c) of the process of the present invention is carried out using a forced mixer operating at a Froude number ("Fr") in the range of 1 to 10. In another embodiment, step (c) of the process of the present invention is carried out using a free-fall mixer operating at a Froude number less than 1. In relation to the present invention, the Froude number is given by Fr = v 2 It is defined as / g·l, where the variable v is the periphery velocity, the variable l is, for example, the diameter of each forced mixer or free-fall mixer, and the variable g is the acceleration due to gravity.

[0099] In a preferred version of the present invention that enables the air transport of the aforementioned particulate material, a pressure difference in the range of up to 400 millibars is applied. The granules can be ejected from the mixer or removed by suction.

[0100] In one embodiment of the present invention, the inlet pressure is higher but close to the desired reactor pressure. It is necessary to compensate for the pressure drop at the gas inlet.

[0101] In one embodiment of the present invention, step (c) is carried out at a temperature of 115°C from the ambient temperature, preferably in the range of 30 to 80°C. Preferably, the material obtained from step (b) is introduced directly into step (c) and cooled in step (c).

[0102] In one embodiment of the present invention, the duration of step (c) is in the range of 1 minute to 5 hours, preferably 5 to 30 minutes.

[0103] During process (c), the gas atmosphere may be replaced with fresh gas up to five times per hour, for example.

[0104] After step (c), granules with excellent spherical particle shape are obtained. These exhibit reduced hygroscopicity and can be used directly, for example, in the manufacture of formulations for automatic dishwashers.

[0105] One object of the present invention is also granules comprising at least one chelating agent and / or polymer (PA) selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), and optionally at least one homo- or copolymer of (meth)acrylic acid (PB) with a comonomer having at least one sulfonic acid group per molecule, partially or completely neutralized with alkali, and / or optionally a polyaspartate having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol, in a weight ratio of (A):(B) from 2:1 to 1,000:1, wherein the granules comprise at least 75% by weight of the chelating agent (A) and / or polymer (PA), and the granules have an average width-to-length ratio in the range of 1:1 to 1:0.75.

[0106] Another object of the present invention is the use of the granules of the present invention, or granules obtained (or obtainable) by the process of the present invention, for preferably producing a cleaning agent for fibers or hard surfaces, wherein the aforementioned cleaning agent optionally comprises at least one peroxy compound selected from percarbonates, persulfates and perborates.

[0107] The detergent may be a dishwashing detergent, particularly one intended for use in automated dishwashing systems.

[0108] Purpose Accordingly, another aspect of the present invention is the use of the granules of the present invention for the manufacture of a cleaning agent that may contain at least one bleaching agent, in particular for the manufacture of a cleaning agent for textiles or hard surfaces, the aforementioned cleaning agent containing at least one peroxy compound. Another aspect of the present invention is a manufacturing process for a cleaning agent by combining at least one granule of the present invention with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, which will hereafter also be referred to as the cleaning agent of the present invention.

[0109] The cleaning agent of the present invention may comprise at least one bleaching agent and at least one granule of the present invention. The cleaning agent of the present invention has a reduced tendency to yellow and therefore has a long shelf life.

[0110] Suitable examples of peroxy compounds include sodium perborate as anhydrous or, for example, monohydrate, tetrahydrate, or so-called dihydrate; sodium percarbonate as anhydrous or, for example, monohydrate; in any case, free acids or alkali metal salts, particularly hydrogen peroxide as a sodium salt; persulfates; organic peracids, such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxidedodecanediic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, and similarly sulfonyl peroxy acids and cationic peroxy acids.

[0111] In preferred embodiments, the peroxy compound is selected from inorganic percarbonates, persulfates, and perborates. An example of sodium percarbonate is 2Na2CO33H2O2. An example of sodium perborate is (Na2[B(OH)2(O2)]2), which is sometimes written as NaBO2O2·3H2O instead. The most preferred peroxy compound is sodium percarbonate.

[0112] The term "cleaning agent" includes compositions for washing dishes, particularly compositions for hand washing dishes, compositions for automatic dishwashers and ceramics, as well as compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe scale removal, window cleaning, automobile cleaning including truck cleaning, and compositions for cleaning hard surfaces such as open-type plants, on-site cleaning, metal cleaning, sterilization, farm cleaning, and high-pressure cleaning, in addition to laundry detergent compositions.

[0113] Such cleaning agents may be liquid, gel, or preferably solid at ambient temperature, with solid cleaning agents being preferred. They may be in the form of powder or granules, or in the form of unit doses, such as tablets.

[0114] In one embodiment of the present invention, the cleaning agent of the present invention is The granules of the present invention in the range of 2 to 50% by weight, Bleach in the range of 0.5 to 15% by weight and It may include. The percentage is based on the solid content of each detergent of the present invention.

[0115] The cleaning agent of the present invention may contain further components such as one or more surfactants selected from nonionic, zwitterionic, cationic, and anionic surfactants. Other components that may be included in the cleaning agent of the present invention may be selected from bleach activators, bleach catalysts, corrosion inhibitors, metal ion sequestering agents other than chelating agents (A), enzymes, fragrances, dyes, defoamers, and builders.

[0116] Particularly advantageous detergents of the present invention may comprise one or more complexing agents other than MGDA or GLDA. Advantageous detergent compositions for cleaners and advantageous laundry detergent compositions may comprise one or more metal ion chelating agents other than the mixtures according to the present invention. Examples of metal ion chelating agents other than the mixtures according to the present invention include citrates, phosphonic acid derivatives, for example, disodium salt of hydroxyethane-1,1-diphosphonic acid ("HEDP"), and polymers having complexing groups, for example, 20 to 90 mol% of N atoms being at least one CH2COO - These include polyethyleneimines having a group, and their respective alkali metal salts, particularly their sodium salts, such as IDS-Na4 and trisodium citrate, and phosphates, such as STPP (sodium tripolyphosphate). Due to the fact that phosphates cause environmental problems, it is preferable that the detergents of the present invention are phosphate-free. In relation to the present invention, "phosphate-free" should be understood to mean that the phosphate and polyphosphate content is determined by gravimetric methods and is in the range of 10 ppm to 0.2% by weight in total, based on the corresponding detergent of the present invention.

[0117] The detergent of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

[0118] Preferred nonionic surfactants include alkoxylated alcohols, diblock copolymers and multiblock copolymers of ethylene oxide and propylene oxide, reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers, and amine oxides.

[0119] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols include, for example, general formula (I): [ka] (In the formula, the variables are defined as follows: R1 These are identical or different, hydrogen, and linear C1-C 10 Selected from alkyl groups, preferably the same in each case and being ethyl, and particularly preferably hydrogen or methyl, R 2 C8-C 22 - Alkyl, branched or linear, e.g., n-C8H 17 nC 10 H 21 nC 12 H 25 nC 14 H 29 nC 16 H 33 or nC 18 H 37 Selected from, R 3 C1-C 10 -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 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. It is a compound of [formula]. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0120] In one embodiment, the compound of general formula (I) may be a block copolymer or a random copolymer, with block copolymers being preferred.

[0121] Other preferred examples of alkoxylated alcohols include, for example, general formula (II): [ka] (In the formula, the variables are defined as follows: R 1These are the same or different, selected from hydrogen and linear C1-C0-alkyl, preferably the same and ethyl in each case, and particularly preferably hydrogen or methyl. R 4 C6-C 20 Alkyl, branched, or linear, especially n-C8H 17 nC 10 H 21 nC 12 H 25 nC 14 H 29 nC 16 H 33 nC 18 H 37 Selected from, a is a number in the range of 0 to 10, preferably 1 to 6. b is a number in the range of 1 to 80, preferably 4 to 20. (d is a number in the range of 0 to 50, preferably 4 to 25.) It is a compound of [the compound].

[0122] The sum of a + b + d is preferably in the range of 5 to 100, and more preferably in the range of 9 to 50.

[0123] A preferred example of a hydroxyalkyl mixed ether is general formula (III): [ka] (In the formula, the variables are defined as follows: R 1 These are identical or different, hydrogen, and linear C1-C 10 - Selected from alkyl groups, preferably the same in each case and being ethyl, and particularly preferably hydrogen or methyl, R 2 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 21nC 12 H 25 nC 14 H 29 nC 16 H 33 , or nC 18 H 37 Selected from, R 3 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) It is a compound of [the compound].

[0124] The variables m and n are in the range of 0 to 300, and the sum of m and n 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.

[0125] Compounds of general formulas (II) and (III) may be block copolymers or random copolymers, with block copolymers being preferred.

[0126] Further suitable nonionic surfactants are selected from diblock copolymers 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, in particular linear C4-C 16 -Alkyl polyglucoside and branched C8-C 14 -Alkyl polyglycosides, such as compounds of average general formula (IV), are also suitable. [ka] (In the formula, is defined as follows: R 5 These are C1-C4 alkyl groups, particularly ethyl, n-propyl, or isopropyl groups. R 6 is -(CH2)2-R 5 And, G 1 It is selected from monosaccharides having 4 to 6 carbon atoms, particularly glucose and xylose. x is in the range of 1.1 to 4, and is the average number.

[0127] Further descriptions of suitable nonionic surfactants can be found in European Patent Application Publication A0851023 and German Patent Application Publication A19819187.

[0128] A mixture of two or more different nonionic surfactants may also exist.

[0129] Other possible surfactants are selected from amphoteric (zwitterionic) surfactants, anionic surfactants, and mixtures thereof.

[0130] An example of an amphoteric surfactant is one that has both positive and negative charges in the same molecule under the conditions of use. A preferred example of an amphoteric surfactant is the so-called betaine surfactant. Many examples of betaine surfactants have one quaternary nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0131] An example of an amine oxide surfactant is the general formula (V) R 7 R 8 R 9 N→O (V) (In the formula, R 7 , R 8 and R 9 These are, independently of each other, aliphatic, alicyclic, or C2-C4-alkylene C 10 -C 20 (Selected from alkylamide moieties) is a compound. Preferably, R 7 is selected from C8-C 20 -alkyl or C2-C4-alkylene C 10 -C 20 -alkylamide, and R 8 and R 9 are both methyl.

[0132] A particularly preferred example is lauryldimethylamine oxide, which is sometimes also referred to as lauramine oxide. A further particularly preferred example is cocamidopropyl dimethylamine oxide, which is sometimes also referred to as cocamidopropylamine oxide.

[0133] Examples of suitable anionic surfactants are alkali metal salts and ammonium salts of C8-C 18 -alkyl sulfates, C8-C 18 -fatty alcohol polyether sulfates, sulfuric half-esters of ethoxylated C4-C 12 -alkylphenols (degree of ethoxylation: 1 to 50 mol of ethylene oxide per mol), C 12 -C 18 sulfo fatty acid alkyl esters, for example C 12 -C 18 sulfo fatty acid methyl esters, and further alkali metal salts and ammonium salts of C 12 -C 18 -alkyl sulfonic acids and C 10 -C 18 -alkylaryl sulfonic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0134] Further examples of suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearic acid, oleic acid, palmitic acid, ether carboxylates, and alkyl ether phosphates.

[0135] In one embodiment of the present invention, the detergent of the present invention, which is determined to be 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.

[0136] In one embodiment of the present invention, the cleaning agent of the present invention, which is determined to be used for cleaning hard surfaces, may contain 0.1 to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants, and amine oxide surfactants.

[0137] The detergent of the present invention may contain one or more bleaching catalysts. The bleaching catalyst can be selected from transition metal salts that promote bleaching, or transition metal complexes such as manganese-, iron-, cobalt-, ruthenium-, or molybdenum-salen complexes or carbonyl complexes. Complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium, and copper with a nitrogen-containing tripod ligand, as well as cobalt-, iron-, copper-, and ruthenium-amine complexes, can also be used as bleaching catalysts.

[0138] The detergent of the present invention may contain one or more bleaching activators, such as N-methylmorpholinium-acetonitrile salt ("MMA salt"), trimethylammonium acetonitrile salts, such as N-anonoylsuccinimide and other N-acylimides, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT"), or nitrile quat (trimethylammonium acetonitrile salt).

[0139] Further examples of suitable bleaching agents include tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0140] The cleaning agent of the present invention may contain one or more corrosion inhibitors, which are understood to include compounds that inhibit metal corrosion. Examples of suitable corrosion inhibitors are triazoles, particularly benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, or pyrogallol.

[0141] In one embodiment of the present invention, the cleaning agent of the present invention contains a total of 0.1 to 1.5% by weight of a corrosion inhibitor.

[0142] The detergent of the present invention may comprise one or more builders selected from organic and inorganic builders. Suitable examples of inorganic builders include sodium sulfate or sodium carbonate or sodium silicate, particularly sodium disilicate and sodium metasilicate, zeolites, layered silicates, especially those of 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, diacetate tartrate, monoacetate tartrate, oxidized starch, and polymer builders, such as polycarboxylates and polyaspartic acid.

[0143] Examples of organic builders are polymers and copolymers in particular. 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 completely neutralized with alkali.

[0144] Suitable comonomers for (meth) are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid, and citraconic acid. Suitable polymers are particularly those with an average molecular weight M in the range of 2,000 to 40,000 g / mol, preferably 3,000 to 10,000 g / mol. w It is a polyacrylic acid that preferably has the following properties.

[0145] Monoethylenically unsaturated C3-C 10 -Mono- or C4-C 10 It 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, and at least one hydrophilic or hydrophobic monomer as listed below.

[0146] Suitable hydrophobic monomers include, 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-olefin, C 20 -C 24 It is a mixture of -α-olefin and polyisobutene, which has an average of 12 to 100 carbon atoms per molecule.

[0147] Suitable hydrophilic monomers include monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxyl functionality or alkylene oxide 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 especially 10 to 30 alkylene oxide units per molecule.

[0148] Particularly preferred sulfonic acid group-containing monomers in this case are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of the aforementioned acids, such as sodium, potassium, or ammonium salts thereof.

[0149] Particularly preferred phosphate-containing monomers are vinylphosphonic acid and its salts.

[0150] Furthermore, amphoteric polymers can also be used as builders.

[0151] The cleaning agent of the present invention may contain, for example, a builder in the range of 10 to 50% by weight in total, preferably up to 20% by weight.

[0152] In one embodiment of the present invention, the cleaning agent according to the present invention may include one or more cobuilders.

[0153] The cleaning agent of the present invention may include one or more defoaming agents selected from, for example, silicone oil and paraffin oil.

[0154] In one embodiment of the present invention, the cleaning agent of the present invention contains a total amount of an antifoaming agent in the range of 0.05 to 0.5% by weight.

[0155] The cleaning agent of the present invention may contain one or more enzymes. Examples of enzymes include lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase, and peroxidase.

[0156] In one embodiment of the present invention, the detergent of the present invention may contain, for example, up to 5% by weight of an enzyme, preferably 0.1 to 3% by weight. The aforementioned enzyme may be, for example, at least one C1-C3-carboxylic acid or C4-C 10 -The dicarboxylic acid can be stabilized with a sodium salt. Formate, acetate, adipinate, and succinate are preferred.

[0157] In one embodiment of the present invention, the detergent 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 connection therewith, in relation to the present invention, water-insoluble is used to refer to a zinc salt having a solubility of 0.1 g / l or less in distilled water at 25°C. Therefore, a zinc salt with higher solubility in water is referred to as a water-soluble zinc salt in relation to the present invention.

[0158] 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.

[0159] In another embodiment of the present invention, the zinc salt is selected from ZnO, an aqueous solution of ZnO, Zn(OH)2, and ZnCO3. An aqueous solution of ZnO is preferred.

[0160] 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.

[0161] The cations in the zinc salt can exist in complexed forms, for example, with an ammonia ligand or a water ligand, and can particularly exist in a hydrated form. For the sake of simplicity, in relation to this invention, the ligand is generally omitted when it is a water ligand.

[0162] Depending on how the pH value of the mixture according to the present invention is adjusted, the zinc salt may change. For example, zinc acetate or ZnCl2 can be used to prepare the formulation according to the present invention, which converts to ZnO, Zn(OH)2, or aqueous ZnO in an aqueous environment at a pH of 8 or 9, and these may exist in uncomplexed or complexed forms.

[0163] Zinc salts may be present in the cleaning agent of the present invention, which is solid at room temperature. In such a cleaning agent of the present invention, zinc salts preferably exist in the form of particles having an average diameter (number mean) in the range of, for example, 10 nm to 100 μm, preferably 100 nm to 5 μm, as determined by, for example, X-ray scattering.

[0164] The zinc salt may be present in the detergent of the present invention, which is liquid at room temperature. In such a detergent of the present invention, the zinc salt preferably exists in a dissolved form, a solid form, or a colloidal form.

[0165] In one embodiment of the present invention, the detergent of the present invention contains, in each case, a total of 0.05 to 0.4% by weight of zinc salts based on the solid content of the detergent.

[0166] Here, the proportion of zinc salts is given as zinc or zinc ions. From this, it is possible to calculate the proportion of counterions.

[0167] In one embodiment of the present invention, the detergent of the present invention does not contain heavy metals other than zinc compounds. In relation to the present invention, this may be understood to mean that the detergent of the present invention does not contain heavy metal compounds that do not act as bleaching catalysts, particularly iron and bismuth compounds. In relation to the present invention, with respect to heavy metal compounds, "does not contain" is understood to mean that the content of heavy metal compounds that do not act as bleaching catalysts is determined by leaching and is in the range of 0 to 100 ppm in total, based on the solid content. Preferably, the detergent of the present invention has a heavy metal content of less than 0.05 ppm based on the solid content of the formulation, with the exception of zinc. Therefore, the proportion of zinc is not included.

[0168] In relation to the present invention, "heavy metals" refers to metals other than zinc with a specific gravity of at least 6 g / cm³. 3 All metals are considered to be metals. In particular, heavy metals include bismuth, iron, copper, lead, tin, nickel, cadmium, and chromium.

[0169] Preferably, the detergent of the present invention does not contain, for example, a measurable proportion of bismuth compounds less than 1 ppm.

[0170] The cleaning agent of the present invention is excellent at cleaning hard surfaces and fibers.

[0171] Some aspects of the present invention are illustrated by the following non-limiting embodiments. [Examples]

[0172] In the first row of orientation experiments using a central mixer (Eirich) and a plowshare mixer (Loedige), water was added to an aqueous composition containing a specific amount of foam-generating surfactant (in addition to water), which, at 0.1 g / l, 25°C, and atmospheric pressure, generated at least 100 ml of foam after immersion in water for 10 minutes, as measured according to EN 14371:20004. Although not bound by theory, due to the prolonged exposure of MGDA-containing particles in a humid environment, it appears that the surfaces of larger particles become smoother, and finer particles are incorporated into the larger particles, which are clearly incorporated into the structure / morphology of the larger particles (see Figures 1 and 2). These effects resulted in the desired monodispersity and the desired increased particle density of the granules containing MGDA and polymers. No deposits were observed on the mixer walls or mixer tools.

[0173] In the second column of the experiment, specific combinations of water with either (i) anionic or (ii) nonionic surfactants were tested. In each case, a high bulk density of the resulting granules was detected.

[0174] 2000 g of MGDA granules, obtained by spray granulation of an MGDA-containing solution or slurry in a fluidized bed, were introduced into a plowshare mixer (Loedige mixer). Then, 100 g of a 1% by weight surfactant solution (see Table 1) was gradually sprayed into the mixer through a foam-generating nozzle over 3 minutes. The mixer was operated at a rotational speed of 300 rpm. Mixing was continued at the same rotational speed for a further 7 minutes.

[0175] The product was removed from the container and its bulk density was measured according to a method known to those skilled in the art. (See, for example, ScienceDirect, “Particle, Powder, and Compact Characterization,” GE Amidon et al. in “Developing Solid Oral Dosage Forms,” 2nd ed., 2017.)

[0176] [Table 1]

[0177] Experiments demonstrate that the process of the present invention, using an aqueous composition containing at least one surfactant, results in a significantly improved (i.e., increased) bulk density of the resulting granules.

[0178] drawing The figures show particles obtained from the process of the present invention (Figure 2) and particles obtained from a comparative process (without using the aqueous surfactant composition of the present invention), including undesirable fine particles (Figure 1), the comparative process lacking process step (c) described in claim 1 below, i.e., the granules are not treated with the surfactant composition. Figure 3 schematically shows a mixer having a foam generator, and Figure 4 is a (diagrammatic) depiction of a foam nozzle.

Claims

1. (A) at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), and / or at least one polymer (PA), and optionally, (B) A graft copolymer comprising (i) a polyaspartate having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol, determined by gel permeation chromatography (GPC) based on the respective free acids, (ii) a homo- or copolymer of (meth)acrylic acid partially or completely neutralized with alkali, (iii) at least one graft substrate selected from nonionic mono-, di-, oligo- and polysaccharides, and a polymer P that can be obtained by grafting an ethylenically unsaturated monomer M onto the graft substrate, wherein the monomer M is at least one homo- or copolymer (PB) selected from a list of graft copolymers comprising at least one monomer b1 selected from monoethylenically unsaturated mono- and dicarboxylic acids, and at least one monomer b2 selected from ethylenically unsaturated monomers having a permanent cationic charge. A method for producing high bulk density granules containing, The aforementioned method, (a) A step of providing an aqueous solution or slurry containing a chelating agent (A) and / or a polymer (PA), and, where applicable, a (co) polymer (B), (b) A step of removing most of the water in a fluidized bed by spray granulation to obtain granules, (c) A step of treating the granules obtained from step (b) with air or an inert gas in a container in which at least a portion rotates about a horizontal or vertical axis, wherein the container is selected from a high-speed mixer, a paddle mixer, a plow shear mixer, a free-fall mixer, a mixer having an additional chopper unit to enhance mixing and mixing, the container further comprises an aqueous composition (AC) comprising at least one surfactant (S), the surfactant (S) preferably generating at least 100 ml of foam when measured according to EN 14371:2004 after circulation in desalted water for 10 minutes at 0.1 g / l, 25°C, and atmospheric pressure, the surfactant (S) preferably being selected from a list consisting of a nonionic surfactant (S1), anionic surfactant (S2), amphoteric surfactant (S3) and mixtures thereof, the aqueous composition preferably being introduced through a foam-generating nozzle. Methods that include...

2. The method according to claim 1, wherein the nonionic surfactant (S1) is selected from alkyl polyglycosides (APG), alkoxylates, and mixtures thereof.

3. The method according to claim 1 or 2, wherein the anionic surfactant (S2) is selected from sodium lauryl sulfate (SLS), sodium laureth sulfate having 1 to 5 EO units, and mixtures thereof.

4. The method according to any one of claims 1 to 3, wherein the amphoteric surfactant (S3) is selected from acylamidopropyl betaine, preferably cocamidopropyl betaine.

5. The method according to any one of claims 1 to 4, wherein the aqueous composition (AC) contains 0.01 to 10.00% by weight of surfactant S, preferably 0.10 to 3.00% by weight of surfactant S.

6. The method according to any one of claims 1 to 5, wherein, after most of the water has been removed in step (b), 1 to 20% by weight of an aqueous composition (AC), preferably 2 to 10% by weight of an aqueous composition (AC) based on the total weight of the aqueous solution or slurry containing a chelating agent (A) and / or polymer (PA), and, if applicable, a (co)polymer (B), the aqueous composition is introduced into the container, preferably through a foam-generating nozzle.

7. The method according to any one of claims 1 to 6, wherein the polymer (PA) is a graft copolymer that can be obtained by grafting polymer P onto the graft substrate a polymer that is (i) a polyaspartate having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol based on each of the free acids, determined by gel permeation chromatography (GPC), (ii) a homo- or copolymer of (meth)acrylic acid partially or completely neutralized with alkali, (iii) at least one graft substrate selected from nonionic mono-, di-, oligo- and polysaccharides, and an ethylenically unsaturated monomer M, wherein the monomer M is selected from a list of graft copolymers comprising at least one monomer c1 selected from monoethylenically unsaturated mono- and dicarboxylic acids, and at least one monomer c2 selected from ethylenically unsaturated monomers having a permanent cationic charge.

8. The method according to any one of claims 1 to 7, wherein the granules comprise at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), and optionally at least one homo- or copolymer (PB), but without polymer (PA).

9. The method according to any one of claims 1 to 8, wherein step (c) is performed in a temperature range of -10°C to 200°C, preferably 0°C to 100°C and / or in a pressure range in the container of 0 bar (vacuum) to 100 bar, preferably 0.1 bar to 10 bar, and / or in step (c) the liquid passes through the nozzle in a pressure range of 0.1 bar to 100 bar, preferably in a pressure range of 1 bar to 10 bar.

10. The method according to any one of claims 1 to 9, wherein step (c) is carried out such that the mass ratio of the liquid to the gas passing through the nozzle is in the range of 0.001 kilograms of liquid per kilogram of gas and 1,000 kilograms of liquid per kilogram of gas, preferably in the range of 0.1 kilograms of liquid per kilogram of gas and 10 kilograms of liquid per kilogram of gas.

11. The method according to any one of claims 1 to 10, wherein step (c) is carried out such that no gas passes through the nozzle and only the liquid passes through the nozzle, and is carried out in a range between 0.001 kilograms of liquid per kilogram of gas phase and 1000 kilograms of liquid per kilogram of gas phase, preferably in a range between 0.1 kilograms of liquid per kilogram of gas phase and 10 kilograms of liquid per kilogram of gas phase.

12. The method according to any one of claims 1 to 11, wherein step (c) is carried out such that the amount of liquid added to the granules per hour is in the range of 0.001 grams of liquid per kilogram of solid per hour and 10 kilograms of liquid per kilogram of solid per hour, preferably in the range of 0.1 grams of liquid per kilogram of solid per hour and 100 grams of liquid per kilogram of solid per hour [kg_liquid / (kg_solid × h)].

13. The method according to any one of claims 1 to 12, wherein step (c) is performed using a mesh, and the foam is generated at the tip of the foam nozzle, and the mesh size is preferably 0.1 μm to 10 mm.

14. Step (c) is the method according to any one of claims 1 to 13, performed over a period of time from one minute to five hours.

15. Step (c) is the method according to any one of claims 1 to 14, performed in a mixer.

16. The method according to any one of claims 1 to 15, wherein step (d), which includes the removal of fine powder, is performed following step (c).

17. The use of an aqueous composition comprising at least one nonionic surfactant (S1) and / or at least one anionic surfactant (S2) for increasing the bulk density of granules obtained by a spray granulation method, which include at least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), wherein the container is selected from a high-speed mixer, a paddle mixer and a free-fall mixer.

18. At least one chelating agent selected from alkali metal salts of methylglycine diacetic acid (MGDA) and iminodisuccinic acid (IDS), and / or at least one polymer (PA), and optionally, At least one homo- or copolymer (PB) of (meth)acrylic acid with a comonomer having at least one sulfonic acid group per molecule, partially or completely neutralized with alkali, and / or, optionally, a polyaspartate having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol, as determined by gel permeation chromatography (GPC) with respect to each of the free acids, The weight ratio of chelating agent (A) to polymer (B) ranges from 2:1 to 1,000:

1. It contains granules, The granules comprise at least 75% by weight of a chelating agent (A) and / or a polymer (PA), The granules are granules in which the ratio of average width to length is in the range of 1:1 to 1:0.

75.

19. Use of granules according to claim 18, or granules obtained by the method of any one of claims 1 to 16, for producing a cleaning agent preferably for fibers or hard surfaces, wherein the cleaning agent optionally comprises at least one peroxy compound selected from percarbonates, persulfates and perborates.

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