EP3008158B1 - Bleaching-agent co-granules, method for producing said bleaching-agent co-granules, and use of said bleaching-agent co-granules - Google Patents

Description

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 is done on the one hand 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 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. Process for the preparation of bleach catalyst granules are described in EP 0 544 440 . WO 95/06710 and WO 2008/069935 disclosed. 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 items to be washed, improves the odor of the wash liquor 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. In EP 0 710 714 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 reduced, since instead of two different granules, only one co-granulate must be produced.

WO 03/093405 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating. As shown in Example 1, a manganese (II) complex is mixed with TAED powder and a tallow fatty alcohol ethoxylate (Genapol® T500, Clariant) in a Lödigemischer at 40 to 50 ° C and then by means of an extruder to noodle-shaped 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 are described. 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, is Genapol® T500.

A variety of in WO 2010/115581 As a result, said bleach catalysts, in particular manganese salts, can be converted into storage-stable, odorless co-granules which are suitable for use in detergents and cleaners.

Surprisingly, it has been found that co-granules consisting of TAED, [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O and Genapol® T500, prepared according to the teachings of WO 03/093405 or WO 2010/115581 , 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, using as binder a solid at room temperature homo- or copolymeric 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 relates to storage-stable and odorless bleach co-granules according to claim 1, which comprises a bleach activator, a metal-containing bleach catalyst comprising at least one ligand selected from the group consisting of di- or trimethyltriazacyclononanes or derivatives thereof, and a homo- or copolymer based on ( Meth) acrylic acid, or its salts or Teilneutralisate having a pH in the range of 3 to 9, the characteristic feature is seen in that they are prepared in an anhydrous granulation process, preferably by compaction, and that the temperature in the anhydrous granulation process kept below 100 ° C.

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

1. a) 50 bis 90 Gew.-% eines oder mehrerer Bleichaktivatoren
2. b) 0,01 bis 10 Gew.-% eines oder mehrerer metallhaltiger Bleichkatalysatoren mit mindestens einem Liganden aus der Gruppe Di- oder Trimethyltriazacyclononan oder Derivate davon
3. c) 5 bis 40 Gew.-% eines oder mehrerer Bindemittel auf Basis Poly(meth)acrylsäuren oder deren Salzen mit einem pH-Wert im Bereich von 3 bis 9, gemessen als 1 Gew. % gelöst in Wasser,

enthalten.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,

1. a) 50 to 90 wt .-% of one or more bleach activators
2. 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
3. c) from 5 to 40% by weight of one or more binders based on poly (meth) acrylic acids or salts thereof having a pH in the range from 3 to 9, measured as 1% by weight dissolved in water,

contain.

1. a) 65 bis 85 Gew.-% eines oder mehrerer Bleichaktivatoren,
2. b) 0,05 bis 6 Gew.-% eines oder mehrerer metallhaltiger Bleichkatalysatoren mit mindestens einem Liganden aus der Gruppe Di- oder Trimethyltriazacyclononan oder Derivate davon, und
3. c) 10 bis 30 Gew.-% eines oder mehrerer Bindemittel auf Basis von Poly(meth)acrylsäuren oder deren Salzen mit einem pH-Wert im Bereich von 3 bis 8, gemessen als 1 Gew. % in Wasser.

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

1. a) 65 to 85% by weight of one or more bleach activators,
2. 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, and
3. c) 10 to 30 wt .-% of one or more binders based on poly (meth) acrylic acids or their salts having a pH in the range of 3 to 8, measured as 1 wt.% In water.

Bleach activators (component a)

As bleach activators, the co-granules according to the invention can 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 phenolsulfonates, in particular n-nonanoyloxy or n-lauroyl oxbenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, in particular nonanoyloxy or decanoyloxibenzoic 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), pentaacetylfraktose, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated it contains 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.

mit R= H, CH₃, C₂H₅, oder C₃H₇
Bevorzugte Liganden sind 1,4,7-Trimethyl-1,4,7-triazacyclononan (Me-TACN), 1,4,7-Triazacyclononan (TACN) oder verbrückte Liganden wie 1,2-bis-(4,7-Dimethyl-1,4,7-triazacyclonono-1-yl) ethan (Me4-DTNE), wie sie z. B. in EP 0 458 397 , EP 0 458 398 , EP 0 549 272 , WO 96/06154 , WO 96/06157 oder WO 2006/125517 beschrieben sind.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

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 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-TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (SO ₄ ), [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (OAc) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (Cl) ₂ , [Mn ^IV Mn ^III ₂ (μ-O) ₂ (OAc) (Me4-DTE)] (Cl) ₂ , Mn ^IV Mn ^III ₂ (μ-O) ₂ (OAc) (Me4-DTE)] (PF ₆ ) ₂ or the mononuclear complexes [Mn ^IV (Me-TACN) (OCH ₃ ) ₃ ] PF ₆ , (according to EP 544 519 prepared), [Mn ^IV (Me-TACN) (OC ₂ H ₅ ) ₃ ] PF ₆ and [Mn ^IV (Me-TACN) (acac) OH] PF ₆ or [Mn ^III (Me-TACN) (acac) OC ₂ H ₅ ] PF ₆ , the latter produced 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 preferably used, an example of which is. [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ * H ₂ O.

• [Mn^III ₂(µ-O)₁(µ-OAc)₂(Me-TACN)₂](PF₆)₂, [Mn^IV ₂(µ-O)₃(Me-TACN)₂](PF₆)₂*H₂O, [Mn^IV ₂(µ-O)₂(µ-OAc)(Me4-DTE)]Cl₂, [Mn^IV(Me-TACN)(OCH₃)₃]PF₆ oder [Mn^IV(Me-TACN)(acac)OCH_3] PF₆.

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

• [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me-TACN) ₂ ] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ * H ₂ O, [Mn ^IV ₂ (μ-O) ₂ (μ-OAc) (Me4-DTE)] Cl ₂ , [Mn ^IV (Me-TACN) (OCH ₃ ) ₃ ] PF ₆ or [Mn ^IV (Me-TACN) (acac) OCH _3] PF ₆ .

Binders (component c)

As a further ingredient, the co-granules according to the invention contain a binder in order to ensure cohesion of the co-granules.

The binder is characterized in that it is 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 teilneutralisierter form. The binder used, 1% dissolved in water, a pH of 3 to 9, but especially between 3.5 and 8.5. 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 of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid or of methacrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid or methacrylic acid and 50 to 10% by weight of maleic acid, have proven to be particularly suitable. Their average molecular weight, based on free acids, is preferably 2,000 to 70,000 g / mol, particularly 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.

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 co-granules according to the invention are not provided with a protective layer (so-called coating).

In a preferred embodiment of the invention, the co-granules of the invention is additionally provided with a protective layer, whereby the storage stability further improved and the co-granules can optionally be 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 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, however, 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 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 particularly 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 detergents and cleaners and preferably of agents for the automated cleaning of dishes.

Another subject of the present invention are also detergents and cleaners, preferably detergents for dishwashing, comprising a bleach co-granules according to the invention.

Preferred detergents and cleaners according to the invention, in particular the detergents for dishwashing, contain the bleach co-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 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 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 co-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. %, bevorzugt 5 bis 20 Gew.-%, und besonders bevorzugt 8 bis 17 Gew.-%, einer Persauerstoffverbindung,
3. iii) 0,5 bis 6 Gew.-% eines erfindungsgemäßen Bleichmittel-Co-Granulates, und
4. iv) 0 bis 50 Gew.-% weitere Zusatzstoffe wie Enzyme, Alkaliträger, oberflächenaktive Tenside, pH-Regulatoren, organische Lösungsmittel oder weitere Hilfsstoffe, wie Glaskorrosionsinhibitoren, Silberkorrosionsinhibitoren und Schaumregulatoren, jeweils bezogen auf das Gesamtgewicht des Wasch- und Reinigungsmittels.

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 5 to 20% by weight, and particularly preferably from 8 to 17% by weight, of a peroxygen compound,
3. iii) from 0.5 to 6% by weight of a bleach co-granule according to the invention, and
4. iv) 0 to 50 wt .-% of other additives such as enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents or other auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, each based on the total weight of the detergent 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 detergents and cleaners according to the invention, in particular the agents 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 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 range from 15 to about 65% by weight, preferably from 20 to 60% 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 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. 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 diacetate (MDGA, eg Trilon® M, BASF), L-glutamic acid, N, N, (biscarboxymethyl) -tertra sodium salt (GLDA, Dissolvine® DL, Akzo Nobel), sodium Polyaspartates (Baypure®, Lanxess) or iminodisuccinic acid salts (Baypure®, Lanxess).

peroxygen compounds

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

enzymes

The enzymes present in the detergents and cleaners of the invention, in particular the detergents for dishwashing, include 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 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. The alkali carriers used conventionally include carbonates, bicarbonates and alkali silicates having a molar ratio of SiO ₂ / M ₂ O (M = alkali metal) of 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. 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 .-%, 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 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 with 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, based in each case on the total weight of the agent.

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 the composition 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 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

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 suppressant 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 may be 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 in principle be carried out in a known manner, for example by spray drying or granulation, with peroxygen compound and co-granules according to the invention optionally being separated later be added.

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 admixing the more sensitive components, which in particular enzymes, bleaching agents and the bleach catalyst are 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 · 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 more than 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 bulk densities in the range from 800 to 1000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, can thereby take place, that mixed 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 and subsequently - optionally after an intermediate drying - the other ingredients of the agent, including the inventive co-granules, with the thus obtained Pre-mix united.

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 expediently supplemented and terminated by a few intermediate rinses with clear water following a cleaning cycle and a rinse cycle with a customary 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 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 ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O and 80 g of citric acid were placed in a laboratory mixer, mixed and brought to the required starting temperature of T> 40 ° C heated. Then, with vigorous stirring, the melt-shaped binder 200 g of Genapol® T 500 (fatty alcohol polyglycol ether, commercial product from Clariant based on cetearyl alcohol with an average of 50 ethylene oxide units in the molecule) at a temperature of T = 70-75 ° C was 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 microns.

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 stored with the lid closed under climatic conditions (T = 40 ° C, 75% relative humidity) 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 ^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 screened in a laboratory fluid bed dryer at about 60-80 ° C and then for the separation of coarse and fines of 200-1600 microns.

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 microns.

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 Sweco sieve at 200 to 1040 microns. Batch size: 5 to 7 kg.

The table shows an overview of the co-granules 1 to 4 according to the invention Co-granules 1 2 3 4 substances bleach TAED TAED TAED TAED Bleach catalyst *) Complex 1 Complex 1 Complex 2 Complex 3 binder Sokalan® CP 45 G Sokalan® CP5G Sokalan® CP 45 G Sokalan® CP5G Addition of organic acid - - - oxalic acid composition bleach % 85 75 79 80 bleach catalyst % 3 2 1 2 binder % 12 23 20 17 Organic acid % - - - 1 TAED tetraacetylethylenediamine
*) Complex 1 [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ .H ₂ O, prepared according to EP 0 458 397
*) Complex 2 [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (OAc) _2, prepared according to WO 2006/125517
*) Complex 3 [Mn ^IV (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 (14)

1. A storage stable and odorless bleaching agent co-granulate containing each referring to the overall weight of the co-granulate

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

   b) 0.01 to 10 % by weight of one or more metal-containing bleach catalysts comprising at least one ligand from the group of di- or trimethyltriazacyclononanes or derivatives thereof, and

   c) 5 to 40 % by weight of one or more polymers or copolymers of acrylic acid and/or methacrylic acid or their salts or partial neutralisates having a pH-value in the range from 3 to 9, measured as 1 % by weight dissolved in water, as a binder, characterized in that it is obtained in an anhydrous granulating process, in particular by compaction, wherein the temperature in the anhydrous granulating process is maintained below 100 °C.
2. The bleaching agent co-granulate 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 bleaching agent co-granulate as claimed in claim 1, characterized in that it contains, referring to the overall weight of the co-granulate

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

   b) 0.05 to 6 % by weight of one or more of a metal-containing bleach catalysts comprising at least one ligand from the group of di- or trimethyltriazacyclononanes or derivatives thereof; and

   c) 10 to 30 % by weight of one or more binders based on poly(meth)acrylic acids or their salts having a pH-value in the range from 3 to 9, measured as 1 % by weight dissolved in water.
4. The bleaching agent co-granulate as claimed in at least one of claims 1 to 3, characterized in that it contains as bleaching activator of component a) multiple acylated alkylenediamines, preferably tetraacetylethylenediamine (TAED), acylated triazine derivatives, preferably 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycoluriles, preferably tetraacetylglycoluril (TAGU), N-acylimides, preferably N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, preferably n-nonanoyloxi- or n-lauroyloxibenzenesulfonate (NOBS or LOBS), acylated phenolcarboxylic acids, preferably nonanoyloxy- or decanoyloxybenzoic acid (NOBA bzw. DOBA), carboxylic acid anhydrides, preferably phthalic acid anhydride, acylated polyvalent alcohols, preferably triacetine, ethyleneglycol diacetate and 2,5-diacetoxy-2,5-dihydrofurane as well as acetylated sorbitol and mannitol or their mixtures respecively (SORMAN), acylated sugar derivatives, preferably pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and/or N-acylated lactames, for example N-benzoylcaprolactam.
5. The bleaching agent co-granulate as claimed in at least one of claims 1 to 4, characterized in that the bleach catalyst is selected from the group of manganese complexes containing at least one ligand of formulae A or B

   

   with R = H, CH₃, C₂H₅, or C₃H₇
6. The bleaching agent co-granulate as claimed in at least one of claims 1 to 5, characterized in that the metal containing 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(Me-TACN)(OCH₃)₃]PF₆ or [Mn^IV(Me-TACN)(acac)OCH₃]PF₆.
7. The bleaching agent co-granulate as claimed in at least one of claims 1 to 6, characterized in that it contains as a binder of component c) a polymer or a copolymer of (meth)acrylic acid, preferably in the form of their salts or in partially neutralised form, wherein the binder has a pH-value in the range from 3.5 to 8.5, as 1 % by weight dissolved in water.
8. The bleaching agent co-granulate as claimed in at least one of claims 1 to 7, characterized in that the binder is a polyacrylic acid or a polymethacrylic acid with an average molar mass in the range from 500 to 70.000 g/mol, or a copolymer of acylic acid or of methacrylic acid with maleic acid comprising 50 to 90 % by weight of acrylic aid or of methacrylic acid and 50 to 10 % by weight of maleic acid.
9. The bleaching agent co-granulate as claimed in at least one of claims 1 to 8, characterized in that the bleaching agent co-granulate has been provided with a coating layer.
10. A process for manufacturing of the bleaching agent co-granulate as claimed in one of claims 1 to 9, wherein the pulverulent actives first being mixed and the mixture then being compacted, thereafter ground with or without subsequent sieving into individual particle size fractions, wherein the temperature during the anhydrous granulating process is kept below 100 °C and wherein the compacting is preferably effected on roll compactors.
11. Use of a bleaching agent co-granulate as claimed in one of claims 1 to 9 for the manufacture of washing and cleaning agents, preferably of machine dishwasher detergents.
12. A washing and cleaning agent, in particular an agent for machine cleaning of dishes comprising a bleaching agent co-granulate of one of claims 1 to 9.
13. The washing and cleaning agent as claimed in claim 12, characterized in that the bleaching agent co-granulate is contained in an amount in the range from 0.1 to 10 % by weight, preferably in an amount from 0.2 to 8 % by weight, and most preferably in an amount from 0.5 to 6 % by weight, referring to the overall amount the of washing and cleaning agent.
14. The washing and cleaning agent as claimed in at least one of claims 12 to 13, characterized in that it contains

    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 bleaching agent co-granulate as claimed in any of claims 1 to 9, and

    iv) 0 to 50 wt% of further additives, such as enzymes, alkali carriers, sufactants, pH regulators, organic solvents or other adjuvants, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators, all referring to the overall weight of said washing and cleaning agent.