EP3008157B1 - Bleach catalyst granules, use thereof and washing and cleaning agents containing the same - Google Patents

Description

The present invention relates to bleach catalyst granules and their use in detergents and cleaners, especially in machine dishwashing detergents.

In order to obtain spotless dishes, persalts such as perborates and percarbonates are used in automatic dishwashing detergents. In order to activate these bleaching agents and to achieve an improved bleaching effect during cleaning at temperatures of 60 ° C. and below, automatic dishwashing detergents generally also contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

Bleach catalysts based on various manganese-containing transition metal complexes are z. In EP 0 458 397 . EP 0 458 398 and EP 0 530 870 described. The catalysts described in these applications are characterized in that they contain at least one ligand from the group of triazacyclononanes. Particularly preferred are dinuclear oxygen-bridged complexes with manganese or iron as the central atom and 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN) as ligands.

The said complexes are highly active, that is to say that the smallest application concentrations per rinse are sufficient to ensure complete removal of tea stains from dishes. In most cases, 2 - 8 mg of the complex in a dishwashing tablet will suffice. Bleach catalysts are therefore used in automatic dishwasher detergents, preferably in the form of prefabricated granules. This is done to one, in order to increase their storage stability, on the other hand, but also to ensure a homogeneous incorporation of tiny amounts of catalyst in the formulations, especially in tablet applications.

Bleach catalyst granules and methods of making bleach catalyst granules are described in various patent applications. So is, for. In EP 509 787 a catalyst granules is claimed, consisting of 2% manganese catalyst, 84% sodium sulfate and 4% sodium silicate. EP 0 544 440 describes abrasion-resistant granules containing the manganese catalyst, an inert salt from the group of chlorides or carbonates, and mixtures thereof and a binder from the series of oxidation-stable polymers, alkali metal silicates or saturated fatty acids. DE 2007 039 651 sees advantages for a granulate composed of 0.1 to 30% of a bleach catalyst, 10 to 99% of a carrier material containing carbonates and silicates, and 0.1 to 5% of a binder from the group of organic polymers. In the granulation step, the binder (polymer) is used as a solution or dispersion in water or an organic solvent. In WO 95/06710 and WO 95/06711 Granules are described which in addition to the catalyst, an inert material (zeolite or silicate) and binder from the groups of silicone oils, waxes, fatty acids / soaps or ethoxylated fatty alcohols or polyglycols, preferably having a melting point of 30 to 100 ° C.

WO 97/16521 claims catalyst-containing particles containing 40 to 99% of a carrier / binder having a melting point of 38 to 77 ° C, preferably selected from the group of polyethylene glycols, paraffin waxes or mixtures thereof.

WO 03/093405 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating. As shown in Example 1 of the application, a manganese (II) complex with TAED powder and a Talgfettakoholethoxylat (Genapol ^® T500, Clariant) are mixed in a Lödigemischer at 40 - 50 ° C and then pressed by means of an extruder to noodle-shaped granules. WO 2010/115581 describes co-granules comprising a) one or more bleach activators, b) one or more bleach catalysts and c) at least 5% by weight of one or more organic acids. Possible binders mentioned are fatty acids, alcohol ethoxylates or polymers. Preferred binder, as can be seen from the examples, Genapol ^® T500 is. DE 10 2006 056 248 describes bleach catalyst granules prepared in an anhydrous granulation process, containing homo- or copolymer of (meth) acrylic acid. It has been shown that granules based on fatty acids / soaps, silicone oils or waxes no longer meet the high demands on a modern granulate for use in machine dishwasher detergents. With the low rinsing temperatures and the short rinses used today, these granules no longer dissolve fast enough to completely liberate the catalyst and thus only result in insufficient cleaning performance.

Surprisingly, it has further been found that granules containing [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O or related compounds which have a Triazacyclononanring, and as a carrier / binder contain one or more Polyethylengklykole or fatty alcohol ethoxylates, after a certain storage time have a distinct smell of amines and are therefore unsuitable for commercial use in household products. It can be assumed that during production and / or storage of the granules, a certain proportion of the manganese complex decomposes and liberates the ligand trimethyltriazacyclononane (TACN) or Me ₃ -TACN, which has a strong amine-like odor. The same is observed when aqueous solutions of polyacrylates are used in the granulation step as a binder and the granules are then dried at elevated temperature. In this case it can be assumed that there are interactions of the acid function with the catalyst, wherein a part of the catalyst is decomposed or converted into an acid-bridged variant of the original catalyst, and therefore no longer has the full effectiveness.

It is an object of the present invention to provide catalyst granules which contain a bleach catalyst comprising at least one ligand from the group consisting of di- or trimethyltriazacyclononanes or derivatives thereof and a binder, these granules being chemically stable when stored in alkaline detergents and cleaners, have no unpleasant odor and quickly dissolve in the rinsing process at temperatures below 50 ° C to achieve the full cleaning effect of the catalyst.

The present invention therefore provides bleach catalyst granules which contain from 0.01 to 50% by weight, based on the total weight of the granules, of a metal-containing bleach catalyst comprising at least one ligand selected from the group consisting of di- or Trimethyltriazacyclononane or derivatives thereof, and 50 to 99.9 wt.%, Based on the total weight of the granules, of a homo- or copolymer of (meth) acrylic acid or its salts or partial neutralizers having a pH of 3 to 9, measured as 1 Wt.% Dissolved in water, characterized in that they are prepared in an anhydrous granulation process, in particular by compaction, wherein the processing temperature is kept below 100 ° C. A preferred bleach catalyst granules of the invention is characterized by being free of alcohol ethoxylates or of ethylene or propylene oxide derivatives.

1. a) 0,1 bis 50 Gew.-% eines oder mehrerer metallhaltiger Bleichkatalysatoren mit mindestens einem Liganden aus der Gruppe Di- oder Trimethyltriazacyclononane oder Derivaten davon
2. b) 99,9 bis 50 Gew.-% eines oder mehrerer Bindemittel auf Basis Poly(meth)-acrylsäuren oder deren Salzen mit einem pH-Wert im Bereich von 3 bis 9.

With regard to their odor, performance and storage stability, the bleach catalyst granules according to the invention are particularly advantageous. These are produced in an anhydrous granulation process and contain, based on the total weight of the granules,

1. a) 0.1 to 50 wt .-% of one or more metal-containing bleach catalysts having at least one ligand selected from the group di- or Trimethyltriazacyclononane or derivatives thereof
2. b) 99.9 to 50 wt .-% of one or more binders based on poly (meth) -acrylic acids or their salts having a pH in the range of 3 to 9.

1. a) 2 bis 10 Gew.-% eines oder mehrerer metallhaltiger Bleichkatalysatoren mit mindestens einem Liganden aus der Gruppe Di- oder Trimethyltriazacyclononane oder Derivaten davon
2. b) 98 bis 90 Gew.-% eines oder mehrerer Bindemittel auf Basis Poly(meth)acrylsäuren oder deren Salzen mit einem pH-Wert von 4 bis 8.

The bleach catalyst granules according to the invention particularly preferably contain, based on the total weight of the granules,

1. a) 2 to 10 wt .-% of one or more metal-containing bleach catalysts having at least one ligand selected from the group di- or Trimethyltriazacyclononane or derivatives thereof
2. b) 98 to 90 wt .-% of one or more binders based on poly (meth) acrylic acids or their salts having a pH of 4 to 8.

bleach catalysts

Bleach catalysts used in the context of the present invention are preferably bleach-enhancing transition metal salts or complexes of manganese, iron, cobalt, ruthenium, molybdenum, titanium or vanadium.

Also preferred are complexes of iron in oxidation states II or III and manganese in oxidation state II, III, IV or IV, preferably one or more macrocyclic ligand (s) having the donor functions N, NR, PR, O and / or S included. Preferably, ligands are used which have nitrogen donor functions.

mit R = H, CH₃, C₂H₅, oder C₃H₇
enthalten.Mono- or dinuclear complexes of manganese or iron which contain at least one ligand of the general formulas A or B are preferably used as transition metal complexes in the co-granules according to the invention

with R = H, CH ₃ , C ₂ H ₅ , or C ₃ H ₇
contain.

Preferred ligands are 1,4,7-trimethyl-1,4,7-triazacyclononane (Me ₃ -TACN), 1,4,7-triazacyclononane (TACN) or bridged ligands such as 1,2-bis (4,7-tri- (4,7-triazacyclononane) Dimethyl-1,4,7-triazacyclonono-1-yl) ethane (Me4-DTNE), as z. In EP 0 458 397 .
EP 0 458 398 . EP 0 549 272 . WO 96/06154 . WO 96/06157 or WO 2006/125517 are described.

Examples of suitable manganese complexes are the polynuclear complexes [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (SO ₄ ), [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] ( OAc) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (Cl) ₂ ,
[Mn ^IV Mn ^III ₂ (μ-O) ₂ (OAc) (Me ₄ -DTE)] (Cl) ₂ , [Mn ^IV Mn ^III ₂ (μ-O) ₂ (OAc) (Me ₄ -DTE)] ( PF ₆ ) ₂ or the mononuclear complexes [Mn ^IV (Me ₃ -TACN) (OCH ₃ ) ₃ ] PF ₆ , (nach EP 544 519 prepared), [Mn ^IV (Me ₃ -TACN) (OC ₂ H ₅ ) ₃ ] PF ₆ and [Mn ^IV (Me ₃ -TACN) (acac) OH] PF ₆ or [Mn ^III (Me ₃ -TACN) (acac) OC ₂ H ₅ ] PF ₆ , the latter prepared according to K. Wieghardt et al., Zeitschrift fur Naturforschung 43b, 1184-1194 (1988). Since some of these complexes crystallize in hydrated form (with water of crystallization), these forms are preferred, for example. [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ * H ₂ O.

• [Mn^III ₂(µ-O)₁(µ-OAc)₂(Me₃-TACN)₂](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me₃-TACN)₂](PF₆)₂*H₂O,
• [Mn^IV ₂(µ-O)₂(µ-OAc)(Me₄-DTE)]Cl₂, [Mn^IV(Me₃-TACN)(OCH₃)₃]PF₆ oder
• [Mn^IV(Me₃-TACN)(acac)OCH₃]PF₆.

Particularly preferred metal-containing bleach catalysts are selected from the group:

• [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ * H ₂ O,
• [Mn ^IV ₂ (μ-O) ₂ (μ-OAc) (Me ₄ -DTE)] Cl ₂ , [Mn ^IV (Me ₃ -TACN) (OCH ₃ ) ₃ ] PF ₆ or
• [Mn ^IV (Me ₃ -TACN) (acac) OCH ₃ ] PF ₆ .

binder

As a second ingredient, the bleach catalyst granules according to the invention contain a binder which ensures the cohesion of the individual catalyst particles.

The binder is characterized in that it is homopolymers or copolymers of acrylic acid and / or methacrylic acid (in this specification "poly (meth) acrylic acid" banned), preferably in the form of their salts or in teilneutralisierter form. The binder used, 1% dissolved in water, has a pH of 3 to 9, preferably between 3.5 and 8.5, but in particular a pH of 4 to 8. These are homo- or copolymeric poly (meth) acrylates, preferably with maleic acid. For example, preference is given to using polyacrylic acid or polymethacrylic acid, in particular those having an average molar mass of from 500 to 70,000 g / mol.

Among these, preference is given to poly (meth) acrylates which preferably have an average molar mass of from 2,000 to 20,000 g / mol. Because of their superior solubility preferred from this group are in turn the short-chain poly (meth) acrylates having an average molecular weight of 2,000 to 10,000 g / mol and preferably from 3,000 to 5,000 g / mol.

Among these, furthermore preferred are copolymeric polycarboxylates of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid or methacrylic acid with maleic acid containing 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid. Their average molecular weight is preferably 2,000 to 70,000 g / mol, more preferably 20,000 to 50,000 g / mol, and particularly preferably 30,000 to 40,000 g / mol. Preferred polymers are Sokalan ^® CP45 and CP5 from BASF in substantially anhydrous form, preferably in powder or granular form.

To improve the solubility in water, the polymers may also contain structural units derived from allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid. Also particularly preferred are biodegradable polymers from more than two different monomer units, for example those which contain structural units from salts of acrylic acid or methacrylic acid and maleic acid and from vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units from salts of acrylic acid or acrylic acid of methacrylic acid and 2-alkylallylsulfonic acid and of sugar derivatives.

Further preferred copolymers are those which have structural units derived from acrolein and acrylic acid / acrylic acid salts or methacrylic acid / methacrylic acid salts or acrolein and vinyl acetate.

Further anionic polymers used with preference as binders are polymers containing sulfonic acid groups, in particular copolymers of unsaturated carboxylic acids, monomers containing sulfo-acid groups and optionally further ionic or non-ionogenic monomers.

Optional additives

As an additive, the co-granules of the invention may contain substances which are known to enhance the effectiveness of the TACN-containing bleach catalyst. Examples of these are, in particular, oxalic acid, ascorbic acid and glyoxylic acid esters and their acetals or hemiacetals.

In the simplest embodiment of the invention, the bleach catalyst granules according to the invention are not provided with a protective layer (coating).

In a preferred embodiment of the invention, the bleach catalyst granules according to the invention are provided with a protective layer, whereby the storage stability can be further improved and the bleach catalyst granules can optionally be colored. The proportion of the protective or coating layer in the total granulate should then be at least 5% by weight, more preferably at least 7% by weight and especially preferably at least 15% by weight. The upper limit of the proportion of the protective or coating layer on the total granules is preferably not more than 30% by weight.

Preferred coating layers are solid, organic compounds with film-forming properties, eg. As waxes, polyvinyl alcohols or the substances already used as binders. Optionally, the coating layer may additionally contain small amounts of water-soluble or water-insoluble organic dyes.

Production of the Co-Granules According to the Invention

To provide the co-granules according to the invention, fundamentally different, anhydrous granulation processes are possible. Anhydrous in this case means that in the granulation step no water is added and no aqueous solution of the component (s) is used, but in the catalyst or binder water in the form of water of crystallization may be present.

In a further preferred embodiment, the pulverulent active substances are first mixed and this mixture is then compacted, then ground and then optionally sieved into individual grain fractions. The compaction is preferably carried out on so-called roll compactors (eg of
Hosokawa-Bepex, Alexanderwerk, Köppern). By choosing the roll profile can be on the one hand produce lumpy pellets or briquettes and on the other hand pressing slugs. While the lumpy pellets are usually separated only from the fine fraction, the slugs must be crushed in a mill to the desired particle size. Typically come as a mill type preferably gentle grinding apparatus, such. B. sieve and hammer mills (eg from Hosokawa-Alpine, Hosokawa-Bepex) or roll mills (eg from Bauermeister, Bühler) are used.

From the granules thus produced are separated by screening the fine grain content and optionally the coarse grain fraction. The coarse grain fraction is again fed to the mill, the fine grain content again the compaction. For classifying the granules common screening machines such. As tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.

Characteristic of the bleach catalyst granules according to the invention is primarily their chemical composition. Nevertheless, it has been found that the bleaching action of these bleach catalyst granules can also be advantageously influenced by influencing physical parameters such as particle size, fines content and bleach catalyst content of selected screen fractions.

For this reason, preferred bleach catalyst granules according to the invention are characterized in that they have an average particle size of between 0.1 and 1.6 mm, preferably between 0.2 and 1.2 mm and particularly preferably between 0.3 and 1.0 mm through sieve analysis.

The co-granules according to the invention are suitable for use in all detergents or cleaners, and their use in detergents for dishwashing has proven to be particularly advantageous.

It is assumed that the organic acid of the bleach catalyst granules of the invention takes on a protective function and prevents the reaction of alkaline detergent ingredients with the alkali-labile and hydrolysis-sensitive bleach activators and bleach catalysts of the bleach catalyst granules of the invention.

Another object of the present invention is therefore the use of a bleach catalyst granules according to the invention for the production of washing and Detergents and preferably detergents for dishwashing.

Another object of the present invention are also detergents and cleaning agents, preferably means for the automatic cleaning of dishes, containing a bleach catalyst granules according to the invention.

Preferred detergents and cleaners according to the invention, in particular the means for machine dishwashing, contain the bleach catalyst granules according to the invention in amounts of between 0.1 and 10% by weight, preferably in amounts of between 0.2 and 8% by weight and more preferably in amounts between 0.5 and 6 wt .-%.

The detergents and cleaners according to the invention, in particular the means for the automated cleaning of dishes, which may be present as granules, as powdery or tablet-like solids, but also in liquid or pasty form, can in principle all known and. Apart from the co-granules of the invention contain usual ingredients in such agents. The detergents and cleaners according to the invention, in particular the compositions for the automated cleaning of dishes, may in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and further auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators. The bleach catalyst granules according to the invention are suitable both for use in phosphate-containing and phosphate-free formulations.

1. i) 15 bis 65 Gew.-%, vorzugsweise 20 bis 60 Gew.-% einer wasserlöslichen Builderkomponente,
2. ii) 5 bis 25 Gew.-%, vorzugsweise 8 bis 17 Gew.-%, einer Persauerstoffverbindung,
3. iii) 0,5 bis 6 Gew.-% eines erfindungsgemäßen Bleichkatalysatorgranulates und
4. iv) 0 bis 54 Gew.-% weitere Komponenten wie Enzyme, Alkaliträger, oberflächenaktive Tenside, pH-Regulatoren, organische Lösungsmittel, Glaskorrosionsinhibitoren, Silberkorrosionsinhibitoren und Schaumregulatoren, jeweils bezogen auf das Gesamtgewicht an Wasch- und Reinigungsmittel.

Particularly preferred detergents and cleaners, in particular detergents for dishwashing, contain

1. i) from 15 to 65% by weight, preferably from 20 to 60% by weight, of a water-soluble builder component,
2. ii) from 5 to 25% by weight, preferably from 8 to 17% by weight, of a peroxygen compound,
3. iii) from 0.5 to 6% by weight of a bleach catalyst granulate according to the invention and
4. iv) 0 to 54 wt .-% of other components such as enzymes, alkali carriers, surfactants, pH regulators, organic solvents, glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, each based on the total weight of detergents and cleaning agents.

Such an agent is particularly low alkaline, that is, its 1-weight percent solution has a pH of 8 to 11.5, preferably from 9 to 11, on.

Water-soluble builder component or builder substances

Suitable water-soluble builder components in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, are in principle all builders customarily used in such compositions, for example alkali phosphates, in the form of their alkaline, neutral or acidic sodium or potassium salts may be present. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Their amounts may be in the range of up to about 60% by weight, preferably from 5 to 20% by weight, based on the total agent. Further possible water-soluble builder components, in addition to polyphosphonates and phosphonate alkyl carboxylates, are, for example, organic polymers of the type of the polycarboxylates of native or synthetic origin, which act as co-builders, in particular in hard water regions. For example, polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymeric acids are suitable. Commercially available products are, for example, Sokalan ™ CP 5, CP 10 and PA 30 from BASF. Examples of co-builder polymers of native origin include oxidized starch and polyamino acids such as polyglutamic acid or polyaspartic acid. Other possible water-soluble builder components are naturally occurring hydroxycarboxylic acids, such as, for example, mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. The preferred organic water-soluble builder components include the salts of citric acid, especially Na citrate. As sodium citrate, anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable.

Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the pH ultimately set in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, the acids corresponding to the said co-builder salts may also be present. Particularly preferred builder components in phosphate-free formulations are methylglycine (MDGA such as Trilon ^® M, BASF), L-glutamic acid, N, N, (biscarboxymethyl) - tertra sodium salt (GLDA, Dissolvine ^® DL, Akzo Nobel), sodium polyaspartate ( Baypure ^®, Lanxess) or salts of Iminodibernstaeinsäure (Baypure ^®, Lanxess).

peroxygen compounds

Preferred peroxygen compounds are perborates and percarbonates, especially the corresponding sodium salts of these compounds.

enzymes

Proteases, amylases, pullulanases, cutinases and / or lipases, for example proteases such as BLAPT ™, Optimase ™, Opticlean ™, Maxacal ™, belong to the detergents and cleaning agents, in particular the detergents for dishwashing, optionally contained enzymes according to the invention, Maxapem ™, Durazym ™, Purafect ™ OxP, Esperase ™ and / or Savinase ™, amylases such as Termamyl ™, Amylase-LT ™, Maxamyl ™, Duramyl ™ and / or lipases such as Lipolase ™, Lipomax ™, Lumafast ™ and / or Lipozyme ™. The enzymes used may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably in amounts of up to 10% by weight and more preferably in amounts of from 0.05 to 5% by weight, with particular preference being given be used against oxidative degradation stabilized enzymes.

alkali carriers

The detergents and cleaners according to the invention, in particular the means for the automated cleaning of dishes, preferably contain the customary alkali carriers, for example alkali metal silicates, alkali metal carbonates and / or alkali hydrogen carbonates. Among the commonly used alkali carriers include Carbonates, bicarbonates and alkali metal silicates with a molar ratio of SiO ₂ / M ₂ O (M = alkali metal) of 1 to 1 to 2.5 to 1. Alkali silicates can in amounts of up to 40 wt .-%, in particular from 3 to 30 wt .-%, based on the total agent, be included. The alkali carrier system preferably used in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight and preferably from 5 to 40 wt .-% may be included.

In a further preferred embodiment of the invention, in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, from 20 to 60% by weight of water-soluble organic builders, in particular alkali citrate, from 3 to 20% by weight of alkali metal carbonate and 3 contain up to 40 wt .-% Alkalidisilikat.

surfactants

Surfactants, in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the detergents and cleaners according to the invention, in particular the detergents for dishwashing, where appropriate, as a wetting agent and optionally in the context of Production of these agents serve as Granulierhilfsmittel. Their amount may be up to 20 wt .-%, preferably up to 10 wt .-% and is more preferably in the range of 0.5 to 5 wt .-%. Usually extremely low-foam compounds are used in particular for means for the automatic cleaning of dishes. These include preferably C ₁₂ -C ₁₈ -Alkylpolyethylenglykolpolypropylen-glycol ethers each having up to 8 moles of ethylene oxide and propylene oxide in the molecule. But you can also use other known low-foam nonionic surfactants, such as C ₁₂ -C ₁₈ alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule, endgruppenverschlossene Alkylpolyalkylenglykolmischether and the foaming, but ecologically attractive C ₈ -C ₁₄ - Alkylpolyglucoside having a degree of polymerization of about 1 to 4 and / or C ₁₂ -C ₁₄ alkyl polyethylene glycols having 3 to 8 ethylene oxide units in the molecule. Also suitable are surfactants from the family of glucamides such as, for example, alkyl-N-methylglucamides, in which the alkyl moiety preferably originates from a fatty alcohol having the C chain length C ₆ -C ₁₄ . It is partially advantageous if the surfactants described are used as mixtures, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides. The presence of amine oxides, betaines and ethoxylated alkylamines is also possible.

pH regulators

To set a desired, by the mixture of the other components not automatically resulting pH value, detergents and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, system and environmentally compatible acids, especially citric acid, acetic acid, tartaric acid, Malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid or alkali hydrogen sulfates, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, preferably not more than 10% by weight and more preferably from 0.5 to 6% by weight.

Organic solvents

The organic solvents which can be used in the detergents and cleaners of the invention, in particular the detergents for dishwashing, in particular when in liquid or pasty form, include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are present in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, preferably in an amount not exceeding 20% by weight and more preferably from 1 to 15% by weight.

Glass corrosion inhibitors

In order to prevent glass corrosion during the rinse cycle, corresponding inhibitors can be used in the detergents and cleaners according to the invention, in particular the detergents for dishwashing machines. Particularly advantageous here are crystalline layered silicates and / or zinc salts. The crystalline layered silicates are sold, for example, by the company Clariant under the trade name Na-SKS, z. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite). Of these, especially Na-SKS-5 (alpha-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (beta-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (delta-Na ₂ Si ₂ O ₅ ). An overview of crystalline phyllosilicates can be found, for. In the in " Soap-Oils-Grease-Waxes, 116 vintage, no. 20/1990 ", on pages 805-808 published article.

In a further preferred embodiment of the invention, the detergents and cleaners according to the invention, in particular the detergents for dishwashing, have an amount of the crystalline layered silicate of preferably from 0.1 to 20% by weight, more preferably from 0.2 to 15 Wt .-% and particularly preferably 0.4 to 10 wt .-%, each based on the total weight of these agents on.

To suppress the glass corrosion, detergents and cleaners according to the invention, in particular means for machine dishwashing, contain at least one zinc or bismuth salt, preferably selected from the group of organic zinc salts, more preferably selected from the group of soluble organic zinc salts selected from the group of soluble zinc salts of monomeric or polymeric organic acids and most preferably selected from zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc oxalate, zinc ricinoleate, zinc abietate, zinc valerate and zinc p-toluenesulfonate. Alternatively or in combination with these zinc salts bismuth salts such. B. bismuth acetates are used.

In the context of the present invention, preference is given to washing and cleaning agents according to the invention, in particular means for the mechanical cleaning of Dishes in which the amount of the zinc salt based on the total weight of this agent is 0.1 to 10 wt .-%, preferably 0.2 to 7 wt .-% and particularly preferably 0.4 to 4 wt .-% and that independently of which zinc salts are used, ie in particular regardless of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used.

Silver corrosion inhibitors

To effect silver corrosion protection, silver corrosion inhibitors can be used in detergents and cleaners according to the invention, in particular detergents for dishwashing machines. Preferred silver corrosion inhibitors are organic sulfides such as cystine and cysteine, di- or trihydric phenols, optionally alkyl- or aryl-substituted triazoles such as benzotriazole, isocyanuric acid, titanium, zirconium, hafnium, cobalt or cerium salts and / or complexes in which the abovementioned Metals depending on the metal in one of the oxidation states II, III, IV, V or VI.

Foam regulators

If the detergents and cleaners according to the invention, in particular the means for the automated cleaning of dishes, for example in the presence of anionic surfactants, foam too much during use, they may still contain up to 6% by weight, preferably about 0.5 to 4 Wt .-% of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobized silica, paraffins, paraffin-alcohol combinations, hydrophobized silica, the Bisfettsäureamide, and other further known commercially available defoamer added.

The washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, as further ingredients, for example from the prior art for such agents known sequestering agents, electrolytes, additional peroxygen activators, dyes or fragrances such. B. perfume oils.

Preparation of detergents and cleaning agents according to the invention

The preparation of the solid detergents and cleaners according to the invention, in particular the means for machine dishwashing, presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and inventive bleach catalyst granules optionally being added separately later ,

The anhydrous granulation according to the invention takes place at temperatures below 100 ° C, in particular at temperatures between 25 and 90 ° C.

Inventive detergents and cleaners in the form of aqueous or other conventional solvent-containing solutions, in particular corresponding means for the automated cleaning of dishes, are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

The detergents and cleaning agents according to the invention, in particular means for the automated cleaning of dishes, are preferably in the form of powdered, granular or tablet-like preparations which are known per se, for example by mixing, granulating, roll compacting and / or spray-drying the thermally stable components and subsequently admixing the more sensitive components, which in particular enzymes, bleaching agents and the bleach catalyst are to be expected, can be prepared.

For the preparation of detergents and cleaners according to the invention, in particular detergents for dishwashing, in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture is compressed by means of conventional tablet presses, for example eccentric presses or rotary presses Range of 200 · 105 Pa to 1500 · 10 ⁵ Pa pressed.

It gives so easily unbreakable, yet sufficiently soluble under application conditions tablets with flexural strengths of usually about 150 N. Preferably, a tablet produced in this way has a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.

The preparation of detergents and cleaners according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1,000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, can be carried out by in a first part of the process, the builder components mixed with at least a proportion of liquid mixture components to increase the bulk density of this premix and subsequently - optionally after an intermediate drying - the other constituents of the agent, including the bleach catalyst according to the invention, combined with the thus obtained premix.

Means for the automatic cleaning of dishes according to the invention can be used both in household dishwashers and in commercial dishwashers. The addition is carried out by hand or by means of suitable metering devices. The application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.

A machine wash program is generally supplemented and terminated by a few rinses of clear water following a cleaning cycle and a rinse cycle with a common rinse aid. After drying, when using agents according to the invention, a completely clean and hygienically perfect dishes are obtained.

Examples

In the following examples, percentages% by weight (% by weight) unless explicitly stated otherwise. With regard to the stated relative humidities, the% values have the usual meaning.

Comparative granules 1 (V1):

Preparation of [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O Granules with fatty alcohol ethoxylate as binder
10 g of [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF 6) ₂ .H ₂ O were introduced into a laboratory mixer and heated to the required starting temperature of T> 40 ° C. A melt of 200 g Genapol ^® T 500 have been under intense stirring then at a temperature of T = 70 (fatty alcohol polyglycol ether, a product of Clariant.) - added 75 ° C. The mixture was regranulated for a few minutes, then cooled to room temperature and sieved to remove coarse and fines of 200-1600 microns. The granules had a bright red color.

Comparative granules 2 (V2):

Preparation of [Mn ^IV ₂ (μ-O) ₃ (Me ₃ TACN) _2] (PF _{6) 2} · H ₂ O granules with Sokalan ^® CP13 as a binder

20 g of [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O were placed in a laboratory mixer and mixed. Subsequently, an aqueous solution of a polyacrylate (Sokalan CP 13, commercial product of BASF) was metered in with vigorous stirring and the mixture was granulated. The moist co-granules were dried in a laboratory fluid bed dryer at about 60-80 ° C and then sieved to remove coarse and fines of 200-1600 microns. The granules had a bright red color.

Immediately after production, the co-granules had an unpleasant odor.

Examples 1 to 4 Preparation of Granules 1 to 4 According to the Invention

To prepare the bleach catalyst granules was worked anhydrous and the binder used in the form of their powder or granules. In a preferred production process, the commercially available binder granules were first ground to a particle size of 200 to 1000 μm.

The powdery bleach catalysts 1 to 3 and solid binder were mixed in the amounts shown in Table 1 in a Eyrisch mixer and then compacted using a Bepex laboratory compactor. The resulting slugs were crushed by means of an Alexanderwerk sieve mill at 1.25 mm and fractionated by means of Sweco sieve at 200-1040 microns. Batch size: 5 to 7 kg. The granules had a bright red color.

The following Table I shows an overview of the granules 1 to 4 according to the invention Table I granules 1 2 3 4 substances Bleach catalyst *) Complex 1 Complex 1 Complex 2 Complex 3 binder Sokalan ^® CP 45 G Sokalan ^® CP5G Sokalan ^® CP 45 G Sokalan ^® CP 45 G composition bleach catalyst [%] 10 10 5 2 binder [%] 90 90 95 98 pressing force [KN] 33 - 55 55 - 58 55 - 56 50 - 63 *) Complex 1 [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O prepared according to EP 0 458 397
*) Complex 2 [Mn ^IV ₂ (μ-O) ₃ (Me ₃ -TACN) ₂ ] (OAc) ₂ , prepared according to WO 2006/125517
*) Complex 3 [Mn ^IV (Me ₃ -TACN)] (OCH ₃ ) ₂ (PF ₆ ) prepared according to EP 0 544 519
Sokalan ^® CP copolymers of acrylic acid, commercial product of BASF

Testing of the produced granules 1. Storage test of the granules in the base washing powder

To check the chemical and physical stability of the granules so produced, the storage behavior was investigated in a typical detergent powder formulation. For this purpose, the respective granules were incorporated into IEC-A basic washing powder, so that the finished formulation contained 1% of the granules. The mixture was transferred to a glass bottle and covered with the lid closed Climatic conditions (T = 40 ° C, 75% relative humidity) stored over several days. The color of the granules and the smell of the washing powder mixture were evaluated after 14 days.

2. Hygroscopicity of the granules

The granules were stored at constant atmospheric humidity (65% RH) for 3 hours and then the water absorption was determined gravimetrically and the flow properties of the granules were assessed.

3. Bleaching performance

In each case, 20 g of the IEC-C machine dishwashing detergent were mixed with corresponding quantities of the unavailable granules V1, V2 or granules 1 to 4, so that in each case 4 mg of bleach catalyst (calculated as 100% active) were present in the formulation. The formulations were used to each 6 teacups (soiled according to IKW test protocol) in an automatic dishwasher (Miele G 688 SC) according to IKW test protocol (IKW test method; SOFW, 132 (8), 2006, 35-49 ) in the rinse program 45 ° C-fine. The evaluation was made optically; 0% performance = no tea removal, 100% performance: complete removal of tea soiling. The experiments were repeated in each case 3 times and the mean value was formed. The pH was measured in the dishwasher during the cleaning cycle.

Table II below shows an overview of the test results Table II granules V1 V2 1 2 3 4 storage test Color of the granules brown colorless OK OK OK OK odor amine-like amine-like OK OK OK OK water absorption [%] 0 13 baked 0 25 flowable 1 0 bleaching performance [%] 56 32 100 95 98 93

It was found that comparative granules V1 are unstable during storage, browning and odor of the mixture after storage indicate decomposition of the granules. In addition, the (non-stored) granules had a low bleaching performance. The same applies to comparative granules V2. The decolorization of the granules, the appearance of the amine-like odor and the lack of bleaching performance make such granules unsuitable for use in consumer products. By contrast, the granules 1 to 4 according to the invention are clearly superior to the comparative granules both in storage behavior and in use. Although granules 2 in which Sokalan ^® CP5 was used as a binder tends to hygroscopicity, although not a negative effect on the product properties.

Claims (11)

1. A bleach catalyst granule containing 0.01 to 50 % by weight, referring to the overall weight of the granule, of a metal-containing bleach catalyst comprising at least one ligand from the group of di- or trimethyltriazacyclononanes or derivatives thereof, and 50 to 99.9 % by weight, referring to the overall weight of the granule, of a homo- or copolymer of (meth)acrylic acid or its salts or partial neutralizates having a pH between 3 and 9, measured as 1 % by weight dissolved in water, characterized in that it is obtained in an anhydrous granulating process, in particular by compaction, wherein the processing temperature is maintained below 100 °C.
2. The bleach catalyst granule as claimed in claim 1, characterized in that it is free from alcohol ethoxylates or from derivatives of ethylene oxide or of propylene oxide.
3. The bleach catalyst granule as claimed in at least one of claims 1 to 2, charcterized in that it contains

   a) a metal-containing bleach catalyst comprising at least one ligand of formulae AorB

   

   with R = H, CH₃, C₂H₅, or C₃H₇
   and

   b) a homo- oder copolymer of (meth)acrylic acid, its salts or partial neutralizates having a pH of 3 to 9, measured as 1 % by weight dissolved in water.
4. The bleach catalyst granule as claimed in one or more of claims 1 to 3, characterized in that the metal-containing bleach catalyst is selected from the group of manganese complexes comprising at least one ligand of formula A or B

   

   with R = H, CH₃, C₂H₅, or C₃H₇.
5. The bleach catalyst granule as claimed in one or more of claims 1 to 4, characterized in that the bleach catalyst is selected from the group: [Mn^III ₂(µ-O)₁(µ-OAc)₂(Me₃-TACN)₂](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me₃-TACN)₂](PF₆)₂·H₂O, [Mn^IV ₂(µ-O)₂(µ-OAc)(Me₄-DTE)]Cl₂, [Mn^IV(Me₃-TACN)(OCH₃)₃]PF₆ or [Mn^IV(Me₃-TACN)(acac)OCH₃] PF₆.
6. The bleach catalyst granule as claimed in one or more of claims 1 to 5, characterized in that it has a protective or coating layer, whererin the proportion of the overall granule which is acounted for by the protective or coating layer is at least 5 weight %, preferably at least 7 wt %, more preferably at least 15 wt %, but not more than 30 wt %, and wherein the coating layer preferably utilizes solid organic compounds having film-forming properties, such as waxes, polyvinyl alcohols, or the substances used as binders.
7. The bleach catalyst granulate as claimed in one or more of claims 1 to 6, characterized in that is has an average corpuscle size between 0.1 und 1.6 mm, preferably between 0.2 and 1.2 mm and more preferably between 0.3 and 1.0 mm, as measured by sieve analysis.
8. Use of a bleach catalyst granulate as claimed in one or more of claims 1 to 7 in combination with an inorganic persalt, preferably sodium percarbonate, as a bleaching agent for use in washing and cleaning agents and preferably in machine dishwasher detergents.
9. A washing and cleaning agent, in particular an agent for machine cleaning of dishes comprising

   i) 15 to 65 wt%, preferably 20 to 60 wt% of a water-soluble builder component,

   ii) 5 to 25 wt%, preferably 8 to 17 wt%, of a peroxygen compound,

   iii) 0.5 to 6 wt% of a bleach catalyst granule as claimed in any of claims 1 to 7 and

   iv) 0 to 54 wt% of further components such as enzymes, alkali carriers, sufactants, pH regulators, organic solvents, glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, all referring to the overall weight of said washing and cleaning agent.
10. The washing and cleaning agent as claimed in claim 9, characterized in that it is of low alkalinity, its 1 weight percent solution having a pH of 8 to 11.5, preferably of 9 to 11.
11. The washing and cleaning agent as claimed in one of claims 9 or 10, characterized in that it is in the form of a soluble tablet having a flexural strength of greater than 150 N combined with a weight of 15 to 40 g, in particular of 20 to 30 g, coupled with a diameter of 35 to 40 mm.