EP1723222B1 - Bleach activators and method for the production thereof - Google Patents

Abstract

Bleach activator compatibility with bleach-sensitive dyestuffs can be improved in accordance with various embodiments of the invention including methods for producing coated bleach activators which methods comprise: granulating at least one bleach activator with at least one binding agent to form a granulated material; coating the granulated material with a solution or dispersion of at least one complexing agent to form a coated granulated material; and drying the coated granulated material.

Description

The present invention relates to coated bleach activators, to a process for their preparation and to their use, preferably in dyed detergents or cleaners, in particular detergent tablets, which are used for cleaning dishes in dishwashers.

Agents containing bleach activators are widely described in the art. Usually, the agents contain bleaches which are to be enhanced by the activators in their effect. An important field of use of bleach and bleach activator-containing agents are detergents or detergents. Usually, these agents contain one or more builders. Bleaching agents, bleach activators, corrosion inhibitors and surfactants. To provide the consumer with a typical and distinctive product, these agents are usually both perfumed and colored. There are quite a number of requirements placed on the dyes: they have to dye the cleaning agent to be colored permanently and visually even at low use concentrations, and they must not fade or discolor even on prolonged storage or at elevated temperatures. For this, it is necessary that the dyes used are chemically inert to the sometimes aggressive ingredients (e.g., bleach, alkali carriers) and do not degrade themselves or other ingredients. Since the detergent tablets on the market are often designed bicolor for aesthetic reasons, no fading of the colored phase or a transfer of color into lighter or uncolored areas may result at the phase boundary of differently colored areas.

In the compact form "tablet", however, the contact between the dye and other dye-destabilizing ingredients (especially bleach and / or bleach activators) is so intimate that upon prolonged storage, color changes may occur that affect the appearance of the molded articles. It has also been shown that the obvious separation of bleach and dye in different areas of the tablet alone is not a solution: At the phase boundary, the problems of bleaching and color transfer also occur in this technical measure and lead to optically unacceptable tablets ,

In order to increase the stability of bleaches and bleach activators, as well as to make these substances less aggressive to their environment, it is well understood that the art of providing them with coatings that separate the environment and bleach or bleach activator.

So revealed the EP 482 807 B1 the common granulation of TAED with binders and the subsequent coating of the granules with inorganic salts.

US 6107266 A discloses coated bleach activator granules.

However, it has been found that the solutions disclosed in the prior art are not completely satisfactory. In particular, the stability of dyes in the presence of the prior art coated bleach activators is often insufficient.

The object was therefore to find coated bleach activators and a preparation process for these bleach activators, which make it possible to be used even in the presence of non-bleach-stable dyes without having to accept the aforementioned disadvantages.

It has now been found that a special coating on specially preformed bleach activators leads to a significantly improved compatibility of the bleach activators with bleach-sensitive dyes.

1. a) Granulation mindestens eines Bleichaktivators mit einem Bindemittel;
2. b) Beschichten der Granulate aus Schritt a) mit einer Lösung oder Dispersion mindestens eines Komplexbilders aus der Gruppe der Phosphonate;
3. c) Trocknen der beschichteten Granulate.

The present invention is in a first embodiment, a method for producing coated bleach activators, characterized by the steps

1. a) granulation of at least one bleach activator with a binder;
2. b) coating the granules from step a) with a solution or dispersion of at least one complex image from the group of the phosphonates;
3. c) drying the coated granules.

In the first step of the process according to the invention, at least one bleach activator is granulated with at least one binder. This step can be carried out easily in a wide variety of granulation systems. In a suitable mixing and granulating device, for example in corresponding plants of the Eirich mixer type, a Lödige mixer, for example a ploughshare mixer from Lödige, or a Schugi mixer, at mixing speeds of the mixing devices preferably between 2 and 7 m / s (ploughshare mixer) or 3 to 50 m / s (Eirich, Schugi), in particular between 5 and 20 m / s submitted a solid bed and then granulated with the addition of a granulating liquid. In this case, a predetermined grain size of the granules can be adjusted simultaneously in a conventional manner. The granulation and mixing process requires only a very short period of, for example, about 0.5 to 10 minutes, in particular about 0.5 to 5 minutes (Eirich mixer, Lödige mixer) for homogenizing the mixture to form the flowable granules. In the Schugi mixer, on the other hand, a residence time of 0.5 to 10 seconds is normally sufficient to obtain free-flowing granules. For the implementation of this process step, suitable mixers are, for example Eirich ^® mixer Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi ^® Flexomix, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co. , Japan), the Lödige ^® FM, KM and CB mixer (trade name of Lödige Maschinenbau GmbH, Paderborn) or the Drais ^® -series T or KT (trademarks of Drais-Werke GmbH, Mannheim).

• Lödige CB / Lödige KM
• Lödige KM / Schugi Flexomix
• Schugi Flexomix / Lödige KM / Schugi Flexomix
• Schugi Flexomix / Lödige CB
• Lödige CB / Lödige KM / Schugi Flexomix

It is also possible according to the invention to connect several of the above-mentioned mixers in series. In particular, the following combinations of successive mixers are suitable here:

• Lödige CB / Lödige KM
• Lödige KM / Schugi Flexomix
• Schugi Flexomix / Lödige KM / Schugi Flexomix
• Schugi Flexomix / Lödige CB
• Lödige CB / Lödige KM / Schugi Flexomix

Granulation can be carried out by initially introducing bleach activator and binder as a solid bed and granulating them with the addition of a granulating liquid, preferably an aqueous solution. Preferably, however, the bleach activator is introduced as a solid and granulated with the addition of a solution of the binder.

Examples of bleach activators which can be used according to the invention are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.

As bleach activators it is also possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to 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-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and also acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetyl-xylose 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. Combinations of conventional bleach activators can also be used.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts can also be used. These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂. -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ 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 und X ein Anion ist, enthält.A further preferred bleach activator which can be used according to the invention is a cationic nitrile of the formula (I)

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ . -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independent of one another are 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 and X is an anion.

The general formula (I) includes a variety of cationic nitriles useful in the present invention. With particular advantage, cationic nitriles are used in which R ^{1 is} methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. R ² and R ³ are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, wherein one or both radicals may advantageously also be a Cyanomethylenrest.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, - CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁸ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt, und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- sind besonders bevorzugt.For ease of synthesis, preference is given to compounds in which the radicals R ¹ to R ^{3 are} identical, for example (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH ₂ CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO -CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- . Cationic nitriles of the formula (Ia)

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , - CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁸ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ , and compounds of the formulas (CH ₃ ) ₃ N ^{(+ )} CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH _{3)) 3} N ⁽⁺⁾ CH ₂ -CN X ^-, or (HO-CH ₂ -CH _{2) 3} N ⁽⁺⁾ CH ₂ -CN X ^- are particularly preferred.

Particular preference is given to cationic nitriles of the formula (I), preferably of the formula (Ia), particularly preferably of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , where X ^{- is} an anion selected from the group consisting of Chloride, bromide, iodide, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate or xylenesulfonate, or mixtures thereof

• Polyvinylpyrrolidone, wie sie beispielsweise unter der Bezeichnung Luviskol^® (BASF) vertrieben werden. Polyvinylpyrrolidone [Poly(1-vinyl-2-pyrrolidinone)], Kurzzeichen PVP, sind Polymere der allg. Formel (II)
  
  die durch radikalische Polymerisation von 1-Vinylpyrrolidon nach Verfahren der Lösungs- oder Suspensionspolymerisation unter Einsatz von Radikalbildnern (Peroxide, Azo-Verbindungen) als Initiatoren hergestellt werden. Die ionische Polymerisation des Monomeren liefert nur Produkte mit niedrigen Molmassen. Handelsübliche Polyvinylpyrrolidone haben Molmassen im Bereich von ca. 2500-750000 g/mol, die Ober die Angabe der K-Werte charakterisiert werden und - K-Wert-abhängig - Glasübergangstemperaturen von 130-175° besitzen. Sie werden als weiße, hygroskopische Pulver oder als wäßrige. Lösungen angeboten. Polyvinylpyrrolidone sind gut löslich in Wasser und einer Vielzahl von organischen Lösungsmitteln (Alkohole, Ketone, Eisessig, Chlorkohlenwasserstoffe, Phenole u.a.).
• Vinylpyrrolidon/Vinylester-Copolymere, wie sie beispielsweise unter dem Warenzeichen Luviskol^® (BASF) vertrieben werden. Luviskol^® VA 64 und Luviskol^® VA 73, jeweils Vinylpyrrolidon/Vinylacetat-Copolymere, sind besonders bevorzugte nichtionische Polymere.

Suitable binders which are either mixed in the form of solids with the bleach activators and then granulated with the addition of a granulating liquid, or which may be part of the granulating liquid, are, for example, natural or synthetic polymers. Among these, for example, polyethylene or polypropylene glycols are preferable. Also preferred are non-ionic polymers such as, for example:

• Polyvinylpyrrolidones, as sold for example under the name Luviskol ^® (BASF). Polyvinylpyrrolidones [poly (1-vinyl-2-pyrrolidinones)], abbreviation PVP, are polymers of the general formula (II)
  
  which are prepared by free-radical polymerization of 1-vinylpyrrolidone by the method of solution or suspension polymerization using free-radical initiators (peroxides, azo compounds) as initiators. The ionic polymerization of the monomer provides only low molecular weight products. Commercially available polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, the upper characterizing the K values are characterized and - depending on K value - have glass transition temperatures of 130-175 °. They are called white, hygroscopic powder or aqueous. Solutions offered. Polyvinylpyrrolidones are readily soluble in water and a variety of organic solvents (alcohols, ketones, glacial acetic acid, chlorinated hydrocarbons, phenols, etc.).
• Vinylpyrrolidone / vinyl ester copolymers, as sold, for example, under the trademark Luviskol ^® (BASF). Luviskol ^® VA 64 and Luviskol ^® VA 73, each vinylpyrrolidone / vinyl acetate copolymers, are particularly preferred non-ionic polymers.

als charakteristischem Grundbaustein der Makromoleküle. Von diesen haben die Vinylacetat-Polymere (R = CH₃) mit Polyvinylacetaten als mit Abstand wichtigsten Vertretern die größte technische Bedeutung.The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (III)

as a characteristic building block of the macromolecules. Of these, the vinyl acetate polymers (R = CH ₃ ) with polyvinyl acetates as by far the most important representatives of the greatest technical importance.

• Celluloseether, wie Hydroxypropylcellulose, Hydroxyethylcellulose und Methylhydroxypropylcellulose, wie sie beispielsweise unter den Warenzeichen Culminal^® und Benecel^® (AQUALON) vertrieben werden.

The polymerization of the vinyl esters is carried out free-radically by different processes (solution polymerization, suspension polymerization, emulsion polymerization, bulk polymerization). Copolymers of vinyl acetate with vinylpyrrolidone contain monomer units of the formulas (II) and (III)

• Cellulose ethers, such as hydroxypropylcellulose, hydroxyethylcellulose and methylhydroxypropylcellulose, as sold, for example, under the trademarks Culminal ^® and Benecel ^® (AQUALON).

in R für H oder einen Alkyl-, Alkenyl-, Alkinyl-, Aryl- oder Alkylarylrest steht. In bevorzugten Produkten steht mindestens ein R in Formel für -CH₂CH₂CH₂-OH oder -CH₂CH₂-OH.Cellulose ethers can be described by the following general formula

R is H or an alkyl, alkenyl, alkynyl, aryl or alkylaryl radical. In preferred products, at least one R in formula is -CH ₂ CH ₂ CH ₂ -OH or -CH ₂ CH ₂ -OH.

Polyvinyl alcohols, referred to as PVAL for short, are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

in small proportions also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ ]

contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared via polymer-analogous reactions by hydrolysis, but in particular technically by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.

Commercially available PVOH (eg Mowiol ^® grades from Clariant) are supplied as white-yellowish powders or granules with degrees of polymerization in the range of about 500 to 2500 (corresponding to molecular weights of about 20,000 to 100,000 g / mol) in trade and have different degrees of hydrolysis from 98-99 and 87-89 mole%, respectively. So they are partially hydrolyzed polyvinyl acetates with a residual content of acetyl groups of about 1-2 or 11-13 mol%.

The water-solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus set specifically to desired values.

Particularly preferred processes according to the invention are characterized in that natural polymers, preferably cellulose and / or starch and derivatives thereof, in particular carboxymethylcellulose (CMC) and / or hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are used as binders.

In steps b) and c) of the process according to the invention, the granules from step a) are coated with a solution or dispersion of at least one complex image from the group of the phosphonates and the coated granules are dried. The coating can be carried out simultaneously with the drying (for example in a fluidized bed apparatus in which the granules are treated with a solution or dispersion of at least one complexing agent and dried at the same time), but it is also possible and preferred, the drying after coating, ie in time subsequently to this, perform.

Complex images whose solutions or dispersions are used in a solvent or dispersion medium in the process according to the invention for coating the bleach activator granules are substances which can complex metal ions.

A substance class with complexing represent the phosphonates. These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The complexing agent used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

Processes according to the invention are characterized in that as complexing agents phosphonates, preferably hydroxyalkane or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine tetramethylenephosphonate (EDTMP) or its hexasodium salt and or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta or Octosatriumsalz be used.

After drying, the granules produced according to the invention contain at least the constituents bleach activator, binder and complexing agent. In accordance with the invention preferred methods are characterized in that the dried granules (including coating), based on its weight, 5 to 80 wt .-%, preferably 10 to 75 wt .-% and in particular 20 to 70 wt .-% bleach activator (s ) contains.

The content of the granules of binders according to the invention in preferred processes according to the invention, based on the dried granules (including coating, 1 to 50 wt.%, Preferably 1.5 to 20 wt.% And in particular 2 to 10 wt. ,

With regard to the complexing agents, preferred processes according to the invention are characterized in that the dried granules (including coating), based on their weight, 0.1 to 50 wt .-%, preferably 3 to 25 wt .-% and in particular 5 to 15 wt. Contains% complexing agents.

As already mentioned above, process variants of the process according to the invention are preferred in which step a) is carried out in a mixer granulator, wherein preferably bleach activator (s) and binder are initially introduced in solid form and are granulated with a granulating liquid. In particularly preferred process variants of the process according to the invention, the granulation liquid is free of surfactant (s) and complexing agent (s).

It has also been mentioned above that in preferred processes according to the invention, step b) and optionally step c) are carried out in a fluidized bed apparatus.

Another object of the present invention are coated bleach activators, which can be prepared for example by the process according to the invention. These are coated bleach activators comprising a particle core containing bleach activator (s) and a shell surrounding this core, the shell being at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight. % and in particular to 100 wt .-% of its weight of complexing agent (s).

Bleach activators coated according to the invention are characterized in that the shell as complexing agents phosphonates, preferably hydroxyalkane or aminoalkane phosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or Ethylenediamintetramethylenephosphonate (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta or Octosatriumsalz contains.

It is furthermore preferred that the core of the coated bleach activators according to the invention does not consist exclusively of bleach activator. A content of binders in the core of the particles is preferred, in particular coated bleach activators, in which the core next to bleach activator (s) contains binders, which binders as natural polymers, preferably cellulose and / or starch and their derivatives, in particular carboxymethylcellulose (CMC) and or hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are preferred and preferred amounts of the core of binder 1 to 50 wt .-%, preferably 5 to 40 wt .-% and in particular 10 to 30 wt .-% of binder (each relative to the uncoated core), preferred embodiments of the present invention.

The coated bleach activators according to the invention or prepared according to the invention are distinguished by a high storage stability and are outstandingly suitable for use in a large number of compositions, in particular detergents or cleaners. Sensitive substances such as, for example, dyes have significantly higher stabilities in compositions with the coated bleach activators according to the invention or prepared according to the invention than in compositions with coated bleach activators not according to the invention or prepared according to the invention.

A further subject of the present invention is therefore the use of the coated bleach activators according to the invention or inventively prepared in washing or cleaning agents, in particular in washing or cleaning agent tablets.

The present invention also provides detergents or cleaners containing at least one bleach, at least one dye and at least one coated bleach activator according to the invention or prepared according to the invention.

Particularly preferred detergents or cleaners according to the invention contain the dye in homogeneous distribution, i. are colored through, while individual colored particles ("Sprenkei") are of minor importance in the washing or cleaning agents according to the invention. In the case of detergents or cleaners according to the invention in tablet form, this applies to individual phases (preferably layers) of the tablets, wherein in the case of multiphase tablets, individual phases may also be unstained or differently colored.

Preferred washing or cleaning agents according to the invention, in particular automatic dishwashing detergents, contain, in addition to the above-mentioned bleach, dye and coated bleach activators according to the invention, substances from the groups of builders (builders, cobuilders), surfactants, enzymes, dyes, fragrances, corrosion inhibitors, polymers , or another common ingredient of detergents and cleaners. These ingredients are described below.

images

According to the present invention, all builders conventionally used in detergents and cleaners, in particular silicates, carbonates, organic cobuilders and also the phosphates, may be incorporated in the detergents and cleaners.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layer silicates corresponding to the above formula are those in which M is sodium and x assumes the value 2 or 3. In particular, both .beta.- and δ-sodium Na ₂ Si ₂ O ₅ · yH ₂ O preferably

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

As carbonates, both the monoalkali metal salts and the dialkali metal salts of carbonic acid as well as sesquicarbonates can be contained in the compositions. Preferred alkali metal ions are sodium and / or potassium ions. In one embodiment, it may be preferable to mix the carbonate and / or bicarbonate, at least partially, as a further component, separately or subsequently. Compounds of, for example, carbonate, silicate and optionally other auxiliaries such as, for example, anionic surfactants or other, in particular organic builders, may be present as a separate component in the finished compositions.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

Automatic dishwashing detergents preferred in the context of the present invention contain no sodium and / or potassium hydroxide. A waiver of sodium and / or potassium hydroxide as alkali source has proved to be particularly advantageous when zinc gluconate, zinc formate and zinc acetate are used as zinc salts.

builders

Within the scope of the present invention, organic cobuilders which may be used in the washing or cleaning compositions are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates. The polymers may also be part of the active ingredient-containing polymer matrix, but they may also be contained completely independently of these in the inventive compositions. The mentioned classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 1000 to 20 000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 1,000 to 10,000 g / mol, and more preferably from 1,200 to 4,000 g / mol, may again be preferred from this group.

Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers are particularly preferably used in the compositions according to the invention. The sulfonic acid-containing copolymers will be described in detail below.

In addition, of course, the sulfonic acid-containing polymers described above can be included in the inventive compositions, without having to be part of the active ingredient-containing polymer matrix.

As already mentioned above, in the agents according to the invention it is particularly preferable to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally further ionic or nonionogenic monomers. The polyacrylates were described in detail above. Particularly preferred are combinations of the above-described sulfonic acid-containing copolymers with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons. Such polyacrylates are commercially available under the trade name Sokalan ^® PA15 and Sokalan ^® PA25 (BASF).

Also suitable 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 generally from 2000 to 100,000 g / mol, preferably from 20,000 to 90,000 g / mol and in particular from 30,000 to 80,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or containing as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builders polymeric Aminodlcarbonsäuren, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. As a hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP, used as a builder is preferably from the class of phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

In addition, all compounds capable of forming complexes with alkaline earth ions can be used as co-builders.

In the context of the present application, agents according to the invention are characterized in that they comprise builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates, in amounts of from 0.1 to 99.5% by weight, preferably from 1 to 95% Wt .-%, more preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the agent.

surfactants

For the purposes of the present application, preferred cleaners comprise one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.

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.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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 preferably also 2,3-alkyl sulfates, which are obtained as commercial products of the Shell Oil Company under the name DAN ^® are suitable anionic surfactants.

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. They are due in detergents their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%, used.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

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 present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Another group of detergent substances are the nonionic surfactants. 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 with 3 EO or 4 EO, C _9-11 alcohols 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 Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially 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 polyglucosides, that is to say alkyl polyglycosides which consist of a glucose residue and an n-alkyl chain.

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.

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.

In detergents and cleaners for automatic dishwashing come as surfactants in general all surfactants in question. However, the nonionic surfactants described above and, above all, the low-foaming nonionic surfactants are preferred for this purpose. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally means, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₈ , such as, for example, C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

in der R¹ für einen geradkettigen oder verzweigten, gesättigten oder ein- bzw. mehrfach ungesättigten C₆-₂₄-Alky- oder -Alkenylrest steht; jede Gruppe R² bzw. R³ unabhängig voneinander ausgewählt ist aus - CH₃; -CH₂CH₃, -CH₂CH₂-CH₃, -CH(CH₃)₂ und die Indizes w, x, y, z unabhängig voneinander für ganze Zahlen von 1 bis 6 stehen.In the context of the present invention, particularly preferred nonionic surfactants have been low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units. Among these, in turn, surfactants with EO-AO-EO-AO blocks are preferred, wherein in each case one to ten EO or AO groups are bonded to each other before a block of the other groups follows here are preferred automatic dishwashing detergents according to the invention as nonionic surfactant (s) containing surfactants of the general formula XX

in which R ¹ is a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ - ₂₄ is -Alky- or alkenyl radical; each group R ² or R ^{3 is} independently selected from - CH ₃ ; -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , -CH (CH ₃ ) ₂ and the indices w, x, y, z independently of one another are integers from 1 to 6.

The preferred nonionic surfactants of formula XX can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula 1 may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually undisplayed, wherein the linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position in the mixture, as they are usually present in oxo alcohol radicals. Irrespective of the type of alcohol used to prepare the nonionic surfactants contained in the compositions according to the invention, automatic dishwasher detergents according to the invention are preferred in which R ¹ in formula I is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 carbon atoms.

As the alkylene oxide unit which is contained in the preferred nonionic surfactants in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or -CH (CH ₃ ) ₂ are suitable. Preferred automatic dishwashing agents are characterized in that R ² and R ³ are each a residue -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another represent values of 1 or 2.

In summary, for use in the compositions of the invention, particular preference is given to nonionic surfactants which have a C _9-15 -alkyl radical having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.

Low-foaming nonionic surfactants are used as preferred additional surfactants. With particular preference, the automatic dishwasher detergents according to the invention contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized by containing nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C, and most preferably between 26.6 and 43, 3 ° C, included.

Suitable nonionic surfactants in addition to the nonionic surfactants according to the invention which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred

Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.

In a preferred embodiment of the present invention, the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged

A particularly preferred nonionic surfactant which is solid at room temperature is selected from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 -alcohol), preferably a C ₁₈ -alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene. oxide recovered. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) consisting of C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _16-20 fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was recovered (n).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, particularly preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants. Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic surfactant.

More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred machine dishwashing detergent according to the invention contains nonionic surfactants of the formula

R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ],

in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, dishwashing agents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula

R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ²

in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type

R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ²

in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Anionic, cationic and / or amphoteric surfactants may also be used in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in dishwasher detergents and usually only in amounts below 10% by weight, in most cases even below 5% by weight .-%, for example, from 0.01 to 2.5 wt .-%, each based on the agent used. The agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as surfactant component.

In the context of the present invention, it is preferred that the automatic dishwashing detergents comprise surfactant (s), preferably nonionic surfactant (s), in amounts of from 0.5 to 10% by weight, preferably from 0.75 to 7.5 Wt .-% and in particular from 1.0 to 5 wt .-%, each based on the total agent included.

bleach

Bleaching agents are important constituents of detergents and cleaning agents, and a washing and cleaning agent may in the context of the present invention contain one or more substances from the group mentioned. Among the compounds which serve as bleaches and deliver H ₂ O ₂ in water, sodium percarbonate has particular significance. Further useful bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

As a rule, the percarbonate is stabilized by an additional coating. Coating methods and materials used for coating are widely described in the patent literature.

In principle, all commercially available percarbonate types can be used according to the invention, as offered for example by the companies Solvay Interox, Degussa, Kemira or Akzo.

Dishwashing detergents may also contain bleaches from the group of organic bleaches. Typical organic bleaches that can be used as ingredients in the present invention are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleach, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40 wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.

enzymes

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens as well as from their genetically modified variants obtained enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases.

Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases. Cellulases used are preferably cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof. Since different types of cellulases differ in their CMCase and avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases ,

The enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation. Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts of from 0.1 to 10% by weight, preferably from 0.5 to 8 wt .-% and in particular from 1 to 5 wt .-%, each based on the total agent.

dyes

In order to improve the aesthetic impression of detergents and cleaners, they can be dyed with suitable dyes. Dyes which are preferred in the context of the present invention and whose selection does not present any difficulty to a person skilled in the art have a high storage stability and insensitivity to the other ingredients of the compositions and to light and no pronounced substantivity to textile fibers so as not to stain them.

Preferred for use in the detergents and cleaners according to the invention are all colorants which can be oxidatively destroyed in the cleaning process and mixtures thereof with suitable blue dyes, so-called blue toners. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020), which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, is, as well as mixtures thereof with suitable. blue dyes. Further suitable colorants Pigmosol ^® come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

• Sicovit Amaranth 85 E 123; Acid red 27; 16185; 915-67-3
• Iragon Bright Pink liquid; Acid red 52 +
• Acid blue 80; 45100 61585; 3520-42-1; 4474-24-2
• Vitasyn Ponceau 4RC 82
• Basovit Red 400 E; Acid red 18; 16255; 2611-82-7
• Duasyn Red R-F3B liquid; Reactive red 180; 181055;
• Dragocolor Rhodamin EB4 ; Acid red 52; 45100; 3520-42-1
• Sandolan Rhodamine EB 400;
• Telon Red M-GWN ; Acid red 276;
• D&C Red No. 33 K 7057; Acid red 33; 17200; 3567-66-6
• Lilas solide W5001; Xantenic dye ( Acid Violet 9 ); 45190; 6252-76-2
• Liquitint Red ST; (Disperse Red 156); (11235);
• Sicovit Tartrazine 85 E 102
• E 102 Giallo Tartrazina HC
• Food yellow 4,
• Acid Yellow 23; 19140; 1934-21-0
• Sicovit Quinoline Yellow 70 E 104; Acid yellow 3; ( Food yellow 13 ); 47005; 8004-92-0; 95139-83-2
• Basacid Yellow 094; Acid yellow 3; 47005; 8004-92-0
• Sudan Yellow 172 liquid; Solvent yellow 174; ;
• Macrolex Yellow G; Disperse yellow 54
• Solvent yellow 114; 47020;
• Iragon Bright Yellow liquid; Acid yellow 17; 18965; 6359-98-4
• Sanolin Yellow BG; Direct yellow 28; 19555;
• Cosmenyl Yellow 10 G; Pigment yellow 3; 11710;
• FAT Yellow 3 G ; Solvent yellow 16; 12700; 4314-14-1
• Liquitint Yellow LP; (Disperse yellow 31); (48000);
• E110 Sunset Yellow; Food Yellow 3; 15985; 2783-94-0
• Liquitint Yellow BL ; (Acid orange 52) ; (13025);
• Color Guide 40; ; ;
• Basacid Green 970; Acid green 1; 10020; 19381-50-1
• Verde Basacid T 461 Liquid; Acid Yellow 9+
• Acid Blue 9; 19140+; 42090; 1934-21-0
• Disperse Green 87-3007; Pigment Green 7; 74260;
• Pyranine 120%; Solvent Green 7; 59040;
• Macrolex Green 5 B; Solvent Green 3; 61565;
• Hostafine Green GN ; Pigment Green 7; 74260; 1328-53-6
• Liquitint Teal ; ; (42165);
• PV Fast green GNX ; Pigment Green 7; 74260; 1328-53-6
• Color Guide 40; ; ;
• Basacid Azul V20; Acid blue 3; 42051; 3536-49-0
• Basacid Blue 762 liquid; Direct blue 199; 74190; 12222-04-7
• Disperse Blue 69-0007 paste; Pigment blue 15:1; 74160; 147-14-8
• Iragon Blue ABL 9; Acid blue 9; 42090; 2650-18-2
• Iragon brilliant blue liquid; Acid blue 80 +
• Acid red 52; 61585; 45100; 4474-24-2; 3520-42-1
• Iragon Blue ABL 182 liquid; Acid blue 182; not ex.; 12219-26-0 72152-54-6
• Sanolin Blue EHRL p _- ; Acid blue 182; not ex.; 72152-54-6
• Cosmenyl Blue A2R; Pigment blue 15:1; 74160; 147-14-8
• Hostafine-Blue B2G liquid; Pigment Blue 15:3; 74160; 147-14-8
• Sandoplast Blue 2B p; Solvent blue 104; 61568; 116-75-6
• Supranol Blue GLW; Acid Blue 221; not ex.; 12219-32-8
• Sicovit Patentblue 85 E 131; E 131 Patentblue 85%; Acid Blue 3,
• Food Blue 5, 42051; 3536-49-0
• Liquitint Blue MC; (Acid blue 9); (42090);
• Basacid Blue 756 liquid ; Acid blue 9; 42090; 3844-45-9
• Basacid Yellow 093 liquid; Acid Yellow 3; 47005;
• Telon Blue RR ;
• Sanolin Rhodamine E-B 400; Acid red 52; 45100; 3520-42-1
• Pigmosol Green 8730; Pigment Green 7; 74260; 1328-53-6
• Sicovit Green Z 6120 ; Acid Blue 3 + Tartrazine; 42051+ 19140; 1934-21-0 + 3536-49-0

Particularly preferred within the scope of the present invention are the dyes mentioned below. The first name is the name of the dye, the second name is the generic name in the Color Index (CI generic name) the five-digit number is the number of the relevant dye in the Color Index (CI No.), a three- or four-digit number followed by an indent, a two-digit number, a further indent and a one-digit number, indicate the Chemical Abstracts Number (CAS No.):

• Sicovit Amaranth 85 E 123; Acid red 27; 16185; 915-67-3
• Iragon Bright Pink liquid; Acid red 52 +
• Acid blue 80; 45100 61585; 3520-42-1; 4474-24-2
• Vitasyn Ponceau 4RC 82
• Basovit Red 400 E; Acid red 18; 16255; 2611-82-7
• Duasyn Red R-F3B liquid; Reactive red 180; 181055;
• Dragocolor Rhodamine EB4; Acid red 52; 45100; 3520-42-1
• Sandolan Rhodamine EB 400;
• Telon Red M-GWN; Acid red 276;
• D & C Red No. 33K 7057; Acid red 33; 17200; 3567-66-6
• Lilas solid W5001; Xantenic dye (Acid Violet 9); 45190; 6252-76-2
• Liquitint Red ST; (Disperse Red 156); (11235);
• Sicovit Tartrazine 85 E 102
• E 102 Giallo Tartrazina HC
• Food yellow 4,
• Acid Yellow 23; 19140; 1934-21-0
• Sicovit Quinoline Yellow 70 E 104; Acid yellow 3; (Food yellow 13); 47005; 8004-92-0; 95139-83-2
• Basacid Yellow 094; Acid yellow 3; 47005; 8004-92-0
• Sudan Yellow 172 liquid; Solvent yellow 174; ;
• Macrolex Yellow G; Disperse yellow 54
• Solvent yellow 114; 47020;
• Iragon Bright Yellow liquid; Acid yellow 17; 18965; 6359-98-4
• Sanolin Yellow BG; Direct yellow 28; 19555;
• Cosmenyl Yellow 10G; Pigment yellow 3; 11710;
• FAT Yellow 3G; Solvent yellow 16; 12700; 4314-14-1
• Liquitint Yellow LP; (Disperse yellow 31); (48000);
• E110 Sunset Yellow; Food Yellow 3; 15985; 2783-94-0
• Liquitint Yellow BL; (Acid orange 52); (13025);
• Color Guide 40; ; ;
• Basacid Green 970; Acid green 1; 10020; 19381-50-1
• Verde Basacid T 461 Liquid; Acid Yellow 9+
• Acid Blue 9; 19140+; 42090; 1934-21-0
• Disperse Green 87-3007; Pigment Green 7; 74260;
• Pyranins 120%; Solvent Green 7; 59040;
• Macrolex Green 5B; Solvent green 3; 61565;
• Hostafine Green GN; Pigment Green 7; 74260; 1328-53-6
• Liquitint Teal; ; (42165);
• PV Fast Green GNX; Pigment Green 7; 74260; 1328-53-6
• Color Guide 40; ; ;
• Basacid Azul V20; Acid blue 3; 42051; 3536-49-0
• Basacid Blue 762 liquid; Direct blue 199; 74190; 12222-04-7
• Disperse Blue 69-0007 paste; Pigment blue 15: 1; 74160; 147-14-8
• Iragon Blue ABL 9; Acid blue 9; 42090; 2650-18-2
• Iragon brilliant blue liquid; Acid blue 80 +
• Acid red 52; 61585; 45100; 4474-24-2; 3520-42-1
• Iragon Blue ABL 182 liquid; Acid blue 182; not ex .; 12219-26-0 72152-54-6
• Sanolin Blue EHRL p _- ; Acid blue 182; not ex .; 72152-54-6
• Cosmenyl Blue A2R; Pigment blue 15: 1; 74160; 147-14-8
• Hostafine-Blue B2G liquid; Pigment Blue 15: 3; 74160; 147-14-8
• Sandoplast Blue 2B p; Solvent blue 104; 61568; 116-75-6
• Supranol Blue GLW; Acid Blue 221; not ex .; 12219-32-8
• Sicovit Patent Blue 85 E 131; E 131 Patent Blue 85%; Acid Blue 3,
• Food Blue 5, 42051; 3536-49-0
• Liquitint Blue MC; (Acid blue 9); (42090);
• Basacid Blue 756 liquid; Acid blue 9; 42090; 3844-45-9
• Basacid Yellow 093 liquid; Acid Yellow 3; 47005;
• Telon Blue RR;
• Sanolin Rhodamine EB 400; Acid red 52; 45100; 3520-42-1
• Pigmosol Green 8730; Pigment Green 7; 74260; 1328-53-6
• Sicovit Green Z 6120; Acid Blue 3 + Tartrazine; 42051+ 19140; 1934-21-0 + 3536-49-0

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble dyeing agents are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyeing agents, for example the Basacid Green ^® above or also above Sandolan Blue ^®, dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-% are typically chosen. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the Pigmosol ^® ATTO-dyes mentioned above, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^-3 to 10 ^-4 wt .-% ,

fragrances

Fragrances are added to the compositions within the scope of the present invention in order to improve the aesthetics of the products and to provide the consumer, in addition to the performance of the product, with a visually and sensory "typical and unmistakable" product.

Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

Corrosion inhibitors

Detergents for machine dishwashing may contain corrosion inhibitors to protect the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaner are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Preferred here are the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
[Me-TACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^IV (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ ,
[Me-TACN) Mn ^III (m-0) (m-0Ac) ₂ Mn ^III (Me-TACN)] ²⁺ (PF ₆ ^- ) ₂ and
[Me-MeTACN) Mn ^III (mO) (m-OAc) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ ^- ) ₂ , wherein Me-TACN is 1,4,7-trimethyl-1,4, 7-triazacyclononane and Me-MeTACN stands for 1,2,4,7-tetramethyl-1,4,7-triazacyclononane. Also, zinc compounds can be used to prevent corrosion on the items to be washed.

In the context of the present invention, automatic dishwashing detergents which additionally contain at least one silver protectant selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of from 0.001 to 1% by weight are preferred. %, preferably from 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.25 wt .-%, each based on the total agent.

Claims (13)

1. A method for producing coated bleaching activators, characterised by the steps

   a) granulation of at least one bleaching activator with a binder;

   b) coating of the granules from step a) with a solution or dispersion of at least one complexing agent from the group of phosphonates:

   c) drying of the coated granules.
2. A method according to claim 1, characterised in that natural polymers, preferably cellulose and/or starch and the derivatives thereof, in particular carboxymethylcellulose (CMC) and/or hydroxypropylcellulose (HPC) and/or hydroxypropylmethylcellulose (HPMC) are used as binder.
3. A method according to either of claim 1 or claim 2, characterised in that hydroxyalkane- or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or the di- or tetrasodium salt thereof and/or ethylenediaminetetramethylenephosphonate (EDTMP) or the hexasodium salt thereof and/or diethylenetriaminepentamethylenephosphonate (DTPMP) or the hepta- or octasodium salt are used as complexing agent.
4. A method according to any one of claims 1 to 3, characterised in that the dried granule (including coating) contains, relative to the weight thereof, 5 to 80 wt%, preferably 10 to 75 wt.% and in particular 20 to 70 wt.% of bleaching activator(s).
5. A method according to any one of claims 1 to 4, characterised in that the dried granule (including coating) contains, relative to the weight thereof, 1 to 50 wt.%, preferably 1.5 to 20 wt.% and in particular 2 to 10 wt.% of binder(s).
6. A method according to any one of claims 1 to 5, characterised in that the dried granule (including coating) contains, relative to the weight thereof, 0.1 to 50 wt.%, preferably 3 to 25 wt.% and in particular 5 to 15 wt.% of complexing agent(s).
7. A method according to any one of claims 1 to 6, characterised in that step a) is carried out in a mixer/granulator, wherein the bleaching activator(s) and binder(s) are preferably initially introduced in solid form and converted into granules with a granulating liquid.
8. A method according to claim 7, characterised in that the granulating liquid contains neither surfactant(s) nor complexing agent(s).
9. A method according to any one of claims 1 to 8, characterised in that step b) and optionally step c) are carried out in a fluidised bed apparatus.
10. Coated bleaching activators comprising a particle core which contains the bleaching activator(s) and a shell surrounding said core, characterised in that the shell consists to an extent of at least 50 wt.%, preferably of at least 70 wt.%, more preferably of at least 90 wt.% and in particular of 100 wt.% of the weight thereof of complexing agent(s) from the group of phosphonates.
11. Coated bleaching activators according to claim 10, characterised in that the shell contains hydroxyalkane- or aminoalkanephosphonates and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or the di- or tetrasodium salt thereof and/or ethylenediaminetetramethylenephosphonate (EDTMP) or the hexasodium salt thereof and/or diethylenetriaminepentamethylenephosphonate (DTPMP) or the hepta- or octasodium salt thereof as complexing agent(s).
12. Coated bleaching activators according to either of claim 10 or claim 11, characterised in that, in addition to bleaching activator(s), the core contains binder(s), wherein natural polymers, preferably cellulose and/or starch and the derivatives thereof, in particular carboxymethylcellulose (CMC) and/or hydroxypropylcellulose (HPC) and/or hydroxypropylmethylcellulose (HPMC) are preferred as binder(s) and preferred quantities of binder(s) in the core amount to 1 to 50 wt.%, preferably to 5 to 40 wt.% and in particular 10 to 30 wt.% (in each case relative to the uncoated core).
13. A detergent or cleaning agent containing at least one bleaching agent, at least one colorant and at least one coated bleaching activator according to any one of claims 11 to 13.