EP1723222A1 - 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

 Bleach activators and process for their preparation

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 cleaners. Usually, these agents contain one or more builders, bleaches, 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 is not a solution in itself: At the Phase boundary occur the problems of bleaching and color transfer even 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.

Thus, EP 482 807 B1 discloses the common granulation of TAED with binders and the subsequent coating of the granule particles with inorganic salts.

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.

The present invention is in a first embodiment, a method for producing coated bleach activators, characterized by the steps of a) granulation of at least one bleach activator with a binder; b) coating the granules from step a) with a solution or dispersion of at least one complex image; 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. Suitable for carrying out this process step mixers include 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).

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 may 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, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N- alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. 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.

A further preferred bleach activator which can be used according to the invention is a cationic nitrile of the formula (I)

R ¹

R ^{2 is} -N ⁽⁺⁾ - (CH ₂ ) -CN X ^H (I),

R ³

in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl, 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 Alkenylarylrest with a C ^ alkyl group, or a substituted alkyl or Alkenylarylrest with a and at least one further substituent on the aromatic ring, R ² and R ^{3 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 and X is an anion.

The general formula (I) includes a variety of cationic nitrites 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 the following table are according to the invention Preferred cationic nitriles of the formula (I) are characterized by their radicals R ¹ , R ² and R ³ :

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)

R ⁴

R ^{5 is} -N ⁽⁺⁾ - (CH ₂ ) -CN X ° (la),

R ⁶ 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 may also be -H and X is an anion, preferably wherein R ⁵ = R ⁶ = -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 )) 3N ⁽⁺⁾ 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 Chloride, bromide, iodide, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate or xylenesulfonate or mixtures thereof.

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 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. commercial Polyvinylpyrrolidones have molecular weights in the range of about 2500-750000 g / mol, which are characterized by the specification of the K values 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.

The vinyl ester polymers are vinyl ester-accessible polymers having the moiety of formula (III)

CH ₂ - CH - OI o R (Ml)

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.

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).

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. Cellulose ethers are produced industrially by etherification of alkali cellulose (eg with ethylene oxide). Cellulose ethers are characterized by the average degree of substitution DS or the molar degree of substitution MS, which indicate how many hydroxyl groups of an anhydroglucose unit of the cellulose reacted with the etherifying reagent or how many moles of the etherifying agent were attached on average to an anhydroglucose unit. Hydroxyethylcelluloses are water-soluble from a DS of about 0.6 or an MS of about 1. Commercially available hydroxyethyl or hydroxypropyl celluloses have degrees of substitution in the range of 0.85-1, 35 (DS) and 1, 5-3 (MS). Hydroxyethyl and propylcelluloses are marketed as yellowish-white, odorless and tasteless powders in widely varying degrees of polymerization. Hydroxyethyl and propylcelluloses are soluble in cold and hot water as well as in some (hydrous) organic solvents but insoluble in most (anhydrous) organic solvents; their aqueous solutions are relatively insensitive to changes in pH or electrolyte addition.

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 passed through polymer-analogous reactions Hydrolysis, technically but especially by alkaline catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol) prepared in solution. By these technical methods also PVAL are accessible, which contain a predeterminable residual portion of acetate groups.

Commercially available PVAL (for example, Mowiol ^® types from Clariant) are as a white yellowish powders or granules having degrees of polymerization in the range of about 500-2500 (corresponding to molecular weights of about 20,000-100,000 g / mol) in the trade and have different degrees of hydrolysis of 98 -99 and 87-89 mol%, 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 and the coated granules are dried. The coating can be carried out at the same time as 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 to dry after coating, ie in time subsequently to this, perform.

Complex images, their solutions or dispersions in a solvent or dispersion medium in the process according to the invention for coating the bleach activator. Granules are substances that can complex metal ions. Preferred complexing agents are so-called chelate complexing agents, ie substances which form cyclic compounds with metal ions, a single ligand occupying more than one coordination site on a central atom, ie at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.

Common and preferred chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA). Complex-forming polymers, ie polymers which carry functional groups either in the main chain itself or in a pendent position, which can act as ligands and generally react with suitable metal atoms to form chelate complexes, can be used according to the invention. The polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.

Complexing groups (ligands) of conventional complexing polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific. Activities towards ions of different metals. Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.

In the context of the present invention, it is particularly preferable to use one or more chelating agents from the groups of (i) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5,

(ii) nitrogen-containing mono- or polycarboxylic acids,

(iii) geminal diphosphonic acids,

(iv) aminophosphonic acids,

(v) phosphonopolycarboxylic acids,

(vi) cyclodextrins.

In the context of the present invention, all complexing agents of the prior art can be used. These can belong to different chemical groups. Preferably, used individually or in admixture with each other:

a) polycarboxylic acids in which the sum of the carboxyl and optionally hydroxyl groups is at least 5, such as gluconic acid, b) nitrogen-containing mono- or polycarboxylic acids, such as ethylenediaminetetraacetic acid (EDTA), N-hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, nithdodiacetic acid-3-propionic acid, isoserinediacetic acid , N, N-di (β-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) glycine, N- (1, 2-dicarboxy-2-hydroxyethyl) aspartic acid or nitrite c) geminal diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), the higher homologues of which have up to 8 carbon atoms, and hydroxy- or amino-containing derivatives thereof and 1-aminoethane-1,1-dicarboxylic acid (NTA). diphosphonic acid, the higher homologues of which have up to 8 carbon atoms, and hydroxy- or amino-containing derivatives thereof, d) aminophosphonic acids such as ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (meth ylenphosphonic acid) or nitrilotri (methylene phosphonic acid), e) phosphonopolycarboxylic acids such as 2-phosphonobutane-1,2,4-tricarboxylic acid and f) cyclodextrins.

As polycarboxylic acids a) are understood in the context of this patent application carboxylic acids - including monocarboxylic acids - in which the sum of carboxyl and in the Molecule-containing hydroxyl groups is at least 5. Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. In the case of the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.

Also to be mentioned as further preferred complexing polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives which, in addition to co-builder properties, also have a bleach-stabilizing effect.

Further suitable complexing agents are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Another class of substances with complexing 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 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 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, especially if the agents also contain bleach, it may be preferred Aminoalkanphosphonate, in particular DTPMP use, or to use mixtures of said phosphonates.

Meaning are. These substances will be described below.

Preferred 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 diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt, be used.

After drying, the granules produced according to the invention contain at least the constituents bleach activator, binder and complexing agent. Preferred processes according to the invention are characterized in that the dried granules (including coating), based on their 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).

Coated bleach activators preferred according to the invention are characterized in that the shell contains 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 ethylenediamine tetramethylene phosphonate (EDTMP ) or its hexasodium salt and / or diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt.

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 characterized by a high storage stability and are suitable excellent for use in a variety of means, especially 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 relates to detergents or cleaners containing at least one bleaching agent, 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. In the case of washing or cleaning agents according to the invention in tablet form, this applies to individual phases (preferably layers) of the tablets, in the case of multiphase Shaped individual phases can also be colored undyed or unterschidlich.

Preferred washing or cleaning agents according to the invention, in particular automatic dishwasher 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, cobuiiders), surfactants, enzymes, dyes, fragrances, corrosion inhibitors, polymers , or another common ingredient of detergents and cleaners. These ingredients are described below. Builder

According to the present invention, all builders commonly 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} Η 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 layered silicates of the formula given are those in which M is sodium and x 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.

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. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. 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 may be included in the compositions be. 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 particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of greatest importance in the washing and cleaning agent industry.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO in addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits on machine parts or limescale deposits on the items to be washed and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as dihydrate (density 1, 91 like ^"3 , melting point 60 °) and as monohydrate (density 2.04 like ^{" 3} ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It is formed when phosphoric acid is adjusted to pH 4.5 with narcotic eye and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33, like ^"3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) χ] and is light soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like ^"3 , water loss at 95 °), 7 moles (density 1, 68 like ^{" 3} , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1,52, like ^"3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° C and on more intense heating passes into the diphosphate Na ₄ P ₂ O. Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with sodium carbonate solution prepared using phenolphthalein as an indicator Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 ^"3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) has a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 ^"3 iron. Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 ^"3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulfate Despite the higher price, in the detergent industry, the more soluble, hence highly effective, potassium phosphates are often preferred over corresponding sodium compounds.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 like ^"3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 like ^{" 3} , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% ^"3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, where one can distinguish cyclic representatives, the sodium or Kaliummetaphoshate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ Oιo (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n - Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH -> NasKsPsO, + H ₂ O

These are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; 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 an alkali source has proved to be particularly advantageous if 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. Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

In the context 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 group-containing polymers described above may also be present in the compositions according to the invention, without necessarily having to be part of the active ingredient-containing polymer matrix zuu.

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 containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives ,

Other preferred copolymers have as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymers of amino dicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives. Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable co-builders. 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 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). As Aminoalkanphosphonate are preferably

Ethylenediamine tetramethylene phosphonate (EDTMP),

Diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. 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 builder 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.

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 .-%, particularly preferably from 5 to 90 wt .-% and in particular from 10 to 80 wt .-%, each based on the composition. 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 obtained for example from C ₁₂ -ιβ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration , Also suitable are alkanesulfonates consisting of C ₁₂ . _1s alkanes are obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Similarly, the esters of α-sulfo fatty acids (ester sulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettsäuren are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are 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 become. 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, straight-chain alkyl radical which is prepared on a petrochemical basis and which comprises have similar degradation behavior as the adequate compounds based on oleochemical raw materials. From washing technical interest, the C ₁₂ -C ₁₆ - alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₄ -C ₁₅ alkyl sulfates are preferred. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂ alcohols, such as 2-methyl-branched Cg-u-alcohols having an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

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 -ι ₈ fatty alcohol radicals 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) ylsuccinic acid having preferably 8 to 18 carbon atoms in the Al k (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, as well as soluble salts of organic bases such as mono-, di-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. Preferred ethoxylated alcohols include, for example, C _{12th 14-} alcohols with 3 EO or 4 EO, Cg-n-alcohol with 7 EO, C ₃ . _15- alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ . ι ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₂ .ι ₄ -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 rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are 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). Useful alkypolyglycosides satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular 2-methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The Glycosidierungsgrad 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, ie 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.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (XVIII),

I

R-CO-N- [Z] (XVIII)

in which RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

The group of polyhydroxy fatty acid amides also includes compounds of the formula (XIX), R ¹ -OR ² I R-CO-N- [Z] (XIX)

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein C ^ alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives thereof residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

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 skilled worker generally understands alkoxylated alcohols as 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 ₈ , preferably between C ₁₂ and Cιe, such as C _ι - , C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₈ -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 In the context of the present invention, highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates are very particularly preferred for the purposes of the present invention.

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, preference is given to machine dishwashing agents according to the invention which contain surfactants of the general formula XX as nonionic surfactant (s)

R ^{1 is} -O- (CH ₂ -CH ₂ -O) _w - (CH ₂ -CH-O) _x - (CH ₂ -CH ₂ -O) _y - (CH ₂ -CH-O) _z -H (XX )

R ² R ³

in the R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C ₆ . ₂₄ alkyl 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 formula I above 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 according to the invention, particular preference is given to nonionic surfactants which have a Cg. ₁₅ alkyl 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 solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _{16th 20} alcohol), preferably a C ₁₈ alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Of these, the so-called "narrow rank ethoxylates" (see above) are particularly preferred.

Accordingly, particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which are prepared from C ₆ . ₂ Q monohydroxyalkanols or C ₆ . ₂ o-alkylphenols or C _16-20 - fatty alcohols and more than 12 mol, preferably more than 15 mol and was recovered in particular more than 20 moles of ethylene oxide per mole of alcohol (s).

The nonionic surfactant preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from. 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 makes up 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 comprise 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.

Further 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 Wt .-% 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 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl, x is values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5 stand. 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 ] _{1 <} 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 Is 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, 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.

It is also possible to use anionic, cationic and / or amphoteric surfactants in conjunction with the surfactants mentioned, these having only minor importance because of their foaming behavior in automatic dishwashing detergents, and in most cases only in amounts below 10% by weight, in most cases even below 5 Wt .-%, 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% by weight, 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.

"Sodium percarbonate" is a term used in unspecific terms for sodium carbonate peroxohydrates, which strictly speaking are not "percarbonates" (ie salts of percarbonic acid) but hydrogen peroxide adducts of sodium carbonate. The commercial product has the average composition 2 Na ₂ CO ₃ -3 H ₂ O ₂ and is therefore not peroxycarbonate. Sodium percarbonate forms a white, water-soluble powder of density 2.14 ^"3 , which readily decomposes into sodium carbonate and bleaching or oxidizing oxygen.

Sodium carbonate peroxohydrate was first obtained in 1899 by precipitation with ethanol from a solution of sodium carbonate in hydrogen peroxide, but mistakenly regarded as peroxycarbonate. It was not until 1909 that the compound was recognized as a hydrogen peroxide addition compound, yet the historical name "sodium percarbonate" has prevailed in practice.

The industrial production of sodium percarbonate is predominantly produced by precipitation from aqueous solution (so-called wet process). Here, aqueous solutions of sodium carbonate and hydrogen peroxide are combined and the sodium by salting-out agent (mainly sodium chloride), Kristallisierhilfsmittel (for example, polyphosphates, polyacrylates) and stabilizers (for example, Mg ²⁺ ions). The precipitated salt, which still contains 5 to 12 wt .-% mother liquor is then removed by centrifugation and dried in fluidized bed driers at 90 ° C. The bulk density of the finished product may vary between 800 and 1200 g / l, depending on the manufacturing process. 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 bleaching agents which can be used as ingredients in the present invention are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaching agents 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 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-decyldiperoxybutan-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

As a bleaching agent for automatic dishwashing, chlorine or bromine releasing substances can also be used according to the present invention. Among the suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid,

Tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Advantageous agents in the context of the present invention comprise one or more bleaches, preferably from the group of the oxygen or halogen bleaches, in particular the chlorine bleaches, with particular preference of sodium percarbonate and / or sodium perborate monohydrate, in amounts of from 0.5 to 40 Wt .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25% by weight 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 can 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 enzymatic active ingredients obtained from their genetically modified variants. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. These are 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 cellobiases, or mixtures thereof. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by 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% by weight and in particular from 1 to 5% by weight. , in each case based on the total mean.

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 cleaning agents 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)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, 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, Cl Acidblue 183), pigment Blue 15 (Cl 74160), Supranol Blue ^® GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan ^® Yellow N- 7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan Blue ^® (Cl Acid Blue 182, CAS 12219-26-0) is used. Particularly preferred within the scope of the present invention are the dyes mentioned below. The first name indicates the name of the dye, the second name is the generic name in the Color Index (Cl.generic name), the five-digit number is the number of the relevant dye in the Color Index (Cl.

No.), a three- or four-digit number, followed by an indent, a two-digit number

Number, followed by a further indent and a single digit number, gives the

Chemical Abstracts Number (CAS No.) to:

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 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

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 colorants 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 dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of some 10 ^"2 to ^{10" 3} wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® - dyes, 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.

As perfume oils or fragrances, individual fragrance compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, and Lilial Bourgeonal, to the ketones, for example, the Jonone, oc-lsomethylionon and methyl cedrylketon to the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons include mainly the terpenes such as limonene and pinene.

Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures such as are available from vegetable sources, e.g. 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 automatic 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 cleaners 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, particularly preferably the cobalt (ammine) - Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and the manganese sulfate and the manganese complexes

[Me-TACN) Mn ^lv (m-0) ₃ Mn ^lv (Me-TACN)] ²⁺ (PF ₆ -) ₂ , [Me-MeTACN) Mn ^IV (m-0) ₃ Mn ^lv (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 (m-0) (m-0Ac) ₂ Mn ^III (Me-MeTACN)] ²⁺ (PF ₆ -) ₂ , wherein Me-TACN for

1, 4,7-trimethyl-1,4,7-triazacyclononane and Me-MeTACN is 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

claims:

1. A process for the preparation of coated bleach activators, characterized by the steps d) granulation of at least one bleach activator with a binder; e) coating the granules from step a) with a solution or dispersion of at least one complex image; f) drying the coated granules.

2. The method according to claim 1, characterized in that as binders natural polymers, preferably cellulose and / or starch and derivatives thereof, in particular carboxymethyl cellulose (CMC) and / or hydroxypropyl cellulose (HPC) and / or hydroxypropylmethyl cellulose (HPMC) are used.

3. The method according to any one of claims 1 or 2, characterized in that as complexing agents phosphonates, preferably hydroxyalkane or Aminoalkanphosphonate and in particular 1-hydroxyethane-1,1-diphosphonate (HEDP) or its di- or tetrasodium salt and / or ethylenediamine - Tetramethylenephosphonat (EDTMP) or its hexasodium salt and / or Diethylentriaminpentamethylenphosphonat (DTPMP) or its hepta- or Octasatriumsalz be used.

4. The method according to any one of claims 1 to 3, 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).

5. dried granules (including coating), based on its weight, 1 to 50 wt .-%, preferably 1, 5 to 20 wt .-% and in particular 2 to 10 wt .-% binder.

6. The method according to any one of claims 1 to 5, characterized in that the dried granules (including coating), based on its weight, 0.1 to 50 wt .-%, preferably 3 to 25 wt .-% and in particular 5 to 15 wt .-% complexing agent.

7. The method according to any one of claims 1 to 6, characterized in that step a) is carried out in a Michergranulator, wherein preferably bleach activator (s) and binder are introduced in solid form and granulated with a granulating liquid.

8. The method according to claim 7, characterized in that the granulating liquid is free of surfactant (s) and complexing agent (s).

9. The method according to any one of claims 1 to 8, characterized in that step b) and optionally step c) are carried out in a fluidized bed apparatus.

10. Coated bleach activators comprising a particle core containing bleach activator (s) and a shell surrounding this core, characterized in that the shell is at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% Wt .-% and in particular to 100 wt .-% of its weight consists of complexing agent (s).

11. Coated bleach activators according to claim 10, characterized in that the shell 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 diethylenetriaminepentamethylenephosphonate (DTPMP) or its hepta- or octasodium salt.

12. A bleached bleach activator according to any one of claims 10 or 11, characterized in that the core next bleach activator (s) contains binder, wherein as a binder natural polymers, preferably cellulose and / or starch and derivatives thereof, in particular carboxymethylcellulose (CMC) and / or Hydroxypropylcellulose (HPC) and / or hydroxypropylmethylcellulose (HPMC) are preferred and preferred amounts of the core of binder are 1 to 50% by weight, preferably 5 to 40 wt .-% and in particular 10 to 30 wt .-% of binder (in each case based on the uncoated core) amount.

13. washing or cleaning agent, comprising at least one bleaching agent, at least one dye and at least one coated bleach activator according to any one of claims 11 to 13.