WO2008012183A1 - Coloured granular material - Google Patents

Abstract

A process for producing a coloured granular material, which comprises the steps (a) provision of a support material, (b) mixing of a brightener system and a binder to give a brightener-binder preparation, (c) spraying of the brightener-binder preparation onto the support material and (d) spraying a dye preparation onto the product of process step (c), makes it possible to provide a bright, coloured granular material having a very high luminosity.

Description

 "Colored granules"

The present invention relates to a process for producing a colored granulate, a colored granulate per se and the use of a preparation comprising optical brightener for dyeing a support material.

Granulation, agglomeration, coating and other methods of preparation of particulate solids are well described in the art. The products of these processes will be referred to simply as granules in the following statements, by which the term granules includes granules in the narrow sense, agglomerates, powders, coated particles, prills and the like. Due to the large number of possible production processes for granules and the wide variety of raw materials and individual components used, the respective process end products, the granules, sometimes have significantly different physical properties. Even if the granules are simply examined, the consumer differentiates between more or less round, larger and smaller granules. The consumer perceives whether the granules have a narrower or wider particle size distribution and gains a - perceived - color impression. In short, the funds differ in product design.

Due to the enormous variety of granules offered for all the needs of everyday life, the consumer is faced with the problem of choosing from a variety of products that is almost unimaginable just the one that most suits his needs. Here, product design can make it easier for the consumer to make a purchase decision.

The purchase decision is generally based on very different criteria, but above all on the price of the presented goods and their quality. As an additional criterion for the purchase decision, however, product design is becoming increasingly important. Consumers usually want to use a product that also appeals to their aesthetic sensibilities. For this reason, many products are equipped with visually appealing packaging. The product itself is also of great interest, for example with regard to its color and shape. As an example, particulate detergents or cleaners may be mentioned here. A visually appealing product from this area is, for example, a detergent which consists exclusively of almost spherical particles. exists. Such a detergent of nearly equal and nearly spherical particles, due to its high symmetry and homogeneous appearance in the eyes of the consumer, implies great care in the preparation and high competence in the processing of the particulate detergent, while an agent which is of very irregular shape Particles exists, the consumer does not trigger corresponding positive associations. Similarly, the color impression that the consumer gains from a product. Especially in the field of detergents or cleaners, cosmetic products, pharmaceutical products and foodstuffs, a pure white product gives the consumer selected, ie very pure, high-quality components, while, for example, a yellowish or greyish-shimmering detergent suggests the consumer, that it is an inferior agent in which components of low quality have been processed, that a decomposition of individual ingredients has already taken place, or a graying of the textiles in the direction of the hue of the less than appealing agent is to be feared. In addition, colored speckles enhance the visual appeal of a particulate agent. The consumer is led to suspect that these speckles contain additional, highly active active ingredients which, for example, achieve a higher treatment success in the field of detergents or cleaners in comparison with monochrome, white compositions. Together with an appropriate statement on the package of the product, the consumer is suggested by these colored speckles an effect that significantly increases the performance of the agent containing the colored speckles compared to monochromatic products, thus making the product more attractive to the consumer. The consumer combines the colors of speckies described by him as "radiant" and "bright" in turn a high quality and very good effect of the raw materials used, while speckies with less radiant and bright colors do not trigger this association.

Against this background, the object of the present invention was to develop a method for producing an aesthetically pleasing granulate, which can be used, for example, as a speckle.

This object is achieved by a method in which a carrier material is first sprayed on a brightener-binder preparation and then a dye preparation. Surprisingly, it has been found that colored speckles produced in this way are perceived more radiant and brighter, in short have a better color effect, than colored speckles, which were prepared by known processes.

The present invention is a process for producing a colored granules, comprising the steps

(a) providing a carrier material, (b) mixing a brightener system and a binder into a brightener-binder formulation

(c) spraying the brightener-binder formulation onto the support material and

(D) spraying a dye formulation on the product of step (c).

By the claimed process, granules are produced which contain a core, an inner shell comprising optical brightener and an outer shell comprising dye. In addition to these three elements core, inner and outer shell, the granules may have further shells. In the following, however, the brightener-containing shell should be referred to as the inner shell and the dye-containing shell as the outer shell.

Another object of the present invention is a granulate, which was prepared by the process according to the invention. Preferably, the granulate is a detergent or detergent granule or component for such agent.

In the present documents, the term "granules" includes granules in the narrower sense, agglomerate rate and powder Accordingly, any particulate material which appears suitable to the person skilled in the art can form the carrier material of the granulate according to the invention Base powder, which preferably contains at least two components In the area of washing or cleaning agents, the support material preferably comprises builders which have been agglomerated in a high, moderate or low speed mixer with the addition of agglomeration liquid and subsequently granulated or fluidized bed materials, extruded and / or roll compacted compositions or components may be used as support materials In a preferred embodiment, the support material comprises a co component for a washing or cleaning agent or a full formulation of such an agent, preferably comprising builder and surfactant. The constituents of a suitable carrier material preferably used in the detergents and cleaners as well as the components for corresponding agents are described in detail later. The carrier material may be of homogeneous composition or may already comprise one or more coating layers. The coating of a commercially available and not further processed raw material or compound within the method according to the invention is possible.

The support material forms the core of the granules according to the invention, which in step c) of a method according to the invention preferably at least 30 area%, preferably at least 50 area%, more preferably at least 70 area% and in particular at least 90 area% a coating comprising optical brightener and a binder, the inner layer, is coated. The binder may comprise one or more binder components and preferably acts as a suspension liquid for the optical brightener. The binder may be aqueous or non-aqueous. Examples of suitable binders are aqueous preparations comprising salts, water glass, alkyl polyglycosides, carbohydrates, natural and synthetic polymers such as cellulose ethers, starch, polyethylene glycol, polyvinyl alcohol and / or biopolymers such as xanthan, aqueous organic solvents with swollen polymers, melts, triglycerides, terpenes, Glycerin, silicone oil, paraffin (oil), natural oils, surfactants and surfactant mixtures. The binder particularly preferably contains nonionic, anionic, cationic and / or amphoteric surfactants, preferably nonionic and / or anionic surfactants and in particular nonionic surfactants, preferably from the group of alkoxylated fatty alcohols and fatty acid alkyl esters, alkylphenol polyglycol ethers, fatty aminoalkoxylates, alkoxylated triglycerides, mixed ethers, alkyl polyglycosides , Amine oxides and polyhydroxy fatty acid amides. With particular preference, the binder contains alkoxylated nickel surfactant. In the binder and / or the brightener-binder preparation is preferably water, wherein the water content of the brightener-binder-preparation, however, preferably at most 20 wt .-%, more preferably at most 10 wt .-% and especially at most 5 wt. -% is.

According to the invention, a preparation comprising optical brightener is used in step c) of the process. Suitable optical brighteners are any of those compounds which are capable of converting invisible ultraviolet radiation into visible longer wavelength light. Suitable optical brighteners for example, originate from the substance classes of the 4,4 ^{'diamino-2,2-stilbenedisulfonic} acids (FIA of acids), ^{4,4'-biphenylene} -Distyryl, Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides , Benzoxazole, benzisoxazole and benzimidazole systems, as well as heterocyclic-substituted pyrene derivatives. Particularly preferred derivatives of bis (triazinylamino) are -stilbendisulfosäure and 4,4 ^{'-Distyrylbiphenyls.}

The brightener system used in the process according to the invention preferably comprises one to four, with particular preference two optical brighteners.

The granules according to the invention preferably comprise an inner shell which comprises a binder which preferably contains surfactant, preferably nonionic surfactant, and o a brightener system comprising at least one, preferably one to four and in particular two optical brighteners, and an outer shell which has a Dye comprises.

Furthermore, it has been shown that the color effect of the granules can be further improved if a brightener system containing at least 2 optical brighteners is used in the process according to the invention, the weight ratio between the brightener, which makes up the largest weight fraction of the sum of the optical brighteners, to the brightener, which The proportion by weight of the sum of the optical brighteners is from 1, 0: 1 to 10: 1, preferably from 1, 1: 1 to 8: 1 and in particular from 1, 2: 1 to 6: 1. The brightener-binder composition preferably contains from 2 to 20% by weight, more preferably from 3 to 15% by weight and in particular from 4 to 10% by weight, of optical brightener (s) and / or contains the finished granules advantageously from 0.01 to 0.5% by weight, and in particular from 0.05 to 0.4% by weight, of optical brightener (s). It has furthermore proven to be advantageous if the weight ratio of binder to optical brightener in the brightener-binder preparation of the process according to the invention is from 50: 1 to 1: 1, preferably from 25: 1 to 4: 1 and in particular from 20: 1 to 7: 1.

In the granules according to the invention, the amount of optical brightener - based on the inner shell of the granules according to the invention - preferably from 2 to 20 wt .-%, particularly preferably from 3 to 15 wt .-% and in particular from 4 to 10 wt .-% of , These values are particularly achieved when a brightener-binder formulation comprising from 2 to 20% by weight of optical brightener is used which is less than 10% by weight, preferably less than 7.5% by weight, with particular preference less than 5% by weight and in particular less than 2.5% by weight of water or other volatile / vaporizable components.

Unexpectedly, it has been found that a further improvement in the color effect of the granules can be achieved if in the method according to the invention a brightener-binder preparation is used which contains water and a pH of 4 to 11, preferably from 5 to 9, especially preferably from 4 to 8, preferably from 4.5 to 7 and in particular from 5 to 6. A corresponding pH of the aqueous brightener-binder preparation can be adjusted, for example, by the use of salts, acid or a buffer system. The brightener-binder preparation therefore preferably additionally contains acids and / or salts, preferably a buffer system, preferably in amounts of from 0.01 to 15% by weight and in particular from 0.1 to 3% by weight. In addition to the components mentioned, the brightener-binder preparation may comprise further components. Suitable optional components of the brightener-binder formulation will be mentioned later in the text. However, the weight fraction of these additional optional components is preferably below 20% by weight, preferably below 15% by weight, more preferably below 10% by weight and in particular below 5% by weight, based on the brightener / binder preparation.

Suitable buffer systems preferably contain one or more buffers from the group of citric acid / citrate, acetic acid / acetate, boric acid / sodium borate, phosphoric acid / sodium phosphate, bicarbonate / soda, ammonia / ammonium chloride, [(carbamoylmethyl) -imino] -diacetic acid, Λ /, Λ / bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, Λ /, Λ / bis (2-hydroxyethyl) glycine, 3- (cyclohexylamino) -1-propanesulfonic acid, 2- [4- (2- Hydroxyethyl) piperazino] ethanesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinopropane-1-sulfonic acid, piperazine-Λ /, Λ / -bis (ethanesulfonic acid), 2- {[Tris (hydroxymethyl) methyl] amino} ethanesulfonic acid and Λ / - [2-hydroxy-1, 1-bis (hydroxymethyl) ethyl] glycine. Particular preference is given to using a citric acid / citrate buffer.

A preferred granulate according to the invention contains in the inner shell a buffer system which, with particular preference, has a pH of from 4 to 11 and in particular a pH of from 5 to 9 as the 0.1 M aqueous buffer solution.

A further improvement in the color effect of the granules produced by the method according to the invention can be achieved if the brightener comprises one or more optical brightener and at least one of the optical brightener, preferably all optical brightener have a mean particle diameter d ₅₀ <10 microns.

In a preferred embodiment of the method, the optical brightener (s) before or after, preferably before mixing with the surfactant system to a particle diameter d ₅₀ of 1 to 10 microns, preferably by means of a jet mill milled. Preferably, the average particle diameter d _{50 of} one or all of the optical brighteners after grinding is 2 to 10 μm, in particular 4 to 10 μm.

For special embodiments it can be provided that the optical brightener (s) have an even smaller average particle size. In another likewise preferred embodiment of the method, the optical brightener (s) before or after, preferably after mixing with the surfactant system to a particle diameter d ₅₀ of 0.05 to 1 .mu.m, preferably in the liquid phase and in particular by means of a stirrer mill, crushed.

Another preferred subject of the present invention is a process for producing a colored granulate according to, comprising the steps of a) providing a support material; b) mixing a brightener system and a binder into a brightener-binder preparation; and c) spraying the brightener-binder preparation onto the carrier material; and d) spraying a dye preparation onto the product of process step (c), wherein the brightener system comprises one or more a plurality of optical brighteners, wherein the brightener-binder preparation additionally contains water and one or more acid (s) and / or salt (s), preferably a buffer system and / or at least one of the optical brighteners, preferably all optical brighteners has a particle diameter d ₅₀ <10 microns / have. In the inner shell of the granules according to the invention, at least one of the optical brighteners preferably has an average particle diameter d ₅₀ <10 μm. The average particle diameter d _{50 of} all optical brighteners is particularly preferably at corresponding values.

With particular preference, the effects of the use of a finely ground optical brightener and a suitable buffer system, which reinforce the color effect of the final process product, are combined and thus granules having a particularly good color effect are obtained. The effects of the reduction of the particle diameter of the optical brightener and the pH of the buffer system contained in the coating act synergistically together.

Before and / or after step c) of the process according to the invention, advantageously in an additional step e) a powdering agent is applied to the support material and / or to the support material sprayed with the brightener / binder preparation.

Suitable fining agents are all finely divided substances, it also being possible to use other detergent constituents, such as builder substances. These will be listed later in the text. Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives, etc. are preferably used as additional powdering agents. A part of a possibly existing buffer system can also be used for powdering. Zeolite is preferably used as the powdering agent. The amount of the powdering agent used is preferably 0.5 to 5 wt .-% and in particular from 1 to 2.5 wt .-%, based on the finished granules.

In step d) of the process according to the invention, a dye preparation is sprayed onto the product of process step c). Was after step c) in an additional step e) a powdering applied to the sprayed with the brightener-binder preparation carrier material, the dye formulation is sprayed onto this additional layer. Corresponding process variants are part of the present invention.

The dye formulation can be an aqueous or nonaqueous solution or dispersion. Dye solutions, in particular aqueous dye solutions, are preferably used as the dye preparations. It can be used a combination of several dyes.

When choosing the dye, it should be noted that the dye has a high storage stability and insensitivity to light as well as not too strong affinity for textile surfaces and in particular for synthetic fibers. At the same time, it must also be taken into account when choosing suitable dyes that dyeing agents have different stabilities to the oxidation. In general, water-insoluble dyes are more stable to oxidation than water-soluble dyes. Dyes which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use dyes which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic 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. As a further dye 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.

The proportion by weight of the dye used in the process according to the invention is preferably 0.06 to 2 wt .-% and in particular 0.15 to 1 wt .-%, based on the resulting granules. Advantageously, 2 to 50% by weight, in particular 5 to 25% by weight, of dyestuff preparations are used.

The brightener-binder preparation can be prepared in a stirred tank, for example with a propeller, disk, coil or anchor stirrer or even in a static mixer. The spraying of the brightener-binder preparation onto the support material and subsequent mixing and spraying of the dye preparation is preferably carried out in a low-shear mixer, for example a pneumatic fluidized bed, a bowl or drum mixer, a double-cone, tumble or vibratory mixer. Mixer or even performed on a conveyor belt cascade.

For spraying the brightener-binder preparation and the Farstoff preparation preferably one or two-fluid nozzles are used.

The step of powdering can be done in the same mixer in which the brightener-binder composition is sprayed onto the substrate. However, it may also be envisaged that another mixer, preferably a low shear mixer, is connected upstream or downstream of the mixer in which the brightener-binder composition is sprayed. The dye formulation is advantageously sprayed in a separate mixer.

The positive impression of the colored granules can be further improved if this has a particularly appealing form the consumer. According to a preferred embodiment of the invention, the granules according to the invention are uniform, preferably almost spherical or ellipsoidal. The mean form factor of the granules is preferably at least 0.79, preferably at least 0.81, advantageously at least 0.83, more preferably at least 0.85 and especially at least 0.87. The form factor, also shape factor or Called roundness filter, within the meaning of the present invention can be precisely determined by modern particle measurement techniques with digital image processing. A typical suitable particle shape analysis, which can be carried out, for example, with the Camsizer® system from Retsch Technology or also with the KeSer® @ from Kemira, is based on the fact that the particles are irradiated with a light source and the particles are detected as projection surfaces, digitized and processed by computer technology. The determination of the surface curvature is made by an optical measuring method, in which the "shadow cast" of the parts to be examined is determined and converted into a corresponding form factor. The measurement limits of this optical analysis method are 15 μm and 90 mm, respectively. Methods for determining the shape factor for larger particles are known to those skilled in the art. These are usually based on the principles of the aforementioned methods.

A uniform particle size and thus a narrow particle size distribution also contributes to a positive overall impression of a granulate. This is referred to as a uniform particle size if the particles have a size distribution in which the ratio of d ₅₀ to d _{90 is} at least 0.50, preferably at least 0.6, more preferably at least 0.75 and in particular at least 0.80. The granules according to the invention preferably have these properties.

The use of a preparation comprising a binder which preferably contains surfactant, preferably nonionic surfactant, and optical brightener for staining a carrier material is a further subject of the present invention. The carrier material is preferably a washing or cleaning agent or a component for such an agent.

The carrier material preferably comprises a detergent or cleaning agent granules or a component thereof. The support material particularly preferably contains washing or cleaning substances, preferably from the group of builders, surfactants, polymers, bleaches, bleach activators, bleach catalysts, enzymes, disintegration aids, fragrances and perfume carriers. As described above, selected compounds of these classes may also be part of the brightener-binder preparation and thus form part of the coating of the granules according to the invention. These preferred ingredients will be described in more detail below.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and preferably usable in the context of the present invention is, for example, also a co-crystallizate of zeolite X and zeolite A (about 80 wt .-% zeolite X), represented by the formula

n Na ₂ O ^■ (1-n) K ₂ O ^■ Al ₂ O ₃ ^■ (2 - 2.5) SiO ₂ ^■ (3.5-5.5) H ₂ O

can be described. The zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

With preferred crystalline layered silicates of general formula NaMSi _x O are used _{2x + 1} ^■ y H ₂ O wherein M is sodium or hydrogen, x is a number from 1, 9 to 22, preferably from 1: 9 to 4, wherein particularly preferred values for x are 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ ^.xH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ ^.xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ ^.xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ ^.xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline layer silicates with the formula NaMSi _x O _{2x + 1} ^■ y H ₂ O, in which x stands for 2 h. In particular, both .beta.- and sodium disilicates δ- Na ₂ Si ₂ O ₅ ^■ y H ₂ O, and further in particular Na-SKS-5 ((X-Na ₂ Si ₂ O _5), Na-SKS-7 (.beta. Na ₂ Si ₂ O _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ ^■ H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ ^■ 3 H ₂ O, kanemite), Na-SKS-1 1 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (6-Na ₂ Si ₂ O ₅ ) is 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 preferably delayed release 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 understood to mean 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 , cause. Alternatively or in combination with the abovementioned amorphous sodium silicates, X-ray amorphous silicates are used whose silicate particles produce fuzzy or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such X-ray amorphous silicates also have a dissolution delay compared to conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are the most important in the detergent and cleaner 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 _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Technically particularly important phosphates are the pentasodium triphosphate, Na ₅ P ₃ Oi ₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ Oi ₀ (potassium tripolyphosphate). The sodium potassium tri-phosphates are also preferably used according to the invention.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred may be a builder system containing a mixture of tripolyphosphate and sodium carbonate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners in comparison with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2 wt .-%, in each case based on the total weight of the washing or cleaning agent used. Particularly preferred are agents which are based on their total weight less than 0.5 wt .-% and in particular no alkali metal hydroxides included.

Particularly preferred is the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate.

Particularly suitable organic co-builders are polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and also phosphonates. These classes of substances are described below.

Useful organic builders are, for example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. For example, these are 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 thereof. In addition to their builder effect, the free acids also typically 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 of 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 indicated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were fundamentally determined 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.

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To be particularly suitable Copolymers of acrylic acid with maleic acid containing 50 to 90 wt .-% of acrylic acid and 50 to 10 wt .-% of maleic acid. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.

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 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 ,

Further preferred copolymers are those which have as their monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

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

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. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molecular weights in the range of 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.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. Ethylenediamine-N, ^{N'-disuccinate} (EDDS) is preferably used in form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

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.

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

The group of surfactants includes nonionic, anionic, cationic and amphoteric surfactants.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols. 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 native origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ -i ₄ alcohols containing 3 EO or 4 EO, _C9-11 alcohol containing 7 EO, C ₃ _i ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -i ₈ -Alkoho- Ie with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C ₁₂ -i ₄ alcohol containing 3 EO and C _2-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow ranks ethoxylates). xylates, NRE). Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used, in the R a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position aliphatic radical having 8 to 22, preferably 12 to 18 C-men and G is the symbol representing a glycose moiety having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number between 1 and 10; preferably x is 1, 2 to 1, 4.

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

R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 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 stands. 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

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 from 1 to 8 carbon atoms, where C | _4- 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 propoxylated derivatives of this radical.

[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 be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

With particular preference further combinations of one or more Taigfettalkoholen be used with 20 to 30 EO and silicone defoamers.

Nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO / AO / EO nonionic surfactants, or the PO / AO / PO nonionic surfactants, especially the PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

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- Alkylbenzolsulfonate, olefinsulfona- te, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those from C ₁₂ -i ₈ monoolefins having terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonating products are considered. Also suitable are alkanesulfonates, which are obtained from C _{12-i 8} alkanes, for example by sulfochlorination or sulfoxidation and 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 Taigfettsäuren 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 used in the preparation obtained 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.

The alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C alk (en) yl sulfates ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C ₀ -C ₂ o 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. From the washing are the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ - C ₁₅ alkyl sulfates and preferably C ₁₄ -C ₁₅ alkyl sulfates. 2,3-alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are surfactants suitable anion.

Also, the sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 moles of ethylene oxide. ₂₁ -alcohols, such as 2-methyl-branched C ₉ ^ ₁ -AIkOhOIe with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ . ₁₈ fatty alcohols with 1 to 4 EO are suitable.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also known as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs - ^ - fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. 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 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, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. 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.

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

As cationic active substances, for example, cationic compounds of the following formulas can be used:

Ri

Ri-N- (CH _{2) n} -T-R 2 (CH _{2) n} -T-R2

wherein each R ¹ group is independently selected from CI_ ₆ alkyl, alkenyl or hydroxyalkyl groups; each group R ^{2 is} independently selected from C ₈ . ₂₈ alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "feel" (Avivage) and reduced electrostatic charge (increased wearing comfort) .The active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic radicals, such as, for example, the disteryldimethylammonium however, due to its insufficient biodegradability, it is increasingly being replaced by quaternary ammonium compounds which, in their hydrophobic residues, contain ester groups as breaking points for biodegradation. Such "esterquats" with improved biodegradability are obtainable, for example, by reacting mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Further suitable as a finish is dimethylolethyleneurea.

The group of polymers includes, in particular, the washing or cleaning-active polymers and / or polymers which act as softeners. In general, cationic, anionic and amphoteric polymers can be used in detergents or cleaners in addition to nonionic polymers.

"Cationic polymers" for the purposes of the present invention are polymers which carry a positive charge in the polymer molecule, which can be realized, for example, by (alkyl) ammonium groups or other positively charged groups present in the polymer chain quaternized cellulose derivatives, the polysiloxanes with quaternary groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives of dialkylamino acrylate and methacrylate, the Vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the polymers specified under the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27.

For the purposes of the present invention, "amphoteric polymers" also have, in addition to a positively charged group in the polymer chain, also negatively charged groups or monomer units. These groups may be, for example, carboxylic acids, sulfonic acids or phosphonic acids.

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds which serve as bleaching agents in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids which yield H ₂ O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, e.g. Dibenzoyl. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.

As a bleaching agent and chlorine or bromine releasing substances can be used. Among the suitable chlorine or bromine releasing materials, for example, heterocyclic N-bromine 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. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.

Bleach activators are used in detergents or cleaners, for example, to achieve an improved bleaching effect when cleaning at temperatures of 60 ⁰ C and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 and 2, 5-Diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl-fructose, tetraacetyl-xylose and octaacetyl lactose and also acetylated , optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolac tam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

Ri R2 N _(CH2) -CN X ^"

R3

in which R ¹ is -H, -CH _3, a C ₂ - ₂₄ alkyl or alkenyl group, a substituted C _2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH _2, -CN, alkyl- or alkenylaryl radical is an Al having a C-ι_ ₂₄ alkyl group, or a substituted alkyl- or alkenylaryl radical with a CI_ ₂₄ alkyl group 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, preferably from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate. is.

Particular preference is given to 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 ^" , where from the group of these substances, in turn, the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^"is an anion selected from the group consisting of chloride, bromide, iodide, Hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate is particularly preferred.

In addition to the conventional bleach activators or in their place, 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 salt 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.

Bleach-enhancing transition metal complexes, in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of the 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, manganese sulfate are preferably used

It is particularly preferred to use complexes of manganese in the oxidation state II, IM, IV or IV, which preferably contain one or more macrocyclic ligands with the donor functions N, NR, PR, O and / or S. Preferably, ligands are used which have nitrogen donor functions. It is particularly preferred to use bleach catalyst (s) in the compositions of the invention, which as macromolecular ligands 1, 4,7-trimethyl-1, 4,7-triazacyclononan (Me-TACN), 1, 4,7-triazacyclononane (TACN ), 1, 5,9-trimethyl-1, 5,9-triazacyclododecane (Me-TACD), 2-methyl-1, 4,7-trimethyl-1, 4,7-triazacyclononane (Me / Me-TACN) and or 2-methyl-1,4,7-triazacyclononane (Me / TACN). Examples of suitable manganese complexes are [Mn ¹ " ₂ (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [Mn" ¹ Mn ^lv (μ-O) ₂ (μ-OAc) ₁ (TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^lv ₄ (μ-O) ₆ (TACN) ₄ ] (Clθ ₄ ) ₄ , [Mn ^III ₂ (μ-O) ₁ (μ-OAc) ₂ (Me -TACN) ₂ ] (CIO ₄ ) ₂ , [Mn " ¹ Mn ^lv (μ-0) ₁ (μ-0Ac) ₂ (Me-TACN) ₂ ] (CIO ₄ ) ₃ , [Mn ' ^v ₂ (μ- O) ₃ (Me-TACN) _2] (PF _{6) 2} and [Mn ^'v ₂ (μ-O) ₃ (Me / Me-TACN) _2] (PF _{6) 2} (OAc = OC (O) CH ₃ ). To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicelluloses, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples of these are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger and A. oryzae, as well as the further developments of the aforementioned amylases which are improved for use in detergents and cleaners. Furthermore, for this purpose, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. Furthermore, it is possible, for example, to use the cutinases which were originally isolated from Fusarium solani pisi and Humicola insolens. It is also possible to use lipases, or cutinases, whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

Particular preference is given to using perhydrolases in the compositions according to the invention. Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators). ,

The enzymes can be used in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Furthermore, it is possible to assemble two or more enzymes together so that a single granule has several enzyme activities.

A protein and / or enzyme may be particularly protected during storage against damage such as inactivation, denaturation or degradation, such as by physical influences, oxidation or proteolytic cleavage. In microbial recovery of proteins and / or enzymes, inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases. Detergents may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention. Preference is given to one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in amounts of from 0.1 to 5% by weight, preferably from 0.2 to 4.5% by weight. % and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agent used.

In order to facilitate the disintegration of preformed moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these compositions in order to shorten the disintegration times. By tablet disintegrants or disintegrants are meant excipients which ensure the rapid disintegration of tablets in water or other media and for the rapid release of the active ingredients.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or caseins derivatives.

Preferred disintegrating agents are cellulosic disintegrating agents. Pure cellulose has the formal gross composition (C ₆ H ₁₀ Os) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal luloses, carboxymethyl cellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, more preferably below 20% by weight, based on the cellulose-based disintegration agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives. The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns.

As a further disintegrating agent based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

Furthermore, according to the invention, gas-evolving effervescent systems can furthermore be used as tablet disintegration auxiliaries. The gas-evolving effervescent system may consist of a single substance that releases a gas upon contact with water. Among these compounds, mention should be made in particular of magnesium peroxide, which liberates oxygen on contact with water. Usually, however, the gas-releasing effervescent system in turn consists of at least two constituents which react with one another to form gas. While a variety of systems are conceivable and executable here, which release, for example, nitrogen, oxygen or hydrogen, the bubble system used in detergents and cleaners can be selected both on the basis of economic and environmental considerations. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifying agent which is suitable for liberating carbon dioxide from the alkali metal salts in aqueous solution.

As Acidifizierungsmittel which release carbon dioxide from the alkali metal salts in aqueous solution, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. Acidifying agents in the effervescent system from the group of organic di-, tri- and oligocarboxylic acids or mixtures are preferred.

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. However, mixtures of various are preferred Uses fragrances that together create a pleasing fragrance. Such perfume oils may also contain natural fragrance mixtures such as those available from vegetable sources, such as pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.

In order to be perceptible, a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "middle note" or "body note" ) and "base note" (end note or dry out). Since odor perception is also largely due to odor intensity, the top note of a perfume does not consist solely of volatile compounds, while the base note is largely made up of less volatile, i. adherent fragrances. In the composition of perfumes, for example, more volatile fragrances can be bound to specific fixatives, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.

The fragrances can be processed directly, but it can also be advantageous to apply the fragrances on carriers that provide a slower fragrance release for long-lasting fragrance. As such carrier materials, for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.

In addition to the components described in detail so far, the detergents or cleaners can contain further ingredients which further improve the performance and / or aesthetic properties of these compositions. Preferred agents contain one or more of the group of electrolytes, pH adjusters, fluorescers, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids , Repellents and impregnating agents, swelling and lubricating agents and UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions NEN are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

In order to bring the pH of detergents or cleaners into the desired range, the use of pH adjusters may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000 and viscosities between 10 and 1,000,000 mPa.s.

Suitable anti-redeposition agents, which are also referred to as soil repellents, are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ether as well as the known from the prior art polymers of phthalic acid and / or terephthalic acid or derivatives thereof, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives thereof. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") may also be included in the substrate to remove graying and yellowing of the treated textiles, which will attract the fiber and cause brightening and fake bleaching by converting invisible ultraviolet radiation into visible longer wavelength light wherein the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and gives a whitish white to the yellowed or yellowed wash, and suitable compounds have already been mentioned in the optical brighteners included in the coating.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. For this purpose, water-soluble colloids are usually suitable organic nature, for example, the water-soluble salts polymeric Carboxylic acids, glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful. Also usable as graying inhibitors are cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

Since textile fabrics, in particular of rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and crushing transversely to the fiber direction, synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents may also be included. The antisoiling equipment with repellents and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable hydrophobizing agents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified methylamine resins, chromium complex salts, silicones, tin salts. organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove. Antimicrobial agents can be used to combat microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate, although these compounds can also be dispensed with entirely.

To prevent undesirable changes to the detergents and cleaners and / or the treated fabrics caused by exposure to oxygen and other oxidative processes, the compositions may contain anti-oxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, poly sulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort may result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus enable an improved outflow of formed charges. External antistatic agents are generally substances with at least one hydrophilic molecule ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to laundry detergents, with an avivage effect additionally being achieved.

Silicone derivatives can be used to improve the water absorbency, rewettability of the treated fabrics, and ease of ironing the treated fabrics. These additionally improve the rinsing out of detergents or cleaning agents by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which comprise, for example, polyethylene glycols and the polyalkylene oxide-modified dimethylpolysiloxanes.

Finally, according to the invention, it is also possible to use UV absorbers which are absorbed by the treated textiles and improve the light resistance of the fibers. Compounds having these desired properties are, for example, the compounds which are active by radiationless deactivation and derivatives of benzophenone having substituents in the 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as umbelliferone and the body's own urocanic acid suitable.

Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preference according to the invention is given to the use of protein hydrolysates of plant origin, for example soya, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

Examples

Step a:

Granulation of the solid and liquid components provides a support material of the following composition:

38.5% by weight of sodium carbonate

21, 8 wt .-% zeolite A

12.7 wt .-% C ₁₂ -i ₈ -alkylbenzenesulfonate

9.3 wt .-% sodium sulfate

2.3 wt .-% acrylic acid-maleic acid copolymer

1, 1 wt .-% Stearinseife

0.8% by weight of sodium silicate

Rest minor components and water

Step b:

Brighteners binder preparation:

92.5 parts by weight Lutensol AO7

5.0 parts by weight of Tinopal DMS-X

2.5 parts by weight of Tinopal CBS-X

50% strength by weight aqueous citric acid solution for adjusting the pH values 7, 8, 9 and 12

Lutensol AO 7: C ₁₃ . _15- oxo-alcohol ^■ 7 EO

Tinopal DMS-X: Derivative of bis (triazinylamino) -stilbene disulfonic acid, 67% by weight, granules

Tinopal CBS-X: distyrylbiphenyl disulfonate, 90% by weight, granules

The nonionic surfactant is placed in a dosing tank and brought to the desired pH with a saturated citric acid solution of pH 9.0 (pH values 7, 8, 9 and 12). The whiteners ground to 8 to 10 μm are metered in and the brightener / binder preparation is homogenized using an Ultra Turax stirrer.

Steps c, e and d:

In the method according to the invention, step e is an optional step which can be carried out before and / or after step c. In this case, the step e is performed after the step c. 92.0 wt .-% carrier material are placed in a Forberg mixer and moved. 3.2% by weight of brightener-binder preparation are sprayed onto the support material. 1. 8% by weight of Wessalith 4000 are metered into the mixer and finally 3.0% by weight of dye preparation (35% by weight of Iragon Blue (20% preparation) and 65% by weight of water) are sprayed on ,

Claims

claims

A process for producing a colored granule, comprising the steps

(a) providing a carrier material,

(b) mixing a brightener system and a binder into a brightener-binder formulation

(c) spraying the brightener-binder formulation onto the support material and

(D) spraying a dye formulation on the product of step (c).

2. The method according to claim 1, characterized in that the brightener system comprises 1 to 4, preferably 2 optical brightener.

3. The method according to any one of claims 1 or 2, characterized in that the brightener system contains at least 2 optical brightener and the weight ratio between the brightener, which makes up the largest weight fraction of the sum of the optical brightener, to the brightener, which is the least weight fraction of the sum the optical brightener is from 1, 0: 1 to 10: 1, preferably from 1, 1: 1 to 8: 1 and in particular from 1, 2: 1 to 6: 1.

4. The method according to any one of claims 1 to 3, characterized in that the brightener-binder preparation of 2 to 20 wt .-%, preferably from 3 to 15 wt .-% and in particular from 4 to 10 wt .-% optical (n) contains brightener and / or the finished granules of 0.01 to 0.5 wt .-% and in particular from 0.05 to 0.4 wt .-% optical (brightener) contains.

5. The method according to any one of claims 1 to 4, characterized in that the binder is nonionic, anionic, cationic and / or amphoteric surfactants, preferably nonionic and / or anionic surfactants and in particular nonionic surfactants, preferably from the group of alkoxylated Fettalokohole and fatty acid alkyl esters, Alkylphenolpolyglyco- lether, fatty aminoalkoxylates, alkoxylated triglycerides, mixed ethers, alkyl polyglycosides, amine oxides and polyhydroxy fatty acid amides, in particular alkoxylated nonionic surfactant contains.

6. The method according to any one of claims 1 to 5, characterized in that the weight ratio of binder to optical brightener from 50: 1 to 1: 1, preferably from 25: 1 to 4: 1 and in particular from 20: 1 to 7: 1 is.

7. The method according to any one of claims 1 to 6, characterized in that the brightener-binder preparation contains water and a pH of 4 to 1 1, preferably from 5 to 9, particularly preferably from 4 to 8, preferably from 4 , 5 to 7 and in particular from 5 to 6.

8. The method according to any one of claims 1 to 7, characterized in that the brightener-binder preparation acids and / or salts, preferably as a buffer system, in amounts of 0.01 to 15 wt .-%, preferably from 0.1 to Contains 3 wt .-%.

9. The method according to any one of claims 1 to 8, characterized in that the brightener-binder preparation contains a buffer system containing one or more buffers from the group citric acid / citrate, acetic acid / acetate, boric acid / sodium borate, phosphoric acid / sodium phosphate, bicarbonate / Soda, ammonia / ammonium chloride, [(carbamoylmethyl) -imino] -diacetic acid, Λ /, Λ / -bis (2-hydroxyethyl) -2-aminoethanesulfonic acid, Λ /, Λ / -bis (2-hydroxyethyl) -glycine , 3- (cyclohexylamino) -1-propanesulfonic acid, 2- [4- (2-hydroxyethyl) piperazino] ethanesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinopropane-1-sulfonic acid, piperazine-Λ /, Λ / -bis (ethanesulfonic acid), 2- {[tris (hydroxymethyl) methyl] amino} ethanesulfonic acid, Λ / - [2-hydroxy-1, 1-bis (hydroxymethyl) ethyl] glycine.

10. The method according to any one of claims 1 to 9, characterized in that the brightener binder composition contains a maximum of 20 wt .-%, preferably at most 10 wt .-% and in particular a maximum of 5 wt .-% water.

1 1. A method according to any one of claims 1 to 10, characterized in that the brightener comprises one or more optical brightener and at least one of the optical brightener, preferably all optical brightener has a particle diameter d ₅₀ <10 microns / have.

12. The method according to any one of claims 1 to 11, characterized in that the or the optical (s) brightener prior to mixing with the surfactant system to a particle diameter d ₅₀ from 1 to 10 microns, preferably by means of a jet mill, is ground / be.

13. The method according to any one of claims 1 to 11, characterized in that the or the optical brightener (s) after mixing with the surfactant system to a particle diameter d ₅₀ from 0.05 to 1 .mu.m, preferably in the liquid phase and in particular by means an agitator mill, is / will be.

14. The method according to any one of claims 1 to 13, characterized in that the dye preparation in step (d) in an amount of 0.06 to 2 wt .-%, in particular in an amount of 0.15 to 1 wt. -% is sprayed onto the granules, wherein the percentages are based on the finished granules and the dye within the dye formulation.

15. The method according to any one of claims 1 to 14, characterized in that before and / or after step (c) in an additional step (e) a powdering agent, preferably zeolite, preferably in an amount of 0.5 to 5 Wt .-% and in particular from 1 to 2.5% by weight, is applied to the carrier material and / or on the sprayed with the brightener-binder preparation carrier material, wherein the percentages are based on the finished granules.

16. Granules prepared according to one of the preceding claims.

17. Granules according to claim 16, characterized in that it comprises an inner shell, which comprises a binder which preferably contains surfactant, preferably nonionic surfactant, and a brightener system comprising at least one, preferably one to four and in particular two optical brighteners, and a outer shell containing a dye comprises.

18. Granules according to claim 16 or 17, characterized in that a buffer system is contained in the inner shell, which preferably has a pH of 4 to 11 and in particular a pH of 5 to 0.1 as aqueous 0.1 M aqueous buffer solution 9 has.

19. Granules according to one of claims 16 to 18, characterized in that in the inner shell of at least one of the optical brightener, preferably all optical brightener has a mean particle diameter d ₅₀ <10 microns / have.

20. Use of a preparation comprising a binder, which preferably contains surfactant, preferably nonionic surfactant, and optical brightener for staining a carrier material, preferably for staining detergent or cleaning agent granules or a component thereof.