Process for manufacturing a powder or granule comprising aminocarboxylate chelating agents and polymers

Abstract

The present invention deals with a process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer.

Description

241075W0011Process for manufacturing a powder or granule comprising aminocarboxylate chelating agents and polymersThe present invention deals with a process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer.Chelating agents of the aminocarboxylate type such as methyl glycine diacetic acid (MGDA) and glutamic acid diacetic acid (GLDA) and their respective alkali metal salts are useful sequestrants for alkaline earth metal ions such as Ca2+and Mg2+. A lot of aminocarboxylates show good biodegradability and are thus environmentally friendly. For that reason, they are recommended and used for various purposes such as laundry detergents and for automatic dishwashing (ADW) formulations, in particular for so-called phosphate-free laundry detergents and phosphate-free ADW formulations.Depending on the type of product - liquid home care and fabric care products versus solid home care and fabric care products - and the manufacturing process of solid home care and fabric care products care product manufacturers may either prefer to handle solutions of aminocarboxylates or solid arminocarboxylates, for example joint spray drying or solid mixing. Powders and granules of aminocarboxylates may be shipped economically due to their high active ingredient content that goes along with low water content. Therefore, convenient processes for providing granules are still of great commercial interest.However, chelating agents, for example methyl glycine diacetic acid (MGDA), are strongly alkaline. This may cause problems when they are used together with pH sensitive compounds, e. g. pH sensitive polymers.This may also cause problems when MGDA (or other similar chelating agents, as mentioned above) are cogranulated with pH sensitive compounds, e. g. pH sensitive polymers.In general, biobased and, to some extent, also biodegradable polymers, for example polyaspartic acid or some sugar-based polymers, are more pH sensitive than conventional polymers, like polymers based on acrylic acid. Thus, using these kinds of polymers in combination with chelating agents like MGDA, for example in co-granulation, may cause problems with stability of the polymers (and thus, of the co-granulates).It may be noted that, in general some compounds are considered as "biobased”, but are not biodegradable. On the other hand, some compounds are not biobased, but are readily biodegradable. Furthermore, there are also compounds which are both biobased and biodegradable, as well.US 2021 / 179978 A1 discloses a process for manufacturing granules or powders, comprising a chelating agent which may be selected from MGDA and a polymer which may be selected, e. g., from polyaspartates, by spray-drying or spray-granulation.241075W0012US 2023 / 025816 A1 describes a process for making a granule comprising at least one chelating agent, e. g. EDDS or MGDA, and optionally at least one conventional homo- or copolymer of (meth)acrylic acid, by spray-granulation. Biobased and / or biodegradable polymers are not specifically addressed herein.US 2005 / 101503 A1 discloses a method for making a laundry detergent powder comprising a zeolite, a conventional polycarboxylate polymer (e. g. copolymers of maleic / acrylic acid) and optional additional ingredients by spray-drying, which may include EDDS. There is no mention of biobased and / or biodegradable polymers. A spray-granulation process is not mentioned, either.CA 2 844514 A1 describes copolymers comprising Isoprenol, at least one monoethylenically unsaturated C3 to C8 monocarboxylic acid, and one or more sulfonic acid group-consisting monomers, and their use as deposit inhibitors in water-bearing systems. A process for manufacturing a powder or granule comprising, inter alia, at lest one aminocarboxylate chelating agent, by spray-drying or spray-granulation is not mentioned thereinWO 2023 / 117602 A1 discloses a water-soluble graft polymer comprising as polymer base a polysaccharide, and its use in a composition, e. g. a cleaning composition or dish wash detergent composition. A process for manufacturing a powder or granule comprising, inter alia, at lest one aminocarboxylate chelating agent, by spray-drying or spraygranulation is not mentioned therein.Thus, it was an objective of the present invention to overcome the problems and challenges mentioned above.In particular, it was an objective of the present invention to provide a process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent and at least one bio-based and / or biodegradable polymer which avoids degradation or destruction of the polymer and which leads to storage-stable products (I. e. storage stable co-granules).The inventors have now surprisingly found that a process as set out in the appended claims is able to meet these requirements. Surprisingly, the inventive process leads to a powder or granule comprising at least one aminocarboxylate chelating agent (A) and a bio-based and / or or biodegradable polymer (B) and avoids destruction and degradation of the respective polymer or polymers. Furthermore, surprisingly, the powder or granule (solid coproduct of chelating agent and polymer) obtainable by the inventive process is storage stable.Thus, one object of the present invention is a process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer (B), said process comprising the steps of(a) mixing the at least one chelating agent (A), and at least one polymer (B) in the presence of water,241075W0013(b) removing most of said water by spray-drying or spray-granulation, preferably using a gas with an inlet temperature of at least 125° C, more preferably at least 140° C.In one embodiment (I) of the inventive process, polymer (B) is both biobased and biodegradable.In another embodiment (II) of the inventive process, polymer (B) is biobased. For this embodiment, it does not play a role if polymer (B) is considered, additionally, as biodegradable or not.In another embodiment (II b) of the inventive process, polymer (B) is biobased only, but not biodegradable.In another embodiment (III) of the inventive process, polymer (B) is biodegradable. For this embodiment, it does not play a role if polymer (B) is considered, additionally, as biobased or not.In a preferred embodiment (Ill a) of the inventive process, polymer (B) is biodegradable according to at least the OECD 301 F standard, and the polymer may be biobased or not (I. e., in this preferred embodiment, it does not matter if the polymer is biobased or not).In a further embodiment (III b) of the inventive process, polymer (B) is biodegradable, but not biobased.Particularly, one object of the present invention is a process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer (B), said process comprising the steps of(a) mixing the at least one chelating agent (A), and at least one polymer (B) in the presence of water,(b) removing most of said water by spray-drying or spray-granulation, preferably using a gas with an inlet temperature of at least 125° C, more preferably at least 140° C, wherein polymers (B) which satisfy the OECD 301 F manometric respirometry method test and / or the OECD 301 B method test and / or the OECD 302 B method test are considered as biodegradable, and wherein polymers (B) which stem from alternative carbon sources which do not include fossil resources are considered as bio-based, and wherein the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 3 hours.BiodegradabilityBiodegradability, in the context of the present invention, may be determined by any one of the tests according to the established OECD Guidelines (and ISO standards) for determining biodegradability.In particular, the following test methods may be used to consider if a polymer is considered to be "biodegradable” (or not:OECD 301A (DOC Die-Away test)OECD 301 B (CO2 Evolution test)OECD 301 F (Manometric Respirometry test)241075W0014ISO 9439 (Combination test) OECD 302A (SCAS test) OECD 302B (Zahn-Wellens test) OECD 303 (Activated sludge simulation test) COED 308, 309, 310 (Environment simulation tests)A polymer which does not satisfy any one of the established OECD methods (in particular, the OECD methods mentioned above) or the ISO 9439 method cited above is not considered as biodegradable in the present invention.A preferred method for determining biodegradability, in the context of the present invention, is the OECD 301 F Guideline method, which is described in more detail below. Thus, a polymer which satisfies the test according to the OECD 301 F method is considered as biodegradable. (Conversely, in a preferred embodiment of the present invention, a polymer which does not satisfy the OECD 301 F Guideline method test is not considered to be biodegradable.)Determination of "Ready Biodegradability'' according the OECD 301 F guidelinesBiodegradation in wastewater is tested in triplicate using the OECD 301 F manometric respirometry method. OECD 301 F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen. To a measured volume of medium, 100 mg / L of example 14, which is the nominal sole source of carbon is added along with the inoculum (aerated sludge taken from Mannheim wastewater treatment plant). This is stirred in a closed flask at a constant temperature (25°C) for 28 days. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an Oxi TopC. Evolved carbon dioxide is absorbed in a solution of sodium hydroxide. Nitrification inhibitors are added to the flask to prevent usage of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD (Theoritical oxygen demand, which is measured by the elemental analysis of the compound). A positive control Glucose / Glucosamine is run along with the test samples for each cabinet.241075W0015Calculations: Theoretical oxygen demandAmount of oxygen required to oxidize a compound to its final oxidation products.This is calculated using the elemental analysis data.Biological oxygen demand (from the experiment) x 100% Biodegradation = -Theoretical oxygen demandDuration of test: 28 daysSource of sludge: Mannheim wastewater treatment plantConcentration of sludge: 30mg / LValidity: According to the OECD guidelines the test is valid if:1 . The reference reaches 60% by 14 days.2. The difference of the extremes of the test replicates by the end of the test is less than 20%.3. Oxygen uptake of inoculum blank is 20-30 mg O2 / L and must not be greater than 60mg O2 / L.4. The pH measured at the end of the test is between 6.0 - 8.5.Thus, the term "biodegradable”, as used herein, refers to compounds (e. g. polymers) which satisfy the above test.Furthermore, also the following tests for determining biodegradability may preferably be used in the context of the present invention: OECD 301 B and OECD 302 B. Thus, a polymer which satisfies any one of these two tests is considered as biodegradable. (Conversely, in a preferred embodiment of the present invention, a polymer which does not satisfy any one of the OECD 301 B and OECD 302 B tests is not considered to be biodegradable.)In a preferred embodiment of the present invention, a polymer is considered to be biodegradable if it satisfies any one of the tests according to the OECD methods OECD 301 F, OECD 301 B and OECD 302 B. (Conversely, in this preferred embodiment of the present invention, a polymer which does not satisfy any one of the OECD 301 F, OECD 301 B and OECD 302 B tests is not considered to be biodegradable)In a particularly preferred embodiment, a polymer which satisfies the test according to the OECD 301 F method (described above in detail) is considered as biodegradable. Conversely, in this particularly preferred embodiment of the present invention, a polymer which does not satisfy the OECD 301 F Guideline method test is not considered to be biodegradable.241075W0016Furthermore, the term ''bio-based'', as used herein, may refer to compounds based on alternative carbon sources. In another, stricter sense, "bio-based” may refer to compounds based on alternative carbon sources which do not include fossil resources.Regarding the above "bio-based” compounds (in particular, polymers), based on alternative carbon sources, these alternative carbon sources can be based on (primary) sugars, biomass, waste plastics, municipal solid waste, marine carbon, waste oils, methane capture, carbon capture or combination thereof. Methods on how the alternative carbon sources can be implemented in the synthesis of polymers, e. g. cleaning additives are described in more detail in WO2023036623 A1 on page 25, fifth paragraph to page 27, fifth paragraph.In one embodiment of the inventive process, the at least one aminocarboxylate chelating agent (A) is selected from MGDA, GLDA, IDS, EDDS and their respective alkali metal salts, preferably sodium and / or potassium salts.In a preferred embodiment of the inventive process, the at least one aminocarboxylate chelating agent (A) is selected from MGDA and its alkali metal salts, preferably MGDA trisodium salt.The aminocarboxylate chelating agent (A) may also be MGDA which is only partially neutralized, e. g. as described in claim 7 of unpublished European patent application no. EP 25184868.5.In one embodiment of the inventive process, the at least one polymer (B) is selected from polyaspartic acid (polymer B1), also referred to as "poly aspartate”.Polyaspartic acid is one example of a polymer which is both biobased and readily biodegradable. More specifically, polyaspartic acid is readily biodegradable according to the OECD 301 F standard.In a preferred embodiment, polyaspartates with an average molecular weight Mw in the range of from 1,000 to 20,000 g / mole are used.In one embodiment of the present invention, polyaspartates (polymer B1) are used as salts, partially or fully neutralized, of polyaspartic acid, preferably as alkali metal salts, for example as sodium or potassium salts or combinations of sodium and potassium salts, and even more preferred as sodium salts.Three main methods have been developed for the production of polyaspartates (polymer B1) and especially their alkali metal salts:(1) Thermal polycondensation of aspartic acid followed by alkaline hydrolysis of the intermediate polysuccinimide;(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;241075W0017(3) Polymerization of maleic acid anhydride in the presence of ammonia or ammonium salts followed by alkaline hydrolysis of the intermediate polysuccinimide.Regardless of the synthesis route, the intermediate polysuccinimide is hydrolyzed by means of e.g. alkali metal hydroxide in order to obtain an aqueous polyaspartate solution. Acidification of the polyaspartate solution with mineral acids such as hydrochloric acid or sulfur acid may yield the free polyaspartic acid.The preferred molecular weight Mwof polyaspartate (polymer B1) used according to the present invention is in the range of from 1,000 g / mol to 20,000 g / mol, preferably from 1,500 to 15,000 g / mol and particularly preferably from 2,000 to 10,000 g / mol. The molecular weight of polyaspartates (B1) is preferably determined as sodium salt, fully neutralized. The molecular weight of polyaspartates (polymer B1) is preferably determined by gel permeation chromatography (GPC) in a 0.08 mol / l TRIS buffer at a pH value of 7.0, additionally containing 0.15 M NaCI and 0.07 M NaNa. TRIS refers to tris(hydroxylmethyl)aminomethane.Polyaspartate (polymer B1) may be based upon L- or D- or D, L-aspartic acid or partially racemized L-aspartic acid. Preference is given to using L-aspartic acid.In a further embodiment of the inventive process, the at least one polymer (B) is selected from water-soluble graft polymers (B2) comprising a) at least one water-soluble polyalkylene oxide polymer backbone and b) at least one grafted side chain comprising at least two water-soluble ethy lenically unsaturated monomers, wherein the first monomer comprises at least one structure according to formula (I)(I), and the second monomer comprises at least one structure according to formula (II)(ii), wherein M+in formula (I) and (II) is independently from each other selected from the group consisting of H+, Na+, K+, NH4+, protonated amine and protonated amino alcohol, wherein the polyalkylene oxide polymer backbone, first monomer and second monomer are polymerized by a radically initiated polymerization reaction.241075W0018The grafted side chain in water-soluble graft polymer (B2) may further comprise a chain transfer agent, preferably selected from the group consisting of sodium hypophosphite, potassium hypophosphite, calcium hypophosphite, ammonium hypophosphite, magnesium hypophosphite, hypophosphorous acid, phosphorous acid, sodium phosphite, potassium phosphite, calcium phosphite, ammonium phosphite and magnesium phosphite, mercaptoethanol, sodium bisulfite, more preferably sodium hypophosphite.At least 70%, at least 80% or at least 90% of the weight of the polyalkylene oxide polymer backbone in water-soluble graft polymer (B2) may be based on ethylene oxide, preferably the polyalkylene oxide polymer backbone is polyethylene glycol (PEG) or methoxy polyethylene glycol (mPEG), more preferably PEG having a weight average molecular weight (Mw) ranging from 50 to 20 000 g / mol, preferably 500 to 10 000 g / mol, more preferably 1000 to 6000 g / mol.The first monomer in water-soluble graft polymer (B2) may be selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid, itaconic acid and maleic acid, and metal salts thereof, preferably acrylic acid.The second monomer in water-soluble graft polymer (B2) may be selected from the group consisting of 2-acrylamido- 2-methylpropane sulfonic acid (AMPS), viny Isulfonic acid, styrene sulfonic acid, allylsulfonic acid and methallylsulfonic acid and metal salts thereof, preferably sodium salts, preferably 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and the sodium salt of 2-acrylamido-2-methylpropane sulphonic acid (Na-AMPS).The molar ratio of the first monomer and the second monomer in water-soluble graft polymer (B2) may be 3:1 to 10:1, preferably 5:1 to 7:1.The weight ratio of the polyalkylene oxide polymer backbone and the grafted side chain in water-soluble graft polymer (B2) may be 65:35 to 95:5, preferably 75:25 to 90:10.Water-soluble graft polymer (B2), as defined above, is readily biodegradable.In another embodiment of the inventive process, polymer (B) is selected from water-soluble graft polymers (B3) comprising as polymer base a polysaccharide, and as grafted side chains at least one water soluble ethy lenically unsaturated monomer B, such unsaturated monomer comprising at least one sodium carboxylate unit, being produced by radically initiated polymerization reaction, and further employing during the polymerization at least one organic compound capable of complexing metal ions, preferably iron, containing in its structure at least one carboxylgroup which may be partially or fully present as acid-group or deprotonated in salt-form.The polysaccharide in polymer (B3) may consist of a maximum of n = 30 glucose units on average. The polysaccharide in polymer (B3) may also consist of n = 2 - 20 glucose units on average, or of n = 3 - 10 glucose units on average.241075W0019In one embodiment, the polysaccharide in polymer (B3) is selected from maltodextrin, corn syrups and I or corn syrups solids.Furthermore, the at least one water soluble ethy lenically unsaturated monomer in polymer (B3) may comprise at least 50 mol.%, preferably at least 90 mol.%, sodium acrylate and / or methacrylate, more preferably sodium acrylate, based on the total amount of monomers employed, and optionally other monomers polymerizable.The radical polymerization in polymer (B3) may be of the radical redox polymerization-type.The at least one organic compound in polymer (B3) may be employed to reduce or - preferably - prevent the discoloration before, during and / or after polymerization, more preferably before and / or during polymerization, even more preferably before and during polymerization, and most preferably such that a sufficient amount of the at least one such organic compound is still present after the polymerization and after post-polymerization.Further details regarding polymer (B3), which may be employed in the inventive process, may be found in patent publication WO 2023 / 117602.In a further embodiment of the inventive process, the at least one polymer (B) is selected from graft copolymers (B4) composed of (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (b) at least one ethy lenically unsaturated mono- or dicarboxylic acid and (c) at least one compound of the general formula (I),where the variables are defined as follows: R1 is selected from methyl and hydrogen, A1 is selected from C2-C4- alkylene, R2 are identical or different and selected from C1-C4-alkyl, X is selected from halide, mono-C1-C4-alkyl sulfate and sulfate.Graft copolymers (B4) are described in more detail in the claims (and specification) of patent application published under WO 2015 / 197379.In the inventive process, at least one aminocarboxylate chelating agent (A) is generally used in a range of at least 50% by weight, relative to the total weight of the mixture of aminocarboxylate chelating agent (A), at least one biobased and / or biodegradable polymer (B) and water, before removal of water in step (b) of the inventive process. The at least one bio-based and / or biodegradable polymer (B) is usually contained in a range of 1 to 25 % by weight, particularly 2 to 15 % by weight relative to the total weight of the mixture of aminocarboxylate chelating agent (A), at least one bio-based and / or biodegradable polymer (B) and water, before removal of water in step (b) of the inventive process.241075W00110In one embodiment of the inventive process, the at least one bio-based and / or biodegradable polymer (B) is contained in in a range of 3 to 10 % by weight, particularly 3 to 8 % by weight, relative to the total weight of the mixture of aminocarboxylate chelating agent (A), at least one bio-based and / or biodegradable polymer (B) and water, before removal of water in step (b) of the inventive process.The inventive process is, preferably, performed in a fluidized bed spray-drying apparatus or a fluidized spraygranulation apparatus.In the inventive process, measures may be implemented which avoid extended exposure of the biobased and / or biodegradable polymer (B) to the aminopolycarboxylate chelating agent (A), before and during the spray-drying or, preferably, spray-granulation process. The residence time may be kept as low as possible.Generally, according to the inventive process,, the time period in which the biobased and / or biodegradable polymer (B) and the aminopolycarboxylate chelating agent (A) are in direct contact with each other before and during the spray-drying or, preferably, spray-granulation process is usually lower than one 3 hours, preferably lower than 2 hours.In a preferred embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 60 minutes, preferably lower than 45 minutes, particularly lower than 35 minutes.In another preferred embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 25 minutes, preferably lower than 20 minutes.In a further preferred embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 15 minutes, preferably lower than 10 minutes, particularly lower than 5 minutes.In another preferred embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 3 minutes, preferably lower than 2 minutes, more preferably lower than 60 seconds, particularly lower than 30 seconds or lower than 20 seconds. The time period during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process may also be lower than 10 seconds or lower than 5 seconds.The measures mentioned above may include using a multizone and / or multinozzle apparatus, where the different compounds may be dosed separately, reducing the contact (i. e. mixing) time, reducing the process temperature, and / or using an inert gas.241075W00111Thus, the inventive process may be performed in a multizone and / or multinozzle apparatus, preferably in a multizone and / or multinozzle fluidized bed spray granulation apparatus.In one embodiment of the inventive process, chelating agent (A) and polymer (B) are added in different zones of a multizone apparatus and / or through different nozzles of a multinozzle apparatus.In one embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other is lower than five minutes. In another embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other is lower than two minutes, preferably lower than one minute. In another embodiment of the inventive process, the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other is less than 30 seconds.In the inventive process, in one embodiment, the residence time in the spraying or granulation apparatus may be kept at a minimum by consecutive (but continuous) spraying of several separate portions of pre-mixed components chelating agent (A) and polymer (B). In this embodiment, only small portions of components chelating agent (A) and polymer (B) are mixed (in the presence of water) in step (a) of the inventive process, and then these are directly (without delayed) introduced into the spray-drying or spray-granulation device and spray or granulated immediately afterwards. In other words, longer storage of bigger amounts of pre-mixed components chelating agent (A) and polymer (B) (in the presence of water) is avoided.In one embodiment of the inventive process, the bed temperature in steps (a) and (b) is, separately from each other, lower than 110° C, preferably lower than 105°C. In a preferred embodiment of the inventive process, the bed temperature in steps (a) and (b) is, separately from each other, 100° C or lower. In another embodiment of the inventive process, the bed temperature in steps (a) and (b) is, separately from each other, lower than 90°C. In another embodiment of the inventive process, the temperature in steps (a) and (b) is, separately from each other, lower than 80°C.The inventive process may also be run under an atmosphere which has a lower content of oxygen than normal atmospheric air. For example, at least a certain percentage of oxygen may be replaced by carbon dioxide and / or nitrogen.In one embodiment, the process is run under an inert atmosphere, preferably selected from nitrogen.In the inventive process, it is also possible to mix at least one additional compound (C) in step (a), preferably selected from the list consisting of TIO2, SIO2 and phoshphates (e. g. hydrogen phosphate). Alternatively, the at least one additional compound (C) may be added in a different zone of a multizone apparatus and / or through different nozzles of a multinozzle apparatus.A further object of the present invention is also a powder or granule, obtained or obtainable by the inventive process.241075W00112The powder or granule resulting from the inventive process has a residual moisture content of 1 to 20% by weight, particularly 5 to 15% by weight.Another object of the present invention is the use of an inventive powder or granule in detergent applications. Dishwashing detergent applications are one embodiment of these detergent applications; a preferred embodiment is the use of an inventive powder or granule in automatic dishwashing (ADW) detergent applications.ApplicationsThe inventive powders and granules may be used in a variety of applications, for example in detergent applications. Dishwashing detergent applications are one embodiment, in particular automatic dishwashing applications (ADW).In the following paragraphs, a powder or granule, obtainable or obtained by the process according to any one of the preceding claims (and thus, containing at least one aminocarboxylate chelating agent (A)), is also referred to as "inventive builder”.The publication IPCOM000274907D published on www.IP.com is regarded as Reference RF1, which is incorporated herein by reference in its entirety. The publication Prior Art Disclosure; Issue 684; paragraphs

[3000] to

[3061] ; ISSN: 2198-4786; published: February 12, 2024 will be regarded as Reference RF2, which is incorporated herein by reference in its entirety.The phrase "cleaning composition", as used herein, includes compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind, more preferably compositions for Fabric and Home Care. "Cleaning compositions” are defined in more detail in paragraphs

[0001] ,

[0002] ,

[0004] and

[0007] of Reference RF1."Compositions for Fabric and Home Care” include cleaning compositions and formulations including but not limited to laundry cleaning compositions and detergents and hard surface cleaning compositions including dish washing compositions, more preferably liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions. "Compositions for Fabric and Home Care” are defined in more detail in paragraph

[0003] of Reference RF1.The cleaning compositions of the invention including the inventive builder(s) may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as "adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.Suitable adjunct cleaning additives include polymers, surfactants or surfactant systems, further builders, cobuilders, enzymes, enzyme stabilizing systems, structurants or thickeners, clay soil removal / anti -redeposition agents, solubilizing agents, chelating agents, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti -tarnish241075W00113 and / or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes.In preferred embodiments, the cleaning compositions comprise the inventive builder(s) and a polymer, preferably cleaning polymers and / or soil release polymers. "Cleaning polymers and soil release polymers” are defined in more detail in paragraphs

[0032] to

[0034] of Reference RF1. These polymers include polycarboxylates, alkoxylated polyalkylenamines, alkoxylated polyalkylenimines, polyether-based polymers, rheology-modifying polymers, dye inhibition polymers and soil release polymers as defined in more detail in paragraphs

[3035] to

[3044] of Reference RF2.Polymers may include, without limitation, "multifunctional alkoxylated polyethylene imines”, "multifunctional alkoxylated diamines” and also terephthalic acid-based polyesters like Clariant's TexCare®, such as TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN 260 SG Terra and TexCare® SRA 300 as well as distinct combinations of all of the before mentioned polymers. Also included are graft polymers comprising a polyalkylene oxide based backbone with grafted side chains of vinyl ester monomer and optionally N -vinylpyrrolidone monomers.In preferred embodiments, the cleaning compositions comprise the inventive builder(s) and a surfactant or surfactant system. "Surfactants” are anionic, non-ionic, cationic, amphoteric and zwitter-ionic surfactants defined in more detail in paragraphs

[3008] to

[3034] of Reference RF2. In addition, these surfactants are also described in more detail in paragraphs

[0008] to

[0013] of Reference RF1.Anionic surfactants for inventive cleaning compositions include linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl alkoxy sulfates (AES), alkyl alkoxy carboxylates, modified alkylbenzene sulfonate (MLAS), methyl ester sulfonate (MES), alkyl sulfosuccinates, alpha-olefin sulfonate (AOS), alkyl polyglycosides (APG) and biosurfactants, such as rhamnolipids and sophorolipids. Non-ionic surfactants for inventive cleaning compositions include alkoxy lates, alkoxylated alcohols, alkoxylated fatty acids and alkoxylated (poly-)saccharides. Cationic surfactants for inventive cleaning compositions include surfactants comprising a quaternary ammonium. Amphoteric surfactants for inventive cleaning compositions include amine oxides. Zwitter-ionic surfactants for inventive cleaning compositions include betaines.In preferred embodiments, the cleaning compositions comprise the inventive builder(s) and an additional builder. "(Additional) builders” are defined in more detail in paragraphs

[0014] to

[0018] of Reference RF1. These builders include non-phosphate based builders (NPB) and phosphonates (CoP) described in more detail in paragraphs

[3001] to

[3005] of Reference RF2.Builders may include, without limitation, methylglycinediaceticacid (MGDA), ethylenediaminedisuccinic acid (EDDS), glutamic acid diacetate (GLDA), citric acid and salts thereof.In preferred embodiments, the cleaning compositions comprise the inventive builder(s) and an enzyme. "Enzymes” are defined in more detail in paragraphs

[0020] to

[0027] of Reference RF1.Enzymes may include hydrolases, such as proteases, amylases, lipases, DNases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases,241075W00114 pectinases, lactases and peroxidases. In more preferred embodiments, the cleaning composition comprises, in addition to the inventive compound(s), a protease and a protease stabilizing system comprising a peptide aldehyde. In preferred embodiments, the cleaning compositions comprise the inventive builder(s) and a biocide. "Biocides” are defined in more detail in paragraphs

[0035] and

[0036] of Reference RF1. These biocides also include compounds as defined in more detail in paragraphs

[3006] and

[3007] of Reference RF2.Biocides may include, without limitation, 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydipheny lether.Further adjunct cleaning additives are included and described in more detail in paragraphs

[0005] ,

[0006] ,

[0019] ,

[0028] to

[0031] and

[0037] to

[0039] of Reference RF1.Liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions comprising inventive builder(s) are defined in more detail in paragraph

[0043] of Reference RF1.Working examplesThe following, non-limiting working examples illustrate some aspects of the present invention.MGDA (from BASF, brand name "Trilon® M...”) was used for co-granulation with different kinds of biobased and / or biodegradable polymers, in different amounts.Example 1 (comparative) - Long mixing time of 17 hA vessel was charged with 14,4kg Trilon® M max liquid (MGDA in aqueous solution) and 1,6 kg Polyaspartic acid (40% polyaspartic acid in water, percentage by weight), so that the total content of the polyaspartic acid was 10% (based on weight) in the mixture. The spray liquor so obtained was stirred and heated to 40°C. These conditions were kept for 17 hours.Then a fluidized bed spray granulation was performed: A cylindrical vessel with a perforated plate at the bottom, attached with zig-zag air classifier, commercially available as Glatt Lab System with Vario 3 insert, was charged with 0.9 kg of solid Trilon® M max SG (MGDA) granules and 600 g of milled Trilon® M max SG granules. The milling was performed with a Fritsch mill (Pulverisette 16, 2800rpm, 2mm mesh). An amount of 200m3 / h of air with a temperature of 170°C was blown from the bottom. A fluidized bed of T rilon® M particles was obtained. The above mentioned liquid solution was introduced by spraying 7 kg / h (kilogram per hour) into the fluidized bed from the bottom through a two-fluid nozzle, absolute air pressure of the nozzle: 4, 36bar. Granules were formed, and the bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was 98 to 101 °C.Granules left the granulator through the zig-zag air classifier. Fines (small particles and dust) were blown back into the granulator by the zig-zag air classifier. Particles of the desired size and oversized particles fell through the air classifier and were collected in a 1L sample bottle. Every 8 to 15 minutes, the filled sample bottle was replaced by an empty sample bottle and the granules were subjected to a sieving steps. Two fractions were obtained: Coarse particles (oversized particles, diameter > 1mm), and value fraction (particles <1mm). The coarse particles were241075W00115 milled using a Fritsch mill (Pulverisette 16, 2800rpm, 2mm mesh). The milled particles so obtained were returned into the fluidized bed.After 12 kg of sprayed liquid a steady state was reached. The value fraction was collected as counterexample granules (non-inventive granules).In the above example, hot air of 170°C can be replaced by hot N2 having a temperature of 170°C.Example 2 - medium long contact time periodA lab scale fluidized bed spray granulation unit with 0,0172 m2 bed size and internal filters was used for the cogranulation of Trilon® M (MGDA, trisodium salt) with 10% by weight of polyaspartic acid (based on active content).As an initial bed filling, 500g of solid MGDA-Naa granule and 500g of milled solid MGDA-Na3 was introduced into the granulator. For the milling, a hammer mill type Kinematica Polymix System PM-MFC 90 D, 2mm mesh, 4000rpm was used. The fluidization was accomplished by entering a so-called fluidization gas at the bottom of the fluidized bed spray granulator, said fluidization gas being nitrogen with an inlet temperature of 140-145°C.As soon as the bed temperature of about 100°C was reached, it was started to spray the MGDA and polyaspartic acid mixture into the granulator. To minimize the residence time of MGDA and polyaspartic acid in the feeding vessel, only 1kg of the spray liquor was initially mixed. After this 1kg of spray liquor was sprayed into the unit, a second portion of 1kg was mixed and introduced into the feeding vessel. The spraying was continuous and not interrupted. This procedure was carried out in total 15 times, so that 15kg of spray liquor was used for the granulation. A feed to 2 kg / h of the mixture was sprayed into the granulator with the help of a two-component-nozzle, the nozzle gas pressure was about 2,4bar.About every 30 minutes, an aliquot of granule was withdrawn from the granulator through a discharge screw at the side. This aliquot of granules was classified by sieving in a sieving machine with two sieves, mesh size of 0,355 mm and 1 mm, to obtain lumps (>1mm), value fraction (0,355-1 mm) and fines (<0, 355mm). The lumps were milled down in a hammer mill, type Kinematica Polymix System PM-MFC 90 D, 2mm mesh, 4000rpm. The milled particles (milled lumps) were returned into the granulator together with the fines. The value fraction was dumped until a steady state was reached.After about 8kg of feed was sprayed into the granulator, the process was considered as steady state and the value fraction was collected as a representative sample.The (average) time of contact of MGDA and polyaspartic before and during the spray granulation was approximately 30 minutes.In this experiment, nitrogen can be replaced by air.241075W00116Co-granules containing MGDA and polyaspartic acid were obtained.Example 3 - very short contact time periodA first vessel (vessel 1) was charged with 20kg Trilon® M max liquid and heated to 70°C. A second vessel (vessel 2) was charged with 6kg of Polyaspartic acid (40% polyaspartic acid in water, percentage by weight) at room temperature, about 22°C. Both vessels were put on a balance, to determine the feed rate. For both of the vessels, a separate pump is used, so the feed rate can be adjusted independently. The tubes from both pumps are connected to a T-piece directly in front of the granulator, from where the two liquids flow united to the nozzle of the granulator. Then a fluidized bed spray granulation was performed: A cylindrical vessel with a perforated plate at the bottom, attached with zig-zag air classifier, commercially available as Glatt Lab System with Vario 3 insert, was charged with 0.9 kg of solid Trilon® M max SG granules and 600 g of milled Trilon® M max SG granules. The milling was performed with a Fritsch mill (Pulverisette 16, 2800rpm, 2mm mesh). An amount of 200m3 / h of air with a temperature of 162-168°C was blown from the bottom. A fluidized bed of Trilon® M particles was obtained. Continuously and at the same time, 6,3kg / h of Trilon® M liquid from vessel 1 and 0,7kg / h of polyaspartic acid of vessel 2 were put together in the T-piece and introduced into the fluidized bed from the bottom through a two-fluid nozzle, absolute air pressure of the nozzle: 4, 36bar. Granules were formed, and the bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was 99 to 101 °C.Granules left the granulator through the zig-zag air classifier. Fines (small particles and dust) were blown back into the granulator by the zig-zag air classifier. Particles of the desired size and oversized particles fell through the air classifier and were collected in a 1L sample bottle. Every 8 to 15 minutes, the filled sample bottle was replaced by an empty sample bottle and the granules were subjected to a sieving steps. Two fractions were obtained: Coarse particles (oversized particles, diameter > 1mm), and value fraction (particles <1mm). The coarse particles were milled using Fritsch mill (Pulverisette 16, 2800rpm, 2mm mesh). The milled particles so obtained were returned into the fluidized bed.After 12 kg of sprayed liquid a steady state was reached. The value fraction was collected as inventive granules. In the above example, hot air of can be replaced by hot N2 having the same temperatureIn general, the experimental examples show that, using the inventive process, storage-stable co-granules containing at least one aminocarboxylate chelating agent and at least one biobased and / or biodegradable polymer could be successfully obtained.In summary, the experiments also show, inter alia, that by using the inventive process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer (B), good results may be obtained. In particular, the short period of time during which chelating agent (A) and polymer (B) are in direct contact with each other (before and during the spray-drying or spray-granulation process) leads to improved results in the co-granules.E. g., comparative analyses of the chain-lengths of the polymers in the resulting co-granules show that the - mostly sensitive - biodegradable polymers do not degrade during the inventive process. On the other hand, when using a241075W00117 long period of time during which chelating agent (A) and polymer (B) are in direct contact with each other (before and during the spray-drying or spray-granulation process), degradation of the polymer (B) may be observed.

Claims

1.241075W00118Patent claims1) Process for manufacturing a powder or granule comprising at least one aminocarboxylate chelating agent (A) and at least one bio-based and / or biodegradable polymer (B), said process comprising the steps of(a) mixing the at least one chelating agent (A), and at least one polymer (B) in the presence of water,(b) removing most of said water by spray-drying or spray-granulation, preferably using a gas with an inlet temperature of at least 125° C, more preferably at least 140° C, wherein polymers (B) which satisfy the OECD 301 F manometric respirometry method test and / or the OECD 301 B method test and / or the OECD 302 B method test are considered as biodegradable, and wherein polymers (B) which stem from alternative carbon sources which do not include fossil resources are considered as bio-based, and wherein the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 3 hours.2) Process according to claim 1, wherein the at least one aminocarboxylate chelating agent (A) is selected from MGDA, GLDA, IDS, EDDS and their respective alkali metal salts, preferably sodium and / or potassium salts.3) Process according to claim 1 or 2, wherein the at least one aminocarboxylate chelating agent (A) is selected from MGDA and its alkali metal salts, preferably MGDA trisodium salt.4) Process according to any one of the preceding claims, wherein the polymer (B) is selected from polyaspartic acid (polymer B1).5) Process according to any one of the preceding claims, wherein the polymer (B) is selected from water-soluble graft polymers (B2) comprising a) at least one water-soluble polyalkylene oxide polymer backbone and b) at least one grafted side chain comprising at least two water-soluble ethy lenically unsaturated monomers, wherein the first monomer comprises at least one structure according to formula (I)(I), and the second monomer comprises at least one structure according to formula (II)(ii),241075W00119 wherein M+in formula (I) and (II) is independently from each other selected from the group consisting of H+, Na+, K+, NH4+, protonated amine and protonated amino alcohol, wherein the polyalkylene oxide polymer backbone, first monomer and second monomer are polymerized by a radically initiated polymerization reaction.6) Process according to any one of the preceding claims, wherein the polymer (B) is selected from water-soluble graft polymers (B3) comprising as polymer base a polysaccharide, and as grafted side chains at least one water soluble ethy lenically unsaturated monomer B, such unsaturated monomer comprising at least one sodium carboxylate unit, being produced by radically initiated polymerization reaction, and further employing during the polymerization at least one organic compound capable of complexing metal ions, preferably iron, containing in its structure at least one carboxyl-group which may be partially or fully present as acid-group or deprotonated in saltform.7) Process according to any one of the preceding claims, wherein the polymer (B) is selected from graft copolymers (B4) composed of (a) at least one graft base selected from nonionic monosaccharides, disaccharides, oligosaccharides and polysaccharides, and side chains obtainable by grafting on of (b) at least one ethy lenically unsaturated mono- or dicarboxylic acid and (c) at least one compound of the general formula (I),where the variables are defined as follows: R1 is selected from methyl and hydrogen, A1 is selected from C2-C4- alkylene, R2 are identical or different and selected from C1-C4-alkyl, X’ is selected from halide, mono-C1-C4-alkyl sulfate and sulfate.8) Process according to any one of the preceding claims, wherein the process is performed in a fluidized bed spraydrying apparatus or a fluidized spray-granulation apparatus.9) Process according to any one of the preceding claims, wherein the process is performed in a multizone and / or multinozzle apparatus, preferably in a multizone and / or multinozzle fluidized bed spray granulation apparatus.10) Process according to any one of the preceding claims, wherein chelating agent (A) and polymer (B) are added in different zones of a multizone apparatus and / or through different nozzles of a multinozzle apparatus.11) Process according to any one of the preceding claims, wherein the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 2 hours, preferably lower than 60 minutes, more preferably lower than 45 minutes.241075W0012012) Process according to any one of the preceding claims, wherein the period of time during which chelating agent (A) and polymer (B) are in direct contact with each other before and during the spray-drying or spray-granulation process is lower than 10 minutes, preferably lower than five minutes, more preferably lower than 60 seconds.13) Process according to any one of the preceding claims, wherein the bed temperature in steps (a) and (b) is, separately from each other, lower than 110° C, preferably lower than 90°C.14) Process according to any one of the preceding claims, wherein the process is run under an atmosphere which has a lower content of oxygen than normal atmospheric air.15) Process according to any one of the preceding claims, wherein the process is run under an inert atmosphere, preferably selected from nitrogen.16) Process according to any one of the preceding claims, further comprising mixing at least one additional compound (C) in step (a), preferably selected from the list consisting of TIO2, SIO2, phosphate.17) Process according to any one of the preceding claims, wherein the resulting powder or granule has a residual moisture content of 1 to 20% by weight.18) Powder or granule, obtainable or obtained by the process according to any one of the preceding claims.19) Use of a powder or granule according to claim 18 in detergent applications, preferably dishwashing detergent applications.

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