Fine-Particulate Bleaching Catalysts, Process for Their Preparation and Their Use

Abstract

Disclosed are fine-particulate powders containing particles with at least 80% by weight of a manganese complex with nitrogen-containing ligands, wherein one or more of the ligands are macrocyclic ligands, wherein at least 70% by weight of the particles have particle sizes in the range from 1 m to 50 m, at most 15% by weight of the particles have particle sizes >50 m and at most 15% by weight of the particles have particle sizes <1 m, wherein the percentages refer to the total amount of the particles.

These powders can be used as bleaching catalysts in washing and cleaning agents and display an improved activity and at the same time these are toxicologically non-hazardous during manufacturing and use.

Claims

1. Fine-particulate powder containing particles with at least 80% by weight of a manganese complex with nitrogen-containing ligands, wherein one or more of the ligands are macrocyclic ligands, wherein at least 70% by weight of the particles have particle sizes in the range from 1 m to 50 m, at most 15% by weight of the particles have particle sizes >50 m and at most 15% by weight of the particles have particle sizes <1 m, wherein the percentages refer to the total amount of the particles.

2. The fine-particulate according to claim 1, wherein the manganese complex is a complex of manganese in the oxidation state II, III or IV, which contains one or more macrocyclic ligand(s) with the donor functions N and/or NR, in which R stands for a hydrocarbon residue with up to 20 C-atoms.

3. The fine-particulate powder according to claim 1, wherein the manganese complex has the following formula (1) or (2) ##STR00002## wherein a is 1 or 2, b is a number from 0 to 4, and X stands for any monovalent or bivalent anion.

4. The fine-particulate powder according to claim 3, wherein X stands for PF.sub.6.sup., CH.sub.3COO.sup., Cl.sup., or SO.sub.4.sup.2.

5. The fine-particulate powder according to claim 3, wherein the manganese-complex is bis (N,N,N-trimethyl-1,4,7-triazacyclononane)-trioxo-dimanganese (IV) di(hexafluorophosphate) monohydrate.

6. The fine-particulate powder according to claim 1, wherein the powder does not contain particles with particle sizes of above 100 m and/or does not contain particles with particle sizes of below 100 nm.

7. The fine-particulate powder according to claim 1, wherein at least 90% by weight of the particles have particle sizes in the range from 2 m to 50 m, at most 5% by weight of the particles have particle sizes >50 m and at most 5% by weight of the particles have particle sizes <2 m, wherein the percentages refer to the total amount of particles.

8. The fine-particulate powder according to claim 1, wherein the powder has volume-average particle sizes D.sub.50 in the range from 2 to 25 m.

9. The fine-particulate powder according to claim 1, wherein the powder has volume-average particle sizes D.sub.97 in the range from 8 to 35 m.

10. The fine-particulate powder according to claim 9, wherein the powder has volume-average particle sizes D.sub.97 in the range from 10 to 30 m.

11. The fine-particulate powder according to claim 10, wherein the powder has volume-average particle sizes D.sub.97 in the range from 11 to 25 m.

12. The fine-particulate powder according to claim 11, wherein the powder has volume-average particle sizes D.sub.97 in the range from 12 to 20 m.

13. A process for preparing a fine-particulate powder containing particles with at least 80% by weight of a manganese complex with nitrogen-containing ligands, wherein one or more of the ligands are macrocyclic ligands comprising: i) introducing a milling stock of particulate material comprising at least 80% by weight of manganese complexes with nitrogen-containing ligands, wherein of the ligands one or more are macrocyclic ligands, into a milling device selected from the group consisting of a jet mill or a pen mill equipped with a cooling device, wherein the milling device is equipped with a separator device, ii) milling of the particulate material to a fine-particulate powder, with the proviso that iii) the temperature of the milling stock during the milling process does not exceed 95 C.

14. The process according to claim 13, wherein the milling in step ii) takes place under such conditions, that at least 70% by weight of the total amount of the particles of the obtained fine-particulate powder possess particle sizes in the range of 1 m to 50 m, at most 15% by weight of the particles possess particle sizes of >50 m and at most 15% by weight of the particles possess particle sizes of <1 m.

15. The process according to claim 13, wherein the temperatures of the milling stock during the milling process are from 15 C. to 95 C.

16. The process according to claim 13, wherein the temperature of the milling stock during the milling process is controlled by supply of cooling gas or by supply of liquefied gases.

17. The process according to claim 13, wherein the coarse particles separated in the separator device are reintroduced into the jet mill or into the cooled pen mill.

18. The process according to claim 13, wherein manganese complexes containing particulate material is milled in a dry state.

19. The process according to claim 13, wherein particles with a very broad particle size distribution of 2 m to 0.1 mm containing 80 to 100% by weight of a manganese complex with nitrogen containing ligands, wherein of the ligands one or more are macrocyclic ligands, are milled in a dry process using an air-powered jet mill containing downstream a separator device.

20. A method of formulating washing and cleaning agents comprising incorporating the fine-particulate powder according to claim 1 into the washing and cleaning agents as a bleaching catalyst for per-compounds in the washing and cleaning agents.

21. The method according to claim 20, wherein the washing and cleaning agent is a dishwashing agent.

22. Washing and cleaning agent comprising the fine-particulate powder according to claim 1.

23. The washing and cleaning agent according to claim 22, wherein this contains a per-compound.

24. The washing and cleaning agent according to claim 22, wherein the fine-particulate powder is applied to a carrier material and/or is a compound with a bleach activator.

Description

DETAILED DESCRIPTION

[0039] Especially preferred powders contain as a bleaching catalyst bis (N,N,N-trimethyl-1,4,7-triazacyclononane)-trioxo-dimanganese (IV) di(hexafluorophosphate) monohydrate, which is available as Peractive MnTACN.

[0040] The manganese complexes with nitrogen containing ligands, whereby of the ligands one ore more are macrocyclic ligands, preferably the manganese complexes of the formulae (1) or (2), are present in the fine-particulate particles in at least 80% by weight, preferably in at least 90% by weight and particularly preferred between 95 and 100% by weight.

[0041] It was found that fine-particulate powders containing particles with at least 80% by weight of manganese complexes with nitrogen-containing ligands, wherein of the ligands one or more are macrocyclic ligands, preferably of a manganese complex of formula (1) or formula (2), can be manufactured by a selected milling process, wherein the fine-particulate powders in particular are characterized in that these contain at least 70% by weight of particles with particle sizes in the range from 5 m to 50 m, no more than 15% by weight of the particles with particle sizes of >50 m and no more than 15% by weight of the particles with particle sizes of <; 5 m, wherein the percentages refer to the total amount of the particles.

[0042] This process includes the measures [0043] i) introduction of a milling stock of particulate material comprising at least 80% by weight of manganese complexes with nitrogen-containing ligands, wherein of the ligands one or more are macrocyclic ligands, preferably of a manganese complex of formula (1) or formula (2) into a milling device selected from the group consisting of a jet mill or a pen mill equipped with a cooling device, wherein the milling device is equipped with a separator device, [0044] ii) milling of the particulate material to a fine-particulate powder, with the proviso that [0045] iii) the temperature of the milling stock during the milling process does not exceed 95 C.

[0046] The milling step ii) preferably takes place under such conditions, that at least 70% by weight of the total amount of the obtained particles of the fine-particulate powder possess particle sizes in the range of 1 m to 50 m, up to 15% by weight of the particles possess particle sizes of >50 m and up to 15% by weight of the particles possess particle sizes of <1 m.

[0047] Preferred temperatures of the milling stock during the milling process are from 15 C. to 95 C., preferably <70 C., particularly preferred <60 C., and particularly preferred <50 C. to avoid decomposition of the Mn-complex. This can be achieved by supply of cooling gas, such as for example air with a temperature from 45 C. to 25 C. or by supply of liquefied gases, such as nitrogen, oxygen or air, during the milling process.

[0048] With the process of the invention a gentle method for crushing of bleach catalyst particles to defined particle sizes is provided, in which no or only a very low loss of bleaching catalyst occurs as a result of decomposition during the milling process.

[0049] The proportion of defined particle sizes can be controlled by combining the above mentioned milling devices with a separator device.

[0050] Preferably, the coarse particles separated in separator device are reintroduced into the jet mill or into the cooled pen mill.

[0051] Especially preferred the manganese complexes containing particulate material is milled in a dry state.

[0052] In particular the jet mill is used as a milling device in the process of the invention, which is operated with a gaseous fluid and thus is cooled at the same time. Preferably used fluids are air or nitrogen, which are optionally pre-cooled by using suitable heat transfer agents to enhance the cooling effect of these fluids.

[0053] By using these selected milling devices in combination with a separator device, it is possible to generate the desired fine-particulate powders without accepting significantly negative properties affecting the quality of the milled product, such as partial or complete decomposition, discoloration, or product bonding. Significantly, in this context, means a maximum decomposition of 10% of the originally contained manganese complex. Preferred, however, are values of at most 5% or most preferred no degradation of the proportion of the originally contained manganese complex.

[0054] With other milling devices, for example by using grinding mills, rolling chairs, pin mills without additional cooling, as well as hammer mills and impact mills, creation of fine-particulate powders with unchanged activity in terms of the active content and color retention of the manganese complex does not succeed.

[0055] In a particularly preferred embodiment of the process of the invention particles with a very broad particle size distribution of 2 m to 0.1 mm containing 80 to 100% by weight of a manganese complex with nitrogen containing ligands, wherein of the ligands one or more are macrocyclic ligands, in particular of a manganese complex of formula (1) or of formula (2), are milled in a dry process using an air-powered jet mill containing downstream a separator device.

[0056] The powders of the invention are suited as bleaching catalysts for per-compounds in washing and cleaning agents. This use is also subject of the present invention.

[0057] The washing and cleaning agents preferably are dishwashing agents, in particular machine dishwashing agents.

[0058] Also subject of the present invention are washing and cleaning agents, in particular dishwashing agents, containing the powder of the invention with the above-defined volume-average particle sizes and containing a manganese complex with nitrogen-containing ligands, wherein of the ligands one or more are macrocyclic ligands, preferably a manganese complex according to formula (1) or to formula (2).

[0059] The washing and cleaning agents of the invention preferably contain a per-compound.

[0060] The washing and cleaning agents of the invention products contain the above-disclosed fine-particulate powders, preferably applied on a carrier material and/or as a compound with a bleach activator.

[0061] The powders of the invention with the above defined particle sizes and containing as bleaching catalyst a manganese complex with nitrogen-containing ligands, wherein one or more of the ligands are macrocyclic ligands, preferably a manganese complex according to formula (1) or formula (2), can be mixed with other agents and can be granulated.

[0062] Mixtures or ganulates of the powders of the invention with other agents typically contain at least 2% by weight of manganese complex.

[0063] Appropriate agents are bleaching activators, surfactants, enzymes, binders, builders, dispersants, inert materials and/or further additives.

[0064] As bleaching activators are considered multiple acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, preferably 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glykoluriles, preferably tetraacetylglykoluril (TAGU), N-acylimides, preferably N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates, preferably n-nonanoyloxi- or n-lauroyloxibenzene sulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, preferably nonanoyloxi- or decanoyloxibenzoic acid (NOBA or DOBA), carboxylic acid anhydrides, preferably phthalic acid anhydride, acylated polyvalent alcohols, preferably triacetin, ethylenglycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol or their mixtures, respectively (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated and optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactames, for example N-benzoyl-caprolactame. Hydrophilic substituted acylacetals and acyllactames are also preferably used.

[0065] In addition, nitrile derivatives such as n-methyl morpholinium acetonitrile methyl sulfate (MMA) or cyanomorpholine (MOR) may be used as bleach activators. Also combinations of conventional bleaching activators may be used.

[0066] TAED, NOBS and DOBA are particularly preferred bleaching activators.

[0067] The weight ratio of bleaching catalyst(s) to bleaching activator(s) is typically from 1 to 2000 to 1 to 5, preferably 1 to 1000 to 1 to 500, and most preferred from 1 to 100 to 1 to 25.

[0068] As surfactants one or more surfactants, especially anionic surfactants and non-ionic surfactants and their mixtures can be used but also zwitter-ionic and amphoteric surfactants.

[0069] To be considered are alkylether carboxylates R(OCH.sub.2CH.sub.2).sub.xOCH.sub.2COOM, with R being an alk(en)yl group of 12 to 18 carbon atoms, x stands for a number from 2 to 5 and M for an alkali, earth alkali or ammonium ion.

[0070] The anionic surfactants can be used in the form or their sodium, potassium or ammonium salts, as well as soluble salts of organic bases, such as mono-, di- and triethanolamine.

[0071] Anionic surfactants are preferably contained in the washing and cleaning agents of the invention in quantities of up to 10% by weight, and in particular in quantities of 0.5 to 5% by weight.

[0072] As non-ionic surfactants alkoxylated, preferably ethoxylated and/or propoxylated, preferably primary alcohols with preferably 8 to 18 C-atoms and on average 1 to 12 moles ethylene oxide (EO) and 2 to 17 moles ethylene oxide (EO)/propylene oxide (PO) per mol alcohol are used, in which the alcohol group can be linear or preferably in 2-position methyl-branched or can contain a mixture of linear and methyl-branched groups, as they usually are present in oxoalcohol groups. Preferably used are alcohol ethoxylates with linear groups from alcohols of native origin with 12 to 18 C-atoms, e.g. from coconut oil, palm oil, tallow fat or oleyl alcohol, and an average 2 to 8 EO per mol alcohol, especially preferred C.sub.12-C.sub.14-alcohols with 3 EO or 4 EO, C.sub.9-C.sub.11-alcohols with 7 EO, C.sub.13-C.sub.15-alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C.sub.12-C.sub.15-alcohols with 3 EO, 5 EO or 7 EO and mixtures from these, such as mixtures of C.sub.12-C.sub.14-alcohols with 3 EO and C.sub.12-C.sub.15-alcohols with 7 EO, laurylalcohol with 7 EO and 10 PO, laurylalcohol with 2 EO and 4 PO, laurylalcohol with 4 EO and 5 PO, laurylalcohol with 5 EO and 4 PO, laurylalcohol with 6 EO and 4 PO, laurylalcohol with 8 EO and 4 PO, C.sub.10-C.sub.12-alcohol with 4 EO and 4 PO, isodecylalcohol with 2 PO and 12 EO, isodecylalcohol with 2 PO and 4 EO, undecylalcohol with 8 EO and 2PO, C.sub.12-C.sub.15-oxoalcohol with 2 EO and 5 PO, C.sub.12-C.sub.15-oxoalcohol with 4EO and 4 PO, C.sub.12-C.sub.15-oxoalcohol with 5 PO and 2 EO, C.sub.12-C.sub.15-oxoalcohol with 6 EO and 4 PO, C.sub.12-C.sub.15-oxoalcohol with 8 EO and 4 PO, C.sub.6-C.sub.12-alcohol with 6 EO and 8 PO.

[0073] The above specified degrees of ethoxylation and degrees of propoxylation represent statistical averages, which can be a whole or a fractional number for a specific product.

[0074] The weight ratio of one or more bleaching catalysts to one or more surfactants is typically from 1 to 10000 to 1 to 1000, preferably from 1 to 5000 to 1 to 3000.

[0075] Enzymes to be considered are those enzymes commonly used in washing and cleaning agents, such as proteases, amylases, mannasesn, lipases, endolases, pectinases, cellulases, pullinases, cutinases or peroxidases, phospholipases, cellobiohydrolases, esterases, keratinases, reductases, oxidases, ligninases, arabinosidases, glucosinases and/or perhydrolases.

[0076] Available proteases, for example, are Liquanase<> Ultra 2,0 XL, BLAP<>, Opticlean<C>, Maxacal<>, Maxapem<>, Esperase<>, Savinase<>, Purafect<>, OxP and/or Duraxym<>,

available amylases, for example, are Steinzyme<> Plus 12L, Termamyl<>, Amylase<> LT, Maxamyl<>, Duramyl<> and/or Pruafect<> Ox, available mannases, for example, are Mannaway 4,0 L,
available lipases, for example, are Lipex<>100 L, Lipolase<>, Lipomax<>, Lumafast<> and/or Lipozym<>,
available endolases, for example, are Endolase<>5000L,
available pectinases, for example, are Pectinex 3X L and/or Pectinex Ultra SPL and
available cellulases, for example, are Carezyme 1000 L and/or Celluclast 1.5 L.

[0077] The weight proportion of one or more bleaching catalysts to one or more enzymes is typically from 1 to 100 to 100 to 1, preferred from 1 to 10 to 10 to 1, particularly preferred from 1 to 5 to 5 to 1 and most preferred from 1 to 3 to 3 to 1. The weights of enzymes refer to 100% of enzyme protein.

[0078] Suitable binders are homo- or copolymeric polycarboxylates, in particular polymers or copolymers of acrylic acid and/or of methacrylic acid (hereinafter also called poly-(meth)acrylic acid), preferably in the form of their salts or in partially neutralized form. These can preferably be used 1% dissolved in water and have a pH-value of 3 to 9, but in particular between 3.5 and 8.5. Preferably used are polyacrylic acid or polymethacrylic acid, particularly those with an average molar mass of 500 to 70,000 g/mol.

[0079] Poly(meth)acrylates, preferably those having a molar mass of 2,000 to 20,000 g/mol are preferred. Due to their superior solubility from this group in particular short-chain poly(meth)acrylates are preferred, which have molar masses of 2,000 to 10,000 g/mol, and very preferred of 3,000 to 5,000 g/mol.

[0080] Additional anionic polymers preferably used as binders are sulfone-group containing polymers, in particular copolymers of unsaturated carboxylic acids with sulfone-group containing monomers and optionally with other ionic or non-ionic monomers.

[0081] As builders to be considered are water-soluble organic builder compounds, preferably polycarboxylic acids or their salts, particularly citric acid and sugar acids, aminopoly-carboxylic acids, in particular N-methylglycine diacetic acid or its salt (MGDA), glutamine diacetic acid or its salt (GLDA) and ethylene diamine disuccininc acid or its salt (EDDS), nitrilo triacetic acid and ethylene diamine tetraacetic acid, or polyaspartic acid. Polyphosphonic acids, especially aminotris(methylenephosphonic acid), ethylenediamine tetrakis(methylene-phosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid can also be used.

[0082] Further preferred builders or co-builders are also polycarboxylic acids, in particular the polycarboxylates which are accessible by oxidation of polysaccharides and of dextrins, respectively, as described in WO 93/16110 A1, WO 92/18542 A1 or EP 0 232 202 A2, as well as polymer acrylic acids, methacrylic acids, maleic acids and mixed polymers from these which can contain incorparated by polymerization small amounts of polymerizable substances without carboxylic acid functionality.

[0083] In addition to polyphosphonates and phosphonate alkyl carboxylates further possible water-soluble builder components are for example organic polymers of native or synthetic origin of the above type of polycarboxylates that act particularly in hard water areas as co-builders, and of course naturally occurring hydroxycarboxylic acids, such as mono-, dihydroxy succininc acid, alpha-hydroxypropionic acid and gluconic acid. Equally the salts of citric acid, particularly sodium citrate, as well as anhydrous trisodium citrate or trisodium citrate dihydrate, can be employed.

[0084] As inert substances SiO.sub.2 or TiO.sub.2 come into consideration, for example.

[0085] As further additives, for example, oxalic acid, ascorbic acid and glyoxalic acid esters and their acetals or hemiacetals, which increase the effectiveness of the bleaching catalysts, come into consideration.

[0086] The mixtures containing bleach catalyst powders of the invention and additional agents can be mixed and granulated according to conventional methods.

[0087] According to a preferred manufacturing method the bleach catalyst powders of the invention are mixed with a bleach activator and with a polycarboxylic acid and are processed to co-granulates as described in WO 2014/198369 A1.

[0088] Preferred bleach catalyst co granulates have an average particle size between 0.1 and 1, 6 mm, preferably between 0.2 and 1.2 mm and particularly preferred between 0.3 and 1, 0 is mm, each measured by sieve analysis.

[0089] Preferred washing and cleaning agents of the invention, in particular the agents for the machine cleaning of dishes, contain the bleach catalyst powders of the invention typically in amounts with a manganese content of 0.0005% by weight to 0.3% by weight, referring to the finished agents for the machine cleaning of dishes that can be available as granulates, as powdery solids or in tablet form but also in form of a liquid or paste.

[0090] The dishwashing agents of the invention may contain in particular builders, per-oxygen compounds, enzymes, alkaline media, surface active tensides, pH regulators, organic solvents and additional auxiliary materials, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators. The bleach catalyst powders of the invention are both suitable for the use in phosphate-containing and in phosphate-free formulations.

[0091] Especially preferred washing and cleaning agents, preferably agents for the machine cleaning of dishes, contain

15 to 65% by weight, preferably 20 to 60% by weight, of a water-soluble builder,
5 to 20% by weight, preferably up to 8% by weight, of a per-oxygen compound,
0.0005% by weight to 0.3% by weight Mn-content of a bleach catalyst of the invention, and
0 to 50% by weight of other additives, such as enzymes, alkaline media, surface active tensides, pH regulators, organic solvents or additional auxiliary materials, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, each based on the total weight of the dish washing agent.

[0092] Such an agent is particularly low alkaline, i.e. its 1-% by weight solution has a pH-value in the range of 8 to 11.5, and preferably of 9 to 11.

[0093] The following examples are supposed to illustrate the invention without restricting it. All percentages are understood as weight percent (% by weight), unless explicitly otherwise stated otherwise.

[0094] Example: Process according to the invention for milling of bis (N,N,N-trimethyl-1,4,7-triazacyclononane)-trioxo-dimanganese (IV) di(hexafluorophosphate) monohydrate, prepared according to EP 0 458 397 A2

Example 1 (According to Invention)

[0095] 50 kg of commercial Peractive MnTACN from WeylChem Wiesbaden were milled under nitrogen at a throughput of 8 kg/h in a commercial spiral jet mill from Alpine 100 AFG. The product temperature was measured in the mill stream using PT100 and was maximum 45 C. Connected to the mill was a separation device for separation of coarse material which was immediately re-introduced into the milling process. The parameters of the separation device had been adjusted so that an upper grain size limit D.sub.97<30 m is met.

[0096] The chemical analysis of the milled material showed that there was no measurable degradation of the original activity of the MnTACN. By means of laser diffraction using the standard ISO13320 (2009) in the milled material a D.sub.99<50 m and a D.sub.10<1 m was determined.

Example 2 (Comparison Example)

[0097] Commercial Peractive MnTACN from WeylChem Wiesbaden GmbH was added in doses to a continuous cross hammer mill of IKA (type MFC KB15) using a perforated inset of 0.6 mm and a speed of up tp 5000 rpm. The product thus obtained was investigated by light microscope type SZH-ILLP from Olympos and still contained clearly needle-shaped structures, with high percentages of coarse particles having a particle diameter above 50 m being present in addition to very fine particles. The coarse, needle- or rod-shaped particles having a particle diameter of more than 50 m could not be comminuted with the cross hammer mill or only on a very small scale.

[0098] Also using even finer perforated insets of 0.2 mm and repeated addition into the mill when using this milling technique the proper particle size distribution of the invention could not be adjusted.

Example 3 (Comparison Example)

[0099] 500 kg commercial Peractive MnTACN from WeylChem Wiesbaden with a D.sub.97 of 120 m were milled within 24 hours through a screen of 150 m in a commercial sieve mill from Alexanderwerk (type RFG150) at a rotational speed of 1 m/s. The product temperature measured in the mill stream using PT100 was maximum 45 C. The obtained product had a D.sub.97 of 83 m. Under the microscope (light microscope from Olympus) both very small particles having a particle diameter of <10 m but also a very large proportion of rod-shaped material with a length of clearly above 100 m could be detected. All in all, it was not possible with this milling technique to make the particle size distributions of the invention even when using the finest screen and multiple passages.

Example 4 (Comparison Example)

[0100] In an Alpine pin mill UPZ315 of Alpine with smooth pin disc 500 kg commercial Peractive MnTACN from WeylChem Wiesbaden were milled in continuous milling process at a rotor rotational velocity of 9000 rpm with a throughput of about 240 kg/h. The maximum product temperature here obtained was maximum 44 C. after the milling step (measured at the outlet by means of PT100).

[0101] The product showed a very significant lump formation (up to 2 cm) with black coloring of the interior of the lumps. Size and hardness of these clumps make a further processing of the milled material impossible.

[0102] In addition to the physical disadvantages, a significant loss of activity of the initial product by up to 50% was detected. This is probably caused by a too high heat load during the milling process. Black coverings on the pins indicate such a decomposition mechanism.

Machine Dishwashing Agent

[0103]

TABLE-US-00001 composition % by weight (tel quel) Peractive MnTACN milled 0.015 according to example 1 MGDA 20 sodium citrate 13 sodium carbonate 25.5 Sokalan PA3OCL 6 sodium percarbonate 15 Genapol EP 2544 1.5 Blaze evity 100 T 0.7 Stainzyme 12T 0.6 sodium sulfate 17.685

Commercial Products Used

[0104] MGDA (alanine, N,N-bis(carboxymethyl)-, trisodium salt), manufacturer BASF AG
Peractive MnTACN, Mn-bleaching catalyst, manufacturer Weylchem Wiesebaden
Sokalan PA3OCL, polycarboxylate, manufacturer BASF AG
Genapol EP 2544, C.sub.12/C.sub.15-oxoalcohol EO-PO adduct, manufacturer Clariant
Blaze evity 100 T, enzyme mixture, manufacturer Novozymes
Stainzyme 12T, enzyme, manufacturer Novozymes

[0105] Manufacturing method: The components sodium carbonate, sodium citrate and sodium sulfate were provided, homogenously mixed in a Ldige mixer at room temperature during a period of 15 minutes and transferred into a Turbula mixer. Genapol EP2544 was added slowly into the Turbula mixer and mixed homogeneously during a period of 10 minutes. All other components were added one at a time and were homogeneously mixed for a period of 10 minutes.

[0106] This dishwashing agent showed a very good cleaning effect, notably vis--vis tea stains.