EP2417240B1 - Bleach granules comprising an active coating - Google Patents

Description

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

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

Bleach catalysts are used in automatic dishwasher detergents, preferably in the form of prefabricated granules, in order to increase their storage stability. So describe EP 0 458 397 . EP 0 458 398 and EP 0 530 870 Bleach catalysts based on various manganese-containing transition metal complexes.

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 automatic dishwashing 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 liquor and prevents the Training a biofilm in the dishwasher. The combination of bleach catalysts and bleach activators is therefore useful for increasing the bleaching performance and ensuring hygiene in the use of bleaching agents in laundry detergents and cleaners. So describes EP 0 616 029 a bleaching additive consisting of a dry mixture of percarbonate, a TAED granules and a bleach catalyst granules. Also in this case, the bleach catalyst granules only has an active content of 1.2 wt .-%, the rest consists of support materials and / or binder.

The use of activators and catalysts in separate granules, however, has disadvantages that may adversely affect the bleaching performance. The reactions of the persalt, or of the hydrogen peroxide released therefrom with activator and catalyst take place in parallel. Dissolves the catalyst granules faster than the activator granules, 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.

EP 0 835 926 discloses a process for preparing a coated bleach activator granule by coating a bleach activator base granule with a coating substance and simultaneously and / or subsequently annealing. In the EP 0 835 926 It is described that the bleach activator base granules may contain other additives besides the bleach activator and the granulation aid. As additives, for example, metal complexes and organic catalysts are called to increase the performance of peracid.

EP 1 499 702 describes co-granules consisting of a bleach catalyst, a bleach activator, and optionally a coating. Optionally, stabilizers such as antioxidants, reducing agents or acids may be present in amounts up to 2.5% by weight.

In this and other literature-known manufacturing processes for activator catalyst co-granules are bleach activator and catalyst spatially next to each other in the granules. If the granules dissolve during the washing process, at the same rate of dissolution of the components activator and catalyst should be dissolved in the same quantitative ratio and be available for reaction with hydrogen peroxide released from a persalt. The reactions then proceed in parallel and activator and catalyst take part in the bleaching process in the same proportions. This is not the case if the dissolution rate of either component, activator or catalyst, is delayed, which is common. If the rate of dissolution of the catalyst is significantly lower than that of the activator, the hydrogen peroxide or the persalt is already consumed by reaction with the activator, so that no or only a minor amount of hydrogen peroxide is available for the reaction with the catalyst. As indicated above, however, the catalyst is mainly responsible for the low-temperature bleaching performance, the activator in particular for the hygiene during the bleaching process. The focus of new bleach granules is mainly in the field of low temperature bleaching.

There is therefore a need for novel detergent granules which have good low-temperature performance and ensure the hygiene aspect and the medium-temperature performance only in the second respect. It must therefore be ensured that activator / catalyst co-granules dissolve so that first the catalyst is released and in a second step, the activator in the wash liquor. This requirement is not met by the prior art.

It is an object of the present invention to provide bleach activator bleach catalyst co-granules which are distinguished from granules known from the prior art by first liberating the catalyst during use in the wash liquor and then releasing the activator in a second step becomes.

• a) einen oder mehrere Bleichaktivatoren,
  • a2) 0 Gew.-% der Gesamtmenge eines oder mehrerer im Co-Granulat
    enthaltener Bleichkatalysatoren und
• c) ein oder mehrere Bindemittel
  enthält und die Hüll- oder Coatingschicht
• d) 100 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren und
• e) ein oder mehrere Coatingmittel

enthält und das Gewichts-Verhältnis von Granulatkern zu Hüll- oder Coatingschicht von 95:5 bis 50:50 beträgt.The stated object could surprisingly be solved by the provision of co-granules containing a granule core and a granulate core surrounding shell or coating layer, characterized in that the granule core

• a) one or more bleach activators,
  • a2) 0% by weight of the total amount of one or more in the co-granules
    contained bleach catalysts and
• c) one or more binders
  contains and the coating or coating layer
• d) 100% by weight of the total amount of the one or more bleach catalysts contained in the co-granulate, and
• e) one or more coating agents

and the weight ratio of granule core to shell or coating layer is from 95: 5 to 50:50.

The activator present in the granule core is preferably in particle form.

The catalyst present in the coating layer is preferably dissolved and / or in particle form.

• a) einen oder mehrere Bleichaktivatoren,
  • a2) 0 Gew.-% der Gesamtmenge eines oder mehrerer im Co-Granulat
    enthaltener Bleichkatalysatoren und
• c) ein oder mehrere Bindemittel
  enthält und die Hüll- oder Coatingschicht
• d) 100 Gew.-% der Gesamtmenge des einen oder der mehreren im Co-Granulat enthaltenen Bleichkatalysatoren und
• e) ein oder mehrere Coatingmittel

enthält und das Gewichts-Verhältnis von Granulatkern zu Hüll- oder
Coatingschicht von 95:5 bis 50:50 beträgt.The present invention therefore relates to co-granules which comprise a granule core and an enveloping or coating layer surrounding the granule core contain, characterized in that the granule core

• a) one or more bleach activators,
  • a2) 0% by weight of the total amount of one or more in the co-granules
    contained bleach catalysts and
• c) one or more binders
  contains and the coating or coating layer
• d) 100% by weight of the total amount of the one or more bleach catalysts contained in the co-granulate, and
• e) one or more coating agents

contains and the weight ratio of granule core to shell or
Coating layer of 95: 5 to 50:50.

In these co-granules according to the invention, the granule core may optionally contain one or more additives, preferably one or more organic acids. The coating layer may optionally contain one or more further additives and optionally one or more dyes.

• a) 1 bis 99 Gew.-%, vorzugsweise 69,1 bis 99 Gew.-% und besonders bevorzugt 70 bis 99 Gew.-%, eines oder mehrerer Bleichaktivatoren und
• c) 0,9 bis 30 Gew.-% und vorzugsweise 1 bis 30 Gew.-% eines oder mehrerer Bindemittel
  und die Hüll- oder Coatingschicht des erfindungsgemäßen Co-Granulats
• d) 1 bis 99 Gew.-%, vorzugsweise 1 bis 98,9 Gew.-% und besonders bevorzugt 1 bis 98,8 Gew.-% eines oder mehrerer Bleichkatalysatoren, und
• e) 1 bis 99 Gew.-%, vorzugsweise 1 bis 98,9 Gew.-% und besonders bevorzugt 1 bis 98,8 Gew.-% eines oder mehrerer Coatingmittel.

Preferably, the granule core of the co-granules according to the invention contains

• a) 1 to 99 wt .-%, preferably 69.1 to 99 wt .-% and particularly preferably 70 to 99 wt .-%, of one or more bleach activators and
• c) 0.9 to 30 wt .-% and preferably 1 to 30 wt .-% of one or more binders
  and the coating or coating layer of the co-granules according to the invention
• d) 1 to 99 wt .-%, preferably 1 to 98.9 wt .-% and particularly preferably 1 to 98.8 wt .-% of one or more bleach catalysts, and
• e) 1 to 99 wt .-%, preferably 1 to 98.9 wt .-% and particularly preferably 1 to 98.8 wt .-% of one or more coating agents.

In the co-granules according to the invention just mentioned, the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight.

In the co-granules according to the invention just mentioned, the coating or coating layer may optionally contain one or more further additives, preferably in an amount of from 0 to 30% by weight and more preferably in an amount of from 0.1 to 30% by weight. ,

In the co-granules according to the invention just mentioned, the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight. ,

• a) 50 bis 95 Gew.-%, vorzugsweise 79,9 bis 95 Gew.-% und besonders bevorzugt 80 bis 95 Gew.-% eines oder mehrerer Bleichaktivatoren und
• c) 4,9 bis 20 Gew.-%, vorzugsweise 5 bis 20 und besonders bevorzugt 5 bis 15 Gew.-% eines oder mehrerer Bindemittel und die Hüll- oder Coatingschicht des erfindungsgemäßen Co-Granulats
• d) 2 bis 60 Gew.-%, vorzugsweise 2 bis 59,9 Gew.-% und besonders bevorzugt 2 bis 59,8 Gew.-% eines oder mehrerer Bleichkatalysatoren und
• e) 40 bis 98 Gew.-%, vorzugsweise 40 bis 97,9 Gew.-% und besonders bevorzugt 40 bis 97,8 Gew.-% eines oder mehrerer Coatingmittel.

Particularly preferably, the granule core of the co-granules according to the invention contains

• a) 50 to 95 wt .-%, preferably 79.9 to 95 wt .-% and particularly preferably 80 to 95 wt .-% of one or more bleach activators and
• c) 4.9 to 20 wt .-%, preferably 5 to 20 and particularly preferably 5 to 15 wt .-% of one or more binders and the coating or coating layer of the co-granules of the invention
• d) 2 to 60 wt .-%, preferably 2 to 59.9 wt .-% and particularly preferably 2 to 59.8 wt .-% of one or more bleach catalysts and
• e) 40 to 98 wt .-%, preferably 40 to 97.9 wt .-% and particularly preferably 40 to 97.8 wt .-% of one or more coating agents.

In the co-granules according to the invention just mentioned, the granule core may optionally contain one or more organic acids, preferably in an amount of from 0 to 10% by weight and more preferably in an amount of from 0.1 to 10% by weight.

In the co-granules according to the invention just mentioned, the coating or coating layer may optionally contain one or more further additives, preferably in an amount of 0 to 15% by weight, particularly preferably in an amount of 0.1 to 15% by weight. and particularly preferably in an amount of 5 to 15 wt .-%.

In the co-granules according to the invention just mentioned, the coating or coating layer may optionally also comprise one or more dyes, preferably in an amount of 0 to 5% by weight and more preferably in an amount of 0.1 to 5% by weight. ,

The quantities given above for the bleach activators of component a) and the binders of component c) and the organic acids optionally present in the granule core of the inventive co-granules are based on the total amount of the granule core of the co-granules according to the invention. In contrast, the quantities given above for the bleach catalysts of component d), the coating agent of component e) and the further additives and dyes optionally contained in the coating or coating layer of the co-granules of the invention to the total amount of the coating or coating layer of the inventive Co Granules related.

The co-granules according to the invention are characterized in that the granule core comprises 0% by weight of the total amount of the one or more bleach catalysts contained in the co-granules and the coating layer comprises 100% by weight of the total amount of the one or more in the Co Granules containing bleach catalysts.

The weight ratio of granule core to shell or coating layer is from 95: 5 to 50:50.

The weight ratio of granule core to shell or coating layer is particularly preferably from 90:10 to 60:40.

Bleach activators

As bleach activators, the 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-lauroylxibenzene sulfonate (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 as well as acetylated sorbitol and mannitol or their mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as 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 and DOBA.

bleach catalysts

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

When using metal salts, in particular manganese salts in the oxidation states +2 or +3 are preferred, for example manganese halides, the chlorides being preferred, manganese sulfates, manganese salts of organic acids such as manganese acetates, manganese acetylacetonates, manganese oxalates and manganese nitrates.

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

Complexes which are preferably used as transition metal complexes in the co-granules according to the invention are complexes which are macromolecular ligands 1,4,7-trimethyl-1,4,7-triazacyclononane (Me-TACN), 1,4,7-triazacyclononane (TACN), 1 , 5,9-trimethyl-1,5,9-triazacyclododecane (Me-TACD), 2-methyl-1,4,7-trimethyl-1,4,7-triazacyclononane (MeMeTACN) and / or 2-methyl-1,4,7-triazacyclononane (Me / TACN) or bridged ligands such as 1,2-bis (4,7-dimethyl-1,4,7-triazacyclonono-1-yl ) ethane (Me4-DTNE) or derivatives of the cyclam or cyclene, such as 1,8-dimethylcyclam, 1,7-dimethylcycles, 1,8-diethylcyclam, 1,7-diethylcycles, 1,8-dibenzylcyclam and 1,7-dibenzylcycles contain, as z. In EP 0 458 397 . EP 0 458 398 . EP 0 549 272 . WO 96/06154 . WO 96/06157 or WO 2006/125517 but also manganese complexes, as they are EP 1 445 305 . EP 1 520 910 or EP 1 557 457 are known.

Suitable manganese complexes are, for example, [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 ₂ (μ-O) ₃ (Me4-DTE)] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O ) ₃ (Me4-DTE)] Cl _2, [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (SO ₄₎ [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (OAc ) ₂ , cis- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride, trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride, 1,8-diethyl 1,4,8,11-tetraazacyclotetradecane iron (II) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride and 1,4,8,11-tetraazacyclotetradecane manganese (II) chloride.

Particularly preferred metal-containing bleach catalysts are selected from manganese salts and manganese complexes, wherein among the manganese salts in turn salts selected from manganese sulfate, manganese acetate and manganese oxalate are preferred, and among the manganese complexes complexes turn is selected from: [Mn ^IV 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 ₂ (μ-O) ₃ (Me4-DTE)] (PF ₆ ) ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] Cl ₂ , [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (SO ₄₎ [Mn ^IV ₂ (μ-O) ₃ (Me4-DTE)] (OAc) _2, cis- (1,4,8,11-tetraazacyclotetradecane) dichloro iron ( III) chloride, trans- (1,4,8,11-tetraazacyclotetradecane) dichloro-iron (III) chloride, 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane-iron (II) chloride, 1.8 Diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride and 1,4,8,11-tetraazacyclotetradecane manganese (II) chloride.

Organic acids

As the organic acid, both monomeric and polymeric acids can be used either in the form of the free acid or in partially neutralized form. In the context of the present invention, the term "organic acid" therefore includes both the organic acids in free form and in partially neutralized form.

Preferred counterions are Na ions.

Preferred organic acids are citric acid, ascorbic acid, oxalic acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, fatty acids and mixtures thereof. Particularly preferred organic acids are oxalic acid, ascorbic acid, citric acid and fatty acids. As polymeric acids are polymers of acrylic acid and copolymers of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid use.

Particularly preferred organic acids are citric acid, ascorbic acid and oxalic acid.

binder

As a further ingredient, the co-granules according to the invention contain one or more binders in order to ensure cohesion of the co-granules.

As binders, substances selected from fatty acids, alcohol ethoxylates, polymers and natural clay minerals may preferably be used. Among the polymers here are synthetic and natural polymers understood as well as modified polymers of natural origin. Among these substances, the natural clay minerals are again preferred.

Suitable are, inter alia, organic fatty acids having 8 to 22 carbon atoms, such as lauric acid, myristic acid, stearic acid or mixtures thereof. Farther preferred are organic polymers. The polymers may be nonionic, anionic, cationic or amphoteric in nature. Natural polymers and modified polymers of natural origin are usable as well as synthetic polymers.

The group of nonionic polymers used with particular preference as binders include polyvinyl alcohols, acetalated polyvinyl alcohols, polyvinylpyrrolidones and polyalkylene glycols, in particular polyethylene oxides. Preferred polyvinyl alcohols and acetalated polyvinyl alcohols have molecular weights in the range from 10,000 to 100,000 g / mol, preferably from 11,000 to 90,000 g / mol, more preferably from 12,000 to 80,000 g / mol and particularly preferably from 13,000 to 70,000 g / mol. Preferred polyethylene oxides have molecular weights in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000.

The anionic polymers used with particular preference as binders are in particular homo- or copolymeric polycarboxylates. Preference is given to using, for example, polyacrylic acid or polymethacrylic acid, in particular those having a relative molecular mass of 500 to 70,000 g / mol.

Preferred among these are polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility preferred from this group, in turn, the short-chain polyacrylates having molecular weights of 2,000 to 10,000 g / mol, and preferably from 3,000 to 5,000 g / mol.

Of these, furthermore preferred are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their molecular weight relative to free acids is preferably 2,000 to 70,000 g / mol, more preferably 20,000 to 50,000 g / mol, and particularly preferably 30,000 to 40,000 g / mol.

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 which contain structural units from salts of acrylic acid and maleic acid and from vinyl alcohol or vinyl alcohol derivatives and sugar derivatives or the structural units from salts of acrylic acid and 2-alkylallyl sulfonic acid and from sugar derivatives.

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

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

Further preferred binders are C ₈ -C ₂₂ alcohol ethoxylates which are solid at room temperature, preferably C ₈ -C ₂₂ alcohol ethoxylates with an average of from 10 to 100 ethylene oxide units in the molecule, such as, for example, B. Genapol ^® T 500 Clariant or carboxymethyl.

Among the natural clay minerals, bentonite is particularly preferred.

Coating layer and coating materials

The materials already used as binders (except the natural clay minerals such as bentonite) can also be used as coating materials. Here, the co-granules are coated after their preparation in a separate step with one or more coating materials, so that a uniform protective layer is formed. In a preferred embodiment of the invention, the content of the total granules is at least 10 wt .-%.

In a further preferred embodiment, the coating layer envelops the granule core as completely and uniformly as possible.

The substances preferred as coating materials correspond to the aforementioned preferred binders (with the exception of the natural clay minerals such as bentonite). In a further preferred embodiment of the invention, the coating materials are therefore selected from fatty acids, alcohol ethoxylates and polymers. Among the polymers, synthetic and natural polymers are understood as well as modified polymers of natural origin. Among the substances just mentioned, the fatty acids are again preferred, in particular fatty acids having 8 to 22 carbon atoms.

dyes

The co-granules according to the invention contain, in a further preferred embodiment of the invention, one or more dyes. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to the substrates to be treated with the dye-containing agents such as textiles, glass, ceramics or plastic dishes do not stain them.

When choosing the dye, it should be noted that the dyes have high storage stability and insensitivity to light. At the same time, it should also be taken into account when choosing suitable dyes that dyes have different stabilities to oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the dye varies in the washing or Detergents. Dyes which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use dyes which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic dyes, for. B. anionic nitrosofarbstoffe.

Other additives

Further additives which may be present in the co-granules according to the invention, in particular in their coating or coating layer, are additives which are known from the prior art in such granules, in particular those intended for use in detergents and cleaners are to be used.

In a further preferred embodiment of the invention, the granutant core of the co-granules according to the invention consists of the bleach activators of component a) and the binders of component c).

In a further preferred embodiment of the invention, the granule core of the co-granules according to the invention consists of the bleach activators of component a), the binders of component c) and organic acids.

In a further preferred embodiment of the invention, the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d) and the coating agents of component e).

In a further preferred embodiment of the invention, the coating or coating layer of the co-granules according to the invention consists of the bleach catalysts of component d), the coating agents of component e) and dyes.

In a further preferred embodiment of the invention, the co-granules of the invention consist of the bleach activators of component a), the binders of component c), the bleach catalysts of component d), the Coatsmittein the component e) and one or more substances selected from in Granule core of the inventive co-granules contained organic acids and contained in the coating or coating layer of the co-granules of the invention dyes and other additives.

Production of the Co-Granules According to the Invention

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

In a first preferred process variant, a build-up granulation is carried out in mixing apparatus. Here, the components are processed in conventional, batch or continuous mixing devices, which are usually equipped with rotating mixing devices. As a mixer moderately operating devices such. As plowshare mixer (Lödige KM types, Drais KT types) but also intensive mixers (eg Eirich, Schugi, Lödige CB types, Drais K-TT types) are used. When mixing all mixed variants are conceivable that ensure adequate mixing of the components. In a preferred embodiment, all components are mixed simultaneously. However, multistage mixing processes are also conceivable in which the individual components are introduced into the overall mixture individually or together with other additives in various combinations. The order of slow mixer and fast mixer can be reversed as needed. The residence times in the mixer granulation are preferably 0.5 s to 20 min, more preferably 2 s to 10 min. The granulating liquid can be pumped via simple guide tubes into the mixing apparatus. For better distribution but also nozzle systems (single-fluid or multi-fluid nozzles) are conceivable.

Depending on the granulation liquid used (solvent or melt-shaped binder), a drying (for solvent) or cooling step (for melting) adjoins the granulation stage, in order to avoid sticking of the granules. The aftertreatment preferably takes place in a fluidized bed apparatus. Subsequently, the coarse grain and the fine grain fraction is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.

Granulation with the aid of a plasticizer

In a further preferred embodiment, the pulverulent components (bleach activator, bleach catalyst and optionally further auxiliaries) are mixed with one or more plastification substances. The plasticizers can be added as a liquid or as a melt, with melt-shaped substances being preferred according to the invention.

The liquid plasticizer is intensively mixed with the powdered active substance and optionally the other additives, so that a plastically deformable mass is formed. The mixing step may be in the o. G. Mixing apparatus, but also kneaders or special extruder types (eg Extrud-o-mix from Hosokawa-Bepex Corp.) are possible. The granulation mass is then pressed by means of tools through the nozzle bores of a press die, so that cylindrically shaped extrudates are formed. Suitable apparatuses for the extrusion process are ring roller presses (eg from Schlüter, Salmatec, Bühler), edge mills (for example from Amandus-Kahl) and extruders, designed as single-shaft machines (eg from Hosokawa Bepex, Fuji-Paudal) or preferably as a twin-screw extruder (eg from Händle). The choice of the diameter of the nozzle bore depends on the individual case and is typically in the range of 0.7 - 4 mm.

The exiting extrudates are to be comminuted by a post-processing step to the desired length or particle size. In many cases, a length / diameter ratio of L / D = 1 is desired. For cylindrical Granules is the particle diameter between 0.2 and 2 mm, preferably between 0.5 and 0.8 mm, the particle length in the range of 0.5 to 3.5 mm, ideally between 0.9 and 2.5 mm. The lengths or size adjustment of the granules can be done for example by fixed scraper blades, rotating blades, cutting wires or blades. To round off the cut edges, the granulate can then be rounded again in a rounding device (eg from Glatt, Schlüter, Fuji-Paudal).

After the size adjustment of the granules, a final solidification step is required in which the solvent is removed or the melt is solidified. Usually, this step is carried out in a fluidized bed apparatus operating as a dryer or condenser as required. Subsequently, the coarse grain and the fine grain fraction is separated by sieving. The coarse grain fraction is comminuted by grinding and, like the fine grain fraction, fed to a renewed granulation process.

compacting

In a further preferred embodiment, the pulverulent active substances are optionally mixed with further preferably solid additives and this mixture is compacted, then ground and then optionally sieved into individual grain fractions. Optionally, liquid additives may also be added to the mixture to a certain extent (eg up to 10% by weight). Examples of compacting aids are water glass, polyethylene glycols, nonionic surfactants, anionic surfactants, polycarboxylate copolymers, modified and / or unmodified celluloses, bentonites, hectorites, saponites and / or other detergent ingredients.

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 fines, the puddles 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 is 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 fed again to the compaction. For classifying the granules common screening machines such. As tumble screen or vibrating screens (eg., From Allgaier, Sweco, Vibra) are used.

Coating method:

The granules prepared by one of the processes described above are provided in the second step with the so-called active coating. For this purpose, the granules are coated in an additional step according to methods known per se with a film-forming substance, wherein the coating shell contains one or more bleach catalysts and optionally further additives.

For a uniform distribution in the coating shell on the one hand and a better processing on the other hand, it may prove advantageous that the bleach catalyst is comminuted prior to incorporation into the coating. The maximum particle size of the milled bleach catalyst to be set is defined inter alia by the starting particle size of the bleach catalyst, the dimensions of the coating layer to be applied and the process conditions of the coating process. Typically, the maximum particle size of the bleach catalyst can be limited to <100 .mu.m, preferably <50 .mu.m.

If the grinding of the bleach catalyst is required, in principle all common milling principles and grinding units are conceivable. For example, an impact crushing can be done in a pin mill. Ultimately, especially determine the grinding properties of the bleach catalyst, such. Brittleness, and the desired fineness of the mill selection.

The prepared bleach catalyst is incorporated in the next process step in the coating substance. For this purpose, the coating liquid is placed in a container and the bleach catalyst is added with stirring. Depending on the fluid system, stirrers to avoid sedimentation of solids or, in the case of highly viscous systems, mixers for introducing shear energy are advantageous in the case of rather low-viscosity systems.

As already mentioned before, the coating materials in a preferred embodiment of the invention are selected from fatty acids, alcohol ethoxylates and polymers.

In a further preferred embodiment of the invention, the coating materials are selected from film-forming substances, such as waxes, silicones, fatty acids, fatty alcohols, soaps, anionic surfactants, nonionic surfactants, cationic surfactants, anionic and cationic polymers, and also polyalkylene glycols. Preference is given to using coating substances having a melting point of 30-100 ° C. Examples of these are: C ₈ -C ₃₁ -fatty acids, for example lauric, myristic, stearic acid; C ₈ -C ₃₁ fatty alcohols; Polyethylene glycols having a molecular weight of 1,000 to 50,000 g / mol; Fatty alcohol polyalkoxylates with 1 to 100 moles of EO (EO: ethylene oxide unit); Alkanesulfonates, alkylbenzenesulfonates, α-olefinsulfonates, alkyl sulfates, alkyl ether sulfates with C ₈ -C ₃₁ -hydrocarbon radicals, polymers, for example polyvinyl alcohols, waxes, for example montan waxes, paraffin waxes, ester waxes, polyolefin waxes, silicones.

In the coating substance which softens or melts in the range from 30 to 100 ° C., further substances which do not soften or melt in this area can be present in dissolved or suspended form, for example homopolymers, copolymers or propylene copolymers of unsaturated carboxylic acids and / or sulfonic acids and their derivatives Alkali salts, cellulose ethers, starch, starch ethers, polyvinylpyrrolidone; mono- and polybasic carboxylic acids, hydroxycarboxylic acids or ether carboxylic acids having 3 to 8 carbon atoms and salts thereof; Silicates, carbonates, bicarbonates, sulfates, phosphates, phosphonates.

For applying the coating substances, mixers (mechanically induced fluidized bed) and fluidized bed apparatuses (pneumatically induced fluidized bed) can be used. As a mixer z. B. plowshare mixer (continuous and batchwise), ring layer mixers or Schugi mixer possible. The tempering can be carried out using a mixer in a granule preheater and / or in the mixer directly and / or in a fluidized bed downstream of the mixer. Granulated coolers or fluid bed coolers can be used to cool the coated granules. In the case of fluidized bed apparatuses, the heat treatment takes place via the hot gas used for fluidization. The granules coated by the fluidized-bed method can be cooled by a granulate cooler or a fluidized-bed cooler, similar to the mixing method. Both in the mixing process and in the fluidized bed process, the coating substance can be sprayed on a single-component or a Zweistoffdüsvorrichtung. The optional tempering consists in a heat treatment at a temperature of 30 to 100 ° C, but equal to or below the melting or softening temperature of the respective shell substance. Preference is given to working at a temperature which is just below the melting or softening temperature.

Furthermore, the coating agents can be applied in the form of solutions or suspensions to the primary particle, which is possible in principle with the aforementioned apparatuses. Fluidized bed apparatuses can preferably be used here, since they offer the advantage that liquid can be sprayed in at the same time and moisture dried off. This often results in increased flexibility in the process and in the achievable product quality.

Characteristic of the co-granules according to the invention is primarily their chemical composition. However, it has been found that the bleaching action of these co-granules also on the influence of physical parameters such as the particle size, the fines content and the Bleach catalyst content of selected Siebfraktionen can be favorably influenced.

For this reason, preferred 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.

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

Another object of the present invention is therefore the use of a co-granule according to the invention for the production of detergents and cleaners and preferably of agents for the machine cleaning of dishes.

Another object of the present invention are also detergents and cleaners, preferably means for the automated cleaning of dishes, containing a co-granules according to the invention.

Preferred detergents and cleaners according to the invention, in particular the detergents for dishwashing, contain the inventive co-granules in amounts of between 0.1 and 10% by weight, preferably in amounts of between 0.2 and 8% by weight 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 cleaning agents according to the invention, in particular the means for the automatic cleaning of dishes, may in particular contain builder substances, peroxygen compounds, enzymes, alkali carriers, surface-active surfactants, pH regulators, organic solvents and other auxiliaries, such as glass corrosion inhibitors, silver corrosion inhibitors and foam regulators.

• i) 15 bis 65 Gew.-%, vorzugsweise 20 bis 60 Gew.-%, einer wasserlöslichen Builderkomponente,
• j) 5 bis 25 Gew.-%, vorzugsweise 8 bis 17 Gew.-%, einer Persauerstoffverbindung, und
• k) 0,5 bis 6 Gew.-% eines erfindungsgemäßen Co-Granulates, jeweils bezogen auf das gesamte Mittel. Ein derartiges Mittel ist insbesondere niederalkalisch, das heißt seine 1-gewichtsprozentige Lösung weist einen pH-Wert von 8 bis 11,5 und vorzugsweise von 9 bis 11 auf.

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,
• j) 5 to 25 wt .-%, preferably 8 to 17 wt .-%, of a peroxygen compound, and
• k) 0.5 to 6 wt .-% of a co-granules of the invention, each based on the total agent. Such an agent is particularly low alkaline, that is, its 1-weight percent solution has a pH of 8 to 11.5 and preferably from 9 to 11.

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

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 in the washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, 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 to using enzymes which are stabilized against oxidative degradation.

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 wt .-%, based on the total agent to be included. The alkali carrier system preferably used in the detergents and cleaners according to the invention, in particular in the detergents for dishwashing, is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, in an amount of up to 50% by weight and preferably from 5 to 40 wt .-% may be included.

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

surfactants

Surfactants, in particular anionic surfactants, zwitterionic surfactants and preferably weakly foaming nonionic surfactants may also be added to the detergents and cleaners according to the invention, in particular the detergents for dishwashing, where appropriate, as a wetting agent and optionally in the context of Production of these agents serve as Granulierhilfsmittel. Their amount can be up to 20 wt .-%, preferably up to 10 wt .-% and is particularly preferably in the range of 0.5 to 5 wt .-%. Usually extremely low-foam compounds are used in particular in the means for the automatic cleaning of dishes. These include, preferably, C ₁₂ -C ₁₈ -alkylpolyethylene glycol-polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units 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.

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. × H ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O _29. × H ₂ O, magadiite), Na-SKS-3 ( Na ₂ Si ₈ O _17. × H ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O _9. × H 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 washing and cleaning agents according to the invention, in particular the means for the machine cleaning of dishes, 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 these agents on.

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

Foam regulators

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

The detergents and cleaners according to the invention, in particular the means for machine dishwashing, may contain, as further ingredients, for example from the prior art, sequestrants, electrolytes, additional peroxygen activators, dyes or fragrances, for example 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 means for machine dishwashing, presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation, with peroxygen compound and co-granules according to the invention optionally being added separately later become.

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

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

You get so unbreakable and yet under

Conditions of use sufficiently quickly soluble tablets with flexural strengths of normally over 150 N. Preferably, such a tablet produced in such a way a weight of 15 to 40 g, in particular from 20 to 30 g, with a diameter of 35 to 40 mm.

The preparation of detergents and cleaners according to the invention in the form of non-dusting, storage-stable free-flowing powders and / or granules with high bulk densities in the range of 800 to 1,000 g / l, in particular corresponding inventive means for the machine cleaning of dishes, can be carried out by in a first process step, the BuilderKomponenten mixed with at least a proportion of liquid mixture components to increase the bulk density of this premix and subsequently - optionally after an intermediate drying - the other constituents of the agent, including the 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 done by hand or by means of suitable Metering devices. The application concentrations in the cleaning liquor are generally about 1 to 8 g / l, preferably 2 to 5 g / l.

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

Examples

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

The industrially available bleach activator TAED (tetraacetylethylenediamine) was obtained from Clariant in powder form, the manganese salts were purchased from Sigma-Aldrich and the metal complexes used were prepared according to literature.

Example 1: Preparation of co-granules according to the invention with active coating These are co-granules containing TAED and a bleach catalyst, such. B. Mn (II) sulfate, which is applied specifically as an active coating. In addition, the co-granules contain the necessary granulation aids, such as binders and coating substance, but optionally also other additives such. B. stabilizers.

To prepare the active coating, stearic acid is initially introduced as a coating substance or coating agent at T = 95 ° C. in a stirred vessel and melted. The bleach catalyst is added to the stirred melt and distributed uniformly. The bleach catalyst was previously comminuted in a laboratory mill.

The basic granulate for the active coating is a TAED granulate (Peractive CB - commercial product from Clariant containing bentonite) in a laboratory mixer submitted. The granules are heated with moderate stirring to the required starting temperature of T> 70 ° C. At a slightly higher stirring speed, the melt mixture is metered in evenly and slowly with the bleach catalyst, so that the mixture is evenly distributed on the base granules and excessive overgranulation is avoided. After application of the desired amount of the melt mixture, the coated granules are briefly emptied from the mixer emptied and cooled. The product is then sieved to remove coarse and fine fractions of 200-1600 μm.

In the case of the inventive co-granule A, instead of using Peractive CB, TAED, bentonite and oxalic acid are first mixed, then granulated and the resulting granules are coated.

Table 1 shows an overview of the prepared co-granules according to the invention with active coating, which were provided for further investigations. Table 1: Co-granules according to the invention with active coating Example co-granules A B C D substances bleach TAED TAED TAED TAED bleach catalyst Mn (II) sulfate Mn (II) sulfate Complex 1 Complex 2 Bleach activator: bleach catalyst 8.3: 1 7.7: 1 5.11: 1 5.11: 1 binder bentonite bentonite bentonite bentonite Organic acid oxalic acid - - - coating agents stearic acid stearic acid stearic acid stearic acid Dye in the coating - - - red composition bleach % 70.08 [K; 84.3] 74.32 [K; 92.0] 75,18 [K; 90.8] 74.88 [K; 91.2] bleach catalyst % 8.41 [H; 50.0] 9.61 [H; 50.0] 6.54 [H; 38.0] 6.51 [H; 36.4] binder % 6.09 [K; 7,3] 6,46 [K; 8.0] 7.62 [K; 9,2] 7.26 [K; 8.8] Organic acid % 7.01 [K; 8,4] - - - coating agents % 8.41 [H; 50.0] 9.61 [H; 50.0] 10.66 [H; 62.0] 11.05 [H; 61.9] dye % - - - 0.30 [H; 1,7] Core: shell [weight ratio] 83.2: 16.8 80.8: 19.2 82.8: 17.2 82.1: 17.9 TAED tetraacetylethylenediamine Complex 1 [Mn ^IV ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ prepared according to EP 0 458 397 Complex 2 1,8-diethyl-1,4,8,11-tetraazacyclotetradecane manganese (II) chloride, prepared according to EP 1 557 457

In Table 1, both the amount of ingredients based on the total inventive co-granules in wt .-% is given, as well as the amount of the respective ingredients in wt .-% either based on the entire granule core or on the entire coating or coating layer depending on in which part of the co-granules according to the invention the corresponding ingredient is contained. In this case, for example, the statement "[K, 84.3]" for the bleach activator of the co-granule A means that the bleach activator is contained in the granule core and its amount is only 84.3% by weight, based on the total mass of the granule core , Accordingly, for example, the specification "[H;50.0]" for the bleach catalyst of the co-granule A means that the bleach catalyst is contained in the coating layer and its amount - based only on the total mass of the coating layer - 50.0 wt .-% is.

Example 2: Hygroscopicity Test - Physical Stability

To check the physical stability of the co-granules according to the invention, the hygroscopic behavior is tested at elevated relative humidity. For this purpose, the co-granules are stored open for several hours at a relative humidity of 65% and room temperature. Over the experimental period, the moisture absorption is registered via a balance and the external change of the sample is observed. After completion of the storage experiment, the free-flowing or the degree of baking is judged by notes (grade 1: very good, free-flowing to grade 6: completely baked, no longer free-flowing).

Table 2 shows the results of the hygroscopicity test for the co-granules described above. Table 2: Hygroscopicity test Hygroscopicity - 65% RH Example co-granules A B C D Moisture absorption% 1.5 1.8 3.3 2.5 Note (free-flowing) 1 1 1 1 Review Granules very well very well very well very well rH: relative humidity

The results show that the co-granules according to the invention remain free-flowing despite a detectable moisture absorption of> 1.5% and do not cake under the effect of increased air humidity.

Example 3: Storage Tests in Basic Washing Powder - Chemical Storage Stability To check the physical stability of the co-granules according to the invention, the storage behavior is determined in a typical manner

Washing powder formulation examined. For this purpose, the coated co-granules incorporated in IEC-A base wash powder, so that the finished formulation contains 5% of the invention co-granules. The mixtures are then stored in a room climate and severe climatic conditions (T = 40 ° C, 75% relative humidity) over several days. At regular intervals, the samples are evaluated for discoloration of the co-granules and rated grades (grade 1: very good, no discoloration to grade 6: strong discoloration, very dark color).

Table 3 shows the results of the storage test in base washing powder for the previously described co-granules. Table 3: Storage test in basic washing powder Storage stability in base wash powder IEC-A Example co-granules A B C D Storage duration room climate [Days] 20 20 13 13 Note (discoloration) 2 1 1 2 Review sample Good very well very well Good Storage time 40 ° C, 75% rH [Days] 20 20 13 13 Note (discoloration) 2 2 3 3 Review sample Good Good acceptable acceptable rH: relative humidity

The results show that all tested co-granules according to the invention have a good to very good storage stability both in room climate and under severe climatic conditions. The active coating therefore also offers the advantage of increased storage stability, so that impairment by a negative color change of the co-granules according to the invention could be avoided.

Claims (9)

1. A cogranule comprising a granule core and a shell layer or coating layer surrounding the granule core, wherein the granule core comprises

   a) one or more bleach activators,

   a2) 0% by weight of the total amount of one or more bleach catalysts present in the cogranule and

   c) one or more binders
   and the shell layer or coating layer comprises

   d) 100% by weight of the total amount of the one or more bleach catalysts present in the cogranule and

   e) one or more coating agents,
   and the weight ratio of granule core to shell layer or coating layer is from 95:5 to 50:50.
2. The cogranule as claimed in claim 1, wherein the granule core comprises

   a) 1 to 99% by weight of one or more bleach activators and

   c) 0.9 to 30% by weight of one or more binders and the shell layer or coating layer comprises

   d) 1 to 99% by weight of one or more bleach catalysts and

   e) 1 to 99% by weight of one or more coating agents.
3. The cogranule as claimed in claim 1 or 2, wherein the granule core comprises

   a) 50 to 95% by weight of one or more bleach activators and

   c) 4.9 to 20% by weight of one or more binders and the shell layer or coating layer comprises

   d) 2 to 60% by weight of one or more bleach catalysts and

   e) 40 to 98% by weight of one or more coating agents.
4. The cogranule as claimed in one or more of claims 1 to 3, wherein the weight ratio of granule core to shell layer or coating layer is from 90:10 to 60:40.
5. The cogranule as claimed in one or more of claims 1 to 4, wherein the one or more bleach activators are selected from tetraacetylethylenediamine and decanoyloxybenzoic acid.
6. The cogranule as claimed in one or more of claims 1 to 5, wherein the one or more bleach catalysts are selected from manganese salts and manganese complexes.
7. The cogranule as claimed in one or more of claims 1 to 6, wherein the one or more binders are selected from fatty acids, alcohol ethoxylates, polymers and natural clay minerals and are preferably selected from natural clay minerals.
8. The cogranule as claimed in one or more of claims 1 to 7, wherein the coating materials are selected from fatty acids, alcohol ethoxylates and polymers and are preferably selected from fatty acids.
9. The use of one or more cogranules as claimed in one or more of claims 1 to 8 for producing detergents and cleaners and preferably compositions for machine dishwashing.