EP3138895B1 - Particles, use of the same or for manufacture of dishwashing agents and their manufacture - Google Patents

Description

1. (A) insgesamt mindestens 90 Gew.-% Komplexbildner, gewählt aus Aminopolycarboxylaten,
2. (B) insgesamt im Bereich von 0,1 bis 9 Gew.-% mindestens ein anionisches Homo- oder Copolymer und
3. (C) insgesamt im Bereich von 1 bis 10 Gew.-% mindestens ein Additiv, gewählt aus Fällungskieselsäuren und pyrogenen Kieselsäuren,

bezogen jeweils auf den Wirkstoffgehalt von gesamtem Partikel,
wobei (Co)polymer (B) und Aminopolycarboxylat (A) molekular dispers miteinander vermischt sind und wobei sich Additiv (C) überwiegend auf der äußeren Oberfläche der Partikel befindet.The present invention relates to particles containing

1. (A) a total of at least 90% by weight of complexing agent selected from aminopolycarboxylates,
2. (B) in total in the range of 0.1 to 9 wt .-% of at least one anionic homo- or copolymer and
3. (C) in total in the range from 1 to 10% by weight of at least one additive selected from precipitated silicas and fumed silicic acids,

in each case based on the active substance content of total particles,
wherein (co) polymer (B) and aminopolycarboxylate (A) are mixed together in a molecularly disperse form and wherein additive (C) is predominantly on the outer surface of the particles.

Furthermore, the present invention relates to a process for the preparation of particles according to the invention and their use as or for the production of solid dishwashing detergents, in particular dishwasher detergents for automatic dishwashing.

On the raw materials of dishwashing detergent and dishwashing itself, high demands are made, both in terms of their cleaning properties as well as in terms of environmental protection. Although many dishwasher detergents containing phosphate show good cleaning properties, they are no longer accepted for ecological reasons. As alternative complexing agents, aminopolycarboxylates and polyaminopolycarboxylates are recommended, for example the alkali metal salts of methylglycinediacetic acid (MGDA) or glutamic acid diacetic acid (GLDA). However, because many aminopolycarboxylates and polyaminopolycarboxylates, and in particular MGDA and GLDA, are hygroscopic, the processing properties leave much to be desired. For example, many granules of MGDA are difficult to process into tablets.

Out WO 2013/000848 It is known that one can treat Aminopolycarboxylate with certain additives, for example with silicic acids or fatty acid salts. For some processing methods, such as tableting, the improvement is not enough. In particular, those detergents which contain nonionic surfactants, such as hydroxy mixed ethers, can be poorly tableted with many aminopolycarboxylates.

It was therefore the object to provide aminopolycarboxylates and polyaminopolycarboxylates in application forms that can be tabletted particularly well. A further object was to provide a process by which it is possible to obtain readily tablettable aminopolycarboxylates and polyaminopolycarboxylates, and there was also the object of providing use for the new uses of the aminopolycarboxylates and polyaminopolycarboxylates in question.

Accordingly, the particles defined above were found, also called particles according to the invention in the context of the present invention. Particulates according to the invention can be present as powders, granules or pellets. There are powders related to of the present invention, an average particle diameter (D50) in the range of 1 micron to a maximum of 0.1 mm, granules an average particle diameter (D50) of at least 0.1 mm to a maximum of 2 mm and pellets an average particle diameter (D50) of at least 2 mm up to a maximum of 5 mm, each determined by sieve analysis. Particular preference is given to particles according to the invention as granules with an average particle diameter (D) in the range from 100 to 800 μm. Such particles of the invention can be processed particularly well to tablets.

1. (A) insgesamt mindestens 90 Gew.-% Komplexbildner, gewählt aus Aminopolycarboxylaten, im Rahmen der vorliegenden Erfindung auch Komplexbildner (A), Verbindung (A) oder Aminopolycarboxylat (A) genannt,
2. (B) insgesamt im Bereich von 0,1 bis 9 Gew.-% mindestens ein anionisches Homo- oder Copolymer, im Rahmen der vorliegenden Erfindung auch kurz (Co)polymer (B) oder anionisches (Co)polymer (B) genannt, und
3. (C) insgesamt im Bereich von 1 bis 10 Gew.-% mindestens ein Additiv, kurz auch Additiv (C) genannt, wobei Additiv (C) gewählt wird aus Fällungskieselsäuren und pyrogenen Kieselsäuren,

bezogen jeweils auf Wirkstoffgehalt von gesamtem Partikel,
wobei (Co)polymer (B) und Aminopolycarboxylat (A) molekular dispers miteinander vermischt sind und wobei sich Additiv (C) überwiegend auf der äußeren Oberfläche der Partikel befindet.Contain particles according to the invention

1. (A) a total of at least 90% by weight of complexing agent selected from aminopolycarboxylates, in the context of the present invention also called complexing agent (A), compound (A) or aminopolycarboxylate (A),
2. (B) in total in the range of 0.1 to 9 wt .-% of at least one anionic homo- or copolymer, in the context of the present invention also short (co) polymer (B) or anionic (co) polymer (B) mentioned, and
3. (C) overall in the range from 1 to 10% by weight of at least one additive, also referred to as additive (C) for short, wherein additive (C) is chosen from precipitated silicas and fumed silicic acids,

in each case based on the active substance content of total particles,
wherein (co) polymer (B) and aminopolycarboxylate (A) are mixed together in a molecularly disperse form and wherein additive (C) is predominantly on the outer surface of the particles.

Examples of aminopolycarboxylates (A) are z. B. Salts of the following aminopolycarboxylic acids: nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), hydroxyethylethylenediaminetriacetic acid (HEDTA), methylglycinediacetic acid (MGDA), glutamic acid diacetic acid (GLDA), 1,3-propylenediaminetetraacetic acid (PDTA), ethylenediamine N, N'-bis (2-hydroxyphenylacetic acid) (EDDHA), hydroxyethyliminodiacetic acid (HEIDA), iminodisuccinic acid (IDS), ethylenediamine disuccinic acid (EDDS) and β-alaninediacetic acid (β-ADA). Preferred aminopolycarboxylates (A) are salts of MGDA and GLDA, very particularly preferred are salts of MGDA and even more preferably dialkali metal salts and trialkali metal salts of MGDA and mixtures of dialkali metal salts and trialkali metal salts of MGDA.

Examples of salts are the ammonium salts and the alkali metal salts, for example sodium salts and potassium salts, and mixtures of sodium and potassium salts. Preferred alkali metal salts are each sodium salts.

For example, aminopolycarboxylates (A) may contain small amounts of alkaline earth metal salts, for example Mg ²⁺ or Ca ²⁺ salts, or Fe ³⁺ salts or the respective complexes as impurities, for example 0.01 to 0.5, due to the production process mol%, based on the anion. Such minor impurities are not explicitly mentioned in the context of the present invention.

In a preferred embodiment of the present invention, aminopolycarboxylate (A) is used as the aminopolycarboxylic acid completely neutralized with alkali. Preferred examples are the trisodium salt of MGDA and the tripotassium salt of MGDA, the tetrasodium salt of GLDA and the tetrapotassium salt of GLDA and mixed sodium potassium salts of MGDA and GLDA, in which the underlying aminopolycarboxylic acid is in each case completely neutralized.

In another preferred embodiment of the present invention, aminopolycarboxylate (A) is used as a mixture of fully alkoxylated and partially alkali neutralized aminopolycarboxylic acid. Preferred examples are mixtures of dialkali metal salt and trialkali metal salt of MGDA, for example in a molar ratio in the range of 1:10 to 10: 1, and mixtures of trialkali metal salt and tetraalkali metal salt of GLDA, for example in a molar ratio in the range of 1:10 to 10: 1.

Many amine polycarboxylates (A) are based on aminopolycarboxylic acids which may be present in the form of the racemate or as L- or D-enantiomer or in partially racemized form. In one embodiment, the aminopolycarboxylate (A) used is a racemic alkali metal salt of MGDA. In another embodiment, the aminopolycarboxylate (A) used is an alkali metal salt of MGDA-for example the trisodium salt or the tripotassium salt-in which predominantly the L-enantiomer is present, for example with an enantiomeric excess (ee) in the range from 5 to 75%. , preferably 10 to 50%.

In another embodiment of the present invention, the aminopolycarboxylate (A) used is an alkali metal salt of GLDA, for example the tetrantrium salt or the tetrapotassium salt, in which predominantly the L-enantiomer is present, for example with an enantiomeric excess (ee) in the range from 5 to 95%, preferably 50 to 90%.

In one embodiment of the present invention, the aminopolycarboxylate used is a mixture of two different aminopolycarboxylates, for example alkali metal salts of MGDA and GLDA, for example in a molar ratio in the range from 50: 1 to 4: 1.

Particulates according to the invention also contain
(B) at least one anionic homo- or copolymer.

In the context of the present invention, anionic (co) polymers (B) are understood as meaning those organic homo- or copolymers which carry at least one carboxylic acid group or at least one sulfonic acid group per molecule. Preferred anionic (co) polymers (B) are those which carry at least one carboxylic acid group or at least one sulfonic acid group per monomer unit. In this case, the carboxylic acid group (s) or sulfonic acid group (s) may be present as free acids or preferably in partially or completely neutralized form with alkali or ammonium. Preferred alkali for neutralization is sodium or potassium or mixtures of sodium and potassium.

In one embodiment of the present invention, anionic (co) polymer (B) is selected from poly (meth) acrylic acids which are partially or completely neutralized with alkali.

In another embodiment of the present invention, anionic copolymer (B) is selected from random or block copolymers of acrylic acid and maleic anhydride and random copolymers of (meth) acrylic acid with one or more radically polymerizable sulfonic acids, for example 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 their sodium, potassium or ammonium salts.

In one embodiment of the present invention, anionic (co) polymer (B) has an average molecular weight M _w in the range of 1,000 to 1,000,000 g / mol, preferably 2,000 to 50,000 g / mol. The average molecular weight M _{w is} based on the free acid.

Aminopolycarboxylat (A) and (co) polymer (B) are molecularly dispersed mixed together. In the context of the present invention, this means that all or a large number of the particles according to the invention, for example at least 80%, of a representative sample contain aminopolycarboxylate (A) and (co) polymer (B). Preferably, molecularly dispersedly mixed means that all or a majority of the particles, for example at least 80%, of a representative sample comprise at least 90% by weight of aminopolycarboxylate (A) and 0.01 to 2% by weight of (co) polymer (B). contain. Furthermore, molecularly dispersed mixed with one another means that particles according to the invention have over their cross-section a substantially or even exactly uniform composition with respect to aminopolycarboxylate (A) and (co) polymer (B).

Particulates according to the invention furthermore have at least one additive (C), with additive (C) being predominantly on the outer surface of the particles according to the invention. Mainly means that at least 75% of the additive (C) is on the outer surface of particles of the invention. The remaining proportions of additive (C) can be present, for example, in particles according to the invention or as separate particles. The morphology can be determined, for example, by light microscopy. Particles of the invention with additive (C) are preferably completely or incompletely encased.

Additives (C) are selected from pyrogenic silicas and precipitated silicas. Pyrogenic silicic acids are obtained by high-temperature flame hydrolysis of silicon tetrachloride in the oxyhydrogen flame. Precipitated silicas are wet-chemically made from alkali silicate solutions obtained by addition of acids. Fumed silicas and precipitated silicas are not crystalline, but of amorphous structure.

Examples of pyrogenic silicic acids are the Aerosil brands® (from Evonik), in particular Aerosil® 200. Examples of precipitated silicas are the Sipernat brands® (Evonik), in particular Sipernat® 320, Sipernat® 320 DS, Sipernat® 360, Sipernat® 500 LS, Sipernat® 2200, Sipernat® 22, Sipernat® 22 S, Sipernat® 22 LS, Sipernat® 50, Sipernat® 50 S, Sipernat® C 600, Sipernat® C 630, Sipernat® 820 A and Sipernat® 880 ,

In particles according to the invention, the abovementioned silicic acids can be used as hydrophilic silicic acids or as hydrophobically modified silicic acids. Examples of hydrophobically modified silicas are, for example, Sipernat® D 10, Sipernat® D 17 and Aerosil® R 812 and R 972. Hydrophobically modified, precipitated silicas and hydrophobically modified fumed silicas are very particularly preferred additives (C).

Hydrophobically modified silicas are obtainable by aftertreatment of silicic acids with after-treatment agents such as silanes, for example trimethylchlorosilane or dimethyldichlorosilane, or with siloxanes. In hydrophobically modified silicas, the aftertreatment agent is linked to the silica via a chemical bond.

In one embodiment of the present invention, additive (C) is selected from silicas having a specific surface area (BET) in the range of 30 to 800 m ² / g.

Preferred precipitated silicas are characterized by a specific surface area of from 25 to 800 m ² / g, preferably from 30 to 500 m ² / g, particularly preferably from 150 to 450 m ² / g, determined by means of the Areameter method, ISO 5794-1 , Annex D. Hydrophobically modified precipitated silicas preferably have a specific surface area of 75 to 125 m ² / g, Areameter method ISO 5794-1, Annex D.

In one embodiment of the present invention, the tamped density of precipitated silicas used is in the range from 50 to 300 g / l, preferably 75 to 200 g / l and very particularly preferably 90 to 150 g / l (determination according to DIN ISO 787/11). ,

In the case of the precipitated silicas, additive (C) preferably has an average particle diameter in the range from 1 to 200 .mu.m, preferably from 5 to 150 .mu.m, more preferably from 6 to 120 .mu.m and most preferably from 8 to 20 .mu.m (D50), each determined by light scattering according to ISO13320-1: 1999.

Additive (C) in the form of fumed silicic acids preferably has a specific surface area in the range of 100 to 400 m ² / g and average particle diameter of 1 nm to 50 nm, based on the primary particles. Primary particles may be fused together or aggregates or agglomerates. The tamped density of fumed silicas is preferably in the range of 50 to 150 g / l.

In one embodiment of the present invention, hydrophobically modified pyrogenic silicas having a specific surface area in the range of 100 to 400 m ² / g and an average particle diameter of 1 nm to 50 nm are selected.

In one embodiment of the present invention, additive (C) has a pH in the range of 3 to 7. The pH of additive (C) can be determined, for example, analogously to ISO 787-9: 1981.

Additive (C) may contain metal ions such as Ca ²⁺ , Mg ²⁺ , Al ³⁺ or Fe ³⁺ in very small amounts, for example in each case <6, preferably <5% by weight, preferably less than 3% by weight, especially preferably less than 2 wt .-% and particularly preferably less than 1.5 wt .-% based on the total weight of the respective silica and determined as the oxide. In one embodiment, at least 0.001% by weight each of the above-mentioned metal ions, based on the total weight of the respective silica and determined as oxide, may be present. In embodiments in which additive (C) is selected from fumed silicas, the content of metal ions such as Ca ²⁺ , Mg ²⁺ , Al ³⁺ or Fe ³⁺ , at max. 0.05 wt .-%, based on the total weight of the respective silica and determined as the oxide, and in the case of precipitated silicas at max. 1% by weight (calcined substance, 2 hours at 1000 ° C.). These are not required or suitable component of the silica, but production-related impurities. As the Na content, determined as Na ₂ O (ISO 3262-18), at <1.5 wt .-%. Crystalline silicates, phyllosilicates and zeolites are not among the preferred additives (C).

Contain particles according to the invention
at least 90% by weight of complexing agent (A), preferably 94.5 to 97.95% by weight,
0.1 to 9 wt .-% of anionic homo- or copolymer (B), and particularly preferably 1 to 5 wt .-%, and
in the range from 1 to 10% by weight of additive (C), preferably from 2 to 5% by weight,
in each case based on the active ingredient content of total particles.

Particulates according to the invention may contain water, for example residual moisture and, in particular, water of crystallization of complexing agent (A). Such water is not taken into account in the determination of the ingredients. Particulates according to the invention can furthermore contain impurities which originate from the synthesis of complexing agent (A). Such impurities are also not taken into account in the determination of the ingredients.

Particulates according to the invention can be processed very well to form solid dishwashing detergents, for example to powders and in particular to those which are present in the form of so-called unit doses, for example in the form of tablets. Another aspect of the present invention therefore relates to the use of particles according to the invention for the production of solid dishwashing detergents. A further aspect of the present invention relates to a process, also called formulation process according to the invention in the context of the present invention, for the production of solid dishwashing detergents, for example tablets, using particles according to the invention. A further aspect of the present invention relates to solid dishwashing detergents, in the context of the present invention also dishwasher detergents according to the invention, comprising particles according to the invention and preferably at least one nonionic surfactant. In a preferred embodiment of the present invention dishwashing compositions according to the invention are designed as tablets.

In the context of the present invention, "solid" is understood to mean "solid at room temperature".

Tablets within the scope of the present invention may be from 5 to 50 g, preferably from 10 to 25 g, and more preferably from 15 to 22.5 g.

Tablets generally have a base which may be triangular, quadrangular, in particular rectangular or square, pentagonal or hexagonal, or which is oval or preferably circular, or which may be angular with rounded corners. Tablets have different thicknesses at different locations, or preferably the same at all points. For example, tablets may have a recess in one location and a compartment fitted into the recess containing ingredients to be separated from the other ingredients during storage.

Dishwashing agents according to the invention are preferably free of phosphates and polyphosphates, with hydrogen phosphates being subsumed, for example free from trisodium phosphate, pentasodium tripolyphosphate and hexasodium metaphosphate. In the context of the present invention, "free from", in the context of phosphates and polyphosphates, is understood to mean that the total content of phosphate and polyphosphate ranges from 10 ppm to 2% by weight, preferably to 0.2% by weight. lies, determined by gravimetry.

Dishwashing agents according to the invention may contain further constituents. Examples include zinc salts, bismuth salts, builders, bleach, or other ingredients.

Zinc salts can be selected from water-soluble and non-water-soluble zinc salts. For the purposes of the present invention, zinc salts which are not water-soluble and which have a solubility of 0.1 g / l or less in distilled water at 25 ° C. Accordingly, zinc salts which have a higher water solubility are referred to in the context of the present invention as water-soluble zinc salts.

In one embodiment of the present invention, zinc salt is selected from zinc benzoate, zinc gluconate, zinc lactate, zinc formate, ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate, ZnCl ₂ , ZnSO ₄ , zinc acetate, zinc citrate, Zn (NO ₃ ) ₂ , Zn (CH ₃ SO ₃ ) ₂ and zinc gallate are preferred.

In another embodiment of the present invention, zinc salt is selected from ZnO, ZnO · aq, Zn (OH) ₂ and ZnCO ₃ . ZnO · aq is preferred.

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

The cation in zinc salt can be complexed, for example, complexed with ammonia ligands or water ligands, and in particular be present hydrated. To simplify the notation, ligands are usually omitted in the context of the present invention, if they are water ligands.

Depending on how to adjust the pH of dishwashing detergent according to the invention, zinc salt can be converted. Thus, for example, it is possible to use zinc acetate or ZnCl ₂ to produce dishwashing detergent according to the invention, but this converts to ZnO, Zn (OH) ₂ or ZnO · aq at a pH of 8 or 9 in an aqueous environment can not be complexed or complexed.

Zinc salt is present in dishwashing compositions according to the invention preferably in the form of particles which have, for example, a mean diameter (number average) in the range from 10 nm to 100 .mu.m, preferably 100 nm to 5 .mu.m, determined for example by X-ray scattering.

In one embodiment of the present invention, dishwashing detergent according to the invention contains one or more bleaching agents (D), for example one or more oxygen bleaching agents or one or more chlorine-containing bleaching agents.

For example, formulations according to the invention may contain from 0.5 to 15% by weight of bleach (D).

Examples of suitable oxygen bleaching agents are sodium perborate, anhydrous or, for example, as monohydrate or as tetrahydrate or so-called dihydrate, sodium percarbonate, 2Na ₂ CO ₃ .3H ₂ O ₂ , anhydrous or, for example, as monohydrate, hydrogen peroxide, persulphates, organic peracids such as peroxylauric acid, peroxystearic acid, Peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, in each case as the free acid or as the alkali metal salt, in particular as the sodium salt, furthermore sulfonyl peroxyacids and cationic peroxyacids.

Dishwashing agents according to the invention may contain, for example, in the range from 0.5 to 15% by weight of oxygen bleach.

Suitable chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

Dishwashing agents according to the invention may contain, for example, in the range from 3 to 10% by weight of chlorine-containing bleach. Because of corrosion problems dishwashing agents according to the invention preferably contain sodium percarbonate, but no chlorine bleach.

In one embodiment of the present invention, dishwashing detergent according to the invention may comprise further ingredients (E), for example one or more surfactants, one or more enzymes, one or more builders, in particular phosphorus-free builders, one or more cobuilders, one or more alkali carriers, one or more alkali carriers a plurality of bleach catalysts, one or more bleach activators, one or more bleach stabilizers, one or more defoamers, one or more corrosion inhibitors, one or more builders, buffers, dyes, one or more perfumes, one or more organic solvents, one or more tableting aids, one or more several disintegrating agents, one or more thickeners, or one or more solubilizing agents.

Examples of surfactants are, in particular, nonionic surfactants and mixtures of anionic or zwitterionic surfactants with nonionic surfactants. Preferred nonionic surfactants are alkoxylated alcohols and alkoxylated fatty alcohols, di- and multiblock copolymers of ethylene oxide and propylene oxide and reaction products of sorbitan with ethylene oxide or propylene oxide, alkyl glycosides and so-called amine oxides.

in der die Variablen wie folgt definiert sind:

• R¹ gleich oder verschieden gewählt aus linearem C₁-C₁₀-Alkyl, bevorzugt Ethyl und besonders bevorzugt Methyl,
• R² gewählt aus C₈-C₂₂-Alkyl, beispielsweise n-C₈H₁₇, n-C₁₀F₂₁, n-C₁₂H₂₅, n-C₁₄H₂₉, n-C₁₆H₃₃ oder n-C₁₈H₃₇,
• R³ gewählt aus C₁-C₁₀-Alkyl, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, iso-Pentyl, sec.-Pentyl, neo-Pentyl, 1,2-Dimethylpropyl, iso-Amyl, n-Hexyl, iso-Hexyl, sec.-Hexyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl oder iso-Decyl,
• m und n liegen im Bereich von null bis 300, wobei die Summe von n und m mindestens eins beträgt. Bevorzugt ist m im Bereich von 1 bis 100 und n im Bereich von 0 bis 30.

Preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (II)

where the variables are defined as follows:

• R ^{1 is the} same or different selected from linear C ₁ -C ₁₀ -alkyl, preferably ethyl and particularly preferably methyl,
• R ^{2 is} selected from C ₈ -C ₂₂ -alkyl, for example nC ₈ H ₁₇ , nC ₁₀ F ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ or nC ₁₈ H ₃₇ ,
• R ^{3 is} selected from C ₁ -C ₁₀ -alkyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or iso-decyl,
• m and n are in the range of zero to 300, where the sum of n and m is at least one. Preferably, m is in the range of 1 to 100 and n is in the range of 0 to 30.

In the case of compounds of the general formula (II), these may be block copolymers or random copolymers, preference being given to block copolymers.

in der die Variablen wie folgt definiert sind:

R⁴

gewählt aus C₆-C₂₀-Alkyl, insbesondere n-C₈H₁₇, n-C₁₀H₂₁, n-C₁₂H₂₅, n-C₁₄H₂₉, n-C₁₆H₃₃, n-C₁₈H₃₇,

R⁵

gleich oder verschieden und gewählt aus linearem C₁-C₄-Alkyl, bevorzugt jeweils gleich und Ethyl und besonders bevorzugt Methyl,

a

eine Zahl im Bereich von 1 bis 6,

b

ist eine Zahl im Bereich von 4 bis 20,

d

ist eine Zahl im Bereich von 4 bis 25.

Other preferred examples of alkoxylated alcohols and alkoxylated fatty alcohols are, for example, compounds of the general formula (III)

where the variables are defined as follows:

R ⁴

selected from C ₆ -C ₂₀ -alkyl, in particular nC ₈ H ₁₇ , nC ₁₀ H ₂₁ , nC ₁₂ H ₂₅ , nC ₁₄ H ₂₉ , nC ₁₆ H ₃₃ , nC ₁₈ H ₃₇ ,

R ⁵

identical or different and selected from linear C ₁ -C ₄ -alkyl, preferably in each case identical and ethyl and particularly preferably methyl,

a

a number in the range of 1 to 6,

b

is a number in the range of 4 to 20,

d

is a number in the range of 4 to 25.

These compounds of the general formula (III) may be block copolymers or random copolymers, block copolymers are preferred.

R⁶

wird gewählt aus C₄-C₃₀-Alkyl, verzweigt oder unverzweigt, und aus C₄-C₃₀-Alkylen, verzweigt oder unverzweigt-, mit mindestens einer C-C-Doppelbindung, bevorzugt sind C₄-C₃₀-Alkyl, verzweigt oder unverzweigt, noch mehr bevorzugt ist n-C₄-C₃₀-Alkyl am meisten bevorzugt ist n-C₁₀-C₁₂-Alkyl.

R⁷

wird gewählt aus C₁-C₃₀-Alkyl, verzweigt oder unverzweigt, und aus C₂-C₃₀-Alkylen, verzweigt oder unverzweigt, mit mindestens einer Doppelbindung, bevorzugt ist C₆-C₂₀-Alkyl und noch mehr bevorzugt ist C₈-C₁₁-Alkyl,

x

wird gewählt aus 1 bis 100, bevorzugt 5 bis 60, noch mehr bevorzugt sind 10 bis 50, noch mehr bevorzugt sind 20 bis 40,

AO

wird aus gleichen oder verschiedenen Alkylenoxidgruppen gewählt, beispielsweise CH₂-CH₂-O, (CH₂)₃-O, (CH₂)₄-O, CH₂CH(CH₃)-O, CH(CH₃)-CH₂-O- und CH₂CH(n-C₃H₇)-O. am meisten bevorzugtes Beispiel für AO ist CH₂-CH₂-O (EO).

Particularly preferred nonionic surfactants are so-called hydroxy mixed ethers, for example of the general formula (IV)

R ⁶ -CH (OH) -CH ₂ -O- (AO) _x -R ⁷ (IV)

where the variables are defined as follows:

R ⁶

is selected from C ₄ -C ₃₀ alkyl, branched or unbranched, and from C ₄ -C ₃₀ alkylene, branched or unbranched, having at least one CC double bond, preferably C ₄ -C ₃₀ alkyl, branched or unbranched even more preferred is nC ₄ -C ₃₀ alkyl most preferred is nC ₁₀ -C ₁₂ alkyl.

R ⁷

is selected from C ₁ -C ₃₀ alkyl, branched or unbranched, and from C ₂ -C ₃₀ alkylene, branched or unbranched, having at least one double bond, preferred is C ₆ -C ₂₀ alkyl and even more preferably C ₈ C ₁₁ alkyl,

x

is selected from 1 to 100, preferably 5 to 60, even more preferred are 10 to 50, even more preferred are 20 to 40,

AO

is selected from the same or different alkylene oxide groups, for example CH ₂ -CH ₂ -O, (CH ₂ ) ₃ -O, (CH ₂ ) ₄ -O, CH ₂ CH (CH ₃ ) -O, CH (CH ₃ ) -CH ₂ -O- and CH ₂ CH (nC ₃ H ₇ ) -O. most preferred example of AO is CH ₂ -CH ₂ -O (EO).

In one embodiment of the present invention, (AO) _{x is} (CH ₂ CH ₂ O) _x1 , where x1 is in the range of 1 to 50.

In one embodiment of the present invention (AO) _x is selected from - (CH ₂ CH ₂ O) _x2 - (CH ₂ CH (CH ₃₎ -O) _x3, and - (CH ₂ CH ₂ O) _x2 - (CH (CH ₃ ) CH ₂ -O) _{x 3} where x ₂ and x ₃ may be the same or different and range from 1 to 30.

In one embodiment of the present invention (AO) _x is selected from - (CH ₂ CH ₂ O) _x4 where x4 is in the range of 10 to 50, AO is EO, and R ⁶ and R ⁷ are independently selected from C ₈ -C ₁₄ alkyl.

In the context of the present invention, x or x1 or x2 and x3 or x4 stands for average values, with a number average being preferred. Accordingly, x or x1 or x2 or x3 or x4, if present, may be a non-integer, although of course in a particular molecule only whole AO units may be.

Other suitable nonionic surfactants are selected from di- and multiblock copolymers, composed of ethylene oxide and propylene oxide. Other suitable nonionic surfactants are selected from ethoxylated or propoxylated sorbitan esters. Also suitable are amine oxides or alkyl glycosides. An overview of suitable further nonionic surfactants can be found in EP-A 0 851 023 and in DE-A 198 19 187 ,

It may also contain mixtures of several different nonionic surfactants.

Examples of anionic surfactants are C ₈ -C ₂₀ -alkyl sulfates, C ₈ -C ₂₀ -alkyl sulfonates and C ₈ -C ₂₀ -alkyl ether sulfates having one to six ethylene oxide units per molecule.

In one embodiment of the present invention, dishwashing detergent according to the invention may contain in the range from 3 to 20% by weight of surfactant.

Dishwashing agents according to the invention may contain one or more enzymes. Examples of enzymes are lipases, hydrolases, amylases, proteases, cellulases, esterases, pectinases, lactases and peroxidases.

Dishwashing agents according to the invention may contain, for example, up to 5% by weight of enzyme, preferably from 0.1 to 3% by weight, based in each case on the total solids content of the dishwashing detergent according to the invention.

Dishwashing agents according to the invention may contain one or more builders, in particular phosphate-free builders. Examples of suitable builders are silicates, in particular sodium disilicate and sodium metasilicate, zeolites, sheet silicates, especially those of the formula α-Na ₂ Si ₂ O ₅ , β-Na ₂ Si ₂ O ₅ , and δ-Na ₂ Si ₂ O ₅ , furthermore citric acid and their alkali metal salts, succinic acid and its alkali metal salts, fatty acid sulfonates, α-hydroxypropionic acid, alkali malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartaric acid diacetate, tartaric acid monoacetate, oxidized starch, and polymeric builders such as polycarboxylates and polyaspartic acid.

In one embodiment of the present invention, builders of polycarboxylates are selected, for example, alkali metal salts of (meth) acrylic acid homo- or (meth) acrylic acid copolymers.

Suitable comonomers 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 M _w in the range from 2000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. Also suitable 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.

It is also possible to use copolymers of at least one monomer selected from the group consisting of monoethylenically unsaturated C ₃ -C ₁₀ -mono- or dicarboxylic acids or their anhydrides, such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, fumaric acid, itaconic acid and citraconic acid, with at least one hydrophilic or hydrophobic Monomers are used as enumerated below.

Suitable hydrophobic monomers are, for example, isobutene, diisobutene, butene, pentene, hexene and styrene, olefins having 10 or more carbon atoms or mixtures thereof, for example 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-hexadecene and 1-octadecene. Eicosene, 1-docoses, 1-tetracoses and 1-hexacoses, C ₂₂ -α-olefin, a mixture of C ₂₀ -C ₂₄ -α-olefins and polyisobutene having an average of 12 to 100 carbon atoms.

Suitable hydrophilic monomers are monomers having sulfonate or phosphonate groups, as well as nonionic monomers having hydroxy function or alkylene oxide groups. Examples include: allyl alcohol, isoprenol, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolybutylene glycol (meth) acrylate, methoxypoly (propylene oxide-coethylene oxide) (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, ethoxypolybutylene glycol (meth) acrylate and ethoxypoly (propylene oxide-co-ethylene oxide) (meth) acrylate. The polyalkylene glycols contain 3 to 50, in particular 5 to 40 and especially 10 to 30 alkylene oxide units.

Particularly preferred sulfonic acid-containing monomers 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 their sodium, potassium or ammonium salts.

Particularly preferred phosphonate group-containing monomers are the vinylphosphonic acid and its salts.

In addition, amphoteric polymers can also be used as builders.

Dishwashing agents according to the invention may contain, for example, in the range from 10 to 50% by weight, preferably up to 20% by weight, of builder.

In one embodiment of the present invention, dishwashing compositions according to the invention may contain one or more co-builders.

Examples of co-builders are phosphonates, for example hydroxyalkane phosphonates and aminoalkane phosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetra-methylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably used in the form of the neutrally reacting sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP.

Dishwashing agents according to the invention may contain one or more alkali carriers. Alkaline carriers, for example, provide the pH of at least 9 when an alkaline pH is desired. Suitable examples are alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal hydroxides and alkali metal metasilicates. Preferred alkali metal is in each case potassium, particularly preferred is sodium.

Dishwashing agents according to the invention may contain one or more bleach catalysts. Bleach catalysts can be selected from bleach-enhancing transition metal salts or transition metal complexes such as manganese, iron, cobalt, ruthenium or molybdenum-salene complexes or manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes. Manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands and cobalt, iron, copper and ruthenium-amine complexes can also be used as bleach catalysts.

Dishwashing agents according to the invention may contain one or more bleach activators, for example N-methylmorpholinium acetonitrile salts ("MMA salts"), trimethylammonium acetonitrile salts, N-acylimides such as N-nonanoyl succinimide, 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.

Dishwashing agents according to the invention may contain one or more corrosion inhibitors. This is to be understood in the present case, such compounds that inhibit the corrosion of metal. Examples of suitable corrosion inhibitors are triazoles, in particular benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, furthermore phenol derivatives such as, for example, hydroquinone, catechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol.

In one embodiment of the present invention, dishwashing agents according to the invention contain a total of from 0.1 to 1.5% by weight of corrosion inhibitor.

Dishwashing agents according to the invention may contain one or more builders, for example sodium sulphate.

Dishwashing agents according to the invention may contain one or more defoamers selected, for example, from silicone oils and paraffin oils.

In one embodiment of the present invention, dishwashing agents according to the invention contain a total of from 0.05 to 0.5% by weight defoamer.

In one embodiment of the present invention, dishwashing agents according to the invention may comprise one or more acids, for example methanesulfonic acid.

Dishwashing agents according to the invention show very good rinsing properties.

1. (A) mindestens einen Komplexbildner, gewählt aus Aminopolycarboxylaten, und
2. (B) mindestens ein anionisches Homo- oder Copolymer

Another object of the present invention is a process for the preparation of particles according to the invention, which is referred to in the context of the present invention as the inventive production process. The preparation process according to the invention is characterized in that

1. (A) at least one complexing agent selected from aminopolycarboxylates, and
2. (B) at least one anionic homo- or copolymer

optionally mixed together in the presence of water, any water present largely removed and then with
(C) at least one additive selected from precipitated silicas and fumed silicas,
mixed in the dry state.

Complexing agent (A), (co) polymer (B) and additive (C) are defined above.

The production process according to the invention comprises several steps. In a first step, complexing agent (A) and (co) polymer (B) are mixed together. You can mix complexing agent (A) and (co) polymer (B) dry together. In order to achieve better mixing of complexing agent (A) and (co) polymer (B), however, it is preferred to mix complexing agent (A) and (co) polymer (B) in the presence of water, for example as an aqueous solution or aqueous suspension having a solids content in the range of 10 to 65 wt .-%, preferably 35 to 590 wt .-%.

Mixing sets the desired ratio of complexing agent (A) and (co) polymer (B). For example, one can use a weight ratio of complexing agent (A) to (co) polymer (B) in the range of 45: 1 to 9900 to 1.

In one embodiment of the present invention, water is removed by spray drying, in another by spray granulation.

In spray-drying, an aqueous suspension or, preferably, an aqueous solution of complexing agent (A) and (co) polymer (B) can be fed into a spray tower with a hot gas stream, for example hot nitrogen or preferably hot air, and thereby sprayed into droplets , "Hot" means at least 120 ° C, preferably at least 125 ° C. In order to avoid decomposition of complexing agent (A) or (co) polymer (B), the hot gas stream should not exceed a temperature of 450 ° C, preferably at most 220 ° C, measured in each case at the beginning of the spray drying, ie at the inlet. The droplets thus produced preferably have an average diameter in the range of 10 to 550 μm, preferably 20 to 180 μm, and more preferably 30 to 100 μm. When spraying, water evaporates.

In a spray granulation, an aqueous suspension or preferably an aqueous solution of complexing agent (A) and (co) polymer (B) with a hot gas stream, for example with hot nitrogen or preferably with hot air, on a fluidized bed of particles, such as complexing agent (A) or of complexing agent (A) and (co) polymer (B), spray. "Hot" means at least 120 ° C, preferably at least 125 ° C. To one To avoid decomposition of complexing agent (A) or (co) polymer (B), the hot gas stream should not exceed a temperature of 350 ° C, preferably at most 220 ° C, measured at the beginning of the spray granulation, ie at the inlet. The droplets thus produced preferably have an average diameter in the range of 10 to 550 μm, preferably 20 to 180 μm, and more preferably 30 to 100 μm. During spray granulation, water evaporates. The droplets containing complexing agent (A) and (co) polymer (B) allow the solid, ie molecularly disperse mixture of complexing agent (A) and (co) polymer (B), to grow on particles already present in the granulator.

By embodiments such as spray-drying or spray granulation, water, as it was present when mixing complexing agent (A) and (co) polymer (B), is largely removed. By "substantially removed" is meant that one obtains particles which may have a residual moisture, for example in the range of 1 to 20 wt .-%, but preferably not more. The particles - ie powder or granules or pellets - are free-flowing powders that leave a dry impression on the unaided eye.

In a further step of the preparation process according to the invention, the particles thus obtainable are mixed with additive (C), in the dry state.

The mixing process can be used in the usual mixing units, such. As drum mixer, V-Blender, tumble or Turbula mixer, cone mixer (eg Nauta mixer), PflugscharMischer (Lödige mixer), high-shear mixer (Diosna mixer) or intensive mixer fast mixer (Eirich Mixer). In a preferred embodiment, the mixing process takes place in mixers that exert low shear forces on the mix, such. As tumble mixer, cone mixer and ploughshare mixer.

Preferably, particles of complexing agent (A) and (co) polymer (B) are added and then additive (C) is added followed by mixing. To ensure a gentle mixing, you work with the shortest possible mixing times. So z. For example, for the production of 100 g of the particles according to the invention in a Turbula mixer, a mixing time of 3 minutes is completely sufficient.

If particles of complexing agent (A) and (co) polymer (B) are prepared in powder form via spray drying, then additive (C) can advantageously be obtained separately from the aqueous solution of complexing agent (A) and (co) polymer (B) directly meter into the spray tower. Possible locations for metering are the upper end of the spray dryer, a metering connection via a sight glass or metering via the hot gas stream. The same applies in principle for a spray granulation.

If a metered addition of additive (C) into the spray tower is not desired or not possible due to the construction of the spray tower, it can be metered in a separate mixing unit, as described above.

By means of the production process according to the invention, particles according to the invention are obtained. Optionally, a sieving step can be connected to remove coarse agglomerated particles containing complexing agent (A) and (co) polymer (B) and additive (C) or coarse particles derived from additive (C). For this purpose, use is made of a sieve with a mesh size of 1200 to 2100 μm, preferably 1300 to 1500 μm. They can be processed excellently to solid dishwashing detergents and in particular to solid dishwashing detergents in the form of tablets. A further aspect of the present invention relates to a process for the preparation of solid dishwashing detergents in the form of tablets, also referred to in the context of the present invention as tabletting process according to the invention.

The tabletting process according to the invention can be carried out by mixing particles according to the invention with at least one nonionic surfactant and optionally one or more further substances and then compressing them into tablets. Examples of suitable nonionic surfactants and other substances such as builders, enzymes are enumerated above. Particularly preferred examples of nonionic surfactants are hydroxy mixed ethers, for example hydroxy mixed ethers of the general formula (IV).

The tabletting process according to the invention can be carried out as a direct tabletting process, that is to say without tabletting excipients, or with the aid of one or more tabletting excipients. It is preferred to carry out the tabletting process according to the invention in rooms which have a suitably low relative humidity, for example up to 50%.

The Tablettierverfahren invention can be carried out at room temperature under conditions with or without conditioned air, wherein the humidity and / or temperature are kept constant. Under these conditions, it is advantageous to encapsulate the tablet device or otherwise isolate it from the environment. These conditions may be necessary or advantageous, for example, in the case of high air humidity of the outside air or high hygroscopicity of individual components

The tableting process according to the invention is preferably carried out with a tablet press. Small quantities of tablets can be produced by means of a manually operated tablet press. Tablet presses suitable for large numbers are rotary tablet presses, roller tablet presses and eccentric presses. Preferably, first portioned according to the invention dishwashing detergent and then pressed it. When pressing one applies a contact pressure, suitable are contact pressures in the range of 50 to 500 MPa.

After tableting, remove the tablets of the tablet press. In an optional step, you can still coat the freshly prepared tablets ("coaten") or pack.

Tablets prepared according to the invention have little tendency for tablet errors such as sticking or lidding. The term "gluing" generally refers to the gluing of the tablet mass to the pressing surfaces of the punches and not to the gluing of the tablet to the die wall, i. the adhesion outweighs the cohesion. When lidding dissolves after compaction still in the die or after or at the ejection of the compact from the fracture point convexly curved cover layer. It can even split the whole tablet in layers. Causes of capping are radial pressures acting on the tablet by the die, an inhomogeneous distribution of porosity and residual stresses in the tablet, and the elastic retraction of the particles and the entire tablet during ejection. In contrast, tablets prepared according to the invention rapidly dissolve in water.

The invention will be further explained by working examples.

I. Preparation of Particles Containing Complexing Agent (A) and (Co) Polymer (B)

• Komplexbildner (A.1): MGDA-Na₃, Racemat, als 40 Gew.-% Lösung in Wasser
• Polymer (B.1): Polyacrylsäure M_w 4.000 g/mol, als Natriumsalz, vollständig neutralisiert, M_w bestimmt durch GPC und auf die freie Säure bezogen.
• Polymer (B.2): Polyacrylsäure M_w 4.000 g/mol, als Natriumsalz, 25 mol-% neutralisiert, M_w bestimmt durch GPC und auf die freie Säure bezogen.

The following starting materials were used:

• Complexing agent (A.1): MGDA-Na ₃ , racemate, as 40 wt .-% solution in water
• Polymer (B.1): polyacrylic acid M _w 4,000 g / mol, as sodium salt, completely neutralized, M _w determined by GPC and based on the free acid.
• Polymer (B.2): polyacrylic acid M _w 4,000 g / mol, neutralized as sodium salt, 25 mol%, M _w determined by GPC and based on the free acid.

The spray granulator used for laboratory purposes was a cylindrical vessel with perforated base plate, diameter 148 mm, upper base area: 0.017 m ² , height 40 cm, with a conical insert, inner surface 0.000785 m ² . For the operation of the spray granulator, 1 kg granules of MGDA trisodium salt were placed, diameters ranging from 350 μm to 1.2 mm. A fluidized bed was created by passing nitrogen at a temperature of 150 ° C through the bottom plate, amount: 42 Nm ³ nitrogen / h.
Nl, Nm ³ : standard liter or standard cubic meter, liter or cubic meter at 1 bar and 20 ° C

I.1 Preparation of a spray solution SL.1 and production of particles

6.37 kg of 40% by weight solution of racemic MGDA-Na ₃ (complexing agent (A.1)) were placed in a vessel. Subsequently, 500 g of a 45 wt .-% aqueous solution of polymer (B.1) was added and stirred for 15 minutes. Spray solution SL.1 was obtained.

One sprayed 1.9 liters SL.1, which had a temperature of 20 ° C, into the fluidized bed in the spray granulator with the aid of a two-flow nozzle, absolute pressure: 3.4 bar, 4.5 Nm ³ / h. Every 30 minutes one took just above the perforated plate so much solids with the help of an inline Discharge screw that 1 kg of granules remained in the spray granulator. The removed solid was divided by sieving into three fractions: coarse fraction, diameter greater than 1.25 mm, fines content, diameter less than 355 μm, average fraction (355 μm diameter <1.25 mm). The coarse fraction was ground using a hammer mill (Kinetatica Polymix PX-MFL 90D) at 4000 rpm (revolutions per minute), 2 mm mesh The resulting powder was mixed with the fines and then returned to the spray granulator The stationary state was reached for 2 hours and the granules had a residual moisture content of 10.5 to 11%.

I.2 Production of a spray solution SL.2 and production of particles

6.69 kg of 40% by weight solution of racemic MGDA-Na ₃ (complexing agent (A.1)) were introduced into a vessel. Subsequently, 297 g of a 45% by weight aqueous solution of polymer (B.1) were added and the mixture was stirred for 15 minutes. Spray solution SL.2 was obtained.

It was granulated according to the instructions of I.1, but using SL.2 instead of SL.1.

I.4 Production of particles according to the invention

To produce particles or comparative particles according to the invention, the required amounts of the two components according to Table 2 were mixed gently in a tumble mixer for 3 min. The corresponding particles were obtained.

Silica (C.1): precipitated silica, (D50) 13.5 μm, pH value: 6.5, BET surface area, ISO 9277: 190 m ² / g, tamped density 90 g / l, commercially available as Sipernat® 22s Silica (C.2): fumed silica, pH 4, BET surface area, ISO 9277: 200 m ² / g, ramming density 50 g / l, commercially available as Aerosil® 200 Table 2: Inventive particles and comparison particles Product / component (A.1) [% by weight] (B) [% by weight] (C) [% by weight] V- (Part.1) 97.5 - 2.5% (C.1) V- (Part.2) 95 - 5% (C.1) V- (Part.3) 98 - 2% (C.2) V- (Part.4) 95 - 5% (C.2) (Part.5) 93 5% (B.1) 2% (C.2) (Part.6) 90 5% (B.1) 5% (C.1) V- (Part.7) 100 - -

All percentages are by weight and refer to solids content. All particles (according to the invention or comparison particles) each had a mean diameter of 600 microns. Fines and chunks were removed by sieving, as described above. The residual moisture was 13% each, determined one hour after production.

II. Tests of Tablettability

The following basic mixtures "Base 1" and "Base 2" were prepared, Table 3: Table 3: Components of the basic mixtures: component "Base 1" [g] "Base 2" [g] Inventive particles or comparative particles 20 30 2Na ₂ CO ₃ .3H ₂ O ₂ 12 12 TAED 5 5 disilicate 4 4 Sodium citrate dihydrate 20 10 Na ₂ CO ₃ 26 26 Polyacrylic acid M _w 4000 g / mol, as sodium salt, completely neutralized 6 6 Nonionic surfactant (IV.1) 1 1 Nonionic surfactant (IV.1): nC ₁₀ H ₂₁ CH (OH) -CH ₂ - (OCH ₂ CH ₂ ) ₄₀ -OnC ₁₂ H ₂₅
Nonionic surfactant (IV.2): nC ₈ H ₁₇ CH (OH) -CH ₂ - (OCH ₂ CH ₂ ) ₂₀ -O-iso-C ₁₀ H ₂₁

All amounts refer to active ingredient.

For this example, a total of 470 grams of base mix 1 or 2 were placed in a laboratory mixer Somakon MP-M Somakon and premixed dry at a temperature of 60 ° C with a mixer speed of 600 rev / min and with a mixing time of 10 minutes. As a mixing element was a mixing tool on the container bottom. Through the use of the counter-rotating tool on the container lid and by a scraping plate on the container wall, the required mixing quality was achieved.

When the mixer was switched on, 30 grams of 65 ° C preheated non-ionic surfactant (IV.2) were then metered liquid while avoiding the formation of agglomerates. Then the mixer was emptied. Dishwashing detergent according to Table 4 was obtained. Table 4: Composition of dishwashing compositions according to the invention and comparative dishwashing detergents Component / name base mixture particle Nio-surfactant (IV.2) V-GSM.1 Base 1 V- (Part.7) 6% V-GSM.2 Base 2 V- (Part.7) 6% V-GSM.3 Base 1 V- (Part.1) 6% V-GSM.4 Base 2 V- (Part.1) 6% V-GSM.5 Base 1 V- (Part.3) 6% V-GSM.6 Base 2 V- (Part.3) 6% GSM.7 Base 1 Part.5 6% GSM.8 Base 2 Part.6 6% Percentages in% by weight and based in each case on the active content of the entire dishwashing detergent.

General procedure: Dishwashing detergent according to Table 3 was tabletted as follows. For each dishwashing detergent, 10 tablets each were measured with respect to their height and breaking strength using the tablet tester WHT 2 from Pharmatest, Hainburg. The average tablet height was 5 mm each. As observed by visual inspection, in the case of using base mixtures containing particles of the present invention, good tablet strength was achieved and there were no tabletting errors. When using base blends containing comparative particles, the number of tableting errors was significantly higher.

The dissolution time was determined as follows: A tablet was placed in a container having a diameter of 65 mm and a volume of 800 ml and dissolved in 600 ml of water with the aid of a propeller stirrer at a constant rotational speed. The time was measured until the refractive index of the solution became constant and visually no solid particles were visible.

Claims (12)

1. A particle comprising

   (A) in total at least 90% by weight of complexing agent, selected from aminopolycarboxylates,

   (B) in total in the range from 0.1 to 9% by weight of at least one anionic homopolymer or copolymer and

   (C) in total in the range from 1 to 10% by weight of at least one additive selected from precipitated silicas and fumed silicas,

   based in each case on the active ingredient content of overall particle,
   where (co)polymer (B) and aminopolycarboxylate (A) are mixed with one another in molecularly disperse form and where additive (C) is located predominantly on the outer surface of the particles.
2. The particle according to claim 1, wherein anionic homopolymer or copolymer is selected from poly(meth)acrylic acids which have been partially or completely neutralized with alkali metal.
3. The particle according to claim 1 or 2, wherein complexing agent (A) is selected from methylglycine diacetate (MGDA) and glutamic acid diacetate, and alkali metal salts thereof.
4. The particle according to any one of claims 1 to 3, wherein it has an average particle diameter (D50) in the range from 100 to 800 µm.
5. The particle according to any one of claims 1 to 4, wherein it is completely or incompletely covered with additive (C).
6. The particle according to any one of claims 1 to 5, wherein additive (C) is a fumed silica with an average particle diameter in the range from 1 nm to 50 µm.
7. The use of particles according to any one of claims 1 to 6 for producing solid dishwashing detergents.
8. A solid dishwashing detergent comprising particles according to any one of claims 1 to 6 and at least one nonionic surfactant.
9. The dishwashing detergent according to claim 8, wherein the nonionic surfactant is a hydroxyalkyl mixed ether.
10. A process for producing particles according to any one of claims 1 to 6, wherein

    (A) at least one complexing agent selected from aminopolycarboxylates, and

    (B) at least one anionic homopolymer or copolymer are mixed with one another, optionally in the presence of water, optionally present water is largely removed and then mixed with

    (C) at least one additive selected from precipitated silicas and fumed silicas,
    in the dry state.
11. The process according to claim 10, wherein water is removed by spray drying or spray granulation.
12. A process for producing solid dishwashing detergents in the form of tablets, wherein particles according to any one of claims 1 to 6 are mixed with at least one nonionic surfactant and optionally one or more further substance and then compressed to give tablets.