Solid composition comprising at least one organic chemical compound and at least one ceramic oxide

Abstract

The present invention deals with a solid composition comprising at least one organic chemical compound (A), com- prising at least one heteroatom selected from N, O, S, and at least one ceramic oxide (B), obtainable by spray-drying or spray-granulation, a process to manufacture the inventive solid composition and the solid composition's uses in home care applications.

Description

[0001] Solid composition comprising at least one orqanic chemical compound and at least one ceramic oxide

[0002] The present invention deals with a solid composition comprising at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, and at least one ceramic oxide (B), obtainable by spray-drying or spray-granulation, and with a process to manufacture the inventive solid composition and the solid composition's uses in home care applications.

[0003] Organic chemical compounds, comprising at least one heteroatom selected from N, 0, S, may be subject to deterioration (e. g. coloring, malodor) in the presence of oxidizing compounds, e. g. oxygen or peroxy compounds. Thus, also solid compositions containing at least one organic chemical compound, comprising at least one heteroatom selected from N, 0, S, may be subject to deterioration in the same manner.

[0004] The organic chemical compound (A) may, for example, be selected from compounds suitable for a detergent formulation or commonly used in a detergent formulation. Thus, the problem of deterioration in a solid composition may occur in a solid composition for detergent applications; the effects of deterioration (e. g., coloring and / or malodor) are undesired by customers.

[0005] Furthermore, the organic chemical compound (A) may be biodegradable and / or biobased.

[0006] The organic chemical compound (A) may also be selected from anionic surfactants, cationic surfactants, non-ionic surfactants, polymers, enzymes, builders and chelating agents.

[0007] Chelating agents (also referred to as "complexing agents” hereinafter) 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+. 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. For shipping such complexing agents, in most cases either solids such as granules are being applied or aqueous solutions.

[0008] Granules and powders have the advantage of being essentially water-free. That means that in case of shipping, no water has to be shipped, and costs for extra weight can be avoided.

[0009] Many industrial users prefer to use chelating agents in the form of granules or powders which may contain, in addition to the at least one chelating agent, at least one additional compound, in particular polymers.

[0010] 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.

[0011] As mentioned above, solid compositions containing at least one organic chemical compound, comprising at least one heteroatom selected from N, 0, S (e. g. aminocarboxylate chelating agents or biobased and / or biodegradable poly- mers), may be subject to deterioration, which may lead to undesired effects, like coloring (yellowing) of the solid composition and / or malodor.

[0012] Thus, one objective of the present invention was to overcome the problems and disadvantages mentioned above.

[0013] In particular, it was an objective of the present invention to provide a solid composition comprising at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, which reduces or avoids deterioration and its side effects (in particular, coloring and / or malodor), and which may be used in detergent applications, e. g. in the field of home care applications.

[0014] It was furthermore an objective of the present invention to provide a process to manufacture said solid composition.

[0015] Surprisingly, it was found that a solid composition which solves the above problems may be provided by adding a ceramic oxide (B), either by co-spraying or co-granulating said ceramic oxide (B) in the process to manufacture the solid composition comprising at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, and / or by coating said ceramic oxide (B) onto the solid composition.

[0016] Thus, one subject of the present invention is a solid composition comprising at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, and at least one ceramic oxide (B), obtainable by spray-drying or spray-granulation, including the steps of

[0017] (I) providing an aqueous solution or slurry of at least one compound (A), and

[0018] (ii) optionally, adding at least one ceramic oxide (B) to said slurry or solution,

[0019] (ill) removing most of the water by spray-drying or spray-granulation,

[0020] (iv) optionally, coating the resulting solid particles with a slurry of (B) in water or in aqueous solution or slurry of at least one compound (A), wherein at least one ceramic oxide is added to the composition in at least one of steps (ii) and (iv).

[0021] The term "solid” refers to its general meaning and normal conditions (at room temperature, I. e. 20° C). The inventive composition may be in the form of a granule (preferred) or a powder.

[0022] A further subject of the present invention is also a process for manufacturing the inventive solid composition, comprising the steps of

[0023] (I) providing an aqueous solution or slurry of at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, and

[0024] (ii) optionally, adding at least one ceramic oxide (B) to said slurry or solution,

[0025] (ill) removing most of the water by spray-drying or spray-granulation,

[0026] (iv) optionally, coating the resulting solid particles with a slurry of (B) in water or in aqueous solution or slurry of at least one compound (A), wherein at least one ceramic oxide is added to the composition in at least one of steps (ii) and (iv). Another subject of the present application is also the use of the inventive solid composition (preferably obtainable or obtained by the inventive process), in home care applications, e. g. detergent applications, more preferably dishwashing applications, in particular automatic dishwashing applications.

[0027] The organic chemical compound (A) in the inventive composition may, in one embodiment, be selected from compounds suitable for a detergent formulation or commonly used in a detergent formulation.

[0028] Furthermore, the organic chemical compound (A) may be biodegradable and / or biobased.

[0029] Biodegradable in the sense of the present invention means that said organic chemical compound (A) demonstrates at least 20%, preferably at least 40% or more preferably at least 60% biodegradability according to standard OECD 301 F within 56 days, preferably within 28 days.

[0030] For the purposes of this invention, aerobic biodegradation in wastewater according to OECD 301 F is expressed as a percentage of the theoretical oxygen demand (ThOD, which is measured by the elemental analysis of the compound of interest), which is needed to completely biodegrade the polymer sample. Thus, 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. The obtained values are preferably measured in triplicate using the OECD 301 F manometric respirometry method. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG).

[0031] The term biobased refers to a compound which is made, at least in a certain percentage (of at least 50% by weight, relating to the final product, preferably at least 75% by weight) based on renewable, carbon-based resources, as opposed to compounds made (at least in a certain percentage of at least 50% by weight, relating to the final product) based on non-renewable resources, such as petroleum. Examples of biobased compounds are sugar-derivatives.

[0032] In a further embodiment of the present invention, the organic chemical compound (A) is selected from anionic surfactants, cationic surfactants, non-ionic surfactants, polymers, enzymes, builders and chelating agents.

[0033] In another embodiment of the inventive solid composition, the organic chemical compound (A) is selected from aminocarboxylates, preferably selected from methylgycline diacetic acid (MGDA), glutamic acid diacetate (GLDA), iminodisuccinic acid (IDS), citric acid and Ethylediamine disuccinic acid (EDDS), their respective alkali metal salts and their mixtures.

[0034] In a preferred embodiment of the inventive solid composition, the organic chemical compound (A) is selected from MGDA and its alkali metal salts, in particular trisodium salt of MGDA.

[0035] The organic chemical compound (A) may also be selected from biobased and / or biodegradable polymers, preferably selected from polyamides, polyesters, polysaccharides and polyaspartic acid.

[0036] Polyaspartic acid is well known as biodegradable dispersing and scale inhibiting polymer. Three main methods have been developed for the industrial production of polyaspartic acid and its sodium salts:

[0037] (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;

[0038] (3) Polymerization of maleic acid anhydride in the presence of ammonia or ammonium salts followed by alkaline hydrolysis of the intermediate polysuccinimide.

[0039] Regardless of the synthesis route, the intermediate polysuccinimide has to be hydrolyzed by means of e.g. sodium hydroxide in order to obtain an aqueous polyaspartate solution. Acidification of the polyaspartate solution with mineral acids such as hydrochlorid or sulfur acid gives the polyaspartic acid.

[0040] Modified polyaspartic acid which can be used according to the present invention is preparable by polycondensation of

[0041] (i) 50 to 99 mol%, preferably 60 to 95 mol%, particularly preferably 80 to 95 mol%, of aspartic acid; and

[0042] (ii) 1 to 50 mol%, preferably 5 to 40 mol%, particularly preferably 5 to 20 mol%, of at least one carboxyl- containing compound, and subsequent hydrolysis of the co-condensates with the addition of a base, for example sodium hydroxide solution, wherein (ii) is not an aspartic acid.

[0043] The carboxyl-containing compound (ii) used in connection with the preparation of the polyaspartic acid to be used according to the invention can be, inter alia, a carboxylic acid (monocarboxylic acid or polycarboxylic acid), a hydroxycarboxylic acid and / or an amino acid (apart from aspartic acid). Such carboxylic acids or hydroxycarboxylic acids are preferably polybasic. In this connection, polybasic carboxylic acids can thus be used in the preparation of the polyaspartic acid to be used according to the invention, e.g. 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-C26 alkylsuccinic acids (e.g. octylsuccinic acid), C2-C26 alkenylsuccinic acids (e.g. octenylsuccinic acid), 1 ,2,3-propane- tricarboxylic 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. Furthermore, in this connection it is also possible to use polybasic hydroxycarboxylic acids, e.g. citric acid, isocitric acid, mucic acid, tartaric acid, tartronic acid, or malic acid. Amino acids that can be used in this connection are, inter alia, aminocarboxylic acids (e.g. glutamic acid, cysteine), basic diaminocarboxylic acids (e.g. lysine, arginine, histidine, aminocaprolactam), neutral amino acids (e.g. glycine, alanine, valine, leucine, isoleucine, methionine, cysteine, norleucine, caprolactam, asparagine, isoasparagine, glutamine, isoglutamine), aminosulfonic acids (e.g. taurine), hydroxylamino acids (e.g. hydroxyproline, serine, threonine), iminocarboxylic acids (e.g. proline, iminodiacetic acid), or aromatic and heterocyclic amino acids (e.g. anthranilic acid, tryptophan, tyrosine, histidine), but not aspartic acid. Preferred carboxyl-containing compounds (ii) in connection with the preparation of the modified polyaspartic acids to be 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.

[0044] The molecular weight (Mw) of the (modified) polyaspartic acid can easily be tuned by varying the reaction conditions. Molecular weights between 1000 g / mol and 100 000 g / mol can be achieved by simple adjustion of the process parameters (temperature, catalyst, reaction time). The preferred molecular weight of the (modified) poly aspartic acid used according to the present invention lies in the range between 1000 g / mol and 20 000 g / mol, preferably between 1500 and 15000 g / mol and particularly preferably between 2000 and 10 000 g / mol.

[0045] The aspartic acid (i) used in connection with the preparation of the (modified) polyaspartic acid to be used according to the invention can either be L- or D- and DL-aspartic acid. Preference is given to using L-aspartic acid

[0046] In an embodiment of the inventive solid composition, the ceramic oxide (B) is selected from the list consisting of, AI2O3, TiO2, CeO2 and ZrO2.

[0047] In a preferred embodiment of the inventive solid composition, the ceramic oxide (B) is TiO2.

[0048] Preferably, the inventive solid composition contains ceramic oxide (B) in an amount of at least 0.01 weight%, referring to the total weight of the organic chemical compounds (A), preferably at least 0.1 weight%, and preferably not more than 10 weight%.

[0049] The inventive solid composition usually contains residual moisture, moisture referring to water including water of crystallization and adsorbed water. The amount of water may be in the range of less than 30% by weight, preferably less than 20% by weight, referring to the total solids content of the respective solid composition, and may be determined by Karl-Fischer-titration or by drying at 160°C or 200° C to constant weight with infrared light.

[0050] The ceramic oxide (B) may be applied as a solid, but also in a slurry in water. Also, a dispersion of ceramic oxide (B) in a polymer solution, e. g. of polyacrylate in water, or in a surfactant, may be used.

[0051] In a preferred embodiment of the invention, less than 1 weight % of the ceramic oxide particles contained in the inventive solid composition have a diameter of less than 10 m.

[0052] The amount of ceramic oxide particles with a certain diameter may be determined by a sieving analysis (e. g. as defined in German industry norms DIN 66165-1 and 66165-2), e. g. by using a sieve with apertures of 10 pm, sieving and weighing.

[0053] Step (iii) of the inventive process, wherein most of the water is removed, and / or the optional coating step (iv), may be done by spray-drying or spray-granulation, preferably spray granulation. Particularly preferred is the use of fluid bed spray granulation technology for step (iii) and for optional step (iv).

[0054] In one embodiment, the process is performed in a multizone and / or multinozzle apparatus, preferably in a multizone and / or multinozzle fluid bed spray granulation apparatus.

[0055] Typical residence times are between 2 minutes and 4 hours, preferably from 30 minutes to 2 hours.

[0056] The pressure in such apparatuses is 850 mbar abs to 1200 mbar abs, preferably normal pressure ± 20 mbar, for example one mbar less than normal pressure.

[0057] Bed temperatures are strongly depended from the product. Typical bed temperatures lay in a range from 40°C to 150°C. Most times, the inlet air temperature is 20 to 150°C higher than the bed temperature. In one embodiment, the inlet air temperature is more than 150°C higher than the bed temperatures. Suitable nozzles are, for example, high-pressure rotary drum atomizers, rotary atomizers, three-fluid nozzles, singlefluid nozzles, single fluid high-pressure nozzles or two-fluid nozzles. Single-fluid nozzles and two-fluid nozzles being preferred. If a two fluid nozzle is used, than the first fluid is the aqueous slurry or aqueous solution, respectively, the second fluid is compressed gas, for example with a pressure of 1.1 to 7 bar, abs.

[0058] Applications

[0059] The inventive solid composition may be used, inter alia, in home care applications, preferably detergent applications. The inventive solid composition may particularly be useful in dishwashing applications, especially automatic dishwashing applications.

[0060] The inventive solid composition may also be used in laundry applications or industrial and institutional cleaning applications.

[0061] The inventive solid composition may be part of a cleaning agent, containing the inventive composition, and, optionally, at least one peroxy compound, and optionally further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol; preferably comprising said antimicrobial agent in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol.

[0062] Another aspect of the present invention is therefore the use of the inventive solid composition for the manufacture of a cleaning agent that contains at least one bleaching agent, and in particular for the manufacture of cleaning agent for fibers or hard surfaces, wherein said cleaning agent contains at least one peroxy compound. Another aspect of the present invention is a process for making at a cleaning agent by combining at least one inventive inventive solid composition with at least one bleaching agent, preferably at least one peroxy compound. Another aspect of the present invention is a cleaning agent, hereinafter also being referred to as inventive cleaning agent. Inventive cleaning agents contain at least one bleaching agent and at least one inventive inventive solid composition. Inventive cleaning agents show a reduced tendency for yellowing and therefore have an extended shelve-life.

[0063] Examples of suitable peroxy compounds are sodium perborate, anhydrous or for example as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, anhydrous or, for example, as monohydrate, hydrogen peroxide, persulfates, organic peracids such as peroxylauric acid, peroxystearic acid, peroxy-o-naphthoic acid, 1 , 12- diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1 ,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as free acid or as alkali metal salt, in particular as sodium salt, also sulfonylperoxy acids and cationic peroxy acids.

[0064] In a preferred embodiment, peroxy compound is selected from inorganic percarbonates, persulfates and perborates. Examples of sodium percarbonates are 2 Na2CC>3-3 H2O2. Examples of sodium perborate are (Na2[B(OH)2(O2)]2), sometimes written as NaBC^C^SfW instead. Most preferred peroxy compound is sodium percarbonate The term "cleaning agents” includes compositions for dishwashing, especially hand dishwash and automatic dishwashing and ware-washing, and compositions for hard surface cleaning such as, but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, descaling of pipes, window cleaning, car cleaning including truck cleaning, furthermore, open plant cleaning, cleaning-in-place, metal cleaning, disinfectant cleaning, farm cleaning, high pressure cleaning, and in addition, laundry detergent compositions. Such cleaning agents may be liquids, gels or preferably solids at ambient temperature, solids cleaning agents being preferred. They may be in the form of a powder or in the form of a unit dose, for example as a tablet or pouch. In one embodiment of the present invention, inventive cleaning agents may contain in the range of from 2 to 50 % by weight of inventive solid composition and in the range of from 0.5 to 15 % by weight of bleach.

[0065] Percentages are based on the solids content of the respective inventive cleaning agent.

[0066] Inventive cleaning agents may contain further ingredients such as one or more surfactants that may be selected from non-ionic, zwitterionic, cationic, and anionic surfactants. Other ingredients that may be contained in inventive cleaning agents may be selected from bleach activators, bleach catalysts, corrosion inhibitors, sequestering agents (other than organic compound (A)), enzymes, fragrances, dyestuffs, antifoams, and builders.

[0067] Particularly advantageous inventive cleaning agents may contain one or more complexing agents other than MGDA or GLDA. Advantageous detergent compositions for cleaners and advantageous laundry detergent compositions may contain one or more sequestrant (chelating agent) other than a mixture according to the present invention. Examples for sequestrants other than a mixture according to the present invention are IDS (iminodisuccinate), citrate, phos- phonic acid derivatives, for example the disodium salt of hydroxyethane-1 , 1 -diphosphonic acid (“HEDP”), and polymers with complexing groups like, for example, polyethyleneimine in which 20 to 90 mole-% of the N-atoms bear at least one CH2COO- group, and their respective alkali metal salts, especially their sodium salts, for example I DS-Na4, and trisodium citrate, and phosphates such as STPP (sodium tripolyphosphate). Due to the fact that phosphates raise environmental concerns, it is preferred that advantageous inventive cleaning agents are free from phosphate. "Free from phosphate" should be understood in the context of the present invention, as meaning that the content of phosphate and polyphosphate is in sum in the range from 10 ppm to 0.2% by weight, determined by gravimetric methods and referring to the respective inventive cleaning agent.

[0068] Inventive cleaning agents may contain one or more surfactant, preferably one or more non-ionic surfactant. Preferred non-ionic surfactants are alkoxy I ated alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl polyglycosides (APG), hydroxyalkyl mixed ethers and amine oxides.

[0069] Preferred examples of alkoxylated alcohols and alkoxy lated fatty alcohols are, for example, compounds of the general formula (II) in which the variables are defined as follows:

[0070] R1is identical or different and selected from hydrogen and linear Ci-Cio-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0071] R2is selected from C8-C22-alkyl, branched or linear, for example n-CsH , n-C H2i, n-C^Fh, n-C Fh, n-C Hss or n-CisHsz, R3is selected from Ci-Cw-alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl or isodecyl, m and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 3 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30.

[0072] In one embodiment, compounds of the general formula (II) may be block copolymers or random copolymers, preference being given to block copolymers.

[0073] Other preferred examples of alkoxylated alcohols are, for example, compounds of the general formula (III) in which the variables are defined as follows:

[0074] R1is identical or different and selected from hydrogen and linear Ci-Co-alkyl, preferably identical in each case and ethyl and particularly preferably hydrogen or methyl,

[0075] R4is selected from C6-C2o-alkyl, branched or linear, in particular n-CsH , n-C H2i, n-Ci2H25, n-C fe, n-C Hss, n-CisHaz, a is a number in the range from zero to 10, preferably from 1 to 6, b is a number in the range from 1 to 80, preferably from 4 to 20, d is a number in the range from zero to 50, preferably 4 to 25.

[0076] The sum a + b + d is preferably in the range of from 5 to 100, even more preferably in the range of from 9 to 50.

[0077] Preferred examples for hydroxyalkyl mixed ethers are compounds of the general formula (IV) in which the variables are defined as follows:

[0078] R1is identical or different and selected from hydrogen and linear Ci-Cw-alkyl, preferably in each case identical and ethyl and particularly preferably hydrogen or methyl,

[0079] R2is selected from Ce-C22-alkyl, branched or linear, for example iso-Cuffe, iso-Ci3H27, n-CsHiz, n-C H2i, n- C12H25, n-CuH29, n-CieH33 or n-C Hs?,

[0080] R3is selected from Ci-C -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1 ,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2- ethylhexyl, n-nonyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, and n-octadecyl.

[0081] The variables m and n are in the range from zero to 300, where the sum of n and m is at least one, preferably in the range of from 5 to 50. Preferably, m is in the range from 1 to 100 and n is in the range from 0 to 30. Compounds of the general formula (II) and (III) may be block copolymers or random copolymers, preference being given to block copolymers.

[0082] Further suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Further suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Amine oxides or alkyl polyglycosides, especially linear C4-Ci6-alkyl polyglucosides and branched Cs-C -alkyl polyglycosides such as compounds of general average formula (V) are likewise suitable. wherein the variables are defined as follows:

[0083] R5is Ci-C4-alkyl, in particular ethyl, n-propyl or isopropyl,

[0084] R6is -(CH2)2-R5,

[0085] G1is selected from monosaccharides with 4 to 6 carbon atoms, especially from glucose and xylose, y in the range of from 1.1 to 4, y being an average number.

[0086] Further examples of non-ionic surfactants are compounds of general formula (VII) and (VIII)

[0087] AO is selected from ethylene oxide, propylene oxide and butylene oxide,

[0088] EO is ethylene oxide, CH2CH2-O,

[0089] R8selected from Ce-Cie-alkyl, branched or linear, and R5is defined as above.

[0090] A3O is selected from propylene oxide and butylene oxide, w Is a number in the range of from 15 to 70, preferably 30 to 50, w1 and w3 are numbers in the range of from 1 to 5, and w2 is a number in the range of from 13 to 35.

[0091] An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187.

[0092] Mixtures of two or more different nonionic surfactants may also be present.

[0093] Other surfactants that may be present are selected from amphoteric (zwitterionic) surfactants and anionic surfactants and mixtures thereof. Examples of amphoteric surfactants are those that bear a positive and a negative charge in the same molecule under use conditions. Preferred examples of amphoteric surfactants are so-called betaine-surfactants. Many examples of betaine-surfactants bear one quaternized nitrogen atom and one carboxylic acid group per molecule. A particularly preferred example of amphoteric surfactants is cocamidopropyl betaine (lauramidopropyl betaine).

[0094] Examples of amine oxide surfactants are compounds of the general formula (IX)

[0095] R7R8R9N^O (IX) wherein R7, R8and R9are selected independently from each other from aliphatic, cycloaliphatic or C2-C4-alkylene Cio-C2o-alkylamido moieties. Preferably, R7is selected from C8-C2o-alkyl or C2-C4-alkylene Cio-C2o-alkylamido and R8and R9are both methyl.

[0096] A particularly preferred example is lauryl dimethyl aminoxide, sometimes also called lauramine oxide. A further particularly preferred example is cocamidylpropyl dimethylaminoxide, sometimes also called cocamidopropylamine oxide.

[0097] Examples of suitable anionic surfactants are alkali metal and ammonium salts of Cs-C -alky I sulfates, of Cs-C -fatty alcohol polyether sulfates, of sulfuric acid half-esters of ethoxylated C4-Ci2-alky I phenols (ethoxylation: 1 to 50 mol of ethylene oxide / mol), C12-C18 sulfo fatty acid alkyl esters, for example of C12-C18 sulfo fatty acid methyl esters, furthermore of C12-C18-al ky Isulfonic acids and of C 10-C1 s-al ky lary Isulfonic acids. Preference is given to the alkali metal salts of the aforementioned compounds, particularly preferably the sodium salts.

[0098] Further examples for suitable anionic surfactants are soaps, for example the sodium or potassium salts of stearoic acid, oleic acid, palmitic acid, ether carboxylates, and alkylether phosphates.

[0099] Preferably, laundry detergent compositions contain at least one anionic surfactant.

[0100] In one embodiment of the present invention, inventive cleaning agents that are determined to be used as laundry detergent compositions may contain 0.1 to 60 % by weight of at least one surfactant, selected from anionic surfactants, amphoteric surfactants and amine oxide surfactants.

[0101] In one embodiment of the present invention, inventive cleaning agents that are determined to be used 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.

[0102] In a preferred embodiment, inventive cleaning agents do not contain any anionic detergent.

[0103] Inventive cleaning agents may comprise one or more bleach catalysts. Bleach catalysts can be selected from bleachboosting transition metal salts or transition metal complexes 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 ligands and also cobalt-, iron-, copper- and ruthenium-amine complexes can also be used as bleach catalysts.

[0104] Inventive cleaning agents may comprise 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 nitrile quats (trimethylammonium acetonitrile salts). Further examples of suitable bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexylenediamine.

[0105] Inventive cleaning agents may comprise one or more corrosion inhibitors. In the present case, this is to be understood as including those compounds which inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotri azoles, aminotriazoles, alkylaminotriazoles, also phenol derivatives such as, for example, hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogal- lol.

[0106] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.1 to 1.5% by weight of corrosion inhibitor.

[0107] Inventive cleaning agents 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, sheet silicates, in particular those of the formula a-Na2Si20s, p-Na2Si20s, and 5- Na2Si20s, also fatty acid sulfonates, o-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders, for example polycarboxylates and polyaspartic acid.

[0108] Examples of organic builders are especially polymers and copolymers. In one embodiment of the present invention, organic builders are selected from polycarboxylates, for example alkali metal salts of (meth)acrylic acid homopolymers or (meth)acrylic acid copolymers, partially or completely neutralized with alkali.

[0109] Suitable comonomers for (meth)acrylic acid are monoethylenically unsaturated dicarboxylic acids such as maleic acid, fumaric acid, maleic anhydride, itaconic acid and citraconic acid. A suitable polymer is in particular polyacrylic acid, which preferably has an average molecular weight Mwin the range from 2000 to 40 000 g / mol, preferably 2000 to 10 000 g / mol, in particular 3000 to 8000 g / mol. Also of suitability are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid, and in the same range of molecular weight.

[0110] It is also possible to use copolymers of at least one monomer from the group consisting of monoethylenically unsaturated Cs-Cio-mono- or C4-C -dicarboxylic acids or anhydrides thereof, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilic or hydrophobic monomer as listed below.

[0111] Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins with 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, C22-a-olefin, a mixture of C2o-C24-a-olefins and polyisobutene having on average 12 to 100 carbon atoms per molecule.

[0112] Suitable hydrophilic monomers are monomers with sulfonate or phosphonate groups, and also nonionic monomers with hydroxyl function or alkylene oxide groups. By way of example, mention may be made of: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, methoxypoly(propylene oxide-co-ethylene oxide) (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethoxypolypropylene glycol (meth)acrylate, ethoxypolybutylene glycol (meth)acrylate and ethoxy- poly (propylene oxide-co-ethylene oxide) (meth)acrylate. Polyalkylene glycols here may comprise 3 to 50, in particular

[0113] 5 to 40 and especially 10 to 30 alkylene oxide units per molecule.

[0114] Particularly preferred sulfonic-acid-group-containing monomers here are 1 -acrylamido-1 -propanesulfonic acid, 2- acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2- methylpropanesulfonic acid, 3-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3-(2-propenyloxy)propanesulfonic acid, 2-methyl-2-propene-1 -sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylamide, and salts of said acids, such as sodium, potassium or ammonium salts thereof.

[0115] Particularly preferred phosphonate-group-containing monomers are vinylphosphonic acid and its salts.

[0116] A further example of builders is carboxymethyl inulin.

[0117] Moreover, amphoteric polymers can also be used as builders.

[0118] Inventive cleaning agents may comprise, for example, in the range from in total 10 to 70% by weight, preferably from in total 10 to 50% by weight, more preferably up to 20% by weight, of builder.

[0119] In one embodiment of the present invention, inventive cleaning agents according to the invention may comprise one or more co-builders.

[0120] Inventive cleaning agents may comprise one or more antifoams, selected for example from silicone oils and paraffin oils.

[0121] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.05 to 0.5% by weight of antifoam.

[0122] Inventive cleaning agents may comprise one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

[0123] In one embodiment of the present invention, inventive cleaning agents may comprise, for example, up to 5% by weight of enzyme, preference being given to 0.1 to 3% by weight. Said enzyme may be stabilized, for example with the sodium salt of at least one Ci-Ca-carboxylic acid or C4-C1 o-dicarboxy lie acid. Preferred are formates, acetates, adipates, and succinates.

[0124] In one embodiment of the present invention, inventive cleaning agents may comprise at least one zinc salt. Zinc salts can be selected from water-soluble and water-insoluble zinc salts. In this connection, within the context of the present invention, water-insoluble is used to refer to those zinc salts which, in distilled water at 25°C, have a solubility of 0.1 g / l or less. Zinc salts which have a higher solubility in water are accordingly referred to within the context of the present invention as water-soluble zinc salts.

[0125] In one embodiment of the present invention, zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnC , ZnSC>4, zinc acetate, zinc citrate, Zn (NOa)?, Zn(CHaSO3)2 and zinc gallate, preferably ZnCI 2, ZnSC>4, zinc acetate, zinc citrate, Zn(NOa)2, Zn(CH3SO3)2 and zinc gallate.

[0126] In another embodiment of the present invention, zinc salt is selected from ZnO, ZnOaq, Zn(OH)2 and ZnCOa. Preference is given to ZnOaq.

[0127] In one embodiment of the present invention, zinc salt is selected from zinc oxides with an average particle diameter (weight-average) in the range from 10 nm to 100 pm. The cation in zinc salt can be present in complexed form, for example complexed with ammonia ligands or water ligands, and in particular be present in hydrated form. To simplify the notation, within the context of the present invention, ligands are generally omitted if they are water ligands.

[0128] Depending on how the pH value of mixture according to the invention is adjusted, zinc salt can change. Thus, it is for example possible to use zinc acetate or ZnCk for preparing formulation according to the invention, but this converts at a pH of 8 or 9 in an aqueous environment to ZnO, Zn(OH)2 or ZnOaq, which can be present in non-complexed or in complexed form.

[0129] Zinc salt may be present in those inventive cleaning agents that are solid at room temperature. In such inventive cleaning agents zinc salts are preferably present in the form of particles which have for example an average diameter (number-average) in the range from 10 nm to 100 m, preferably 100 nm to 5 pm, determined for example by X-ray scattering.

[0130] Zinc salt may be present in those inventive cleaning agents that are liquid at room temperature. In such inventive cleaning agents zinc salts are preferably present in dissolved or in solid or in colloidal form.

[0131] In one embodiment of the present invention, inventive cleaning agents comprise in total in the range from 0.05 to 0.4% by weight of zinc salt, based in each case on the dry content of the cleaning agent in question.

[0132] Here, the fraction of zinc salt is given as zinc or zinc ions. From this, it is possible to calculate the counterion fraction. In one embodiment of the present invention, inventive cleaning agents are free from heavy metals apart from zinc compounds. Within the context of the present, this may be understood as meaning that inventive cleaning agents are free from those heavy metal compounds which do not act as bleach catalysts, in particular of compounds of iron and of bismuth. Within the context of the present invention, "free from" in connection with heavy metal compounds is to be understood as meaning that the content of heavy metal compounds which do not act as bleach catalysts is in sum in the range from 0 to 100 ppm, determined by the leach method and based on the dry content. Preferably, inventive cleaning agents has, apart from zinc, a heavy metal content below 0.05 ppm, based on the dry content of the formulation in question. The fraction of zinc is thus not included.

[0133] Within the context of the present invention, "heavy metals" are deemed to be all metals with a specific density of at least 6 g / cm3with the exception of zinc. In particular, the heavy metals are metals such as bismuth, iron, copper, lead, tin, nickel, cadmium and chromium.

[0134] Preferably, inventive cleaning agents comprise no measurable fractions of bismuth compounds, for example less than 1 ppm.

[0135] Inventive cleaning agents are excellent for cleaning hard surfaces and fibres. For example, they may be used in dishwashing applications, preferably automatic dishwashing applications.

[0136] In one embodiment of the present invention, inventive cleaning agents comprise one or more further ingredient such as fragrances, dyestuffs, organic solvents, buffers, disintegrants for tablets ("tabs”), and / or acids such as methylsulfonic acid.

[0137] From inventive solid compositions (e. g. granules or powders), examplary detergent compositions for automatic dishwashing detergents can be formulated by mixing the respective components according to the following Table F. Table F: Example detergent compositions for automatic dishwashing

[0138] .aundry detergents according to the invention are useful for laundering any type of laundry, and any type of fibres. Fibres can be of natural or synthetic origin, or they can be mixtures of natural of natural and synthetic fibres. Examples of fibers of natural origin are cotton and wool. Examples for fibers of synthetic origin are polyurethane fibers such as Spandex® or Lycra®, polyester fibers, or polyamide fibers. Fibers may be single fibers or parts of textiles such as knitwear, wovens, or nonwovens.

[0139] Another aspect of the present invention is a process for making tablets for automatic dishwashing from inventive solid compositions, e. g. a powder or granule, wherein said granule or powder is selected from inventive granules and inventive powders, respectively. Said process is hereinafter also referred to as pelletizing process according to the invention.

[0140] Inventive tablets are preferably made with the help of a machine, for example a tablet press.

[0141] The pelletizing process according to the invention can be carried out by mixing an inventive solid solid composition, e. g. in the form of a powder, with at least one non-ionic surfactant and optionally one or more further substance and then compressing the mixture to give tablets. Examples of suitable non-ionic surfactants and further substances such as builders, enzymes are listed above. Particularly preferred examples of non-ionic surfactants are hydroxy mixed ethers, for example hydroxy mixed ethers of the general formula (V).

[0142] Working examples

[0143] Some aspects of the present invention are illustrated by the following, non-limiting experimental examples.

[0144] The MGDA which was used in the experiments - unless otherwise stated - generally stems from a manufacturing process (so-called "Strecker synthesis”) wherein the product undergoes aftertreatment steps (e. g. bleaching and / or filtration). The aftertreatment step leads to MGDA products with a low APHA color number and can be purchased as commercial product, e.g. Trilon® M grades of BASF. MGDA which has not been aftertreated can show a higher APHA color number (DIN EN 1557, 25°C) of more than 350.

[0145] Example 1 : co-granulation of MGDA with 0.1 wt% TIO2

[0146] Spray liquor SL.1 was generated by mixing 3kg Trilon® M solution and 1,2g Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M. (Trilon® M is MGDA trisodium salt, available from BASF).

[0147] A lab scale granulator, commercially available as "WFP-Mini” from the company DMR, was charged with 300g of milled MGDA-Na3 particles using the hammer mill Kinetatica Polymix PX-MFL 90D at 4000 rpm (rounds per minute), 2 mm mesh. An amount of about 25 Nm3 / h of nitrogen with a temperature of 140-150°C was blown from the bottom. A fluidized bed was obtained. The above liquor SL.1 was introduced by spraying 14-15g / minute (at room temperature, about 22°C) into the fluidized bed from the bottom through a three-fluid nozzle. The pressure of the atomizing gas was 1 ,5-2,5bar (2,5-3,5bar, abs). Granules were formed, and the bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was about 100°C.

[0148] Every 15-20 minutes an aliquot of granule (150-250g) is removed from the vessel and classified by sieving. Three fractions were obtained: coarse particles (diameter > 1mm), value fraction (diameter >350pim and <1mm) and fines (diameter <350pim). The coarse particles (diameter > 1mm), were milled down using a hammer mill (Kinetatica Polymix PX-MFL 90D) at 4000 rpm (rounds per minute), 2 mm mesh. The powder (milled overs) so obtained and the fines were returned into the fluidized bed. The value fraction, which was not milled down, left the process and was collected.

[0149] After 2kg of sprayed liquid, a steady state was reached. Then, the value fraction was collected as inventive granules (GR. 1).

[0150] In the above example, nitrogen can be replaced by air having the same temperature.

[0151] Example 2: co-granulation of MGDA with 1 .0 wt% TiO2

[0152] Spray liquor SL.2 was generated by mixing 2,988kg Trilon® M solution and 12g Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M.

[0153] The granulation experiment was carried out the same way like in example 1 During the experiment, the inventive granules (GR. 2) were collected. co-granulation of MGDA with 2.0 wt% TiO2

[0154] Spray liquor SL.3 was generated by mixing 2,978kg Trilon® M solution and 24g Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M. The granulation experiment was carried out the same way like in example 1 During the experiment, the inventive granules (GR. 3) were collected.

[0155] Example 4: co-granulation of MGDA with 5.0 wt% TIO2

[0156] Spray liquor SL.4 was generated by mixing 2,938kg Trilon® M solution and 62g Titaniuim dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M.

[0157] The granulation experiment was carried out the same way like in example 1 During the experiment, the inventive granules (GR. 4) were collected.

[0158] Example 5: co-granulation of MGDA (no aftertreatment)with 5.0 wt% TIO2

[0159] Spray liquor SL.5 was generated by mixing 2,894kg of aqueous MGDA solution (43,5 % solid content, no aftertreatment, APHA color number > 350) and 61g Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M.

[0160] The granulation experiment was carried out the same way like in example 1

[0161] During the experiment, the inventive granules (GR. 5) were collected.

[0162] Example 6: co-granulation of MGDA with 2.0 wt% ZrO2

[0163] Spray liquor SL.6 was generated by mixing 2,98kg Trilon® M solution and 24,3g Zirconium dioxide. A slurry was observed, Zirconium dioxide is not soluble in Trilon® M.

[0164] The granulation experiment was carried out the same way like in example 1 During the experiment, the inventive granules (GR. 6) were collected.

[0165] Example 7: coating of MGDA with 5.0 wt% TIO2 in water

[0166] A spray liquor (SL.7) was generated by mixing 475g of water and 25g of Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in water.

[0167] A lab scale granulator, commercially available as "WFP-Mini” from the company DMR, was charged with 300g of Trilon® M max SG spherical particles, diameter 350 to 1000 pm.

[0168] An amount of 23-26Nm3 / h of nitrogen with a temperature of 140-165°C was blown from the bottom. A fluidized bed of Trilon® M max SG particles was obtained. The above-mentioned spray liquor SL.7 was introduced by spraying 8- 12g / minute SL.7 (at room temperate, about 22°C) into the fluidized bed from the bottom through a three-fluid nozzle. The pressure of the atomizing gas was 1 ,5-2bar (2,5-3bar, abs). The bed temperature, which corresponds to the surface temperature of the solids in the fluidized bed, was 95-100°C.

[0169] After 300g of 500g of SL.7 was sprayed, a coating of 5% Titan dioxide was reached. The spray was stopped and the granules in the WFP-Mini are the inventive granules Gr.7.

[0170] In the above example, nitrogen can be replaced by air having the same temperature. coating of MGDA with 0.1 wt% TIO2 in Trilon® M liquid A spray liquor (SL.8) was generated by mixing 50g of Trilon® M and 0,5g of Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in Trilon® M.

[0171] The granulation experiment was carried out the same way like in example 7. After 30g of SL8 was sprayed, a coating of 0,1% Titanium dioxide was reached. The spray was stopped and the granules in the WFP-Mini are the inventive granules Gr.8.

[0172] Example 9: coating of MGDA with slurry of 15 wt% of Sokalan® PA25CI and 2 wt% of TIO2

[0173] 5.0 wt% TIO2 in water (relative to total weight of final product)

[0174] (Sokalan® PA25CI is a polyacrylic polymer, sodium salt; available from BASF.)

[0175] A spray liquor (SL.9) was generated by mixing 532,4g of water, 57,2g of Sokalan® PA25CL granules and 7g of Titan dioxide. A slurry was observed, Titan dioxide is not soluble in water.

[0176] The granulation experiment was carried out the same way like in example 7. After 497.2g of 596.7g of SL9 was sprayed, a coating of 15% Sokalan® Pa25CL and 2% Titan dioxide was reached. The spray was stopped and the granules in the WFP-Mini are the inventive granules Gr.9.

[0177] Example 10: coating of co-granulate, comprising MGDA and 2wt% Ti 02, with 25 wt% of Sokalan® CP 50 (relative to total weight of final product)

[0178] (Sokalan® CP50 is a modified, sulfonated polycarboxylate polymer, sodium salt; available from BASF.) A spray liquor (SL.10) was generated by mixing 863,1g of water 107,9g Sokalan® CP50 granules.

[0179] Deviating from example 7, 300g of granules from example 3 (co-granules of Trilon® M with 2% Titan dioxide) were put into the granulator. These granules were coated, like it is described in example 7, but using SL.10.

[0180] After 809.2g of 971g of SL10 was sprayed, a coating with 25% Sokalan® CP50 was reached. The spray was stopped and the granules in the WFP-Mini are the inventive granules Gr.10.

[0181] Example 11 : coating of polyaspartic acid (milled down, molecular weight Mn ca. 1690, Mw 4040 g / mol) with MGDA containing 2 wt% of TIO2

[0182] A spray liquor (SL.11) was generated by mixing 1774,5g of Trilon® M solution and 14,5g of Titanium dioxide. A slurry was observed, Titanium dioxide is not soluble in water.

[0183] Deviating from example 7, 300g of granules of polyaspartic acid were put into the granulator, having a particle size distribution of 250-600pim. These granules were coated, like it is described in example 7, but using SL.11 . After 696.7g of SL.11 were sprayed, the first coating was finished. The granules in the granulator were sieved, and only 250g of the value fraction (250 - 1250pm) was used for the second coating.

[0184] The second coating was carried out the same way like the first coating, but only 250g of the coated granules from the first coating were used. These granules were coated a second time, like it is described in example 7, but using SL.11.

[0185] After 562g of SL11 was sprayed, the spray was stopped and the granules in the WFP-Mini are the inventive granules Gr.11. Testing of inventive granules and of comparative granule

[0186] Test protocol: 10 g of inventive granule or of comparative granule were mixed with 5 g Na-percarbonate and placed in a vial having a permeable stopper to allow an exchange with the surrounding atmosphere. The vial was stored for 28 days in a climate-chamber at 35°C and 70% humidity. The discoloration of the above stored mixtures was determined by measuring the b-value of the Cl ELAB color space (Mach 5 measurement).

[0187] Table 1. Yellowing behavior of inventive granules and of comparative granule

[0188] The experiments show the positive effect of incorporating ceramic oxides, like TIO2 or ZrO2 (either by co-granulation and / or by coating), into solid compositions comprising at least one organic chemical compound (A), like MGDA, on discoloration behavior.

Claims

Patent claims1) Solid composition comprising at least one organic chemical compound (A), comprising at least one heteroatom selected from N, 0, S, and at least one ceramic oxide (B), obtainable by spray-drying or spraygranulation, including the steps of(I) providing an aqueous solution or slurry of at least one compound (A), and(II) optionally, adding at least one ceramic oxide (B) to said slurry or solution,(ill) removing most of the water by spray-drying or spray-granulation,(iv) optionally, coating the resulting solid particles with a slurry of (B) in water or in aqueous solution or slurry of at least one compound (A), wherein at least one ceramic oxide is added to the composition in at least one of steps (II) and (iv).2) Solid composition according to claim 1, wherein the organic chemical compound (A) is selected from compounds suitable for a detergent formulation.3) Solid composition according to any one of the preceding claims, wherein the organic chemical compound (A) is selected from compounds commonly used in a detergent formulation.4) Solid composition according to any one of the preceding claims, wherein the organic chemical compound (A) is biodegradable, wherein said organic chemical compound (A) demonstrates at least 20% biodegradability according to standard OECD 301 F within 56 days, and / or biobased.5) Solid composition according to any one of the preceding claims, wherein the organic chemical compound (A) is selected from anionic surfactants, cationic surfactants, non-ionic surfactants, polymers, enzymes, builders and chelating agents.6) Solid composition according to any one of the preceding claims, wherein the organic chemical compound (A) is selected from aminocarboxylates, preferably selected from MGDA, GLDA, IDS, EDDS.7) Solid composition according to any one of the preceding claims, wherein the organic chemical compound (A) is selected from biobased and / or biodegradable polymers, preferably selected from polyamides, polyesters, polysaccharides and polyaspartic acid.8) Solid composition according to any one of the preceding claims, wherein the ceramic oxide (B) is selected from the list consisting of AI2O3, TIO2, CeO2 and ZrO2.9) Solid composition according to any one of the preceding claims, wherein the ceramic oxide (B) is TIO2.10) Solid composition according to any one of the preceding claims, wherein the composition contains ceramic oxide (B) in an amount of at least 0.01 weight%, referring to the total weight of the organic chemical compounds (A), preferably at least 0.1 weight%, preferably not more than 10 weight%.11) Solid composition according to any one of the preceding claims, wherein the composition has a moisture content of less than 30 wt%, preferably less than 20 wt%, relative to the total weight of the solid composition.12) Solid composition according to any one of the preceding claims, wherein less than 1% by weight of the ceramic oxide particles contained in the composition have a diameter of less than 10 m, as determined by sieving analysis as defined in German industry norms DIN 66165-1 and 66165-2, using a sieve with apertures of 10 pm.13) Process for manufacturing a solid composition according to any one of claims 1 to 11, comprising the steps of(I) providing an aqueous solution or slurry of at least one organic chemical compound (A), comprising at least one heteroatom selected from N, O, S, and(ii) optionally, adding at least one ceramic oxide (B) to said slurry or solution,(ill) removing most of the water by spray-drying or spray-granulation,(iv) optionally, coating the resulting solid particles with a slurry of (B) in water or in aqueous solution or slurry of at least one compound (A), wherein at least one ceramic oxide is added to the composition in at least one of steps (ii) and (iv).14) Process according to claim 13, wherein the organic chemical compound (A) is selected from compounds suitable for a detergent formulation.15) Process according to any one of claims 13 to 14, wherein the organic chemical compound (A) is selected from compounds commonly used in a detergent formulation.16) Process according to any one of claims 13 to 15, wherein the organic chemical compound (A) is biodegradable, as defined above in claim 4, and / or biobased.17) Process according to any one of claims 13 to 16, wherein the organic chemical compound (A) is selected from anionic surfactants, cationic surfactants, non-ionic surfactants, polymers, builders and chelating agents.18) Process according to any one of claims 13 to 17, wherein the organic chemical compound (A) is selected from aminocarboxylates, preferably selected from MGDA, GLDA, IDS, EDDS.19) Process according to any one of claims 13 to 18, wherein the ceramic oxide (B) is selected from the list consisting of AI2O3, TIO2, CeO2, ZrO2.20) Process according to any one of claims 13 to 19, wherein the ceramic oxide (B) is TIO2.21) Process according to any one of claims 13 to 20, wherein the spray-drying or spray-granulation is done at a bed temperature of 40° to 150° C and / or at a pressure in the range of from 850 mbar abs to 1200 mbar abs.22) Process according to any one of claims 13 to 21, wherein spray-drying or spray-granulation is done with a sieving and milling circuit after step (ill) and / or (iv) which removes particles with a size of less than 50 micrometers, as determined by sieving analysis as defined in German industry norms DIN 66165-1 and 66165-2, and re-introduces them into the spray-drying or spray-granulation process.23) Process according to any one of claims 13 to 22, wherein the resulting composition has a moisture content of less than 30 wt%, preferably less than 20 wt%, relative to the total weight of the solid composition.24) Use of a solid composition according to any of the preceding claims 1 to 12, or obtainable according to the process of any one of claims 13 to 23, in home care applications, preferably detergent applications, more preferably dishwashing applications, in particular automatic dishwashing applications.

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