EP3008158A1

EP3008158A1 - Bleaching-agent co-granules, method for producing said bleaching-agent co-granules, and use of said bleaching-agent co-granules

Info

Publication number: EP3008158A1
Application number: EP14723721.8A
Authority: EP
Inventors: Gerd Reinhardt; Michael Best; Miriam Ladwig; Andreas Schottstedt; Mathias Groeschen; Sven GEHARD
Original assignee: Weylchem Wiesbaden GmbH
Current assignee: Catexel Production GmbH
Priority date: 2013-06-15
Filing date: 2014-05-09
Publication date: 2016-04-20
Anticipated expiration: 2034-05-09
Also published as: DE102013010549A1; WO2014198369A1; DK3008158T3; US20160152929A1; ES2657279T3; US9902922B2; EP3008158B1

Abstract

The invention relates to a bleaching-agent co-granule, which contains a bleach activator, a bleach catalyst containing metal and containing at least one ligand from the group of di- or trimethyl triazacyclononane or derivatives thereof, and a homo- or copolymeric polycarboxylate or salts thereof or products of partial neutralization having a pH value in the range of 3 to 9. The bleaching-agent co-granule is produced in a water-free granulation process, preferably by means of compacting, during which the temperature is held below 100 °C. The invention further relates to the use of the bleaching-agent co-granule in cleaning agents for the cleaning of dishes in a machine and a cleaning agent containing the bleaching-agent co-granule.

Description

Bleach co-granules, process for their preparation and their use

The present invention relates to bleach co-granules, a process for their preparation and their use in detergents and cleaners, in particular in detergents for dishwashing.

To obtain spotless dishes, persalts such as perborates and percarbonates are used in dishwashing detergents for machine cleaning. In order to activate these bleaching agents and to achieve a satisfactory bleaching action during cleaning at temperatures of 60 ° C. and below, the dishwashing detergents generally furthermore contain bleach activators or bleach catalysts, with the bleach catalysts in particular having proven to be particularly effective.

Bleach catalysts are used in dishwasher detergents for machine cleaning, preferably in the form of prefabricated granules. This happens on the one hand, in order to increase their storage stability, on the other hand, however, to a homogeneous

Incorporation of tiny amounts of catalyst in the formulations, especially in tablet applications to ensure.

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. Processes for the preparation of bleach catalyst granules are disclosed in EP 0 544 440, WO 95/06710 and WO 2008/069935. Characteristic of the processes described therein is the use of large amounts of inert materials as carriers and binders, which are optionally used as melts, this method includes cooling and / or drying stages, which requires the use of additional equipment such as fluidized bed plants.

However, the germicidal effect of bleach catalysts is low in most cases. The performance of bleaching agents in dishwasher detergents is therefore higher, if they consist of a combination of a bleach catalyst with a bleach activator. Here, the bleaching effect of the catalyst is effectively supported by the peroxycarboxylic acid formed from the activator. At the same time the

Peroxycarboxylic acid significantly contributes to germ killing on the dishes, improves the smell of the wash and prevents the formation of a biofilm in the

Dishwasher. The combination of bleach catalysts and bleach activators is therefore useful for increasing bleaching performance and ensuring hygiene in the use of bleaching agents in laundry detergents and cleaners.

Detergent formulations containing both a bleach activator such as tetraacetylethylenediamine (TAED), nonanoyloxibenzenesulfonate sodium (NOBS) or decanoyloxibenzoic acid (DOBA) and one or more bleach catalysts are known in the art. So z. For example, EP 0 710 714 describes a bleaching composition containing TAED, a manganese catalyst and a crystalline layered silicate. These components are added as separate particles to the detergent formulation but not in the form of a uniform co-granule.

However, the use of activators and catalysts as separate particles or granules also has disadvantages that can have a negative effect on the bleaching performance. The reactions of the persalt or of the hydrogen peroxide released therefrom with activator and catalyst proceed in parallel. Dissolves the catalyst granules faster than the activator granules, then the persalt is already consumed before it can react with the activator. The same applies to the opposite case. Co-granules of activators and catalysts are also advantageous in order to ensure the homogeneous distribution of both components in the detergent and cleaning agent and to save space in the formulation.

Furthermore, the manufacturing costs are cheaper, because instead of two different

Granules only one co-granules must be produced.

WO 03/093405 describes co-granules consisting of a bleach catalyst, a bleach activator and optionally a coating. As demonstrated in Example 1, a manganese (II) complex with TAED powder and a tallow alcohol ethoxylate (Genapol ^® T500, Clariant) were mixed in a Lodige mixer at 40 to 50 ° C and then nudeiförmigen means of an extruder granules pressed. Preferred bleach catalysts for the preparation of such co-granules are metal complexes with macrocyclic, bridged ligands, as described in WO 01/64826 and WO 98/39098. These are characterized by a particularly good chemical stability.

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.

A large number of the bleaching catalysts mentioned in WO 2010/115581, in particular manganese salts, can therefore be converted into storage-stable, odorless co-granules which are suitable for use in detergents and cleaners.

Surprisingly, it has been shown that co-granulate consisting of TAED, [Mn ^lv ₂ (MO) 3 (Me-TACN) 2] (PF6) 2-H ₂ O and Genapol ^® T500, manufactured according to the teachings of WO 03 / 093405 or WO 2010/11558, after a certain storage time have a distinct smell of amines. They are therefore unsuitable for commercial use in household products. It is believed that during production and / or storage of the co-granules at least a small proportion of the manganese complex decomposes, thereby releasing the ligand trimethyltriazacyclononane (TACN), which has a strong amine-like odor.

It is an object of the present invention to provide storage-stable and, above all, odorless co-granules which, in addition to a bleach activator, also contain a bleach catalyst comprising at least one ligand selected from the group consisting of di- or trimethyltriazacyclononane or a derivative thereof.

Surprisingly, it has now been found that this object is achieved and that storage-stable, odorless co-granular particles containing a bleach activator and a bleach catalyst containing at least one ligand from the group di- or Trimethyltriazacyclononan or a derivative thereof can be prepared when in an anhydrous Granulation process of the bleach activator with the bleach catalyst Temperatures <100 ° C is made up, wherein as a binder at room temperature solid homo- or copolymeric polycarboxylate, in particular a

Poly (meth) acrylic acid or its salts or partial neutralizers having a pH in the range of 3 to 9 is used.

The present invention therefore bleach co-granules containing a bleach activator, a metal-containing bleach catalyst containing at least one ligand from the group di- or Trimethyltriazacyclononane or derivatives thereof, and a homo- or copolymeric polycarboxylate, in particular a homo- or copolymer based of (meth) acrylic acid, or its salts or partial neutralizers having a pH in the range of 3 to 9, whose characteristic feature is that they are produced in an anhydrous granulation process, preferably by compaction, and that the temperature in the anhydrous granulation process is kept below 100 ° C.

Furthermore, the bleach co-granule according to the invention is characterized in that it contains no alcohol ethoxylates or ethylene or propylene oxide derivatives.

Particularly advantageous and therefore preferred in terms of their odor, their performance and their storage stability are co-granules according to the invention which, based in each case on the total weight of the co-granules,

a) 50 to 90 wt .-% of one or more bleach activators

b) 0.01 to 10 wt .-% of one or more metal-containing bleach catalysts having at least one ligand selected from the group di- or

Trimethyltriazacyclononan or derivatives thereof

c) 5 to 40 wt .-% of one or more binders based on polyacrylic acids or their salts having a pH in the range of 3 to 9

contain.

The bleach co-granules according to the invention particularly preferably comprise, based on the total weight of the co-granules,

a) 65 to 85 wt .-% of one or more bleach activators b) 0.05 to 6 wt .-% of one or more metal-containing bleach catalysts having at least one ligand selected from the group di- or

Trimethyltriazacyclononan or derivatives thereof

c) 10 to 30 wt .-% of one or more binders based on polyacrylic acids or salts thereof having a pH in the range of 3 to 8.

Bleach activators (component a)

As bleach activators, the co-granules according to the invention may be polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, in particular n-nonanoyloxy or n-lauroyloxibenzenesulphonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic acid (NOBA or DOBA ), Carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol or their

Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose and

acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.

In addition, nitrile derivatives such as n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA) or cyanomorpholine (MOR) can be used as bleach activators. Combinations of conventional bleach activators can also be used.

Particularly preferred bleach activators are TAED, NOBS and DOBA.

Bleach catalysts (component b)

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 the oxidation states II or III and the manganese in the oxidation state II, III, IV or IV, preferably one or contain several macrocyclic ligand (s) with the donor functions N, NR, PR, O and / or S, in which R is a hydrocarbon radical having up to 5 C atoms. Preferably, ligands are used which have nitrogen donor functions.

Mono- or dinuclear complexes of the general formulas A or B are preferably used as transition metal complexes in the co-granules according to the invention

Formula A Formula B

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

Preferred ligands are 1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me-TACN),

1, 4,7-triazacyclononane (TACN) or bridged ligands such as 1, 2-bis- (4,7-dimethyl-

1, 4,7-triazacyclonono-1-yl) ethane (Me4-DTNE), as described, for. In EP 0 458 397,

EP 0 458 398, EP 0 549 272, WO 96/06154, WO 96/06157 or WO 2006/125517.

Suitable manganese complexes are, for example, the polynuclear complexes

[Mn " ¹ ₂ (MO) ₁ (M-OAc) ₂ (TACN) ₂ ] (PF ₆ ) 2, [Mn ^IV ₂ (MO) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ ,

[Mn ^lv ₂ (MO) ₃ (Me-TACN) ₂ ] (SO ₄ ), [Mn ^lv ₂ (MO) 3 (Me-TACN) ₂ ] (OAc) ₂ ,

[Mn ^lv ₂ (MO) ₃ (Me-TACN) ₂ ] (CI) ₂ ,

[Mn ^lv Mn ^lll ₂ (MO) ₂ (OAc) (Me4-DTE)] (CI) ₂ , [Mn ^lv Mn ^lll ₂ (MO) ₂ (OAc) (Me4-DTE)] (PF ₆ ) ₂ or the mononuclear complexes [Mn ^lv (Me-TACN) (OCH ₃ ) ₃ ] PF ₆ , (according to EP 544 519

prepared), [Mn ^lv (Me-TACN) (OC ₂ H ₅ ) ₃ ] PF ₆ and [Mn ^lv (Me-TACN) (acac) OH] PF ₆ or [Mn ^l "(Me-TACN) (acac) OC ₂ H ₅ ] PF _{6l the} latter prepared according to K. Wieghardt et.

Journal of Natural Science 43b, 1184-1194 (1988). Since some of these complexes crystallize in hydrated form (with water of crystallization), these forms are preferably used, an example of which is. [Mn ^lv ₂ (-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ * H ₂ O. Particularly preferred metal-containing bleach catalysts are selected from the group:

[Mn ^III 2 (MO) i (M-OAc) 2 (Me-TACN) 2] (PF ₆ ) 2 _> [Mn ^IV ₂ (MO) 3 (Me-TACN) 2] (PF ₆ ) 2 ^* H ₂ O,

[ ^Ηη ₂ (μ-Ο) ₂ (M-OAc) (Me4-DTE)] Cl ₂ , [Mn ^lv (Me-TACN) (OCH ₃ ) ₃ ] PF6 or [Mn ^lv (Me-TACN) (acac ) OCH ₃ ] PF ₆ .

Binders (component c)

As a further ingredient, the co-granules according to the invention contain a

Binders to ensure the cohesion of the co-granules.

The binder is characterized in that it is homo- or copolymeric polycarboxylates, in particular polymers or copolymers of acrylic acid and / or methacrylic acid (referred to in this specification "poly (meth) acrylic acid"), preferably in the form of their salts or in The binder used, 1% dissolved in water, should have a pH of from 3 to 9, but in particular between 3.5 and 8.5, in particular homo- or copolymeric polycarboxylates, preferably 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.

Preferred among these are poly (meth) acrylates which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior solubility preferred from this group, especially the short-chain poly (meth) acrylates having molecular weights 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, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid

Maleic acid. Copolymers of acrylic acid or of methacrylic acid with maleic acid which have 50 to 90% by weight of acrylic acid or

Methacrylic acid and 50 to 10 wt .-% maleic acid. Their middle one

Molecular weight, based on the free acids, is preferably 2,000 to 70,000 g / mol, more preferably 20,000 to 50,000 g / mol, and most 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 of more than two different monomer units,

for example, those containing structural units of salts of acrylic acid or of methacrylic acid and of maleic acid and of vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units of salts of acrylic acid or 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.

Other anionic polymers used with preference as binders are

Sulfonic acid-containing polymers, in particular copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally further ionic or nonionic 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 inventive

Co-granules are not provided with a protective layer (so-called coating).

In a preferred embodiment of the invention is the invention

Co-granules additionally provided with a protective layer, whereby the storage stability further improved and the co-granules can be optionally colored. The share of Protective or coating layer on the total granulate should then be at least 5 wt .-%, particularly preferably at least 7 wt .-% and particularly preferably at least 15 wt .-% amount. The upper limit of the content of the protective or coating layer on the total granulate is preferably 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 (c). Optionally, the coating layer may additionally contain small amounts of water-soluble or water-insoluble organic dyes.

Preparation of Bleach Co-Granules According to the Invention

To provide the bleach co-granules according to the invention, fundamentally different, water-free granulation processes are possible.

According to a preferred manufacturing method, the powdered active substances are first mixed and then this mixture is compacted, then ground and then optionally sieved into individual grain fractions. The compaction is preferably carried out on so-called roll compactors (eg from 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. As sieve and hammer mills (eg from the company Hosokawa-Alpine, Hosokawa-Bepex) or roll mills (eg., Fa. Bauermeister, Bühler) are used.

From the granules thus produced are by screening the fine grain content and

optionally the coarse grain fraction separated. The coarse grain fraction is again fed to the mill, the fine grain content, however, again the compaction. to

Classification of the granules can common screening machines such. As tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.

Characteristic of the bleach co-granules according to the invention is primarily their chemical composition. Nevertheless, it has been proven that the Bleaching effect of bleach co-granules can also be influenced by the influence of physical parameters such as the particle size, the fines content and the Blleichkatalysatorgehalts selected sieve fractions advantageous.

For this reason, preferred bleach co-granules according to the invention are characterized in that the co-granules have an average particle size between 0.1 and 1.6 mm, preferably between 0.2 and 1.2 mm and more preferably between 0.3 and 1, 0 mm, each measured by sieve analysis.

The bleach 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 believed that the organic acid of the bleach co-granules of the present invention performs a protective function and inhibits the reaction of alkaline detergent ingredients with the alkali-labile and hydrolysis-sensitive bleach activators and bleach catalysts of the bleach co-granules of the present invention.

Another object of the present invention is therefore the use of a bleach co-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 washing and

Detergent, preferably means for machine dishwashing, comprising a bleach co-granule according to the invention.

Preferred detergents and cleaners according to the invention, in particular the means for machine washing of crockery, contain the inventive compositions

Bleach co-granules in amounts between 0.1 and 10 wt .-%, preferably in amounts between 0.2 and 8 wt .-% and particularly preferably in amounts between 0.5 and 6 wt .-%. The detergents and cleaners according to the invention, in particular the compositions for the automatic cleaning of dishes, which may be in the form of granules, powdered or tablet-like solids but also in liquid or pasty form, may in principle all known and in addition to the co-granules of the invention Means usual ingredients included. The washing and

Detergents, in particular the detergents for dishwashing, 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 co-granules according to the invention are suitable both for use in phosphate-containing and phosphate-free formulations.

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

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

ii) 5 to 20 wt .-%, preferably 8 to wt .-%, one

peroxygen compound,

iii) from 0.5 to 6% by weight of a bleach co-granule according to the invention, and iv) from 0 to 50% by weight of further additives, such as enzymes, alkali carriers,

surfactants, pH regulators, organic solvents or other auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, in each case based on the total weight of the washing and cleaning agent.

Such an agent is especially lower alkaline, d. H. its 1% by weight solution has a pH in the range of 8 to 11, 5 and preferably 9 to 11.

Water-soluble builder component or builder substances

As water-soluble builder components in the washing and

Cleaning agents, in particular the means for the mechanical cleaning of Dishes, in principle, all builders commonly used in such compositions in question, for example, alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. examples for this 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 range from 15 to about 65% by weight, preferably from 20 to 60% by weight, based on the total agent. Other 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 are disclosed in particular in US Pat

Hard water regions act as co-builders. Consider, for example

Polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids. Commercial products are, for example Sokalan ^® CP 5, CP 10 and PA 30 from BASF. Examples of suitable 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 mono-, dihydroxysuccinic acid, alpha-hydroxypropionic acid and gluconic acid. The preferred organic water-soluble builder components include the salts of citric acid, especially sodium citrate. Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder. Depending on the ultimate in the washing and

Cleaning agents, in particular the means for the mechanical cleaning of

Crockery, adjusted pH can also be present corresponding to the said co-builder salts acids. 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, which may be present in the detergents and cleaners according to the invention, in particular the detergents for dishwashing, may contain proteases, amylases, pullulanases, cutinases and / or lipases.

for example, proteases such as BLAP ™, Optimase ™, Opticlean ™, Maxacal ™,

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 Lipozym ™. 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

Preferably, the washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, the usual

Alkaline carriers such as alkali silicates, alkali carbonates and / or

Alkali metal bicarbonates. The alkali carriers commonly used include carbonates, bicarbonates and alkali metal silicates having a molar ratio of S1O2 / M2O

(M = alkali atom) from 1: 1 to 2.5: 1. Alkali silicates may be present in amounts of up to 40% by weight, in particular from 3 to 30% by weight, based on the total weight of the washing and cleaning 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 are in the

Detergents and cleaning agents according to the invention, in particular the detergents for dishwashing, 20 to 60 wt .-% of water-soluble organic builder, in particular Alkaiicitrat, 3 to 20 wt .-% Aikaiicarbonat and 3 to 40 wt .-% Alkalidisilikat included.

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. Your amount can be up to

20 wt .-%, preferably up to 10 wt .-%, and is more preferably in the range of 0.5 to 5 wt .-%, based in each case on the total weight of the washing and cleaning agent.

Usually extremely low-foam compounds are used in particular for means for the automatic cleaning of dishes. These preferably include Ci ₂ -C ₈ -Alkylpolyethylenglykolpolypropylen glycol ethers each having up to 8 mol

Ethylene oxide and propylene oxide units in the molecule. But you can also use other known low-foam nonionic surfactants, such as

C ₂ -C ₈ -alkylpolyethylene glycol-polybutylene glycol ethers having in each case up to 8 mol

Ethylene oxide and butylene oxide units in the molecule, end-capped

Alkylpolyalkylenglykolmischether and the foaming, but ecologically attractive C ₈ -Ci ₄ - alkylpolyglucosides having a degree of polymerization of about 1 to 4 and / or Ci ₂ -Ci ₄ -Alkylpolyethylenglykole with 3 to 8 ethylene oxide units in the molecule. Likewise 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 with the C chain length C ₆ -C ₄ . It is partially advantageous if the surfactants described are used as mixtures, for example the combination

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, the detergents and cleaning agents according to the invention, in particular the means for the automated cleaning of dishes, system and environmentally friendly 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

Alkalihydrogensulfate, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are in the detergents and cleaners of the invention, in particular the means for the mechanical cleaning of

Dishes, preferably not more than 10 wt .-% and particularly preferably from 0.5 to 6 wt .-%, based, in each case, on the total weight of the composition.

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 derived from the above classes of compounds ether. Such water-miscible solvents are in the

Detergents and cleaning agents according to the invention, in particular in the means for the automated cleaning of dishes, preferably in a quantity not above

20 wt .-% and particularly preferably from 1 to 15 wt .-% present.

Glass corrosion inhibitors

To prevent glass corrosion during the rinse cycle, can in the

Detergents and cleaning agents according to the invention, in particular the means for the automated cleaning of dishes, corresponding inhibitors are used. 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 ₅ .xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₄ O ₂₉ x H ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ Oi ₇ 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 05 _{) are} suitable. H ₂ 0),

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 0 ₅ ). An overview of crystalline phyllosilicates can be found, for. For example, in the article published in "Soap-Oils-Fat-Waxes, Volume 116, No. 20/1990", pages 805-808.

In a further preferred embodiment of the invention, the

detergents and cleaners according to the invention, in particular the means for machine dishwashing, an amount of the crystalline layered silicate of preferably 0.1 to 20 wt.%, particularly preferably 0.2 to 15 wt.% and particularly preferably 0, 4 to 10 wt .-%, each based on the

Total weight of the agent, up.

To suppress the glass corrosion can washing and

Detergents, in particular means for the automated cleaning of dishes, 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, more preferably selected from the group of soluble zinc salts monomeric or polymeric organic acids and most preferably selected from the group consisting of 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 to means for machine dishwashing, in which the amount of zinc salt, based on the total weight of this agent, is from 0.1 to 10% by weight, preferably 0.2 up to 7 wt .-% and particularly preferably 0.4 to 4 wt .-% and regardless of which zinc salts are used, in particular therefore irrespective of whether organic or inorganic zinc salts, soluble or non-soluble zinc salts or mixtures thereof are used. Silver corrosion inhibitors

In order 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 metals mentioned are present in one of the oxidation states II, III, IV, V or VI, depending on the metal.

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 % By weight 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 added to bis-fatty acid amides and other further known commercially available defoamers.

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 solid detergents and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, offers no difficulties and can in principle in a known manner, for example by

Spray drying or granulation, wherein peroxygen compound and inventive co-granules are optionally 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 cleaners according to the invention, in particular compositions for machine washing 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 mixing in the more sensitive

Components, which in particular enzymes, bleach and the bleach catalyst can be expected, can be produced.

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 from 200 ^■ 10 ⁵ Pa to 1500 · 10 ⁵ Pa pressed.

This gives puncture-resistant and nevertheless sufficiently rapidly soluble tablets under the intended use conditions with flexural strengths of normally over 150 N. Thus, a tablet produced in this way has a weight of 15 to 40 g, in particular 20 to 30 g, with a diameter of 35 up 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 yields

Bulk densities in the range of 800 to 1,000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, thereby be carried out, that in a first process step, the builder components with at least a proportion of liquid mixture components to increase the

Bulk density of this premix is mixed and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the inventive co-granules, 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 useful by some on the

Cleaning cycle following intermediate rinses with clear water and a

Rinse with a common rinse aid supplemented and finished. 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 Example 1

Preparation of TAED-MnTACN Co-granules according to WO 2010/115581, Example 1

700 g of TAED powder and 20 g of [Mn ^lv ₂ (MO) ₃ (Me-TACN) ₂ ] (PF ₆ ) 2-H ₂ O and 80 g

Citric acid were placed in a laboratory mixer, mixed and placed on the

required starting temperature of T> 40 ° C heated. Subsequently, under intensive stirring the melt-shaped binder 200 g Genapol ^® T 500

(Fettalkoholpolyglykolether, commercial product of Fa. Clariant based on

Cetearyl alcohol with an average of 50 ethylene oxide units in the molecule) at a temperature of T = 70 - 75 ° C added. The mixture was regranulated for a few minutes, then cooled to room temperature and sieved to remove coarse and fines of 200 - 1.600 μιτι.

Storage test of the co-granules in the base washing powder

To check the chemical and physical stability of the co-granules thus prepared, the storage behavior was investigated in a typical detergent powder formulation. For this purpose, the co-granules were incorporated into IEC-A basic washing powder so that the finished formulation contained 2% of co-granules. The mixture was transferred to a glass bottle and with the lid closed under climatic conditions

(T = 40 ° C, 75% relative humidity) stored over several days. After one day of storage, a very noticeable, amine-like odor appeared on opening the glass bottle.

Comparative Example 2:

Production of Co-Granulates According to WO 2010/115581, Example 2

800 g of TAED powder and 20 g of [Mn ^lv ₂ (MO) 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 screened in a laboratory fluid bed dryer at about 60-80 ° C and then to remove coarse and fines from 200 to 1,600 pm.

Already immediately after production, the co-granules had an unpleasant odor, which increased significantly after storage in a base detergent.

Examples 1 to 4 (according to the invention)

Production of Co-Granules 1 to 4 According to the Invention

To prepare the co-granules, anhydrous was used and the binders used in the form of their granules. The commercial binder granules were first ground to a particle size of 200 to 1000 pm.

Bleach activator TAED, bleach catalyst 1-3 and solid binder were mixed in the amounts shown in Table 1 in a Eyrisch mixer and then compacted by means of 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 a Sweco sieve at 200 to 1040 μm. Batch size: 5 to 7 kg.

The table shows an overview of the co-granules 1 to 4 according to the invention

tetraacetylethylenediamine

[Mn ^> (M-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ -H ₂ O, prepared according to EP 0 458 397

[Mn ^lv ₂ (M-O) ₃ (iv-TACN) ₂ ] (OAc) _2, prepared according to WO 2006/125517

[Mn ^lv (Me-TACN)] (OCH ₃ ) ₂ (PF ₆ ), prepared according to EP 0 544 519

Sokalan ^® CP copolymers of acrylic acid, commercial product of BASF

Storage test of the co-granules in the base washing powder

To check the chemical and physical stability of the co-granules thus prepared, the storage behavior was investigated in a typical detergent powder formulation. For this purpose, the co-granules were incorporated into IEC-A basic washing powder, so that the finished formulation contained 2% co-granules. The mixture was then transferred to a glass bottle and stored with the lid closed under climatic conditions (T = 40 ° C, 75% relative humidity) over several days. After 28 days storage, the formulations were free-flowing, not discolored and odorless.

Claims

claims:

Bleach co-granules containing a bleach activator, a metal-containing

Bleach catalyst containing at least one ligand from the group di- or Trimethyltriazacyclononan or derivatives thereof, and a homo- or

copolymeric polycarboxylate or its salts or partial neutralizers having a pH in the range of 3 to 9, characterized in that it is prepared in an anhydrous granulation process, preferably by compaction and the temperature is kept below 100 ° C in the anhydrous granulation process.

Bleach co-granules according to claim 1, characterized in that it is free of alcohol ethoxylate or ethylene or propylene oxide derivatives.

Bleach co-granules according to at least one of claims 1 or 2, characterized in that homo- or copolymeric polycarboxylate is a homo- or copolymer based on (meth) acrylic acid.

Bleach co-granules according to at least one of Claims 1 to 3, characterized in that, in each case based on the total weight of the co-granules,

a) 50 to 90% by weight of one or more bleach activators;

Trimethyltriazacyclononane or derivatives thereof; and

c) 5 to 40 wt .-% of one or more binders based on poly (meth) acrylic acids or salts thereof having a pH in the range of 3 to 9.

Bleach co-granule according to claim 4, characterized in that, based on the total weight of the co-granules,

a) 65 to 85% by weight of one or more bleach activators;

b) 0.05 to 6 wt .-% of one or more metal-containing bleach catalysts having at least one ligand selected from the group di- or

Trimethyltriazacyclononane or derivatives thereof; and c) 10 to 30 wt .-% of one or more binders based

Poly (meth) acrylic acids or their salts having a pH in the range of 3 to 9

contains.

Bleach co-granules according to at least one of claims 1 to 5, characterized in that it acylated as bleach activator of component a) polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED)

Triazine derivatives, in particular 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine

(DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulphonates, in particular n-nonanoyloxy or n-lauroylxibenzene sulphonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyl-benzoic acid (NOBA or DOBA), carboxylic acid anhydrides, in particular

Phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated

Sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams,

for example, N-benzoyl-caprolactam.

Bleach co-granules according to at least one of claims 1 to 6, characterized in that the bleach catalyst is selected from the group of manganese complexes containing at least one ligand of formula A or B.

Formula A Formula B

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

8. bleach co-granules according to at least one of claims 1 to 7, characterized in that the metal-containing bleach catalyst is selected from the group:

[Mn ^l " ₂ (M-O) ₁ (M-OAc) 2 (Me-TACN) 2] (PF ₆ ) 2, [Mn ^lv ₂ (MO) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ -H ₂ ^O , [ ^ηηιν ₂ (μ-Ο) ₂ (M-OAc) (Me4-DTE)] Cl ₂ , [Mn ^lv (Me-TACN) (OCH ₃ ) 3] PF ₆ or

[Mn ^lv (Me-TACN) (acac) OCH _3] PF. ₆

9. bleach co-granules according to at least one of claims 1 to 8, characterized in that it contains as a binder of component c) a polymer or copolymer of (meth) acrylic acid, preferably in the form of their salts or in teilneutralisierter form, wherein the Binder, 1% dissolved in water, a pH in the range of 2 to 10, preferably from 3 to 9, in particular from 3.5 and 8.5.

10. bleach co-granules according to at least one of claims 1 to 9, characterized in that the binder is a homo- or copolymeric polycarboxylate, preferably with maleic acid, more preferably polyacrylic acid or polymethacrylic acid having an average molecular weight in the range of 500 to 70,000 g / mol.

11. A process for producing bleach co-granules according to any one of claims 1 to 10, wherein the powdered active substances are first mixed and in which the mixture is then compacted, then ground and then optionally sieved into individual grain fractions, wherein the temperature at the anhydrous granulation process is kept below 100 ° C, and wherein the compaction is preferably carried out on roller compactors.

12. Use of a bleach co-granule according to any one of claims 1 to 10 for the manufacture of detergents and cleaners, preferably of means for the machine cleaning of dishes.

13. Washing and cleaning agents, preferably means for the machine cleaning of dishes, containing a bleach co-granules according to any one of claims 1 to 10.

14. Washing and cleaning agent according to claim 14, characterized in that the bleach co-granules in an amount ranging from 0.1 to 10 wt .-%, preferably in an amount of 0.2 to 8 parts by weight. % and more preferably in an amount of 0.5 to 6 wt .-%, based on the total weight of detergents and cleaning agents.

15. Washing and cleaning agent according to at least one of claims 13 to 14, characterized in that it

ii) 5 to 25% by weight, preferably 8 to 17% by weight, of one

peroxygen compound,

ii) from 0.5 to 6% by weight of a bleach co-granule according to any one of claims 1 to 10 and

iv) 0 to 50% by weight of further additives, such as enzymes, alkali carriers,

containing surface-active surfactants, pH regulators, organic solvents or other auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators,

in each case based on the total weight of the washing and cleaning agent.