Method for producing powder or pellet comprising at least one chelating agent

Abstract

The invention relates to a method for producing a powder or pellet comprising (A) in the range of 40% to 85% by weight of at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and their corresponding alkali metal salts; (B) at least one homopolymer or copolymer of (meth) acrylic acid (which is partially or completely neutralized by a base) in the range of 15 to 60% by weight, the percentage being the solids content of the powder or pellet.

Description

[0001] The present invention relates to a method for producing a powder or granules comprising (A) at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and the corresponding alkali metal salts thereof in a range of 40% to 85% by weight; (B) at least one homopolymer or copolymer of (meth)acrylic acid, which is partially or completely neutralized with a base, and / or polyaspartate in a range of 15% to 60% by weight, the percentages referring to the solids content of the powder or granules.

[0002] Complexing agents such as methylglycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their corresponding alkali metal salts are alkaline earth metal ions such as Ca 2+ and Mg 2+ Therefore, they are recommended and used in various applications such as laundry detergents and automatic dishwashing (ADW) formulations, in particular so-called phosphate-free laundry detergents and phosphate-free ADW formulations. For the transportation of such complexing agents, in most cases solids such as pellets or aqueous solutions are used.

[0003] Pellets and powders have the advantage of being essentially free of water. This means that in the event of transport, no water has to be transported and the cost of extra weight can be avoided.

[0004] Many industrial users prefer to use chelating agents in the form of granules or powders which contain at least one additional compound, particularly a polymer, in addition to at least one chelating agent. Some consumers also wish to incorporate a large amount of an additional compound, such as a polymer, into granules or powders containing at least one chelating agent.

[0005] Methods for providing granules or powders of chelating agents (also in combination with other compounds like polymers) have been described in the art, for example in WO 2015 / 121170 A1.

[0006] US2020 / 407544 A1 discloses a premix formulation of a water conditioner, which contains an MGDA chelating agent and a high content of "water conditioning polymer A". The document does not describe how to make the premix formulation.

[0007] In addition, US2017 / 058239 A1 describes a method for producing (solid) pellets containing MGDA and polyacrylic acid polymers by spray granulation. The method does not include a step of physically mixing the pellets containing MGDA and a relatively low content of a certain polymer with another amount of polymer. In addition, the document does not disclose pellets with a high polymer content and a method for producing the same.

[0008] However, providing a pellet or powder having a certain amount of chelating agent and a relatively high content of polymer has proven difficult, but may be desirable.

[0009] The use of large amounts of polymer in co-granulation with a complexing agent such as MGDA often leads to problems in manufacturing equipment such as pipe blockage, thereby significantly reducing cost effectiveness.

[0010] Furthermore, consumers who use chelating agent pellets or powders often complain about high levels of hygroscopicity, which can hamper the storage and use of these products.

[0011] Therefore, the object of the present invention is to provide a chelating agent preferably in the form of a powder or granules, such powder or granules having a high polymer content. In addition, the object of the present invention is to provide a chelating agent in the form of a powder or granules, such powder or granules preferably having a high polymer content and reduced hygroscopicity.

[0012] Another object is to provide a process for producing a chelating agent, preferably in the form of a powder or granules, preferably with a high polymer content, and preferably with low hygroscopicity.

[0013] Accordingly, surprisingly, the method defined in the appended claims has been found, hereinafter also referred to as "the method of the invention" or as "the method according to the invention".

[0014] The process of the invention provides a granulate or a powder, also referred to hereinafter as "granulate of the invention" or "powder of the invention", respectively. The powder of the invention and the granulate of the invention can be produced according to the process of the invention.

[0015] The inventors have found that using a two-step process overcomes the above mentioned problems and disadvantages and provides pellets or powders with a large amount of polymer, wherein a chelating agent like MGDA is co-granulated with a certain amount of polymer in a first step and then additional polymer is physically mixed in a second step.

[0016] Furthermore, it has surprisingly been found that the granules or powders produced according to the process of the invention show reduced hygroscopicity.

[0017] In the process of the present invention, the powder of the present invention is a granular material which is solid at ambient temperature and preferably has an average particle size in the range of 0.1 μm to 3500 μm, preferably 1 μm to 2000 μm. The average particle size of the powder of the present invention can be determined, for example, by laser diffraction, for example with a Malvern instrument, and refers to the volume average. The granules of the present invention are granular materials which are solid at ambient temperature and preferably have an average particle size in the range of 0.1 μm to 3500 μm, preferably 1 μm to 2000 μm. The average particle size of the granules of the present invention can be determined, for example, by optical methods or preferably by sieving methods. The sieve used can have a mesh in the range of 60 to 1,250 μm.

[0018] In one embodiment of the present invention, the powder of the present invention or the granules of the present invention have a wide particle size distribution. In another embodiment of the present invention, the powder of the present invention or the granules of the present invention have a narrow particle size distribution. If necessary, the particle size distribution can be adjusted by multiple sieving steps.

[0019] Granules and powders may contain residual moisture, which refers to water, including crystal water and adsorbed water. The amount of water may be in the range of 1% to 30% by weight, preferably 5% to 25% by weight, relative to the total solid content of the corresponding powder or granule, and may be determined by Karl Fischer titration or by drying to constant weight at 160°C with infrared light.

[0020] The powder particles of the present invention may have a regular or irregular shape. The preferred shape of the powder particles of the present invention is a spherical shape.

[0021] The granulate particles of the present invention may have a regular or irregular shape. The preferred shape of the granulate particles of the present invention is a spherical shape.

[0022] The powders and granules produced according to the method of the present invention contain

[0023] (A) at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and the corresponding alkali metal salts thereof in the range of 40% to 85% by weight,

[0024] (B) at least one homopolymer or copolymer of (meth)acrylic acid, partially or completely neutralized with a base, and / or polyaspartate, in the range of 15% to 60% by weight, the percentage being relative to the solid content of the powder or granules.

[0025] For the sake of clarity it is mentioned that if more than one polymer (B) is present, the content of polymer (B) given above refers to the sum by weight of the polymers (B).

[0026] The solids content can be determined by Karl-Fischer titration (for water content), Fe titration (for the content of chelating agent such as MGDA) and residual content calculation (for polymer content).

[0027] In the context of the present invention, the alkali metal salt of methylglycine diacetic acid is selected from the lithium salt, potassium salt and preferably the sodium salt of methylglycine diacetic acid. The methylglycine diacetic acid can be partially or preferably completely neutralized with a corresponding base. In a preferred embodiment, an average of 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.

[0028] Likewise, the alkali metal salt of glutamic acid diacetic acid is selected from the lithium salt, potassium salt, and preferably the sodium salt of glutamic acid diacetic acid. Glutamic acid diacetic acid can be partially or preferably completely neutralized with a corresponding base. In a preferred embodiment, an average of 3.5 to 4 COOH groups of MGDA are neutralized with an alkali metal, preferably sodium. In a particularly preferred embodiment, the chelating agent (A) is the tetrasodium salt of GLDA.

[0029] Likewise, the alkali metal salt of iminodisuccinic acid is selected from the lithium salt, potassium salt and preferably the sodium salt of iminodisuccinic acid. The iminodisuccinic acid can be partially or preferably completely neutralized with the corresponding base. In a preferred embodiment, an average of 3.5 to 4 COOH groups of IDS are neutralized with an alkali metal, preferably sodium. In a particularly preferred embodiment, the chelating agent (A) is the tetrasodium salt of IDS.

[0030] Preference is given to MGDA and GLDA and the corresponding alkali metal salts thereof; particular preference is given to MGDA and the corresponding alkali metal salts thereof.

[0031] MGDA and its corresponding alkali metal salts can be selected from racemic mixtures, i.e., D-isomers and L-isomers, and mixtures of D-isomers and L-isomers other than these racemic mixtures. Preferably, MGDA and its corresponding alkali metal salts are selected from racemic mixtures and mixtures containing L-isomers in the range of 55 to 85 mol-%, the balance being D-isomers. Particularly preferred are mixtures containing L-isomers in the range of 60 to 80 mol-%, the balance being D-isomers.

[0032] The distribution of the L- and D-enantiomers can be determined by measuring polarization (polarimetry) or preferably by chromatography, for example by HPLC with a chiral column, for example a chiral column with one or more cyclodextrins as stationary phase. Preferably, the ee is determined by HPLC with a fixed optically active ammonium salt, such as D-penicillamine.

[0033] GLDA and its corresponding alkali metal salts can be selected from racemic mixtures, i.e. D-isomers and L-isomers, and mixtures of D-isomers and L-isomers other than these racemic mixtures. Preferably, GLDA and its corresponding alkali metal salts are selected from mixtures containing L-isomers in the range of 75 to 99 mol-%, the balance being D-isomers. Particularly preferred are mixtures containing L-isomers in the range of 80 to 97.5 mol-%, the balance being D-isomers.

[0034] Likewise, IDS and its corresponding alkali metal salts may be in the form of pure isomers, or preferably a mixture of isomers including the meso form.

[0035] In any case, small amounts of the chelating agent (A) may carry cations other than alkali metals. Thus, it is possible that small amounts, such as 0.01 to 5 mol-%, based on the total chelating agent (A), carry alkaline earth metal cations such as Mg 2+ or Ca 2+ , or Fe 2+ or Fe 3+ cation.

[0036] In one embodiment of the present invention, the chelating agent (A) may contain one or more impurities, which may be produced by the production of the corresponding chelating agent. In the case of MGDA and its alkali metal salts, such impurities can be selected from alkali metal propionates, lactic acid, alanine, etc. Such impurities are usually present in a small amount. In this context, "a small amount" refers to a total of 0.1% to 1% by weight relative to the chelating agent (A). In the context of the present invention, when determining the composition of the powder of the present invention or the granules of the present invention, respectively, such a small amount is ignored.

[0037] In one embodiment of the present invention, the chelating agent as a starting material of the method of the present invention has a white or light yellow appearance.

[0038] The polymer (B) is selected from homopolymers (B) of (meth)acrylic acid, preferably acrylic acid, and copolymers (B) of (meth)acrylic acid, preferably acrylic acid, which are partially or completely neutralized with a base, and / or polyaspartates. In the context of the present invention, copolymers (B) are those in which at least 50 mol-%, preferably at least 75 mol-%, even more preferably 80 to 99 mol-% of the comonomers are (meth)acrylic acid.

[0039] Suitable comonomers of the copolymer (B) are ethylenically unsaturated compounds, such as styrene, isobutylene, ethylene, α-olefins such as propylene, 1-butene, 1-hexene, and ethylenically unsaturated dicarboxylic acids and their alkali metal salts and anhydrides, such as, but not limited to, maleic acid, fumaric acid, itaconic acid, disodium maleate, disodium fumarate, itaconic anhydride, and especially maleic anhydride. Further examples of suitable comonomers are C1-C4-alkyl esters of (meth)acrylic acid, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate.

[0040] In one embodiment of the present invention, polymer (B) is 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 can be incorporated into polymer (B) as a free acid or at least partially neutralized by a base. Particularly preferred comonomers containing sulfonic acid groups 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 the salts of the acids, such as the sodium, potassium or ammonium salts thereof.

[0041] The copolymer (B) may be selected from random copolymers, alternating copolymers, block copolymers and graft copolymers, alternating copolymers and especially random copolymers being preferred.

[0042] Useful copolymers (B) are, for example, random copolymers of acrylic acid and methacrylic acid, random copolymers of acrylic acid and maleic anhydride, terpolymers of acrylic acid, methacrylic acid and maleic anhydride, random or block copolymers of acrylic acid and styrene, random copolymers of acrylic acid and methyl acrylate. More preferred are homopolymers of methacrylic acid. Even more preferred are homopolymers of acrylic acid.

[0043] Polymer (B) may constitute a linear or branched molecule. In this context, branching will occur when at least one repeat unit of such polymer (B) is not part of the main chain but forms a branch or part of a branch. Preferably, polymer (B) is not cross-linked.

[0044] In one embodiment of the present invention, polymer (B) has an average molecular weight M determined by gel permeation chromatography (GPC) and in the range of 1,200 to 30,000 g / mol, preferably 5,000 to 25,000 g / mol relative to the corresponding free acid. w .

[0045] In another embodiment of the present invention, polymer (B) has an average molecular weight M determined by gel permeation chromatography (GPC) and is in the range of 2,500 to 15,000 g / mol, and preferably 3,000 to 10,000 g / mol relative to the corresponding free acid. w .

[0046] In one embodiment of the present invention, polymer (B) is at least partially neutralized by a base, such as lithium or potassium or sodium or a combination of at least two of the foregoing, especially sodium. For example, 10 to 100 mol-% of the carboxyl groups in polymer (B) may be neutralized by a base, especially sodium.

[0047] In one embodiment of the present invention, polymer (B) is selected from the persodium salt of polyacrylic acid, thus polyacrylic acid completely neutralized with sodium.

[0048] In one embodiment of the present invention, polymer (B) is selected from the combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer carrying at least one sulfonic acid group per molecule, both polymers being completely neutralized with a base.

[0049] In one embodiment of the present invention, polymer (B) is selected from the full sodium salt of polyacrylic acid having an average molecular weight M determined by gel permeation chromatography (GPC) and ranging from 1,200 to 30,000 g / mol, preferably from 2,500 to 15,000 g / mol and even more preferably from 3,000 to 10,000 g / mol relative to the corresponding free acid. w .

[0050] As mentioned above, polymer (B) may be selected from polyaspartates, preferably having an average molecular weight Mw in the range of 1,000 to 20,000 g / mol.

[0051] Polyaspartic acid is a well-known biodegradable dispersing and scale-inhibiting polymer. Three main processes have been developed for the industrial production of polyaspartic acid and its sodium salt:

[0052] (1) Thermal polycondensation of aspartic acid followed by alkaline hydrolysis of the intermediate polysuccinimide;

[0053] (2) thermal polycondensation 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 polysuccinimide;

[0054] (3) Polymerization of maleic anhydride in the presence of ammonia or an ammonium salt, followed by alkaline hydrolysis of the intermediate polysuccinimide.

[0055] Regardless of the synthetic route, the intermediate polysuccinimide must be hydrolyzed by, for example, sodium hydroxide to obtain a polyaspartate solution. The polyaspartate solution is acidified with an inorganic acid (such as hydrochloric acid or sulfuric acid) to obtain polyaspartic acid.

[0056] The modified polyaspartic acid which can be used according to the invention can be prepared by polycondensation of:

[0057] (i) 50 to 99 mol %, preferably 60 to 95 mol %, particularly preferably 80 to 95 mol % of aspartic acid; and

[0058] (ii) 1 to 50 mol %, preferably 5 to 40 mol %, particularly preferably 5 to 20 mol % of at least one carboxyl group-containing compound,

[0059] and subsequently hydrolyzing the cocondensate by adding a base (eg sodium hydroxide solution), wherein (ii) is not aspartic acid.

[0060] The carboxyl-containing compounds (ii) used in connection with the preparation of the polyaspartic acid to be used according to the invention may in particular be carboxylic acids (monocarboxylic acids or polycarboxylic acids), hydroxycarboxylic acids and / or amino acids (other than aspartic acid). Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. In this connection, polybasic carboxylic acids may be used for the preparation of the polyaspartic acid to be used according to the 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 26 Alkyl succinic acid (e.g. octyl succinic acid), C2-C 26Alkenyl 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. In addition, polyhydroxycarboxylic acids, such as citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid or malic acid, can also be used in this context. In this connection, amino acids that can be used are, in particular, aminocarboxylic acids (for example glutamic acid, cysteine), basic diaminocarboxylic acids (for example lysine, arginine, histidine, aminocaprolactam), neutral amino acids (for example glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (for example taurine), hydroxyamino acids (for example hydroxyproline, serine, threonine), iminocarboxylic acids (for example proline, iminodiacetic acid) or aromatic and heterocyclic amino acids (for example anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid. Preferred carboxyl-containing compounds (ii) in connection with the preparation of the modified polyaspartic acid used according to the invention are 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine, glutamic acid, itaconic acid, succinic acid, taurine, maleic acid and glutaric acid, particularly preferably 1,2,3,4-butanetetracarboxylic acid, citric acid, glycine and glutamic acid.

[0061] The molecular weight (Mw) of (modified) polyaspartic acid can be easily adjusted by varying the reaction conditions. Molecular weights between 1000 g / mol and 100 000 g / mol can be achieved by simple adjustment of the process parameters (temperature, catalyst, reaction time).

[0062] The preferred molecular weight of the (modified) polyaspartic acid used according to the invention is in the range between 1000 and 20 000 g / mol, preferably between 1500 and 15 000 g / mol and particularly preferably between 2000 and 10 000 g / mol.

[0063] The aspartic acid (i) used in connection with the preparation of the (modified) polyaspartic acid used according to the invention may be L-aspartic acid or D-aspartic acid and DL-aspartic acid. Preference is given to using L-aspartic acid.

[0064] The method of the present invention comprises two initial steps,

[0065] (a) mixing at least one chelating agent (A) and at least one homopolymer or copolymer (B) in the presence of water,

[0066] (b) removing a substantial portion of said water by spray drying or spray granulation,

[0067] Also referred to as step (a) and step (b) hereinafter. Typically, step (b) is performed after step (a).

[0068] Step (a) and step (b) will be described in more detail below.

[0069] The mixing of chelating agent (A) and polymer (B) is usually carried out in the presence of water. The mixing can be carried out in a manner that the aqueous solution of polymer (B) and the aqueous solution of chelating agent (A) are combined in a container (preferably under stirring). The aqueous solution of polymer (B) and solid chelating agent (A) can also be combined, or the aqueous solution of chelating agent (A) and solid polymer (B) are combined, or the aqueous slurry of chelating agent (A) and polymer (B) are combined. In an alternative embodiment, water is provided and polymer (B) is subsequently added and then chelating agent (A) is added. In a preferred embodiment, a solution of chelating agent (A) having a temperature of 35°C to 50°C is provided, and polymer (B) is added in the form of a body or solution.

[0070] Step (a) may be performed at ambient temperature. In other embodiments, step (a) is performed at 20°C or at elevated temperature, for example at a temperature in the range of 25°C to 90°C, preferably 60°C to 75°C.

[0071] The water used in step (a) may be present in an amount such that both the chelating agent (A) and the polymer (B) are dissolved. However, a smaller amount of water may be used and the chelating agent (A) and the polymer (B) may be mixed in a slurry. A solution or slurry may be used.

[0072] In one embodiment of the present invention, the total solids content of such solution or slurry formed by step (a) is in the range of 20% to 75%, preferably 35% to 50%.

[0073] In one embodiment of the present invention, such solution or slurry has a pH value in the range of 2.5 to 13, preferably 8 to 13, and even more preferably at least 9.

[0074] Mixing can be performed with mechanical support such as shaking or stirring.

[0075] In step (b), spray drying or spray granulation is carried out, preferably using a gas with an inlet temperature of at least 125° C. The gas (hereinafter also referred to as "hot gas") can be nitrogen, a noble gas or preferably air. During step (b), most of the water used in step (a), for example at least 55%, preferably at least 65%, will be removed. In one embodiment of the invention, up to 99% of the water will be removed.

[0076] Spray drying and spray granulation will be described in more detail below.

[0077] In one embodiment of the present invention, a drying vessel, such as a spray chamber or a spray tower, is used in which the spray granulation process is carried out by using a fluidized bed. Such a drying vessel is equipped with a fluidized bed of a solid mixture of a chelating agent (A) and a polymer (B) obtained by any drying method such as spray drying or evaporative crystallization, and a solution or slurry of a solid mixture of a chelating agent (A) and a polymer (B) is sprayed onto or into this fluidized bed together with a hot gas stream. The hot gas inlet stream may have a temperature in the range of 125°C to 350°C, preferably 160°C to 220°C.

[0078] In one embodiment of the invention, the fluidized bed may have a temperature in the range of 80°C to 150°C, preferably 100°C to 120°C.

[0079] Each drying container is sprayed by one or more nozzles. Suitable nozzles are, for example, high-pressure drum atomizers, rotary atomizers, single-fluid nozzles and two-fluid nozzles, preferably two-fluid nozzles and rotary atomizers. The first fluid is the solution or slurry obtained according to step (a), and the second fluid is a compressed gas, for example a compressed gas at a pressure of 1.1 to 7 bar.

[0080] 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, even more preferably 30 to 100 μm.

[0081] In one embodiment of the invention, the off-gas leaving the drying vessel may have a temperature in the range of 40° C. to 140° C., preferably 80° C. to 110° C., but in any case cooler than the hot gas stream. Preferably, the temperature of the off-gas leaving the drying vessel is the same as the temperature of the solid product present in the drying vessel.

[0082] In another embodiment of the invention, the spray granulation is carried out by carrying out two or more consecutive spray drying processes, for example in a cascade of at least two spray dryers, for example in a cascade of at least two consecutive spray towers or a combination of a spray tower and a spray chamber, the spray chamber containing a fluidized bed. In the first dryer, the spray drying process is carried out in the following manner.

[0083] Spray drying may be preferred in a spray dryer, such as a spray chamber or a spray tower. The solution or slurry obtained according to step (a) at a temperature preferably above ambient temperature, for example in the range of 50°C to 95°C, is introduced into the spray dryer through one or more spray nozzles into a hot gas inlet stream (for example nitrogen or air), the solution or slurry is converted into droplets and the water is vaporized. The hot gas inlet stream may have a temperature in the range of 125°C to 350°C.

[0084] The second spray dryer is equipped with a fluidized bed with solids from the first spray dryer, and the solution or slurry obtained according to the above steps is sprayed on or in the fluidized bed together with a hot gas inlet stream. The hot gas inlet stream may have a temperature in the range of 125°C to 350°C, preferably 160°C to 220°C.

[0085] In one embodiment of the present invention, in particular in the process for producing the pellets of the present invention, the average residence time of the chelating agent (A) and the polymer (B) in step (b) is respectively in the range of 2 minutes to 4 hours, preferably 30 minutes to 2 hours.

[0086] In another embodiment, in particular in the process for making the powder of the present invention, the average residence time of the chelating agent (A) and the polymer (B) in step (b) is in the range of 1 second to 1 minute, in particular 2 to 20 seconds.

[0087] In one embodiment of the present invention, the pressure in the drying container in step (b) is atmospheric pressure ±100 mbar, preferably atmospheric pressure ±20 mbar, for example 1 mbar lower than atmospheric pressure.

[0088] In one embodiment of the invention, one or more additives may be added to the solution obtained according to step (a) before carrying out step (b), or one or more of such additives (C) may be added at any stage during step (a). Examples of useful additives (C) are, for example, titanium dioxide, sugars, silica gel and polyvinyl alcohol. Polyvinyl alcohol in the context of the present invention refers to fully or partially hydrolyzed polyvinyl acetate. In partially hydrolyzed polyvinyl acetate, at least 95 mol-%, preferably at least 96 mol-%, of the acetate groups have been hydrolyzed.

[0089] In one embodiment of the present invention, the polyvinyl alcohol has an average molecular weight M in the range of 22,500 to 115,000 g / mol, for example up to 40,000 g / mol. w .

[0090] In one embodiment of the present invention, the polyvinyl alcohol has an average molecular weight M in the range of 2,000 to 40,000 g / mol. n .

[0091] The amount of the additive (C) may be 0.1 to 5% by weight relative to the total of the chelating agent (A) and the polymer (B).

[0092] Preferably, no additive (C) is used in step (b).

[0093] One or more further steps (c) may be carried out at any stage of the process of the invention, preferably after step (b). Thus a sieving step (c) may be carried out to remove lumps from the powder or granules. Optionally, the composition obtained from step (d) is purified.

[0094] Furthermore, a post-drying step (c) is possible. Air classification may be performed during or after step (b) to remove fines.

[0095] Fines, especially those with a diameter of less than 50 μm, can impair the flow behavior of the powder or granules obtained according to the process of the invention. However, amorphous or preferably crystalline fines can be returned to the spray container as seeds for crystallization. Agglomerates can be removed and redissolved in water or ground and used as seeds for crystallization in the spray container.

[0096] The method of the present invention comprises step (d) after steps (a), (b) and optionally (c).

[0097] this Step (d) comprising combining the composition obtained from step (b) or step (c) with additionally in the range of 1% to 50% by weight of at least one homopolymer or copolymer of (meth)acrylic acid, which is partially or completely neutralized with a base physics mix .

[0098] Furthermore, the method of the present invention may comprise a further step (e) comprising physically mixing the composition obtained from step (b), (c) or (d) with at least one organic acid having a molecular weight not exceeding 500 g / mol, preferably citric acid.

[0099] The percentages given above are relative to the solids content of the powder or pellets.

[0100] The physical mixing in step (d) and or step (e) may be carried out by any type of physical mixing, preferably in a ploughshare mixer or a free fall mixer, and / or preferably at a temperature of 10°C to 190°C, more preferably 20°C to 90°C, and / or preferably at a speed of 30 to 120 rpm, more preferably 40 to 80 rpm, and / or preferably with a Froude number of 0.1 to 10, more preferably 1 to 3, and / or preferably at a charge level of 10% to 95%, more preferably 40% to 75%, and / or preferably at atmospheric pressure, and / or preferably with an average residence time of at least two minutes, more preferably 5 to 60 minutes.

[0101] The process of the present invention provides powders or granules containing a chelating agent (A) and a polymer (B) and optionally one or more additives (C). Such powders and granules exhibit generally advantageous properties, including but not limited to excellent yellowing behavior.

[0102] Another aspect of the present invention is a powder or granules optionally obtained or obtainable by the process of the present invention, the powder or granules comprising

[0103] (A) at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and the corresponding alkali metal salts thereof in the range of 40% to 85% by weight,

[0104] (B) at least one homopolymer or copolymer of (meth)acrylic acid, partially or completely neutralized with a base, and / or polyaspartate, in the range of 15% to 60% by weight, the percentage being relative to the solid content of the powder or granules.

[0105] Chelating agent (A) and polymer (B) have been defined above.

[0106] In one embodiment of the present invention, the granules or powders of the present invention are selected from granules or powders having an average particle size ranging from 0.1 μm to 3500 μm, preferably from 1 μm to 2000 μm.

[0107] In one embodiment of the present invention, the granules or powders of the present invention are selected from granules or powders having an average particle size ranging from 10 μm to 1500 μm, preferably from 50 μm to 1000 μm, more preferably from 100 to 800 μm.

[0108] In one embodiment of the present invention, the powder of the present invention or the granules of the present invention contains a chelating agent (A) in the range of 40 to 85% by weight and a homopolymer or copolymer (B) in the range of 15 to 60% by weight, the percentages being relative to the solids content of the powder or granules.

[0109] In one embodiment of the present invention, the powders of the present invention and the granules of the present invention are selected from the group consisting of the homopolymer or copolymer (B) having an average molecular weight M determined by gel permeation chromatography and in the range of 1,200 to 30,000 g / mol, preferably 5,000 to 25,000 g / mol, relative to the corresponding free acid. w Those.

[0110] In one embodiment of the present invention, the powders according to the present invention and the granules according to the present invention are selected from those in which the chelating agent (A) is selected from the trisodium salt of MGDA and the tetrasodium salt of GLDA.

[0111] In one embodiment of the present invention, the inventive powders and the inventive granules are chosen from those in which the homopolymers and copolymers (B) are chosen from the persodium salts of polyacrylic acid.

[0112] In one embodiment of the present invention, the powders of the present invention and the granules of the present invention are selected from those in which the polymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer carrying at least one sulfonic acid group per molecule. The comonomer carrying at least one sulfonic acid group per molecule can be incorporated into the polymer (B) as a free acid or at least partially neutralized with a base. Particularly preferred comonomers containing sulfonic acid groups 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 the salts of the acids, such as the sodium, potassium or ammonium salts thereof.

[0113] In one embodiment of the present invention, the powders of the present invention and the granules of the present invention are chosen from those in which the polymer (B) is chosen from the combination of at least one polyacrylic acid and at least one copolymer of (meth)acrylic acid and a comonomer carrying at least one sulfonic acid group per molecule, both polymers being completely base neutralized.

[0114] The powders of the invention and the granules of the invention exhibit generally advantageous properties, including but not limited to excellent yellowing behavior, especially in the presence of bleaching agents. Therefore, they are very suitable for the manufacture of cleaning agents containing at least one bleaching agent, such cleaning agents are also referred to as bleaching agents hereinafter. In particular, the powders of the invention and the granules of the invention are suitable for the manufacture of cleaning agents for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxy compound.

[0115] The granules according to the invention and in particular the powders according to the invention can be easily converted into compacts and agglomerates.

[0116] Therefore, another aspect of the present invention is the use of a powder according to the present invention or a granulate according to the present invention for the manufacture of a cleaning agent containing at least one bleaching agent, and in particular for the manufacture of a cleaning agent for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxy compound. Another aspect of the present invention is a method for manufacturing a cleaning agent by combining at least one powder according to the present invention or at least one granulate according to the present invention with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, also referred to as the cleaning agent according to the present invention hereinafter. The cleaning agent according to the present invention contains at least one bleaching agent and at least one powder according to the present invention or at least one granulate according to the present invention. The cleaning agent according to the present invention shows a reduced tendency to yellowing and therefore has an extended shelf life.

[0117] Examples of suitable peroxy compounds are sodium perborate (anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate), sodium percarbonate (anhydrous or, for example, as the monohydrate), hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid (in each case as the free acid or as an alkali metal salt, in particular as the sodium salt), and also sulfonylperoxyacids and cationic peroxyacids.

[0118] In a preferred embodiment, the peroxygen compound is selected from inorganic percarbonates, persulfates and perborates. An example of sodium percarbonate is 2Na2CO3·3H2O2. An example of sodium perborate is (Na2[B(OH)2(O2)]2), sometimes also written as NaBO2·O2·3H2O. The most preferred peroxygen compound is sodium percarbonate.

[0119] The term "cleaner" includes compositions for dishwashing, especially manual dishwashing and automatic dishwashing and warewashing, and compositions for hard surface cleaning, such as but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, car cleaning (including truck cleaning), further open plant cleaning, cleaning in place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, and also laundry detergent compositions.

[0120] Such detergents may be liquid, gel or preferably solid at ambient temperature, solid detergents being preferred. They may be in powder form or in unit dosage form, for example as tablets.

[0121] In one embodiment of the present invention, the cleaning agent of the present invention may contain the powder of the present invention or the granules of the present invention in the range of 2 to 50% by weight, and the bleaching agent in the range of 0.5 to 15% by weight.

[0122] The percentages are based on the solids content of the respective cleaning agents according to the invention.

[0123] The powders and / or granules according to the invention are very suitable for the production of laundry detergents or cleaning agents.

[0124] Therefore, another aspect of the present invention is the use of the powder and / or granules for the manufacture of a cleaning agent which may contain at least one bleaching agent, and in particular for the manufacture of a cleaning agent for fibers or hard surfaces, wherein the cleaning agent contains at least one peroxy compound. Another aspect of the present invention is a method for the manufacture of a cleaning agent by combining the powder and / or granules of the present invention with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, also referred to hereinafter as the cleaning agent of the present invention.

[0125] The cleaning agents according to the invention may contain at least one bleaching agent and the powders and / or granules according to the invention.The cleaning agents according to the invention exhibit a reduced tendency to yellowing and therefore have an extended shelf life.

[0126] Examples of suitable peroxy compounds are sodium perborate (anhydrous or, for example, as the monohydrate or as the tetrahydrate or so-called dihydrate), sodium percarbonate (anhydrous or, for example, as the monohydrate), hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid (in each case as the free acid or as an alkali metal salt, in particular as the sodium salt), and also sulfonylperoxyacids and cationic peroxyacids.

[0127] In a preferred embodiment, the peroxygen compound is selected from inorganic percarbonates, persulfates and perborates. An example of sodium percarbonate is 2Na2CO3·3H2O2. An example of sodium perborate is (Na2[B(OH)2(O2)]2), sometimes also written as NaBO2·O2·3H2O. The most preferred peroxygen compound is sodium percarbonate.

[0128] The term "cleaner" includes compositions for dishwashing, especially manual dishwashing and automatic dishwashing and warewashing, and compositions for hard surface cleaning, such as but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, car cleaning (including truck cleaning), further open plant cleaning, cleaning in place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, and also laundry detergent compositions.

[0129] Such detergents may be liquid, gel or preferably solid at ambient temperature, solid detergents being preferred. They may be in powder form or in unit dosage form, for example as tablets.

[0130] In one embodiment of the present invention, the cleaning agent of the present invention may contain the powder and / or granules of the present invention in the range of 2 to 50% by weight, and bleach in the range of 0.5 to 15% by weight.

[0131] The percentages are based on the solids content of the respective cleaning agents according to the invention.

[0132] The cleaning agent of the present invention may contain additional ingredients such as one or more surfactants, which may be selected from nonionic, zwitterionic, cationic and anionic surfactants. Other ingredients that may be included in the cleaning agent of the present invention may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestrants other than chelating agent (A), enzymes, perfumes, dyes, defoamers and builders.

[0133] Particularly advantageous cleaning agents according to the invention may contain one or more complexing agents in addition to MGDA or GLDA. Advantageous detergent compositions for cleaning agents and advantageous laundry detergent compositions may contain one or more sequestrants (chelants) in addition to the mixtures according to the invention. Examples of sequestrants in addition to the mixtures according to the invention are IDS (iminodisuccinates), citrates, phosphonic acid derivatives such as the disodium salt of hydroxyethane-1,1-diphosphonic acid ("HEDP"), and polymers having complexing groups such as, for example, polymers in which 20 to 90 mol-% of the N atoms carry at least one CH2COO - The invention also contains polyethyleneimines of the group, as well as the corresponding alkali metal salts thereof, in particular the sodium salts thereof (e.g. IDS-Na4 and trisodium citrate), and phosphates such as STPP (sodium tripolyphosphate). Due to the fact that phosphates cause environmental problems, it is preferred that the cleaning agents according to the invention are advantageously "phosphate-free". In the context of the present invention, "phosphate-free" is understood to mean that the sum of the contents of phosphates and polyphosphates, determined by the gravimetric method and relative to the corresponding cleaning agent according to the invention, is in the range of 10 ppm to 0.2% by weight.

[0134] The cleaning agent of the present invention may contain one or more surfactants, preferably one or more nonionic surfactants.

[0135] Preferred nonionic surfactants are alkoxylated alcohols, diblock and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APGs), hydroxyalkyl mixed ethers and amine oxides.

[0136] Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are compounds such as those having the general formula (II)

[0137]

[0138] The variables are defined as follows:

[0139] R 1 are the same or different and are selected from hydrogen and straight chain C1-C 10 - alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0140] R 2 Selected from branched or straight chain C8-C 22 -alkyl, such as n-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C 16 H 33 Or positive-C 18 H 37 ,

[0141] R 3 Selected from C1-C 10 - alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl,

[0142] 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.

[0143] In one embodiment, the compound having the general formula (II) may be a block copolymer or a random copolymer, preferably a block copolymer.

[0144] Other preferred examples of alkoxylated alcohols are compounds such as those having the general formula (III)

[0145]

[0146] The variables are defined as follows:

[0147] R 1 are identical or different and are selected from hydrogen and straight-chain C1-C0-alkyl, are preferably identical in each case and are ethyl and particularly preferably hydrogen or methyl,

[0148] R 4Selected from branched or straight chain C6-C 20 -alkyl, especially n-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C 16 H 33 , Positive-C 18 H 37 ,

[0149] a is a number in the range of 0 to 10, preferably 1 to 6,

[0150] b is a number in the range of 1 to 80, preferably 4 to 20,

[0151] d is a number in the range of 0-50, preferably 4-25.

[0152] The sum of a+b+d is preferably in the range of 5-100, even more preferably in the range of 9-50.

[0153] Preferred examples of hydroxyalkyl mixed ethers are compounds having the general formula (IV)

[0154]

[0155] The variables are defined as follows:

[0156] R 1 are the same or different and are selected from hydrogen and straight chain C1-C 10 - alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0157] R 2 Selected from branched or straight chain C8-C 22 -alkyl, such as iso-C 11 H 23 , Iso-C 13 H 27 、positive-C8H 17 , Positive-C 10 H 21 , Positive-C 12 H 25 , Positive-C 14 H 29 , Positive-C 16 H 33 Or positive-C 18 H 37 ,

[0158] R 3 Selected from C1-C 18-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isopentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

[0159] The variables m and n are in the range of 0 to 300, wherein the sum of n and m is at least 1, preferably in the range of 5 to 50. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

[0160] The compounds having the general formulae (II) and (III) may be block copolymers or random copolymers, preferably block copolymers.

[0161] Other suitable nonionic surfactants are selected from diblock and multiblock copolymers composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-C 16 -Alkyl polyglucosides and branched C8-C 14 -Alkyl polyglycosides such as compounds having the average general formula (V) are likewise suitable.

[0162]

[0163] The variables are defined as follows:

[0164] R 5 is C1-C4-alkyl, in particular ethyl, n-propyl- or isopropyl,

[0165] R 6 Yes -(CH2)2-R 5 ,

[0166] G 1 is chosen from monosaccharides having 4 to 6 carbon atoms, in particular from glucose and xylose,

[0167] y is in the range of 1.1 to 4, y is the average.

[0168] Further examples of nonionic surfactants are compounds of the general formula (VII) and (VIII)

[0169]

[0170] AO is selected from ethylene oxide, propylene oxide and butylene oxide,

[0171] EO is ethylene oxide, CH2CH2-O,

[0172] R 8 Selected from branched or straight chain C8-C 18 -alkyl, and R 5 As defined above.

[0173] A 3 O is selected from propylene oxide and butylene oxide,

[0174] w is a number in the range of 15 to 70, preferably 30 to 50,

[0175] w1 and w3 are numbers in the range of 1 to 5, and

[0176] w2 is a number in the range of 13 to 35.

[0177] An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and DE-A 198 19187.

[0178] Mixtures of two or more different nonionic surfactants may also be present.

[0179] Additional surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof.

[0180] Examples of amphoteric surfactants are those which carry a positive charge and a negative charge in the same molecule under the conditions of use. Preferred examples of amphoteric surfactants are so-called betaine surfactants. Many examples of betaine surfactants carry one quaternary nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of an amphoteric surfactant is cocamidopropyl betaine (lauramidopropyl betaine).

[0181] Examples of amine oxide surfactants are compounds having the general formula (IX)

[0182] R 7 R 8 R 9 N→O(IX)

[0183] Where R 7 , R 8 and R 9 independently selected from aliphatic, alicyclic or C2-C4-alkylene 10 -C 20 -alkylamide moiety. Preferably, R 7 Selected from C8-C 20 -alkyl or C2-C4-alkylene C 10 -C 20 -alkylamide and R 8 and R 9 They are all methyl.

[0184] A particularly preferred example is lauryl dimethylamine oxide, sometimes also referred to as lauryl amine oxide.Another particularly preferred example is cocamidopropyl dimethylamine oxide, sometimes also referred to as cocamidopropylamine oxide.

[0185] Examples of suitable anionic surfactants are C8-C 18 -Alkali metal and ammonium salts of alkyl sulfates, C8-C 18 -Alkali metal salts and ammonium salts of fatty alcohol polyether sulfates, ethoxylated C4-C 12 -Alkali metal and ammonium salts of sulfuric acid half esters of alkylphenols (ethoxylation: 1 to 50 mol of ethylene oxide / mol), C 12 -C 18 Sulfonic fatty acid alkyl esters (such as C 12 -C 18 Alkali metal salts and ammonium salts of sulfo fatty acid methyl esters), in addition C 12 -C 18 -Alkali metal and ammonium salts of alkylsulfonic acids and C 10 -C 18 - Alkali metal salts and ammonium salts of alkylarylsulfonic acids. Alkali metal salts of the above compounds are preferred, and sodium salts are particularly preferred.

[0186] 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.

[0187] Preferably, the laundry detergent composition contains at least one anionic surfactant.

[0188] In one embodiment of the present invention, the cleaning agent of the present invention intended for use as a laundry detergent composition may contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0189] In one embodiment of the present invention, the cleaning agent of the present invention intended for hard surface cleaning may contain 0.1% to 60% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0190] In a preferred embodiment, the cleaners of the present invention do not contain any anionic detergents.

[0191] Cleaning agents of the present invention may contain one or more bleaching catalysts. The bleaching catalyst may be selected from transition metal salts or transition metal complexes that promote bleaching, such as, for example, manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexes or carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod-type ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes may also be used as bleaching catalysts.

[0192] The cleaning agents of the present invention may contain one or more bleach activators, for example N-methylmorpholinium-acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as, for example, N-nonanoylsuccinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine ("DADHT") or quaternary ammonium nitrile salts (trimethylammonium acetonitrile salts).

[0193] Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexanediamine.

[0194] The cleaning agent of the invention may contain one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metals. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, and phenol derivatives, such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

[0195] In one embodiment of the present invention, the cleaner of the present invention comprises a total of 0.1% to 1.5% by weight of corrosion inhibitor.

[0196] Cleaning agents according to the invention may comprise one or more builders selected from organic and inorganic builders. Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular sodium disilicate and sodium metasilicate, zeolites, phyllosilicates, in particular those of formula α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5, also fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartrate diacetate, tartrate monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.

[0197] Examples of organic builders are in particular polymers and copolymers other than (co)polymer (B), and include polymers and copolymers other than (co)polymer (B), or a further (co)polymer (B). In one embodiment of the invention, the organic builder is selected from polycarboxylates, such as alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, which are partially or completely neutralized with a base.

[0198] Suitable comonomers of (meth)acrylic acid are monoethylenically unsaturated dicarboxylic acids, such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. Suitable polymers are in particular polyacrylic acids, which preferably have an average molecular weight M in the range of 2000 to 40 000 g / mol, preferably 2000 to 10 000 g / mol, in particular 3000 to 8000 g / mol. w Also suitable and in the same molecular weight range are copolymer polycarboxylates, in particular those of acrylic acid with methacrylic acid and those of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid.

[0199] It is also possible to use copolymers of at least one monomer selected from the group consisting of: monoethylenically unsaturated C3-C4 polyols and at least one hydrophilic or hydrophobic monomer as listed below. 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.

[0200] Suitable hydrophobic monomers are, for example, isobutylene, diisobutylene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, such as, for example, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracosene and 1-hexacosene, C 22 -α-olefins, C 20 -C 24 - mixtures of α-olefins and polyisobutylenes having an average of 12 to 100 carbon atoms per molecule.

[0201] Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl functions or alkyleneoxy groups. By way of example, mention may be made of: allyl alcohol, prenyl alcohol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate. The polyalkylene glycols here may contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkyleneoxy units per molecule.

[0202] Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide and the salts of the acids, such as the sodium, potassium or ammonium salts thereof.

[0203] Particularly preferred monomers containing phosphonate groups are vinylphosphonic acid and its salts.

[0204] A further example of a builder is carboxymethylinulin.

[0205] Furthermore, amphoteric polymers can also be used as builders.

[0206] The detergents of the invention may contain, for example, in the range of 10 to 70% by weight in total, preferably 10 to 50% by weight in total, more preferably up to 20% by weight of builder.

[0207] In one embodiment of the present invention, the inventive cleaning agent according to the present invention may comprise one or more co-builders.

[0208] The cleaning agent of the present invention may contain one or more defoaming agents selected from, for example, silicone oil and paraffin oil.

[0209] In one embodiment of the present invention, the cleaning agent of the present invention comprises a total of 0.05% to 0.5% by weight of defoaming agent.

[0210] The cleaning agents of the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

[0211] In one embodiment of the invention, the cleaning agent of the invention may contain, for example, up to 5% by weight, preferably 0.1% to 3% by weight, of an enzyme. The enzyme may, for example, be a C1-C3-carboxylic acid or a C4-C 10 - The sodium salts of dicarboxylic acids are preferred. The formates, acetates, adipates, and succinates are preferred.

[0212] In one embodiment of the present invention, the cleaning agent of the present invention may comprise at least one zinc salt. The zinc salt may be selected from water-soluble zinc salts and water-insoluble zinc salts. In this connection, in the context of the present invention, water-insoluble is used to refer to those zinc salts having a solubility of 0.1 g / l or less in distilled water at 25° C. Correspondingly, zinc salts having a higher solubility in water are referred to as water-soluble zinc salts in the context of the present invention.

[0213] 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.

[0214] In another embodiment of the present invention, the zinc salt is selected from ZnO, ZnO aqueous solution, Zn(OH)2 and ZnCO3. ZnO aqueous solution is preferred.

[0215] In one embodiment of the present invention, the zinc salt is selected from zinc oxides having an average particle size (weight average) ranging from 10 nm to 100 μm.

[0216] The cations in the zinc salt may be present in complexed form, for example with ammonia ligands or water ligands, and in particular in hydrated form. To simplify notation, within the context of the present invention, ligands are generally omitted if they are water ligands.

[0217] Depending on how the pH of the mixture according to the invention is adjusted, the zinc salt may change. Thus, for example, zinc acetate or ZnCl2 can be used for the preparation of the formulation according to the invention, but this is converted into ZnO, Zn(OH)2 or aqueous ZnO solutions at a pH of 8 or 9 in an aqueous environment, which may be present in uncomplexed or complexed form.

[0218] The zinc salt may be present in those cleaning agents according to the invention which are solid at room temperature. In such cleaning agents according to the invention, the zinc salt is preferably present in the form of particles which have, for example, an average diameter (number average) in the range of 10 nm to 100 μm, preferably 100 nm to 5 μm, as determined, for example, by X-ray scattering.

[0219] The zinc salt may be present in those cleaning agents according to the invention which are liquid at room temperature. In such cleaning agents according to the invention, the zinc salt is preferably present in dissolved or solid or colloidal form.

[0220] In one embodiment of the invention, the inventive cleaning agent comprises in total in the range from 0.05 to 0.4% by weight of zinc salt, based in each case on the dry matter content of the cleaning agent in question.

[0221] Here, the fraction of zinc salt is given as zinc or zinc ion. From this, the counterion fraction can be calculated.

[0222] In one embodiment of the present invention, the cleaning agent of the present invention is free of heavy metals other than zinc compounds. In the context of the present invention, this is understood to mean that the cleaning agent of the present invention is free of those heavy metal compounds that do not act as bleaching catalysts, in particular free of iron and bismuth compounds. In the context of the present invention, "free" in relation to heavy metal compounds is understood to mean that the content of heavy metal compounds that do not act as bleaching catalysts is in the range of 0 to 100 ppm in total, which is determined by a leaching method and is based on the dry matter content. Preferably, the cleaning agent of the present invention has a heavy metal content other than zinc of less than 0.05 ppm based on the dry matter content of the formulation in question. The zinc fraction is therefore not included.

[0223] In the context of the present invention, "heavy metals" are considered to be metals other than zinc having a specific density of at least 6 g / cm 3 Heavy metals are in particular metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

[0224] Preferably, the cleaning agents of the present invention contain unmeasurable fractions (eg, less than 1 ppm) of bismuth compounds.

[0225] The cleaning agents of the present invention are excellent for cleaning hard surfaces and fibers. For example, they can be used in dishwashing applications, preferably automatic dishwashing applications.

[0226] In one embodiment of the present invention, the cleaning agent of the present invention comprises one or more additional ingredients such as fragrances, dyes, organic solvents, buffers, disintegrants for tablets ("tabs"), and / or acids such as methanesulfonic acid.

[0227] Exemplary detergent compositions for automatic dishwashing detergents can be formulated from aqueous solutions, granules or powders of the present invention by mixing the corresponding components according to Table F below.

[0228] Table F: Exemplary Detergent Compositions for Automatic Dishwashing

[0229]

[0230]

[0231] The laundry detergent according to the invention can be used for washing any type of laundry and any type of fiber. The fibers may be of natural or synthetic origin, or they may be a natural mixture of natural fibers and synthetic fibers. Examples of fibers of natural origin are cotton and wool. Examples of fibers of synthetic origin are polyurethane fibers such as or Polyester fiber, or polyamide fiber. The fiber can be a single fiber or a part of a textile such as a knitted fabric, a woven fabric, or a nonwoven fabric.

[0232] Another aspect of the invention is a process for producing automatic dishwashing tablets from powders or granules, wherein the granules or powders are selected from the group consisting of granules of the invention and powders of the invention, respectively. The process is also referred to hereinafter as the granulation process according to the invention.

[0233] The tablets of the invention are preferably produced with the aid of a machine, such as a tablet press.

[0234] Granulation method according to the present invention can be carried out by mixing pellet of the present invention or powder with at least one nonionic surfactant and one or more other materials optionally and then compressing the mixture to provide tablet. Suitable nonionic surfactant and other materials such as the example of detergent builder, enzyme are listed above. The particularly preferred example of nonionic surfactant is hydroxy mixed ether, for example has the hydroxy mixed ether of general formula (V).

[0235] The present invention is further illustrated by the following working examples.

[0236] Working Example

[0237] Pellets containing MGDA (trisodium salt) and polymer (sulfonated acrylic acid polymer) were produced.

[0238] Sample 1 was prepared according to the (two-step) process of the invention, wherein (i) an aqueous composition containing MGDA and a polymer (approximately 6 wt. %) was spray granulated, and (ii) subsequently, additional polymer was mixed in. The total polymer content in the final product was approximately 25 wt. %.

[0239] Comparative Sample 1 was prepared by spray granulation of only MGDA and the same polymer, ie in a one-step process.

[0240] The samples (approximately 5 g each, in a petri dish made of glass, 70 mm in diameter) were then subjected to hygroscopicity measurements in a climate chamber at 35° C. and 70% relative humidity. The results of the hygroscopicity measurements are shown in the table below.

[0241] Table 1: Results of hygroscopicity measurements

[0242]

[0243] It can be seen that the samples obtained by the process of the present invention show significantly reduced hygroscopicity compared to the comparative samples produced according to the conventional (one-step) spray granulation process (ie without a second step of physical mixing with the polymer).

Claims

1. A method for producing a powder or granules, the powder or granules comprising (A) at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and the corresponding alkali metal salts thereof in the range of 40% to 85% by weight, (B) at least one homopolymer or copolymer of (meth)acrylic acid, partially or completely neutralized with a base, and / or polyaspartate, in the range of 15% to 60% by weight, relative to the solids content of the powder or granules, The method comprises the following steps (a) mixing in the presence of water 80% to 99% by weight of the at least one chelating agent (A) and in the range of 1% to 20% by weight of the at least one homopolymer or copolymer (B), (b) removing the majority of the water by spray drying or spray granulation, preferably using a gas having an inlet temperature of at least 125°C. (c) optionally, purifying the composition obtained from step (b), and (d) physically mixing the composition obtained from step (b) or step (c) with further at least one homopolymer or copolymer (B) in the range of 1% to 50% by weight, (e) optionally, physically mixing the composition obtained from step (b), (c) or (d) with at least one organic acid having a molecular weight not exceeding 500 g / mol, preferably citric acid, The percentages are relative to the solids content of the powder or granules, wherein the addition of the polymer in step (d) by physical mixing and the optional addition of the organic acid in step (e) is carried out in such a way that the total amount of chelating agent (A) and polymer (B) defined above is achieved.

2. The method according to claim 1, wherein: The chelating agent (A) is selected from the trisodium salt of MGDA and the tetrasodium salt of GLDA.

3. A method according to any one of the preceding claims, wherein: The homopolymers and copolymers (B) are selected from the group consisting of sodium peroxides of polyacrylic acid.

4. A method according to any one of the preceding claims, wherein: The homopolymer or copolymer (B) has an average molecular weight M determined by gel permeation chromatography and is in the range of 1,200 to 30,000 g / mol, preferably 5,000 to 25,000 g / mol relative to the corresponding free acid. w .

5. A method according to any one of the preceding claims, wherein: The homopolymer or copolymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer carrying at least one sulfonic acid group per molecule, preferably 2-acrylamido-2-methylpropanesulfonic acid (AMPS).

6. A method according to any one of the preceding claims, wherein: The physical mixing in step (d) is carried out by any type of physical mixing, preferably in a ploughshare mixer or a free fall mixer, and / or preferably at a temperature of 10°C to 190°C, more preferably 20°C to 90°C, and / or preferably at a speed of 30 to 120 rpm, more preferably 40 to 80 rpm, and / or preferably with a Froude number of 0.1 to 10, more preferably 1 to 3, and / or preferably at a charge level of 10% to 95%, more preferably 40% to 75%, and / or preferably at atmospheric pressure, and / or preferably with an average residence time of at least two minutes, more preferably 5 to 60 minutes.

7. A powder or granules, optionally obtained or obtainable by the method according to any one of claims 1 to 6, the powder or granules containing (A) at least one chelating agent selected from the group consisting of methylglycine diacetic acid (MGDA) and glutamic acid diacetate (GLDA) and iminodisuccinic acid (IDS) and the corresponding alkali metal salts thereof in the range of 40% to 85% by weight, (B) at least one homopolymer or copolymer of (meth)acrylic acid, partially or completely neutralized with a base, and / or polyaspartate, in the range from 15% to 60% by weight, relative to the solids content of the powder or granules.

8. The powder or granules according to claim 7, which has a residual moisture content determined by Karl Fischer titration in the range from 1 to 30% by weight, preferably from 5 to 25% by weight.

9. The powder or granules according to claim 7 or 8, having an average diameter determined by laser diffraction in the range of 0.1 μm to 3500 μm, preferably 1 to 2000 μm, more preferably 10 to 1500 μm, even more preferably 50 to 1000 μm, most preferably 100 to 800 μm.

10. The powder or granules according to any one of claims 7 to 9, wherein The powder or granules contain a chelating agent (A) in the range of 50 to 80% by weight and a homopolymer or copolymer (B) in the range of 20 to 50% by weight, the percentages being relative to the solid content of the powder or granules.

11. The powder or granules according to any one of claims 7 to 10, wherein The homopolymer or copolymer (B) has an average molecular weight M determined by gel permeation chromatography and is in the range of 1,200 to 30,000 g / mol relative to the corresponding free acid. w .

12. The powder or granules according to any one of claims 7 to 11, wherein The chelating agent (A) is selected from the trisodium salt of MGDA and the tetrasodium salt of GLDA.

13. The powder or granules according to any one of claims 7 to 12, wherein The homopolymers and copolymers (B) are selected from the group consisting of sodium peroxides of polyacrylic acid.

14. A powder or granulate according to any one of claims 7 to 13, wherein The homopolymer or copolymer (B) is selected from copolymers of (meth)acrylic acid and a comonomer carrying at least one sulfonic acid group per molecule.

15. Use of a powder or granulate according to any one of claims 7 to 14 for the manufacture of a cleaning agent for fibers or surfaces, preferably hard surfaces, wherein The cleaning agent preferably contains at least one peroxy compound.

16. The use according to claim 15, wherein The at least one peroxygen compound is selected from the group consisting of percarbonates, persulfates and perborates.

17. Use according to claim 15 or 16 in dishwashing applications, preferably automatic dishwashing applications, and in industrial and institutional cleaning applications.

18. A cleaning agent comprising at least one peroxy compound and at least one powder or granulate according to any one of claims 7 to 14.

19. The cleaning agent according to claim 18, further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; the cleaning agent preferably comprises said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; more preferably comprising 0.1% to 2% of phenoxyethanol.

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