EP3075835A2 - Particulate detergent composition with bleaching catalyst - Google Patents

Abstract

The present invention relates to a solid particulate detergent containing certain acylhydrazones as a discrete particle bleach catalyst in combination with discrete particles of a tower powder as well as other components such as percarbonate, bleach activators, enzymes and other standard detergent ingredients. Also included is its use for improving stain removal, especially bleachable, hydrophilic stains such as red wine stains, tea stains, red fruit stains or beverages and foodstuffs therefrom or those containing appropriate colorants when washing fabrics or cleaning hard surfaces.

Description

The present invention relates to a solid particulate detergent containing certain acylhydrazones as a discrete particle bleach catalyst in combination with discrete particles of a tower powder as well as other components such as percarbonate, bleach activators, enzymes and other standard detergent ingredients. Also included is its use for improving stain removal, especially bleachable, hydrophilic stains such as red wine stains, tea stains, red fruit stains or beverages and foodstuffs therefrom or those containing appropriate colorants when washing fabrics or cleaning hard surfaces.

Detergents, especially those intended for household use, are generally not marketed as simple mixtures of their ingredients but in the form of granular preparations in which all or most of the ingredients are intimately mixed in the individual grains available. This form has several advantages in the use of detergents, of which only the most dust-free and safety against segregation during transport should be mentioned. Such granular detergents can be prepared in various ways. Thus, processes are known to convert the individual components of the detergent by compacting granulation, for example by means of extruders in the granular form. In addition, there are processes in which the finely divided constituents are agglomerated to larger particles with the aid of liquids, for example alkali silicate solutions. For a variety of technical reasons, the spray-drying process has long been preferred for the continuous production of relatively large quantities of granular detergents. In this process, in large towers, an aqueous slurry of detergent ingredients in free fall is dried by hot gases into granular products called tower powder. In addition to the ease of manufacture in large quantities, these products also have various performance advantages over those obtained by other methods detergents. A disadvantage, however, is that not all constituents of a conventional detergent are suitable for such a production process and must also be formulated and mixed separately for compatibility reasons.

Conventional bleaching agents based on active oxygen, even in the presence of stoichiometric activators (such as TAED, NOBS, DECOBS, DOBA), show good performance at use temperatures of 40 ° C and above. At low temperatures, however, the bleaching performance is limited.

The use of acylhydrazones as a bleach catalyst as described in U.S. Pat WO 2013/104631 A1 described, leads to the improved removal of the above spots even at low temperatures. However, it has been found that the optimal effect depends on the interaction with other components of the formulation. Surprisingly, it has been found that the washing performance of formulations in which the bleach catalyst is formulated in the form of discrete particles, especially in combination with discrete particles of other ingredients of the composition, is improved. This is because effective separation of the bleach catalyst from certain other ingredients of the formulation, such as soda, protects it from degradation, thus ensuring that wash performance is ensured even after storage. In addition, such detergents are advantageous in that the adjustment of the particle size results in a homogeneous powder which can be easily metered.

• in der R¹ für eine CF₃ oder für eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, Phenyl-, Naphthyl-, C_7-9-Aralkyl, C_3-20-Heteroalkyl- oder C_3-12-Cycloheteroalkylgruppe, R² und R³ unabhängig voneinander für Wasserstoff oder eine gegebenenfalls substituierte C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-28-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl-, Naphthyl- oder Heteroarylgruppe oder R2 und R3 zusammen mit dem sie verbindenden Kohlenstoffatom für einen gegebenenfalls substituierten 5-, 6-, 7-, 8- oder 9-gliedrigen Ring, der gegebenenfalls Heteroatome enthalten kann, und
• R⁴ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe oder eine gegebenenfalls substituierte Phenyl- oder Naphthyl- oder Heteroarylgruppe stehen,
• in Form diskreter Partikel enthält, wobei die diskreten Partikel eine Teilchengrößenverteilung aufweisen, bei der mindestens 70 Gew.-%, vorzugsweise mindestens 80 Gew.-%, noch mehr bevorzugt mindestens 90 Gew.-% der Teilchen eine Teilchengröße zwischen 0,2 und 2,0 mm, vorzugsweise zwischen 0,4 und 1,5 mm aufweisen, und wobei mindestens ein Tensid und mindestens eine Buildersubstanz in Form diskreter Partikel eines Turmpulvers in dem Mittel enthalten sind, wobei die Partikel des Turmpulvers eine Teilchengrößenverteilung aufweisen, bei der mindestens 70 Gew.-%, vorzugsweise mindestens 80 Gew.-%, noch mehr bevorzugt mindestens 90 Gew.-% der Teilchen eine Teilchengröße zwischen 0,1 und 2,0 mm, vorzugsweise zwischen 0,1 und 1,6 mm aufweisen.

A first subject of the invention is therefore a solid, particulate detergent which comprises an acylhydrazone of the general formula (I),

• in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, R ² and R ³ independently of one another represent hydrogen or an optionally substituted C _1-28 -alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _{3 -12-} cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl or R2 and R3 together with the carbon atom connecting them to an optionally substituted 5-, 6-, 7-, 8- or 9-membered Ring, which may optionally contain heteroatoms, and
• R ^{4 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 Aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group,
• in the form of discrete particles, the discrete particles having a particle size distribution wherein at least 70%, preferably at least 80%, more preferably at least 90%, by weight of the particles have a particle size between 0.2 and 2 , 0 mm, preferably between 0.4 and 1.5 mm, and wherein at least one surfactant and at least one builder substance in the form of discrete particles of a tower powder are contained in the agent, wherein the particles of the tower powder have a particle size distribution at least 70 Wt .-%, preferably at least 80 wt .-%, more preferably at least 90% by weight of the particles have a particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm.

The registrations DE102014218805 and DE102014218807 disclose how corresponding particulate tower powders can be made.

In various embodiments, the detergent contains further constituents, in particular percarbonate, bleach activators, in particular TAED, builder substances, in particular soda, and enzymes, likewise in the form of discrete particles.

Another object of the invention is the use of the herein described combination of particulate detergent ingredients to enhance the cleaning performance of peroxygen-containing detergents.

Yet another aspect of the invention relates to a process for washing textiles in which an agent according to the invention is used.

All amounts stated in connection with the detergents described herein are, unless stated otherwise, by weight in each case based on the total weight of the detergent. Furthermore, such amounts referring to at least one constituent always refer to the total amount of that type of constituent contained in the composition, unless explicitly stated otherwise. That is, such amounts, for example in connection with "at least one anionic surfactant", refer to the total amount of anionic surfactants contained in the middle.

"At least one" as used herein refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or more. In the context of ingredients of the compositions described herein, this indication does not refer to the absolute amount of molecules but to the nature of the ingredient. Thus, "at least one anionic surfactant" means, for example, one or more different anionic surfactants, i. one or more different types of anionic surfactants. Together with quantities, the quantities refer to the total amount of the corresponding designated type of ingredient as defined above.

In the context of the invention, cleaning performance (washing power) is understood to mean the removal of one or more soiling, in particular laundry soiling, which are pale-sensitive. The distance can be measured by a brightening of the soiling measured as well as assessed visually.

The detergents described herein may be detergents for textiles or natural fibers. Detergents in the context of the invention also include washing aids which are metered into the actual detergent during manual or automatic textile washing in order to achieve a further effect or to enhance an effect. Furthermore, laundry detergents within the scope of the invention also include textile pre-treatment and post-treatment agents, ie those agents with which the laundry item is brought into contact before the actual laundry, for example for dissolving stubborn soiling, and also agents which are in a downstream of the actual textile laundry step give the laundry further desirable properties such as comfortable grip, crease resistance or low static charge. Among the latter, i.a. calculated the fabric softener.

When referring to particle sizes herein, the figures always refer to values determined by sieve analysis. For example, particle sizes can be determined by sieving the particles by means of a VE1000 sieve (Retsch GmbH, Haan) for 2 minutes with an interval of 10 seconds and an amplitude of 2 mm and determining the proportion of particles per sieve gravimetrically. For this purpose, 100 g sample are given by means of the top sieve of a sieve set, which is assembled in such a way that the mesh size decreases towards the bottom, and which is provided with a closure bottom. After sieving under the conditions mentioned, the proportion of particles per sieve is determined gravimetrically by transferring and weighing the different fractions, including the particles stuck in the sieve meshes, into weighing dishes.

The acylhydrazones of formula (I) may be in E or Z configuration; when R ^{2 is} hydrogen, the compound of general formula (I) may be in one of its tautomeric forms or as a mixture of these.

In the compounds of general formula (I), R ^{2 is} preferably hydrogen. R ¹ and / or R ³ is preferably an electron-withdrawing group-substituted methyl, phenyl or naphthyl group. R ⁴ is preferably hydrogen. As an electron-withdrawing group is preferably an ammonium group in question, which optionally carries alkyl or hydroxyalkyl groups or is formed with the inclusion of the N-atom carrying an alkyl group as heterocycloalkyl optionally carrying further heteroatoms.

in der R¹ für eine C_1-4-Alkylgruppe, die einen Substituenten ausgewählt aus

trägt, in dem

• R¹⁰ für Wasserstoff oder eine C_1-28-Alkyl-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkylgruppe und A^- für das Anion einer organischen oder anorganischen Säure steht,
• R² und R⁴ die für Formel (I) angegebenen Bedeutung haben und
• R⁵, R⁶, R⁷ und R⁸ unabhängig voneinander für R¹, Wasserstoff, Halogen, eine Hydroxy-, Amino-, eine gegebenenfalls substituierte N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-amino-, C_1-28-Alkyl-, C_1-28-Alkoxy-, Phenoxy-, C_2-28-Alkenyl-, C_2-22-Alkinyl-, C_3-12-Cycloalkyl-, C_3-12-Cycloalkenyl-, C_7-9-Aralkyl-, C_3-20-Heteroalkyl-, C_3-12-Cycloheteroalkyl-, C_5-16-Heteroaralkyl-, Phenyl- oder Naphthylgruppe stehen, wobei die Substituenten ausgewählt werden aus C_1-4-Alkyl-, C_1-4-Alkoxy-, Hydroxy-, Sulfo-, Sulfato-, Halogen-, Cyano-, Nitro-, Carboxy-, Phenyl-, Phenoxy-, Naphthoxy-, Amino-, N-mono-oder di-C_1-4-alkyl- oder C_2-4-hydroxyalkyl-amino-, N-Phenyl- oder N-Naphthyl-aminogruppen, oder
• R⁵ und R⁶ oder R⁶ und R⁷ oder R⁷ und R⁸ unter Ausbildung von 1, 2 oder 3 carbocyclischen oder O-, NR¹⁰- oder S-heterocyclischen, gegebenenfalls aromatischen und/oder gegebenenfalls C_1-6-alkylsubstituierten Ringen miteinander verbunden sind.

Preferred embodiments of the compounds according to general formula (I) include those of general formula (II),

in the R ^{1 is} a C _1-4 alkyl group having a substituent selected from

carries in which

• R ^{10 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 -Aralkyl-, C _3-20 -Heteroalkyl-, C _3-12 -cycloheteroalkyl-, C _5-16 -Heteroaralkylgruppe and A ^{- represents} the anion of an organic or inorganic acid,
• R ² and R ^{4 have} the meaning given for formula (I) and
• R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another are R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 alkenyl, C _2-22 Alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl , Phenyl or naphthyl group, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro, carboxy, Phenyl, phenoxy, naphthoxy, amino, N-mono or di-C _1-4 alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino groups, or
• R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C _1-6 alkyl substituted Rings are interconnected.

The anion A ^- is preferably a carboxylate such as lactate, citrate, tartrate or succinate, perchlorate, tetrafluoroborate, hexafluorophosphate, alkyl sulfonate, alkyl sulfate, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, isocyanate, rhodanide, nitrate, fluoride, chloride, bromide, bicarbonate or carbonate, wherein in polyvalent anions, the charge balance can be achieved by the presence of additional cations such as sodium or ammonium ions.

Particular preference is given to the acylhydrazone of the formula (III)

The performance of compounds of general formula (I) may optionally be controlled by the presence of manganese, titanium, cobalt, nickel or copper ions, preferably Mn (II) - (III) - (IV) - (V), Cu ( I) - (II) - (III), Fe (I) - (II) - (III) - (IV), Co (I) - (II) - (III), Ni (I) - (II) - (III), Ti (II) - (III) - (IV), and particularly preferably those selected from Mn (II) - (III) - (IV) - (V), Cu (I) - (II) - (III ), Fe (I) - (II) - (III) - (IV) and Co (I) - (II) - (III); Optionally, the acylhydrazone can also be used in the form of complex compounds of said metal central atoms with ligands of general formula (I) and in particular of general formula (II). A bleach-enhancing complex which has a ligand with a skeleton of the formula (I) may have the corresponding ligand once or more than once, in particular twice. It may be one or possibly two or more nuclear. It may also contain other neutral, anion or cationic ligands such as H ₂ O, NH ₃ , CH ₃ OH, acetylacetone, terpyridine, organic anions such as citrate, oxalate, tartrate, formate, a C _2-18 -carboxylate, a C _1-18 alkyl sulfate, especially methosulfate, or a corresponding alkanesulfonate, inorganic anions such as halide, especially chloride, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, bisulfate, hydroxide or hydroperoxide. It may also have bridging ligands such as alkylenediamines.

The bleach catalysts of the formula (I) are present in the detergents according to the invention as discrete particles. The particles have a particle size distribution in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0 , 4 and 1.5 mm. The particles are preferably approximately spherical, the shape being not limited thereto.

"Discrete particles" as used herein means that the particles are separate from other particles also included in the formulation. The particles may consist of the bleach catalyst of formula (I) or may contain this in combination with other ingredients. However, it is preferred that the particles consist of the bleach catalyst and the remaining constituents are contained in the composition in the form of further discrete particles, these further particles each containing one or more of the further constituents. The particulate further ingredients of the detergent are defined more fully below. The particles can each be coated (co-coated) to interact with others Components of the formulation. Suitable coating agents and methods of coating such particles are known in the art.

Surprisingly, it has been found that particulate bleach catalysts formulated in tower powder-containing particulate detergents have better bleaching performance. Without wishing to be bound by any particular theory, it is believed that this finding is due to the balanced combination of various measures and effects. First, the spatial separation of the bleach catalyst from other ingredients prevents the bleach catalyst from being inactivated by the other ingredients. In addition, the bleach catalyst is available more quickly as an individual particle after adding the detergent to the water, so its performance in the wash liquor starts faster. On the other hand, the metering as a particle, in particular after adjustment of the particle sizes, in particular of the bleach catalyst and the tower powder as an essential component of the washing and cleaning agent, ensures a homogeneous, stable and storable mixture. Therefore, it is possible even after a long storage to achieve excellent bleaching performance. At the same time, the homogeneous distribution of the bleach catalyst in the detergent ensures uniform metering in washing and cleaning processes via the consumption of the entire detergent and cleaner pack. In addition, the bleach catalyst particles are finely distributed in the wash liquor due to the presence of the particulate tower powder and, if appropriate, further particulate constituents, so that a homogeneous concentration of the bleach catalyst in the wash liquor is quickly achieved. Thus, even with short washes, a satisfactory bleaching performance can be achieved. Surprisingly, all of these benefits are particularly pronounced at low wash temperatures, e.g. at 20 ° C. Thus, the subject invention leads to a surprisingly improved detergent.

Preferably in detergents 0.001 wt .-% to 1 wt .-%, in particular 0.001 wt .-% to 0.5 wt .-% and particularly preferably 0.04 wt .-% to 0.1 wt .-% of the compound according to formula (I) in the form of discrete particles. In particular, when a compound of the formula (I) is present, it is preferred that the agent additionally comprises a manganese, titanium, cobalt, nickel or copper salt and / or a manganese, titanium, cobalt, nickel or copper complex without a ligand which corresponds to a compound according to formula (I). Then, the molar ratio of said transition metal or the sum of said transition metals to the compound of formula (I) is preferably in the range of 0.001: 1 to 2: 1, especially 0.01: 1 to 1: 1. In a further preferred embodiment of the compositions, 0.05 to 1% by weight, in particular 0.1 to 0.5% by weight, of bleach-enhancing complex containing a ligand of the formula I) included. Preferred transition metal is Mn.

As peroxygen compounds contained in the agents are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperoxododecanedioic acid, other peroxo acids or peroxoacid salts, such as alkali metal or peroxodisulfates or caroates, or diacyl or tetraacyldiperoxides, hydrogen peroxide and among the Washing conditions hydrogen peroxide-releasing substances, such as alkali metal perborates, alkali metal peroxides, alkali metal peracidates and urea perhydrate, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. The solid peroxygen compounds used may be used in the form of powders or granules, which may also be coated in a manner known in principle. Preferably, peroxygen compounds are present in the compositions in amounts of up to 50% by weight, more preferably from 2% to 45% and more preferably from 5% to 20% by weight. The peroxygen compounds may preferably be used in the form of discrete particles in the agents described herein.

In a further preferred embodiment of the invention, in particular in the presence of H ₂ O ₂ releasing peroxygen compound, a conventional bleach activator is used together with the acylhydrazone of the general formula (I), the general formula (II) and in particular the formula (III). In detergents such bleach activators are preferably present in amounts of up to 10 wt .-%, in particular from 1.5 wt .-% to 5 wt .-%. Preference is given to using peroxycarboxylic acid-forming compound and acylhydrazone in molar ratios in the range from 4: 1 to 100: 1, in particular from 25: 1 to 50: 1, under perhydrolysis conditions. The bleach activators may also preferably be employed in the form of discrete particles in the agents described herein.

Compounds which give peroxocarboxylic acid under perhydrolysis conditions can in particular be compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable are bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, especially nonanoyl or Isononanoyl- or Lauroyloxybenzolsulfonat (NOBS or iso-NOBS or LOBS) or Decanoyloxybenzoat (DOBA), their formal carbonic ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose , acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam.

in der R¹¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_1-24-Alkyl- oder C_2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN und -N⁽⁺⁾-CH₂-CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C_1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R¹² und R¹³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R¹⁴ und R¹⁵ unabhängig voneinander eine voranstehend für R¹¹, R¹² oder R¹³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R¹² und R¹³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C_9-15-Alkylbenzolsulfonaten, den C_1-20-Alkylsulfaten, den C_8-22-Carbonsäuremethylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Auch sauerstoffübertragende Sulfonimine können eingesetzt werden.In addition to or as an alternative to the compounds which form peroxycarboxylic acids under perhydrolysis conditions, further bleach-activating compounds, such as, for example, nitriles, from which perimides acids are formed under perhydrolysis conditions, may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula

in the R ^{11 is} -H, -CH ₃ , a C _2-24 -alkyl or alkenyl radical, a substituted C _1-24 -alkyl or C _2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN and -N ⁽⁺⁾ -CH ₂ -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C _1-24 -alkyl group (s) and optionally further substituents on the aromatic ring, R ¹² and R ^{13 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6, R ¹⁴ and R ¹⁵ independently of one another have the meaning given above for R ¹¹ , R ¹² or R ¹³ , where at least 2 of the radicals mentioned, in particular R ¹² and R ¹³ , are also suitable under Einsc and optionally a further morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumene sulfonate, the C _9-15 -alkylbenzenesulfonates, the C _1-20 - Alkyl sulfates which are C _8-22 carboxylic _acid methyl _ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof can be used. Oxygen-carrying sulfonimines can also be used.

In order to avoid the interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, and / or particulate form trialkylammonium acetonitrile is particularly preferred.

In addition to the combination to be used according to the invention, it is also possible to use customary bleach-activating transition metal complexes. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane and its substituted derivatives such as 1,4,7-trimethyl-1,4,7-triazacyclononane, 1.5 , 9-triazacyclododecane and its substituted derivatives such as 1,5,9-trimethyl-1,5,9-triazacyclododecane 1,4,8,11-tetraazacyclotetradecane and its substituted derivatives such as 5,5,7,12,12,14- Hexamethyl-1,4,8,11-tetraazacyclotetradecane, 1,5,8,12-tetraaza-bicyclo [6.6.2] hexadecane and its substituted derivatives such as 5,12-diethyl-1,5,8,12-tetraazabicyclo [ 6.6.2] hexadecane, (bis ((1-methylimidazol-2-yl) -methyl)) - (2-pyridylmethyl) -amine, N, N '- (bis (1-methylimidazol-2-yl) - methyl) ethylenediamine, N-bis (2-benzimidazolylmethyl ) -aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N'-tetrakis- (2-benzimidazolylmethyl) -2-hydroxy-1,3 diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol , Inositol, lactose, and optionally substituted salene, porphins, and porphyrins. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO ₂ ) ^- group, that is, a nitro ligand or a nitrito ligand. The (NO ₂ ) ^- group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or η ¹ -O-bridge. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands lacking or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of transition metal complex compounds that can be used are Mn (IV) ₂ (μ-O) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'- Bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminoethane] - manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) -methylene] -1,2-diaminoethane] -manganese (III) chloride, manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride and the peroxo complex [(NH ₃ ) ₅ Co-OO-Co (NH ₃ ) ₅ ] Cl ₄ .

The detergents, which may be present in particulate form, in particular as pulverulent solids or in densified particulate form, may contain, in principle, all known ingredients customary in such compositions, in addition to the bleach catalyst according to formula (I), the tower powder and optionally the abovementioned bleaching agents and bleach activators. In particular, the compositions may include other ingredients selected from builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing polymeric actives, and shape-retaining polymers Active ingredients, and other auxiliaries, such as optical brighteners, foam regulators, dyes and fragrances included. These ingredients can be used individually or as compounds, each in the form of discrete particles, and formulated with the bleach catalysts in a manner known per se. It is preferred that at least some of the remaining ingredients be used in the form of a tower powder. The tower powder contains at least one surfactant and at least one builder. The tower powder is in the form of discrete particles in the composition, wherein the particles of the tower powder have a particle size distribution at which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles Particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm. Preferably, the proportion of turpentine in the composition is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight.

An agent may be used to further enhance the disinfecting effect, for example against specific germs, in addition conventional antimicrobial agents such as alcohols, aldehydes, acids, carboxylic acid esters, acid amides, phenols and phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, bound to organic frameworks O-acetates and O. -Formals, benzamidines, isothiazolines, phthalimide derivatives, pyridine derivatives, amines, quaternary ammonium compounds, guanidines, amphoteric compounds, quinolines, benzimidazoles, IPBC, dithiocarbamates, metals and metal compounds such as silver and silver salts, halogens such as chlorine, iodine and theirs Compounds, other oxidizing agents and inorganic nitrogen compounds. Such antimicrobial additives are preferably present in amounts of up to 10 wt .-%, in particular from 0.01 wt .-% to 5 wt .-%, each based on the total agent included; in a preferred embodiment, however, they are free of such additional disinfecting agents.

The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

in der R' und R" unabhängig H oder Alkyl sind und zusammen 6 bis 19, vorzugsweise 7 bis 15 und insbesondere 9 bis 13 C-Atome enthalten. Ein ganz besonders bevorzugter Vertreter ist Natriumdodecylbenzylsulfonat.Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula

in which R 'and R "are independently H or alkyl and together contain from 6 to 19, preferably from 7 to 15, and in particular from 9 to 13, carbon atoms A particularly preferred representative is sodium dodecylbenzylsulfonate.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Suitable alkyl ether sulfates are, for example, compounds of the formula

R ^{1 is} -O- (AO) _n -SO ₃ ^- X ⁺

In this formula, R ^{1 is} a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, more preferably a fatty alcohol radical. Preferred radicals R ¹ are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, where the representatives with an even number of carbon atoms Atoms are preferred. Particularly preferred radicals R ¹ are derived from C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols. AO represents an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index n stands for an integer from 1 to 50, preferably from 1 to 20 and especially from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7 or 8. X stands for a monovalent cation or the nth part of an n-valent cation, the alkali metal ions are preferred, and Na ⁺ or K ⁺ including Na, with Na ^{+ being} extremely preferred. Other cations X + may be selected from NH ₄ ⁺ , ½Zn ²⁺ , ½Mg ²⁺ , ½Ca ²⁺ , ½Mn ²⁺ , and mixtures thereof.

mit k = 11 bis 19, n = 2, 3, 4, 5, 6, 7 oder 8. Ganz besonders bevorzugte Vertreter sind Na-C_12-14 Fettalkoholethersulfate mit 2 EO (k = 11-13, n = 2 in Formel A-1). Der angegebenen Ethoxylierungsgrad stellt einen statistischen Mittelwert dar, der für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein kann. Die angegebenen Alkoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoxylate/Ethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE).In various embodiments, the alkyl ether sulfate may be selected from fatty alcohol ether sulfates of the formula

with k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na-C _12-14 fatty alcohol _ether sulfates with 2 EO (k = 11-13, n = 2 in formula A-1). The stated degree of ethoxylation represents a statistical average that may be an integer or a fractional number for a particular product. The indicated degrees of alkoxylation represent statistical averages, which may be an integer or a fractional number for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium, potassium or magnesium salts, in particular in the form of the sodium salts.

In the selection of anionic surfactants are the freedom from formulation no conditions to be observed in the way. Preferred anionic surfactants to be used are the alkylbenzenesulfonates and fatty alcohol sulfates, in particular the alkylbenzenesulfonates.

Anionic surfactants including the soaps, i. in particular alkylbenzenesulfonates, alkyl ether sulfates and soaps, are preferably present in the detergent at a certain proportion by weight, namely from 5 to 25% by weight, based on the total weight of the detergent formulation. Preference is given to amounts of from 7 to 20% by weight of anionic surfactants, based on the total weight of the detergent formulation. Regardless of whether the detergent contains one or more of the anionic surfactants, the amounts given refer to the total amount of all anionic surfactants contained in the detergent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 -alcohols 3 EO or 4 EO, C _9-11 -alcohol with 7 EO, C _13-15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.

Another class of nonionic surfactants that can be used to advantage are the alkyl polyglycosides (APG). Usable alkylpolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular in the 2-position methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglycosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.

A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and Hydroxyiminodisuccinate, ethylenediaminetetraacetic acid and Polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative average molecular weight (here and hereinafter: weight average) of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50 000 g / mol to 120 000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to polymers in which the weight ratio of (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2 , 5: 1 lies. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt% to 40 wt%, preferably 20 wt% to 40 wt% of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred. Particularly preferred is sucrose. The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builders may optionally be present in amounts of up to 40% by weight, more preferably up to 25% by weight, and preferably from 1% to 8% by weight.

Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. Crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of from 5% by weight to 15% by weight, are used as water-insoluble inorganic builder materials. % used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably included in the compositions in amounts of 1% to 20% by weight, especially 5% to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O used _{2x + 1} · y H ₂ O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to Is 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in the compositions. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Water-soluble builder systems, in particular those which are free of aluminosilicates and optionally also free of DTPMP and alkali citrate, are preferred according to the invention. In various preferred embodiments, the soluble builder system consists of a) an alkali silicate having a modulus M ₂ O: SiO ₂ , wherein M is an alkali metal ion, in the range of 1: 1.9 to 1: 3.3, b) an alkali carbonate , c) a polymeric polycarboxylate having a molecular weight of less than 10,000 g / mol, and d) a phosphonate capable of complexing, and e) optionally an acid-acting component. Typically, the soluble builder system constitutes less than 40% by weight of the total composition.

Suitable enzymes in the detergents are, in particular, those from the class of proteases, cutinases, amylases, lipases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipases and / or or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Suitable gravel inhibitors or soil release agents are cellulose ethers, such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preferably, sodium carboxymethylcellulose and mixtures thereof with methylcellulose are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.

As optical brighteners for particular textiles made of cellulose fibers (for example cotton), detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. Brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable for polyamide fibers. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, and preferably in the range of 0.05 wt .-% to 0.5 wt .-%.

The customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C ₁₆ - to C ₁₈ -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

To establish a desired, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable acids, in particular 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 metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included.

In various preferred embodiments, the detergent contains the above-mentioned other ingredients at least partially also in the form of discrete particles. Very particularly preferred are agents which contain part of the constituents in the form of tower powder particles. The amount of such tower powder particles in the composition is typically 20 to 70% by weight, preferably 45-55% by weight, based on the total weight of the composition. Such tower powders are typically granulated by spray drying from a slurry and contain various detergent ingredients such as surfactants, builders, chelants and binders, each of which may be as defined above. Particularly preferred are tower powders which comprise (1) surfactants, in particular linear alkylbenzenesulfonates and / or salts thereof, in particular sodium salts, (2) water-soluble builder systems which contain complexing agents, in particular HEDP, polycarboxylates, in particular polyacrylates, alkali silicate and alkali metal carbonate, and optionally (3 ) Sodium sulfate and / or (4) a binder such as carboxymethyl cellulose. A suitable tower powder contains, for example, 20-25 wt.% LAS-Na, 2-4 wt.% 1-hydroxyethane-1,1-diphosphonic acid (HEDP), 3-10 wt.% Polycarboxylate, 10-15 wt. % Alkali metal silicate, in particular sodium silicate 2.1, 5 to 10% by weight alkali metal carbonate, in particular sodium carbonate, 2-3% by weight CMC and ad 100% by weight alkali metal sulphate, in particular sodium sulphate.

Also all other ingredients, i. in addition to the bleach catalyst and the above-mentioned tower powder ingredients, may be used in the form of discrete particles. Their proportion of the agent is usually also 20 to 70 wt .-%, preferably 35-55 wt .-%. In particular, these ingredients are the above-described bleaching agents, bleach activators and bleach catalysts, especially percarbonate and TAED, as well as enzymes which may each be formulated as separate discrete particles.

It is generally preferred that all ingredients used in the detergent according to the invention are used in particulate form, wherein the particle sizes and distributions described above in connection with the bleach catalyst particles are preferred as particle sizes. In particular, it is preferred that the total agent consists of 70% by weight, preferably 80% by weight, more preferably 90% by weight, of particles having a particle size distribution of 0.1 to 2 mm. Preferably, 85 to 100% of the particles of the composition have a particle size in the range of 0.1 to 1.6 mm. The particles are preferably approximately spherical, the shape being not limited thereto.

Any of the detergents described herein may be any method known in the art. The preparation of the agents can be carried out in a manner known in principle, for example by spray-drying or granulation, with thermally sensitive ingredients optionally being added separately later.

The compositions are preferably in the form of pulverulent, granular or tablet-like 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 them more sensitive components, which in particular enzymes, bleaching agents and bleach-activating agents are to be expected, can be produced. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 · 10 ⁵ Pa to 1 500 · 10 ⁵ Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

The invention also relates to the use of the above-described combination of particulate detergent ingredients comprising bleach catalyst and tower powder, each in the form of discrete particles, to enhance the cleaning performance of peroxygen-containing detergents.

Preferably, when using the combination, the compound of formula (I) is in the form of discrete particles, the discrete particles having a particle size distribution at least 70%, preferably at least 80%, even more preferably at least 90% Wt .-% of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0.4 and 1.5 mm, and wherein the combination comprises discrete particulate tower powder, wherein the particles of the tower powder have a particle size distribution, in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm, wherein preferably the proportion of turpentine in the combination is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight.

In the context of the use according to the invention it is preferred if the concentration of the bleach catalysts according to formula (I) in aqueous liquor, as used for example in washing machines or dishwashers, 0.5 .mu.mol / l to 500 .mu.mol / l, in particular 5 .mu.mol / l to 100 .mu.mol / l. The above-mentioned complex-forming metal ions are preferably not intentionally added, but they may be present from possible sources of such metal ions, which include, in particular, the tap water, the washing machine itself, adhesions to textiles, and stains on the fabrics.

Optionally, metal ions inadvertently introduced with other detergent ingredients may also be considered. Preferred peroxygen concentrations (calculated as H ₂ O ₂ ) in the liquor are in the range from 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l and particularly preferably from 0.2 g / l to 0.5 g / l. The use according to the invention is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular from 20 ° C. to 40 ° C., and particularly preferably at temperatures below 30 ° C. The water hardness of the water used for preparing the aqueous liquor is preferably in the range from 0 ° dH to 21 ° dH, in particular 0 ° dH to 3 ° dH. In the wash liquor, the water hardness is preferably in the range of 0 ° dH to 16 ° dH, in particular 0 ° dH to 3 ° dH, which can be achieved for example by the use of conventional builder materials or water softeners. The use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

The use according to the present invention is preferably carried out by subjecting a peroxygen compound and a detergent containing an acylhydrazone of the general formula (I) in the form of discrete particles in combination with a particulate tower powder to a contaminated by a machine or hand washing operation Textile can act. The use according to the invention can be realized particularly simply by the use of a detergent containing peroxygen compound, tower powder, a compound of formula (I) or a bleach catalyst obtainable therefrom by complexing with a transition metal ion mentioned in the laundry of textiles requiring cleaning. Alternatively, the peroxygen compound and / or the compound of the formula (I) and / or a complex obtainable therefrom and / or the tower powder may also be added separately to a wash liquor which has a detergent without the respective stated ingredient.

Within the scope of the medium preferred embodiments also apply to the category of use; in particular, the compound of formula (I) may also be used in the form of a bleach catalyst obtainable by complexing with a said transition metal ion therefrom in the composition.

Another object of the invention is a method for washing textiles in which an agent according to the invention is used. Washing processes, ie in particular processes for cleaning textiles, are generally distinguished by the fact that cleaning-active substances are applied to the cleaning product in one or more process steps and washed off after the exposure time, or the cleaning product is otherwise treated with a detergent or a solution of this agent is treated.

In the described washing processes, in various embodiments of the invention, temperatures of up to 95 ° C or less, 90 ° C or less, 60 ° C or less, 50 ° C or less, 40 ° C or less, 30 ° C or less, or 20 ° C or less used. These temperature data refer to the temperatures used in the washing steps.

In various embodiments, the uses, compositions and methods described above in connection with detergents are also applicable to hard surface cleaners. The invention thus also encompasses the use of the described combinations for improving the cleaning performance of hard surface cleaners, corresponding cleaning agents and methods in which such cleaners are used.

Furthermore, all facts, objects and embodiments described for the uses and detergents are also applicable to the washing processes and vice versa.

Examples Example 1: Detergent formulations

Table 1 shows a powder detergent A according to the invention and its structure from the various discrete particles (all data in% by weight, unless stated otherwise): Table 1: Detergent compositions ingredient A tower powder 53.0 alkylbenzenesulfonate 0.9 FA7EO 3.0 sodium 20.0 sodium carbonate peroxyhydrate 14.0 TAED 4.0 Acylhydrazone ¹⁾ 0.29 carboxymethylcellulose 2.5 defoamers 0.5 Soil-release polymer 0.25 enzymes + Optical brightener 0.3 Perfume 0.16 perfume capsules 0.1 Balance (sodium sulfate, etc.) Ad 100 ¹⁾ Morpholinium 4- (2- (2 - ((2-hydroxyphenylmethyl) methylene) hydrazinyl) -2-oxoethyl) -4-methyl chloride (Tinocat LT B200, BASF SE)

The composition of the tower powder is shown in Table 2. Table 2: Tower powder ingredient A LAS-Na 23.0 HEDP-Na 4 2.2 polycarboxylate 5.2 Sodium silicate 2.1 13.9 sodium 7.1 sodium sulphate 40.0 Carboxymethylcellulose, Na salt 2.2 rest Ad 100

Example 2: Particle sizes of powder detergent particles

Table 3 shows the particle sizes of the particles used in the powder detergent. Since these are within a narrow range between 0.1 and 2 mm, segregation is prevented and ensures a homogeneous distribution of the active ingredients in the powder detergent. Thus, the desired dosage of active ingredients per wash load is secured by the consumer. Table 3: Particle sizes particle size Tower powder A > 2.0 mm: 1% > 1.6 mm: 1-3% > 0.8mm: 10-25% > 0.4 mm 35-45% > 0.2mm: 20-35% > 0.1mm: 5-10% <0.1 mm: <3% alkylbenzenesulfonate > 1.6 mm: <1% > 0.8 mm: 80% > 0.4 mm: 18% > 0.2 mm: 1-2% sodium > 2.0 mm: ≤ 1.5% > 1.0 mm: ≤ 5% sodium carbonate peroxyhydrate > 1.6 mm: <3% > 0.8 mm: 0-60% (target 15%) > 0.4 mm: 25-85% (target 65%) > 0.2 mm: 0-30% (target 20%) <0.2 mm: <5% TAED > 1.6 mm: <15% > 0.8mm: 25-75% > 0.4mm: 15-55% > 0.2 mm: <10% <0.2 mm: <2.5% Acylhydrazone (tinocate) <400μm: <1% > 1500μm: <5% Carboxymethylcellu loose > 2.0 mm: 0% > 1.6 mm: 1-3% > 0.8mm: 15-35% > 0.4 mm 35-65% > 0.2mm: 5-20% > 0.1mm: 5-15% <0.1 mm: <20% defoamers Avg. Particle size: 400-800μm Soil-release polymer > 1.6 mm: ≤1% > 0.4mm: 50-80% > 0.1mm: 15-45% <0.1 mm: ≤5% enzymes <600μm: ≤5% > 1500 μm: ≤5% brighteners > 0.8 mm: ≤1% <0.1 mm: ≤32% perfume capsules > 2.0 mm: 2% <2.0 -> 0.2 mm: 90% <0.2mm: 8%

Example 3: Improved stability by discrete particles

By using discrete particles of the bleach catalyst (Tinocat LT B200) in addition to discrete particles of the other detergent ingredients, this is protected from decomposition by inhibiting interaction. At the same time, a more homogeneous distribution in the wash liquor is achieved.

Claims (10)

Solid, particulate detergent, characterized in that it comprises an acylhydrazone of the general formula (I),

in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, R ² and R ³ are each independently hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, or R 2 and R 3 together with them connecting carbon atom for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and R ^{4 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 -Aralkyl, C _3-20 -heteroalkyl, C _3-12 -cycloheteroalkyl, C _5-16 -heteroaralkyl or an optionally substituted phenyl or naphthyl or heteroaryl group; in the form of discrete particles, the discrete particles having a particle size distribution in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0.4 and 1.5 mm, and wherein at least one surfactant and at least one builder substance in the form of discrete particles of a tower powder are contained in the agent, wherein the particles of the tower powder have a particle size distribution in which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of the particles have a particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm. Composition according to claim 1, characterized in that it contains 0.001 wt .-% to 1 wt .-%, in particular 0.001 wt .-% to 0.5 wt .-% of the compound of formula (I) in the form of discrete particles. Composition according to Claims 1 to 2, characterized in that the proportion of discrete particles of the turpentine in the composition is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight. Composition according to claim 1 or 3, characterized in that it contains peroxygen compounds in amounts of up to 50 wt .-%, in particular from 2 wt .-% to 45 wt .-%, preferably in the form of discrete particles. Agent according to one of claims 1 to 4, characterized in that it contains bleach activators in amounts of up to 10 wt .-%, particularly from 1.5 wt .-% to 5 wt .-%, preferably in the form of discrete particles, Agent according to one of claims 1 to 5, characterized in that the agent further constituents selected from builders, surfactants, enzymes, sequestering agents, electrolytes, pH regulators, polymers, dye transfer inhibitors, grayness inhibitors, wrinkle-reducing polymeric agents and shape-retaining polymeric agents, and others Auxiliary substances and mixtures of the abovementioned in the form of discrete particles, wherein the total agent to 70 wt .-%, preferably to 80 wt .-%, still more preferably to 90 wt .-% of particles having a particle size distribution of 0.1 to 2 mm, preferably from 0.1 to 1.6 mm. Use of a combination of a compound of the formula (I)

in the R ^{1 is} a CF ₃ or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl- , Phenyl, naphthyl, C _7-9 -aralkyl, C _3-20 -heteroalkyl or C _3-12 -cycloheteroalkyl, R ² and R ³ are each independently hydrogen or an optionally substituted C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 Cycloalkenyl, C _7-9 aralkyl, C _3-28 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, phenyl, naphthyl or heteroaryl, or R 2 and R 3 together with them connecting carbon atom for an optionally substituted 5-, 6-, 7-, 8- or 9-membered ring, which may optionally contain heteroatoms, and R ^{4 is} hydrogen or a C _1-28 alkyl, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 -Heteroaralkylgruppe or an optionally substituted phenyl or naphthyl, or heteroaryl group; and a tower powder containing at least one surfactant and at least one builder, wherein the compound of formula (I) and the tower powder are each in the form of discrete particles to increase the cleaning performance of peroxygen-containing detergents. Use according to claim 7, wherein the compound of formula (I) is in the form of discrete particles, the discrete particles having a particle size distribution at which at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight % of the particles have a particle size between 0.2 and 2.0 mm, preferably between 0.4 and 1.5 mm, and wherein the combination comprises discrete particulate tower powder, wherein the particles of the tower powder have a particle size distribution at least 70 wt .-%, preferably at least 80 wt .-%, more preferably at least 90 wt .-% of the particles have a particle size between 0.1 and 2.0 mm, preferably between 0.1 and 1.6 mm, wherein preferably the proportion of turpentine in the combination is at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 50% by weight. Use according to claim 7 or 8, characterized in that the concentration of the compound according to formula (I) in aqueous liquor is 0.5 μmol / l to 500 μmol / l, in particular 5 μmol / l to 100 μmol / l and / or the Peroxygen concentration (calculated as H ₂ O ₂ ) in the liquor in the range of 0.001 g / l to 10 g / l, in particular from 0.1 g / l to 1 g / l. Agent according to one of claims 1 to 6 or use according to one of claims 7 to 9, characterized in that the compound of the general formula (I) corresponds to the general formula (II),

in the R ^{1 is} a C _1-4 alkyl group having a substituent selected from

in which R ^{10 represents} hydrogen or a C _1-28 -alkyl, C _2-28 -alkenyl, C _2-22 -alkynyl, C _3-12 -cycloalkyl, C _3-12 -cycloalkenyl-, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _5-16 heteroaralkyl, and A ^{- represents} the anion of an organic or inorganic acid; R ² and R ^{4 represent} the Have the meaning given in formula (I) and R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another are R ¹ , hydrogen, halogen, a hydroxy, amino, an optionally substituted N-mono or di-C _1-4 -alkyl or C _2-4 hydroxyalkylamino, N-phenyl or N-naphthylamino, C _1-28 alkyl, C _1-28 alkoxy, phenoxy, C _2-28 alkenyl, C _2-22 alkynyl, C _3-12 cycloalkyl, C _3-12 cycloalkenyl, C _7-9 aralkyl, C _3-20 heteroalkyl, C _3-12 cycloheteroalkyl, C _{5 -16} heteroaralkyl, phenyl or naphthyl group, wherein the substituents are selected from C _1-4 alkyl, C _1-4 alkoxy, hydroxy, sulfo, sulfato, halogen, cyano, nitro -, carboxy, phenyl, phenoxy, naphthoxy, amino, N-mono or di-C _1-4 -alkyl or C _2-4 -hydroxyalkylamino, N-phenyl or N-naphthyl -amino groups, or R ⁵ and R ⁶ or R ⁶ and R ⁷ or R ⁷ and R ⁸ to form 1, 2 or 3 carbocyclic or O-, NR ¹⁰ - or S-heterocyclic, optionally aromatic and / or optionally C _{1 -6} alkyl-substituted rings are interconnected.