EP2007863A1

EP2007863A1 - Granulates for a sensitive washing- or cleaning agent containing material

Info

Publication number: EP2007863A1
Application number: EP07728143A
Authority: EP
Inventors: Peter Schmiedel; Petra Padurschel; Heribert Kaiser; Anette Nordskog; Wolfgang Von Rybinski; Regina Stehr; Karl-Heinz Maurer; Cornelius Bessler; Sören HÖLSKEN; Rolf Tenhaef
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-04-20
Filing date: 2007-04-16
Publication date: 2008-12-31
Anticipated expiration: 2027-04-16
Also published as: DE102006018780A1; ATE529499T1; EP2007863B1; JP2009534493A; WO2007122126A1; PL2007863T3; US20090156454A1; ES2373994T3

Abstract

Granulates for washing- or cleaning agents, containing (a) a sensitive washing- or cleaning agent component, (b) an adsorbent carrier material, (c) a binder that is different from (b), and (d) optional additional substances that are different from (b) and (c). The granulates display a disintegration index of at least 50 percent after 24 hours. These granulates are particularly suited for use in liquid- or gel-forming aqueous washing- or cleaning agents. Also, a procedure for the manufacture of such granulates, in regards to washing- or cleaning agents.

Description

Granules of a sensitive detergent or cleaning agent ingredient

The present application relates to granules of sensitive detergent or cleaning agent ingredients, to processes for producing such granules, to corresponding detergents and cleaners and to the use of suitable components for producing such granules.

For the preparation of sensitive detergent ingredients, in particular of enzymes in solid form, there is an extensive state of the art. These include particles or better, because consisting of several ingredients: granules (granules, granules), which in their sum give the form of preparation of the granules. For the preparation of detergents and cleaners, it is customary to incorporate a wide variety of ingredients in the form of granules in appropriate, usually solid means.

A fundamental alternative to this is the preparation of enzymes in liquid form, which are usually incorporated into predominantly liquid or gel detergents and cleaners. However, in this form they are not physically protected against the negative effects of other ingredients of the detergents and cleaners in question. This disadvantage can be compensated for some ingredients by adding chemical agents; For example, by adding inhibitors, proteases are prevented from hydrolyzing other enzyme molecules. The negative effects of alternating freezing and thawing can be compensated for example by the addition of polyols. However, other ingredients, particularly bleaching agents, are difficult to prevent from adversely affecting sensitive ingredients during storage.

In order to protect enzymes as well as other sensitive ingredients in predominantly liquid or gel detergents and cleaning agents against the influence of other ingredients, various solutions are proposed in the prior art. One is to design the recipe as a whole accordingly. For example, WO 2004/110610 A1 discloses the stabilization of peroxycarboxylic acids in a surfactant-containing, aqueous dispersion by minimizing the halide ion content, by lowering the pH to acidic to neutral pH values, by minimizing the content of free or active surfactants, minimizing the Niotensidgehalts, addition of complexing agents, addition of catalases, adding a Solvent with low solubility for peroxycarboxylic acids, etc. Thus, it is aimed so far as possible not to use potential reactants, reduce the resolution of the peroxycarboxylic acid over a lonenstärkeregulation and to slow down the hydrolysis reaction by water.

Another approach is to encapsulate the aggressive ingredient so that it can not interact with any other ingredient during storage of the liquid agent. For example, WO 2004/110610 A1 discloses a storage-stable, multilayered polyelectrolyte capsule system for coating particles with organic peroxycarboxylic acids. WO 2004/110612 A1 describes capsules of this type which have a capsule shell based on at least one inorganic salt such as, for example, a sulfate. A further alternative to this is provided by the formulation forms of the bleaching agent described in WO 2004/110611 A1: gel capsules which contain the organic peroxycarboxylic acids are evident therefrom. However, these approaches lead to unsatisfactory results with regard to the storage stability of the enzymes. In particular, at storage temperatures of 35 ° C increases in almost all these solutions, the concentration of dissolved bleach soon after the preparation of the formulations to a barely acceptable value.

A fundamentally different approach is to add the sensitive ingredients in the form of solid granules to the liquid detergents and cleaners. This idea is based on the extensive experience gained in the production of enzyme granules for use in solid media. In fact, enzyme granules are often described in the art for use in detergents and cleaners, but rarely are there any mention of liquid agents; For the most part, it is generally spoken of detergents and cleaners, without deliberately distinguishing between liquid and solid means. This is due to the fact that liquid and gel remedies have only been intensively developed for a few years now, and in older documents of the State of the art has been virtually always assumed by solid means. As a rule, however, granules developed for solid compositions are not suitable for incorporation into liquid, in particular water-containing, compositions, since they are not physically stable there, ie they rapidly disintegrate under the action of the solvent.

The enzymes are added to liquid agents in solid form, as disclosed in WO 99/00471 A1 and WO 99/00478 A1. In both cases, the enzymes are formulated into so-called PrNIs, which are also customary for use in solid media, that is to say without a protection which goes beyond this solid form. However, both are anhydrous. The first of these applications teaches here the teaching of matching these solid particles with respect to their density to that of the medium, that is below 1.7 g / ml, in order to ensure a sufficient stability of the particles during storage. The second of these applications teaches in this connection the doctrine to increase the cleaning performance of the enzymes contained by adding the compound ethylenediamine-N, N'-disuccinic acid (EDDS) or salts thereof.

The following developments focused on covering the enzyme granules or particles with other ingredients additionally with a protective coating. For example, WO 00/29534 A1 discloses the production of granules in which different layers are applied to an inert core or carrier. This may also include an enzyme layer, which is obligatorily covered to the outside by one or more protective layers. As protective layers for the enzyme herein are disclosed the materials titanium dioxide, methyl cellulose (Methocel A15), polyethylene glycol (PEG 600), polyvinyl alcohol (Elvanol 51 -05) and a specific nonionic surfactant (Neodol 23-6.5). According to the description, these granules have high stability values and low dust levels. The applicability in liquid, and anhydrous or mainly anhydrous means is claimed, but not proven. A possible use for predominantly aqueous agents is not considered at all.

PEG-containing coatings for enzyme-containing granules for this application example, for example, WO 96/38527 A1 and WO 97/391 16 A1. The PEG-containing layer may also contain titanium dioxide in each case. A fundamental one Interchangeability of PEG and PVA for these purposes is disclosed, for example, in WO 00/63336 A1.

A liquid applied coating system for sensitive ingredients, which can also enter into aqueous agents, also discloses EP 1586241 A1. It consists of 60-95% by weight of wax, 3-25% by weight of fatty acid, 0-20% by weight of additives and content of alkali metal ions sufficient to be at least 70% of the total amount of free To neutralize carboxyl groups of the fatty acid. That is, it is a wax / soap / fatty acid mixture.

It is also described in the prior art to encapsulate the sensitive ingredients in hydrophobic or waxy materials or even to establish multiphase systems. Thus, according to WO 01/23513 A1, enzymes can be encapsulated in a wax and added in this form to liquid detergents and cleaners, the agents disclosed in this application being virtually anhydrous.

The application EP 356239 A2 discloses a system according to which enzymes are evenly distributed or coated in a protective special polymer material (matrix) (polymeric shell). These are physically stable when stored in a low-water, liquid detergent or cleaning agent, which ensures the integrity of the enzymes, and they disintegrate only at the moment of dilution with water at the beginning of the washing process. Basically, the same solution WO 92/20771 A1 discloses for liquid detergent formulations with a water content of up to 60 wt .-%.

The applications WO 2005/028603 A1 and WO 2005/028604 A1 disclose liquid detergents and cleaners having a water content of up to 70% by weight, in which the enzymes contained are stabilized by being encapsulated in a gel. This is each formed by using special silanes. Even in these cases, it comes during storage to protect the encapsulated ingredients and only on dilution in the aqueous wash to release them. The application US 2005/0245418 A1 describes the encapsulation of enzymes in a water-soluble gel for use in aqueous detergents and cleaners.

From EP 653485 A1 it is apparent to dissolve or suspend sensitive ingredients such as enzymes in an oil and to include these oil drops in polymer capsules. These capsules are designed so that they can be added to a liquid medium, for example a detergent with up to 35 wt .-% water and only then burst open and release their contents, if in the wash liquor further dilution takes place.

Another compartmentalization method is shown in WO 03/106607 A1. Thus, enzymes or enzyme crystals in the aqueous phase can be stably maintained by surfactants in a hydrophobic silicone environment, with the silicone phase in turn being stabilized via surfactants in a hydrophilic outer phase.

The established methods for the preparation of chemically sensitive ingredients, in particular enzymes for use in liquid or gel, especially water-containing detergents or cleaners are unsatisfactory: either it is liquid and thus chemically very susceptible packaging, it must be on a part of the otherwise desired active substances , in particular bleach are dispensed with, it is physically or chemically unstable granules or they are stable only by very complex, that is consuming and expensive coating systems. This problem is illustrated by the fact that currently virtually no liquid or gel, water, bleach and enzyme-containing detergents or cleaning agents are commercially available.

There is therefore still a need for methods for the largely stable packaging of particular enzymes for use in liquid or gel detergents or cleaners, especially in water-containing agents. In particular, there is a need for comparatively inexpensive, that is inexpensive, packaging methods, for example, without adding more expensive stabilizing compounds such as in liquid preparations or without expensive polymer chemical encapsulation techniques as in the case of solid preparations, and without having to dispense with the washing or cleaning agents in which the sensitive ingredients are to be used, some of the otherwise desired active substances, in particular bleach ,

Against this background, the task a confectioning form to develop, in which sensitive ingredients, especially enzymes during storage in detergents and cleaners, especially in liquid and very particularly in aqueous detergents and cleaners against inactivation, for example, by aggressive, especially bleaching Ingredients are sufficiently protected. It should advantageously also be comparatively inexpensive feasible.

This object is achieved by a granulate of a sensitive detergent or cleaning agent ingredient, containing the components:

(a) the sensitive detergent or cleaning agent ingredient,

(b) a particulate carrier material (adsorbent),

(c) one of (b) different ingredient as binder and

(D) optionally further, different from (b) and (c) ingredients, which has a disintegration index of at least 50% after 24 hours.

These granules are characterized by the fact that they are physically largely stable, especially in liquid or gel detergent or cleaner formulations and, moreover, represent an effective protection against other compounds. Thus, as evidenced in the examples of the present application, the activities of the enzyme components granulated in this way in otherwise liquid compositions are kept at a high level for a surprisingly long time. In particular, there is protection against bleach contained in such agents. In addition, when used in detergents and cleaning agents at the moment of their use, they show a good disintegration and dissolution behavior and allow a rapid release of the substances contained, virtually without leaving any residue on the laundry. In addition, they are relatively easy to produce. For the purposes of the present invention, a granulate is a solid form of preparation in which a plurality of ingredients - in this case components (a), (b), (c) and optionally (d) - are not in the form of a powder but in the form of discrete particles or granules (granules, granules). In sum, these are referred to as granules. Granules generally have no harmonious geometric shape; their surface can be rather smooth, uneven or even jagged. The mass is in many cases more or less porous.

Preference is given to granules whose granules have a largely uniform size and / or approximately spherical shape.

Production processes for granules are known per se to the person skilled in the art. For example, in Chapter 6 ("Production of Powdered Detergents") of the article "Laundry detergents" in Ullmann's Encyclopedia of Industrial Chemistry (Wiley, VCH, 2005), various methods known in the art for compounding various chemical compounds, in particular for use in Washing and cleaning agents described. Among them, the method of extrusion is listed, with the comparatively high densities and low-dust products can be achieved. According to this compilation, extrusion is also applicable to the preparation of sensitive ingredients such as enzymes. In accordance with the invention, this is particularly advantageous because the thermal load on the enzyme preparation can be kept low. In principle, all known processes for extrusion are applicable according to the invention. Preference is thus given to those granules according to the invention which can be designated as extrudates at the same time as a result of this preparation process.

A process which is alternative to extrusion is described, for example, in the manual "Fluidized bed spray granulation" by H. Uhlemann and L. Mörl, Springer-Verlag, Berlin, Heidelberg, New York, 2000, Chapter 1 (Basics of Fluidized Bed Spray Granulation), S. 69 to 126. and chapter 8 (process variants), pp. 219 to 244.

For the purposes of the present invention, a sensitive detergent or cleaning agent ingredient (a) is to be understood as meaning any compound which, as part of a washing or detergent formulation makes a positive and in itself desirable contribution to the washing or cleaning performance of the agent concerned and which can be impaired by the action of at least one other substance of the same formulation or other acting substances (such as from the air or the packaging material) in terms of their performance. Examples of such sensitive detergent or cleaner ingredients are:

Enzymes (for example proteases, amylases or cellulases) which can be at least partially inactivated, for example, by bleaching ingredients;

Fragrances or perfumes (for example, alcohols, aldehydes, ketones, esters or unsaturated compounds), for example, by oxidizing

Ingredients can be converted into the corresponding different or non-fragrant derivatives, such as the carboxylic acids; optical brighteners (for example, biphenyl derivatives with condensed

Double bonds), which can lose the fluorescence capability by forming adducts via the double bonds;

Bleach activators (for example, peracids) which can react by premature, that is, already during storage reaction with the bleaching agent, so that the means lose an overall bleaching capacity.

It is characteristic of the invention that the sensitive detergent or cleaning agent ingredient is processed together with components (b) and (c) into a largely uniform granulate.

For the purposes of the present invention, a particulate carrier material (b) is a solid, room-temperature, pulverulent or particulate material prior to incorporation in granules according to the application, which is chemically inert to such an extent that it is below the production, processing and Storage conditions of the granules reacts with any other of the ingredients of the granules or agent in an affecting the overall efficiency of the granules extent. Due to its structure, it is capable of physically binding liquids or gelatinous or pasty substances to its surface to a certain extent, so that it can also be referred to as an adsorbent in connection with the present invention. These include inorganic substances such as clays, silicates or sulfates, in particular talc, silicic acid, metal oxides, in particular aluminum oxides, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites) and / or titanium dioxide. These include organic compounds such as polyvinyl alcohol (PVA) in particular at least partially hydrolyzed PVA. It is particularly advantageous if these compounds fulfill an additional benefit, for example a builder function when using the washing or cleaning agent. PEG has not been found to be particularly advantageous so that it is at least not included in the present invention as a characterizing feature of a preferred embodiment of the adsorbent, and most preferably is not included as part of the adsorbent.

For the purposes of the present invention, a binder (c) is a solid, pasty (waxy) or liquid material which is chemically inert to such an extent that it can not be mixed with any other of the conditions of manufacture, processing and storage of the granules Ingredients of the granules or agent in an affecting the overall effectiveness of the granules extent reacts. It is one of (b) different stuff. It is or becomes at least so viscous under the conditions of granule production, that it virtually glues the other ingredients together. In this case, in particular, the physicochemical interaction with the adsorbent of importance, which causes the resulting mass to a total of homogeneous phase, which is then convertible into individual granules. In this pulp, which is predominantly formed by the adsorbent and binder components, the other ingredients and in particular the ingredient to be formulated are included. In particular, the interaction between the two components (b) and (c) is responsible for the physical stability of the granule particles.

Suitable binders are inorganic or organic substances which have the properties described, for example non-crosslinked, polymeric compounds selected from the group: polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, polysaccharides or substituted polysaccharides, especially cellulose ethers, polyvinyl alcohols (PVA), preferably partially hydrolyzed polyvinyl alcohols and / or ethoxylated polyvinyl alcohols and their copolymers and mixtures. Polyethylene glycol has not been found to be particularly advantageous in this regard, so that it is not a preferred embodiment of the binder and most preferably is not included as part of the binder.

Some compounds such as PVA are suitable both as component (b) and as component (c) due to their adsorption properties and their co-existing binding effect. They can be used according to the invention as (c) if they have not already been presented as (b).

For the purposes of the present invention, optionally further ingredients (d) are in principle to be understood as meaning all compounds which are chemically inert to such an extent that they are not subject to any of the ingredients of the granules or composition in any of the conditions of preparation, processing and storage of the granules react to the overall effectiveness of the granules impairing extent.

A significant proportion of these optional ingredients are plasticizers. These are compounds or mixtures that can be added to improve the manufacturing process of the granules. In particular, they exert a physico-chemical effect on the viscosity and / or plasticity (tensile strength of the auturing strand in the extrusion, etc.) of the granules to be granulated. Preferably, they account for a weight fraction of 0-50 wt .-% (based on the granules). Preferably, they are selected from the following group: water-dispersible organic compounds, water-dispersible organic polymers, polyethylene glycols (PEG), in particular short-chain PEG, fatty acids or salts of fatty acids, thacetin and / or triethyl citrate or polyfunctional alcohols such as 1, 2-propanediol or glycerol.

A noteworthy proportion of these optional ingredients also have solubility improvers (also called swelling agents, disintegration aids or disintegrants). These are compounds or mixtures that can be added to improve the solubility of the granules the moment they are According to the invention actually disintegrate, namely at the moment of application of the agent concerned. For washing and cleaning agents are generally used in dilute form, that is added to an aqueous wash liquor. In this moment of strong dilution with water, water diffuses into the granules, which then burst open and release their ingredient, so that it can take effect. By adding solubility enhancers, this disintegration process can be improved.

It can also be done in this way, a temporal regulation, such as in the form that the granulated ingredient is only slightly later than one or more other ingredients of the agent in solution. Thus, it is an embodiment of the present invention, for example, when granulated enzymes against a bleaching agent otherwise contained in the agent with a time delay to the effect, so that a part of the bleaching agent has already reacted in the wash liquor and the enzyme is not so much affected. Of course, the bleaching agent or the bleach activator can be brought into action in a similar manner with a time delay.

Preferably, the solubility enhancers make up a weight fraction of 0-50% by weight (based on the granules). Preferably, they are selected from the following group: water-soluble inorganic salts, monosaccharides, preferably glucose, oligosaccharides, and swelling agents, especially compounds suitable as disintegrating agents, in particular cellulose, compacted cellulose, cellulose derivatives and / or crosslinked organic polymers, preferably crosslinked polyvinylpyrrolidones or crosslinked polyacrylates.

Further components of these optional ingredients include, for example, water, enzyme stabilizers, dyes, color pigments, pH buffer substances, antioxidants, density regulating compounds and / or other ingredients. Preferably, they account for a weight fraction of 0-40 wt .-% (based on the granules).

Among the optionally present ingredients may also be, for example, resulting from the enzyme production and not completely separated fermentation media components. Their presence is especially then advantageous if they exert a stabilizing influence on the enzyme. If the ingredient is a more complicated chemical compound, such as a perfume, it may also be associated with other intermediates or stereoisomers resulting from the synthesis and not completely separated.

Other ingredients may be compounds which exert an additional effect in the context of the later intended use for the granulate in a washing or cleaning agent and which may thus also be referred to as a "benefit agent".

In the production of the granules, water is generally supplied merely as an ancillary substance, for example via the aqueous enzyme preparation. In particular during extrusion, a certain amount of water can give the pulp to be processed a favorable consistency. Furthermore, when the granule particles are stored in an aqueous medium, a certain equilibrium content of water is established which, however, does not impair the overall integrity of the particles. In the desired dissolution process, that is at the moment of a strong dilution of the agent in an aqueous liquor, the proportion of water increases so suddenly that the particles completely disintegrate.

An ingredient also included in (d) is thus water. The water content of the granules is regulated in particular by the manner of their preparation. For example, in fluidized-bed spray granulation, an aqueous mixture of ingredients removes a substantial portion of the water by evaporation. In particular, in the production of granules by extrusion of a plastic mass, in which usually no drying step takes place, the water content of the granules over the introduced compounds, for example, an incorporated liquid enzyme preparation is controlled.

Enzyme stabilizers are contained in enzyme-containing granules as preferred further ingredients in particular. They serve especially during storage as protection against damage such as inactivation, denaturation or decay, for example 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. Preferred granules of the invention (or agents, see below) contain stabilizers for this purpose.

One group of stabilizers are reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are frequently used for this purpose, including, in particular, derivatives with aromatic groups, for example ortho, meta or para-substituted phenylboronic acids, in particular 4-formylphenylboronic acid, or the salts or Esters of the compounds mentioned. Also peptide aldehydes, that is, oligopeptides with reduced C-terminus, in particular those of 2 to 50 monomers are used for this purpose. Among the peptidic reversible protease inhibitors include ovomucoid and leupeptin. Also, specific, reversible peptide inhibitors for the protease subtilisin and fusion proteins from proteases and specific peptide inhibitors are suitable.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable for this purpose. Some organic acids used as builders can additionally stabilize an enzyme.

Lower aliphatic alcohols, but especially polyols, such as glycerol, ethylene glycol, propylene glycol, sorbitol or di-glycerol phosphate are other frequently used enzyme stabilizers against physical influences. Likewise, calcium and / or magnesium salts are used, such as calcium acetate or calcium formate.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide-containing polymers act simultaneously as Enzyme stabilizers and as color transfer inhibitors. Other polymeric stabilizers are linear Cβ-C-iβ polyoxyalkylenes. Also, alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and, preferably, are capable of additionally increasing their performance. Crosslinked N-containing compounds preferably perform a dual function as soil release agents and as enzyme stabilizers. Hydrophobic, nonionic polymer stabilizes in particular an optionally contained cellulase.

Reducing agents and antioxidants increase the stability of the enzymes to oxidative degradation; For example, sulfur-containing reducing agents are familiar, for example sodium sulfite and reducing sugars.

Particular preference is given to using combinatons of stabilizers, for example of polyols, boric acid and / or borax, the combination of boric acid or borate with reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is favorably enhanced by the combination with boric acid and / or boric acid derivatives and polyols, and still further by the additional action of divalent cations, such as calcium ions.

Dyes may be added to improve the aesthetic appearance of the granule particles or to draw on the laundry during use of the detergent or cleaner. They are advantageously incorporated so that they are evenly distributed throughout the particle. They are known per se in the prior art.

Color pigments can also serve to enhance the aesthetic appearance of the granule particles. They can also be distributed uniformly in the particle. In this case, however, in particular the aspect is in the foreground to cover the particle surface with color pigments in order to cover the intrinsic color of the granules. This too is known per se in the prior art. A commonly used white pigment is titanium dioxide. pH buffer substances can be incorporated to protect the respective ingredients during storage against pH influences such as from the surrounding medium. However, they can also be incorporated in order to emerge from the particle into the wash liquor at the same time as the ingredient is being used, and then to influence the pH of the wash medium. In this way, a pH value shift can be triggered, for example, to improve its effectiveness at the same time as the release of an enzyme with a certain pH activity profile.

In particular, antioxidants can be incorporated to provide protection against atmospheric oxygen or other oxidizing compounds during storage.

The use of density-regulating compounds in granules is known per se. For example, by adding perlite, starch or feather particles, the density can be reduced or the density can be increased by adding clay or silicate crystals. This is advantageous for matching the bulk density of the particles to the bulk density of solid detergents and cleaners in order to prevent segregation processes during transport or storage. With regard to an intended use of the granules in liquid or gel compositions, an adjustment to the density of the agent concerned can be achieved in the same way so that the granules are homogeneously distributed macroscopically homogeneously in the agent in question and ideally neither sediment nor float on the surface.

For the purposes of the present invention, disintegration is to be understood as meaning the disintegration of the granules that is to be observed macroscopically. A slight, which does not significantly affect the activity of the granulated ingredients, possibly swelling of the granules in a strongly water-containing environment is not meant hereby and can certainly be observed with granules according to the invention. It is also in accordance with the invention, when a slight abrasion occurs, which is optionally observed in a liquid or gel preparation containing the particles of the invention as a suspended matter and / or leads to a slight turbidity. It is crucial that after the period of storage under consideration can still speak of a discrete granules, which coincides with The naked eye can be distinguished as a separate solid, particulate phase, in particular, from the sodium sulfate / sodium citrate solution used as a reference according to the invention.

For the purposes of the present invention, storage means storage of the respective mixture at a constant 23 ° C. for at least 24 h and increasingly preferably for at least 30 h, 36 h, 42 h, 48 h, 3 days, 4 days, 5 days, 6 days and most preferably for at least 7 days to understand. It takes place in an outwardly hermetically sealed, not evacuated vessel, wherein the volume of the air phase does not exceed that of the measuring liquid. The reference system is an aqueous buffer system consisting of 16% sodium sulfate and 3% sodium citrate, pH 5.0 ± 0.1.

For experimental verification, whether no disintegration according to the invention has taken place after this period, the liquid containing the granules is subjected to a sieve test. It is quantitatively given without applying a pressure or vacuum through a sieve having a smaller mesh size than the granules, so that the granules are retained by the sieve. For example, the mesh size of the screen may be 280μm. The sieve is washed with an equal sodium sulfate / sodium citrate solution and finally with dist. Rinsed with water. A performance of this detection is described in Example 11, which was additionally shaken during incubation at low speed, which is not absolutely necessary according to the invention. A non-disintegration according to the invention is then considered when more than 50% by weight of the initially weighed-in particle mass (before stirring into the solution) remains on the sieve after the sieve residue has dried. More preferably, more than 60, 70, 80, 90 and most preferably more than 95% of the originally weighed particulate mass remains on the screen.

The disintegration index for the particles in question is defined as the quotient of the particle mass (residue) left on the sieve and the originally weighed particle mass and is given as weight% residue, the residue being determined after the particles have been incubated at 23 ° C. aqueous Buffer system consisting of 16% sodium sulfate and 3% sodium citrate in water, pH 5.0 ± 0.1 were stored over a defined period of time. The period is at least 24 hours, and more preferably at least 30 hours, 36 hours, 42 hours, 48 hours, 3 days, 4 days, 5 days, 6 days, and most preferably at least 7 days. The numerical value of the disintegration index is therefore the higher, the fewer particles are disintegrated during the storage period and are not retained on the sieve. A non-disintegration according to the invention is present when the disintegration index is at least 50%. Increasingly, the disintegration index is 60, 70, 80, 90, and most preferably more than 95%.

The solution according to the invention can be applied to all ingredients specified above in connection with the present invention. Because they are all fundamentally equally endangered, especially against oxidation, and are protected according to the invention in principle in the same way.

In a particular embodiment of the enzyme granules, the extent of disintegration can not be related to the substantial retention of the mass of the particles, but to the maintenance of the enzyme activity. The enzyme activity can be determined depending on the processed enzyme according to known methods. Thus, it has been shown experimentally that in the granules described in the examples not only the majority of the initially weighed particle mass (before stirring into the solution) remained on the sieve, but also a large part of the enzymatic activity. This is more than 50%, and more preferably more than 60, 70, 80, 90, and most preferably more than 95%. In contrast, prior art granules, structurally different in structure, exhibited significantly worse values, including those with an inert core (of MgSO ₄ ) on top of which an enzyme-containing layer was coated. These particles showed in the sieving test given above a seemingly quite substantial physical stability (although not more than 50% according to the sieving test given above), but the enzyme-containing layer was washed off quickly, so that these granules are useless for the purpose here according to the invention. Preferred embodiments of the present invention form such granules according to the invention, wherein the components (b) and (c) in a wt .-% ratio of (b) to (c) of 1: 50 to 50: 1, preferably 1:20 to 20: 1, more preferably from 1: 5 to 5: 1.

For the described interaction of these two components results especially in these relations. Particularly suitable weight ratio ratios encompassed by these ranges are those shown in the examples of the present application.

Concrete mixing ratios are to be optimized experimentally in a particular case that on the one hand not too large excess of adsorbent remains, which makes the mass to be brittle, and on the other hand no excessive excess of binder remains, which could lead to the resulting mass to sticky and difficult to process. It should be considered that also the other components exert an influence on the nature of the material and the granule particles according to their respective properties.

Preferred embodiments of the present invention form such granules according to the invention containing the components:

(a) the sensitive detergent or cleaning agent ingredient,

(b) 10 to 80% by weight of a particulate carrier material (adsorbent),

(c) 3-50% by weight of one of (b) different ingredients as a binder and

(d) as optional further ingredients different from (b) and (c): 0-50% by weight (relative to the granules) plasticizer,

0-50 wt .-% (based on the granules) Löslichkeitsverbesserer (swelling agents, disintegration aids, disintegrants), and / or 0 - 40 wt .-% (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, Antioxidants, density regulating compounds and / or other ingredients. Individual, in each case preferred components for these components have already been stated above and are also listed below as correspondingly preferred embodiments in each case once again. It is particularly advantageous to use a combination of two or three of the said substances from each of these groups, in particular that of the adsorbent and that of the binder.

A substance that can be used for several of these components can only be counted once, so that in each case a granulate according to the invention is always at least a mixture of components (a) with (b) and a different component (c). is. The essence of the invention is to obtain granules with favorable properties in such a way that adsorbents and binders are matched to one another in a complementary manner. When adding further optional components or differently prepared components (a) (for example enzyme preparations having different total protein or water contents), an optimum of the respective proportions must be determined experimentally. As a guideline for this purpose, the sieving test indicated above after appropriate storage in said sodium sulfate / sodium citrate solution.

When used in the abovementioned proportions, advantageous stabilization effects were observed on the basis of enzyme-containing granules. Thus, from Example 1 of the present application go granules with about 5 wt .-% of component (a) (enzyme), 36 wt .-% of component (b), 18 wt .-% of component (c) and under ( d) a proportion of 31 wt .-% plasticizer and about 10 wt .-% water. A portion of the particulate carrier material, namely the TiO ₂ , which in itself accounts for 13% by weight of the total mass of the granules, also serves as a color pigment in the formulation given there. From Example 2 of the present application are granules with about 5 wt .-% of component (a) (enzyme), 31 wt .-% of component (b), 22 wt .-% of component (c) and below (d ) a proportion of 24 wt .-% plasticizer, 8 wt .-% Löslichkeitsverbesserer and about 10 wt .-% water. A part of the particulate carrier material, namely the TiO ₂ , which in itself accounts for 8% by weight of the total mass of the granules, also serves as a color pigment in the formulation specified therein. Example 3 discloses granules with only about 5 wt .-% of component (a) (enzyme), 78 wt .-% of different Components (b), 7 wt .-% of component (c) and a water content (d) of about 10 wt .-%.

As can also be seen from example 3, proportions of adsorbent (b) above 50% by weight, preferably above 60% by weight and especially above 70% by weight, are particularly advantageous if the optional further ingredients are used (d) is largely dispensed with, that is, together they make up less than 40% by weight, preferably less than 30% by weight and more preferably less than 20% by weight of the granules.

Preferred embodiments of the present invention form such described granules according to the invention, wherein the sensitive detergent or cleaning agent ingredient (a) is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme is.

These groups of substances have already been listed above, but will be explained in more detail here.

Fragrances are added to laundry detergents or cleaners to improve the aesthetics of the products and provide consumers with a visually and sensory "typical and unmistakable" product in addition to washing or cleaning performance. In particular, it may be desirable to give the laundry, for example the textile, a specific fragrance which is retained even after the washing process has ended.

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 odor of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out) divided. Since the perception of smell is based to a large extent on the odor intensity, the top note of a perfume or fragrance is not only from volatile compounds, while the base note for the most part consists of less volatile, that is adherent fragrances. For example, in the composition of perfumes, more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly. In the subsequent classification of the fragrances in "more volatile" or "adherent" fragrances so nothing is said about the olfactory impression and whether the corresponding fragrance is perceived as the head or middle note.

As fragrances, individual fragrance compounds, for example, the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. 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, LiNaI and Bourgeonal, to the ketones, for example, the Jonone, α-lsomethylionon and methyl - Cedryl ketone, 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 perfumes may also contain natural fragrance mixtures such as those available from vegetable sources, for example, 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. Usually, the content of detergents or cleaners of fragrances is up to 2% by weight of the total formulation. In the design of granules according to the invention, suitable for the use in detergents and cleaners are provided, this must be considered accordingly.

Alternative embodiments of the present invention are granules of optical brighteners. This class of ingredients, especially for textile detergents, leads to a perceived positive impression of the cleaned laundry.

Preferred embodiments of this aspect of the invention are derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which replace the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned brightener can be used. Particularly suitable are mixtures of optical brighteners of a distyryl-biphenyl derivative and a stilbentriazine derivative. These brightener types can be used in any desired mixing ratios. Such brighteners are available, for example, under the trade name Tinopal from Ciba.

In order to achieve a good bleaching effect when washing at temperatures of 60 ° C and below, and in particular during the laundry pretreatment, detergents may also contain bleach activators. Due to their reactivity, it is within the scope of the present invention to formulate these ingredients in the form of granules according to the invention.

As bleach activators, it is 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 1, 3,4,6 Tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC ), Carboxylic acid anhydrides, in particular phthalic anhydride, isoic anhydride and / or succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran and enol esters and acetylated sorbitol and Mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetyl lxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoylcaprolactam and N-acetylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzene sulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA).

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

in the R ^{1 is} -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 alkenylaryl radical with 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.

Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R 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 )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , or (HO-CH ₂ - CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{" are} particularly preferred, whereby from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" in which X ^{" represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred. Bleach activators can in the usual amount range from 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on the total washing or Detergent composition, be included. In the design of granules according to the invention, which are intended for use in detergents and cleaners, this must be taken into account accordingly.

Preferred embodiments of the present invention are granules of enzymes. This inherently established class of ingredients, depending on their respective specificity, leads to a corresponding improvement in the cleaning performance of the agents concerned. These include in particular proteases, other amylases, lipases, hemicellulases, cellulases or oxidoreductases such as peroxidases and / or perhydrolases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents or cleaning agents, which are preferably used accordingly.

Agents provided with granules according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-8 to 5 weight-percent, based on active protein. In the design of granules according to the invention, which are intended for use in detergents and cleaners, this must be taken into account accordingly.

The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method (AG Gornall, CS Bardawill and MM David, J. Biol. Chem., 177 (1948), pp. 751-766).

With regard to the use of the granules according to the invention in the context of detergents and cleaners, component (a) comprises one or more hydrolytic enzymes and / or oxidoreductases, more preferably α-amylases, proteases, lipases, cutinases, hemicellulases, cellulases, β-glucanases, Oxidases, catalases, peroxidases and / or laccases, among these particularly preferred oxidation-stabilized α-amylases, proteases, lipases, cutinases, hemicellulases, cellulases, β-glucanases, oxidases, peroxidases and / or laccases.

Preferred embodiments of this article form such enzyme granules, wherein the enzyme is one or a mixture of the following enzymes: protease, amylase, cellulase, hemicellulase, oxidase and perhydrolase, preferably an oxidation stabilized of these respective enzymes.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. Of the protease from Bacillus lentus DSM 5483 (WO 91/02792 A1) the listed under the name BLAP ^® variants, particularly in WO 92/21760 A1, WO 95/23221 A1, WO 02/088340 A2 and WO 03 derive, / 038082 A2. Other useful proteases from various Bacillus sp. and B. gibsonii are apparent from the patent applications WO 03/054185 A1, WO 03/056017 A2, WO 03/055974 A2 and WO 03/054184 A1.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. Examples of amylases which can be prepared according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus, and also their further developments improved for use in detergents or cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and variants derived from the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore, the α-amylase from Bacillus sp. Disclosed in the application WO 02/10356 A2 for this purpose. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948) described in the application WO 02/44350 A2. Furthermore, the amylolytic enzymes which belong to the sequence space of α-amylases, which is defined in the application WO 03/00271 1 A2, and those which are described in the application WO 03/054177 A2 can be used. Similarly, fusion products of the molecules mentioned can be used, for example those from application DE 10138753 A1 or point mutations thereof.

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Further usable commercial products are, for example, the amylase LT ^® and Stainzyme ^® , the latter also from the company Novozymes. Variants of these enzymes which can be obtained by point mutations can also be incorporated into granules according to the invention.

Granules according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to obtain suitable ones Precursors generate in situ peracids. 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. They are for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Granules according to the invention, especially if they are intended for the treatment of textiles, contain cellulases, depending on the purpose as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components complement each other advantageously with regard to their various performance aspects. These aspects of performance include, in particular, contributions to the primary washing performance, to the secondary washing performance of the composition (anti-deposition effect or graying inhibition) and finishing (fabric effect) up to the exercise of a "stone-washed" effect.

A useful fungal, endoglucanase (EG) -rich cellulase preparation, or its further developments are offered by Novozymes under the trade name Celluzyme ^®. The products Endolase® ^® and Carezyme ^® available also from Novozymes based on the 50 kD EG and 43 kD EG applicable from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ^® and Renozyme ^®. The latter is based on the application WO 96/29397 A1. Performance-enhanced cellulase variants are disclosed, for example, in the application WO 98/12307 A1. Likewise, the cellulases disclosed in the application WO 97/14804 A1 can be used; For example, it revealed 20 kD EG Melanocarpus, available from AB Enzymes, Finland, under the trade names Ecostone® ^® and Biotouch ^®. Further commercial products from AB Enzymes are Econase® ^® and ECOPULP ^®. Other suitable cellulases from Bacillus sp. CBS 670.93 and CBS 669.93 are disclosed in WO 96/34092 A2, wherein those derived from Bacillus sp. CBS 670.93 from the company Genencor under the trade name Puradax ^{® is} available. Further commercial products of the company Genencor are "Genencor detergent cellulase L" and lndiAge ^® Neutra.

Granules according to the invention for use in detergents or cleaners can, in particular for the removal of certain problem soiling, comprise further enzymes which are combined under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases, for example, under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes, under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA and under the name Purabrite ^® from Genencor Int., Inc., Palo Alto, CA, USA. A suitable β-glucanase from a B. alcalophilus is disclosed, for example, in the application WO 99/06573 A1. The .beta.-glucanase obtained from B. subtilis is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, granules according to the invention may also contain oxidoreductases, for example oxidases, oxygenases, catalases (which react at low H ₂ O ₂ concentrations as peroxidase), peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. As example systems for enzymatic perhydrolysis which can be used advantageously, reference is made to the application WO 98/45398 A1. Particularly useful for such a system Choline oxidases are disclosed, for example, WO 2004/058955 A2. Modified proteases having pronounced perhydrolase activity, which can also be advantageously used at this point, in particular for achieving mild bleaching in textile detergents, are disclosed in the application WO 2004/058961 A1. A combined enzymatic bleaching system comprising an oxidase and a perhydrolase describes the application WO 2005/124012. Further perhydrolases which can be used according to the invention are also disclosed in WO 2005/056782 A2. 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 (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

In the context of the present invention, particular preference is given to those granules which contain an enzymatic bleaching system according to International Patent Application WO 2005/124012 or a component thereof. A preferred embodiment of the invention thus constitute granules which contain part of an enzymatic bleaching system comprising at least one oxidase and at least one perhydrolase, wherein the oxidase is selected from a) choline oxidases whose amino acid sequence is identical to those in the international

Patent application WO 2005/124012 in SEQ ID NO. At least 76.5%, more preferably at least 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 97% 98%, 99% and particularly preferably 100%, b) choline oxidases, whose amino acid sequence with that in the international

Patent application WO 2005/124012 in SEQ ID NO. 4 amino acid sequence to at least 89%, increasingly preferably at least 90%, 92%, 94%, 95%, 96%, 97%, 98%, 99% and particularly preferably 100% matches, c) choline oxidases whose amino acid sequence with the one in the international

Patent application WO 2005/124012 in SEQ ID NO. At least 83.8%, more preferably at least 84%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 97%, 98%, 99%, and particularly preferably, of the amino acid sequence indicated 100% matches, d) choline oxidases whose amino acid sequence matches that of the international

Patent application WO 2005/124012 in SEQ ID NO. At least 76.4%, more preferably at least 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 95%, 96%, 97% 98%, 99% and particularly preferably 100%, and e) choline oxidases according to a), b), c) or d) obtained by single or multiple conservative amino acid substitution from a choline oxidase according to a) to d) or by derivatization , Fragmentation, deletion mutation or insertion mutation of a choline oxidase according to a) to d) are obtainable; and / or the perhydrolase is selected from f) perhydrolases whose amino acid sequence is that in the international

Patent application WO 2005/124012 in SEQ ID NO. 26, but carries one or more amino acid substitutions at the sequence positions selected from 11, 15, 21, 38, 50, 54, 58, 77, 83, 89, 93, 96, 107, 117, 120, 134 , 135, 136, 140, 147, 150, 154, 155, 160, 161, 171, 179, 180, 181, 194, 205, 208, 213, 216, 217, 238, 239, 251, 253, 257, 261 , g) perhydrolases, the amino acid sequence of which in the international patent application WO 2005/124012 in SEQ ID NO. 26, but carries one or more amino acid substitutions at the sequence positions selected from 11, 58, 77, 89, 96, 117, 120, 134, 135, 136, 140, 147, 150, 161, 208, 216 , 217, 238, h) perhydrolases whose amino acid sequence is that described in International Patent Application WO 2005/124012 in SEQ ID NO. 26, but carries one or more amino acid substitutions at the sequence positions selected from 58, 89, 96, 117, 216, 217, i) perhydrolases whose amino acid sequence is that described in International Patent Application WO 2005/124012 in SEQ ID NO , 26, but having one or more of the amino acid substitutions T58A or T58Q, L89S, N96D, G117D, L216W and N217D, j) perhydrolases, the amino acid sequence of which is identical to one of those described in international patent application WO 2005/124012 in SEQ ID NO. 8, 10, 12, 14, 16, 18, 20, 22 or 24, more preferably at least 70%, 72.5%, 75%, 77.5%, 80%, 82.5%, 85% , 87.5%, 90%, 92.5%, 95%, 97.5%, and most preferably 100%.

For the disclosure of the abovementioned sequences of perhydrolases, reference is made to the disclosure in international patent application WO 2005/124012.

The enzymes used in granules according to the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or by filamentous fungi ,

The purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.

Analogous to the statements made above, the enzymes can be formulated according to the invention together with accompanying substances, for example from the fermentation or with stabilizers.

Of all these enzymes, particular preference is given to those which have been stabilized per se with respect to oxidation in a comparatively stable manner or, for example, via point mutagenesis. This includes in particular the above-mentioned commercial products Everlase ^® and Purafect OxP are to lead as examples of such proteases and Duramyl as an example of such an α-amylase.

This applies in particular to the embodiments of the present invention in which the granules are not yet protected by an additional coating (see below). In this form, especially when stored in a liquid Washing or cleaning the granules per se with the harmful substances in contact (albeit to a much lesser extent than if they were not granulated or not according to the invention). Thus, in particular, the enzyme molecules close to the granule surface are endangered, in particular in the case where a certain proportion of the solvent penetrates into the granules (even without disintegrating them altogether). Thus, it is particularly advantageous if the enzymes in question have a certain degree of basic stability towards oxidative inactivation.

According to the invention, it is particularly advantageous in the preparation of granules (see below) if a liquid enzyme preparation, for example coming directly from the fermentative preparation, is incorporated into the slurry for the preparation of the granules in aqueous solution. Such "liquid ZyrrT" preparations are also commercially available, in particular of proteases and amylases, which are designed for use in detergents and cleaners. For the preparation of the granules are, for example, liquid protease preparations with an enzyme protein content of 0.1 to 50%, preferably 5 to 40%, particularly preferably 10 to 35%. If appropriate, they can be adjusted to a concentration suitable for further processing by processes known per se to the person skilled in the art (for example concentration by means of rotary evaporation or dilution by addition of buffer).

Preferred embodiments of the present invention form granules according to the invention comprising as component (b) (adsorbent) one or more of the compounds selected from the group: talc, silicic acid, alumina, silicate, in particular phyllosilicate and / or sodium aluminum silicate, bentonite, aluminosilicate (zeolite) , Sulphate, titanium dioxide and / or polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA, particularly preferably a combination of two or three of these compounds.

Commercially available polyvinyl alcohols, which are available as white-yellowish powders or granules with degrees of polymerization in the range from about 500 to 2500 (molar masses of about 20,000 to 100,000 g / mol) have degrees of hydrolysis of 98 to 99 and 87 to 89 mol%, respectively. contain still a residual content of acetyl Groups. Fully saponified polyvinyl alcohols have a glass transition temperature of 85 ° C and a melting point of 228 ° C. The corresponding values for partially hydrolyzed (87 - 89%) products are significantly lower at approx. 58 ° C and 186 ° C, respectively. The latter are the "partially hydrolyzed" PVA which is particularly suitable according to the invention.

Granules containing these components (b) have remarkable stability and, when used as part of a detergent formulation, have excellent solubility under application conditions. This is evidenced by the examples of the present application.

Preferred embodiments of the present invention form granules according to the invention comprising as component (c) (binder) one or more of the compounds selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, polysaccharide or substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of said compounds, in particular methacrylic acid-ethyl acrylate copolymer, more preferably a combination of two or three of these compounds.

For granules with these components (c) were characterized by a remarkable stability and when used in the context of a detergent or cleaning agent formulation by an excellent solubility under conditions of use. This is evidenced by the examples of the present application.

Examples of suitable substances which may be mentioned are the crosslinked polyvinylpyrrolidone Collidone CL (commercial product of BASF, Ludwigshafen) and the methacrylic acid-ethylacrylate copolymers Eudragit L100 (Degussa, Frankfurt / M.) and Collicoat MEA (BASF).

Preferred embodiments of the present invention form granules according to the invention comprising, as part of component (d) (plasticizer), one or more compounds selected from the group consisting of water-dispersible organic compound or water-dispersible organic polymer, in particular polyethylene glycol (PEG), especially short-chain PEG, Fatty acid or salt a fatty acid, triacetin, triethyl citrate and / or polyhydric alcohol, preferably fatty acid or salt of a fatty acid, more preferably sodium stearate and / or sodium oleate.

For granules with these parts of component (d) were characterized by a remarkable stability and when used in the context of a washing or cleaning agent formulation by an excellent solubility under conditions of use. This is evidenced by the examples of the present application.

Preferred embodiments of the present invention form granules according to the invention containing, as part of component (d) (solubility improver), one or more compounds selected from the group: water-soluble inorganic salt, monosaccharide, in particular glucose, oligosaccharide, polysaccharide, in particular cellulose, compacted cellulose or Cellulose derivative, crosslinked organic polymer, in particular crosslinked polyvinylpyrrolidone or crosslinked polyacrylate.

In order to facilitate the disintegration of the granule particles according to the invention, it is possible to incorporate highly hygroscopic and / or swelling in contact with water compounds as so-called Löslichkeitsverbesserer or disintegration aid in these. This shortens the disintegration times. These are known per se in the prior art. Thus, according to Römpp (9th edition, Volume 6, page 4440) and Voigt "textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184) are understood by tablet disintegrants or disintegrators auxiliaries, which are responsible for the rapid disintegration of Make tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as disintegrants due to their action, increase their volume upon ingress of water, on the one hand the intrinsic volume increased (swelling), on the other hand, on the release of gases, a pressure can be generated, which can decay the granular particles into smaller particles. 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 casein derivatives.

Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention.

Preferred embodiments of the present invention form granules according to the invention containing the components:

(a) enzyme, preferably an oxidation-stabilized enzyme,

(b) 20-80% by weight of a particulate carrier material (adsorbent) selected from the group consisting of aluminum oxides, silicates, in particular sodium aluminum silicates, aluminosilicates (zeolites), sulfates, titanium dioxide and / or polyvinyl alcohol (PVA), preferably partially hydrolyzed PVA, in particular preferably a combination of two or three of these ingredients,

(c) 5-50% by weight of a polymeric binder selected from the group consisting of: polyacrylates, methacrylic acid-ethyl acrylate copolymers and / or polyvinyl alcohols (PVA), preferably partially hydrolyzed PVA, more preferably a combination of two or three of these ingredients, and

(d) as optional further ingredients:

0 - 50 wt .-% (based on the granules), plasticizer, selected from the group of fatty acids or salts of fatty acids,

0 - 50 wt .-% (based on the granules) solubility improver, selected from the group of monosaccharides, preferably

Glucose and / or

0 - 25 wt .-% (based on the granules) of water and / or

Color pigments. For granules included herein have been successfully tested in the context of the present invention for their stability and their solubility under conditions of use of a corresponding washing or cleaning agent. This is evident from the examples and has been explained there and already above.

(a) 3 to 30% by weight of the sensitive detergent or cleaning agent ingredient,

(b) 20-80% by weight of a particulate carrier material (adsorbent) selected from the group: talc, silicic acid, aluminum oxides, silicates, in particular phyllosilicates, sodium aluminum silicates, bentonites and / or aluminosilicates (zeolites), sulfates, titanium dioxide and / or Polyvinyl alcohol (PVA), preferably partially hydrolyzed PVA,

(c) 5-25% by weight of a non-crosslinked organic polymeric binder selected from the group consisting of polyacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, polysaccharides or substituted polysaccharides, especially cellulose ethers, polyvinyl alcohols (PVA), preferably partially hydrolyzed PVA and / or ethoxylated polyvinyl alcohols and

(d) as optional further ingredients:

0 - 33 wt .-% (based on the granules), plasticizer, selected from the group: water-dispersible organic compounds, water-dispersible organic polymers, polyethylene glycols (PEG), in particular short-chain PEG, fatty acids or salts of fatty acids, thacetin and / or thiethyl citrate or polyfunctional alcohols such as glycerol or 1,2-propylene glycol,

0-10% by weight (based on the granules) of solubility improver selected from the group consisting of water-soluble inorganic salts, monosaccharides, preferably glucose, oligosaccharides, and swelling agents, in particular compounds suitable as disintegrating agents, in particular cellulose, compacted cellulose, cellulose derivatives and / or cross-linked organic polymers, preferably crosslinked polyvinylpyrrolidones and / or 10-25% by weight (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, antioxidants, density regulating compounds and / or further ingredients.

For granules included herein have been successfully tested in the context of the present invention for their stability and their solubility under conditions of use of a corresponding washing or cleaning agent. This is evident from the examples and has been explained there and already above.

In this respect, very particularly preferred granules according to the invention have the following compositions:

(a) 3 to 7% by weight of enzyme, preferably an oxidation-stabilized enzyme,

(b) 30-80% by weight of a particulate carrier material (adsorbent) selected from the group consisting of aluminum oxides, silicates, in particular sodium aluminum silicates, aluminosilicates (zeolites), sulfates, titanium dioxide and / or polyvinyl alcohol (PVA), preferably partially hydrolyzed PVA, especially preferably a combination of two or three of these ingredients,

(c) 5-25% by weight of a polymeric binder selected from the group consisting of polyacrylates and / or polyvinyl alcohols (PVA), preferably hydrolyzed PVA, more preferably a combination of two or three of these ingredients, and

(d) as optional further ingredients:

0 - 33 wt .-% (based on the granules), plasticizer selected from the group of fatty acids or salts of fatty acids,

0 - 10 wt .-% (based on the granules) Löslichkeitsverbesserer selected from the group of monosaccharides, preferably

Glucose and / or

10 - 25 wt .-% (based on the granules) of water and / or

A further embodiment of the present invention relates to a granulate according to the invention, which is additionally coated with a single or multiple coating.

This additional coating serves, in particular, for the additional protection of the ingredients, but may also serve other purposes, for example delaying the release, improving the bulk material properties, for example lowering the dust rate, increasing the stability and / or improving the visual appearance.

Such granules of the so-called core / shell type and methods and apparatus for their preparation are known per se. The manufacturing processes are usually reflected in the structure of the coating again. Overviews of these methods and apparatuses are available, for example, in the manuals "Fluidized Bed Spray Granulation" by H.Uhlemann and L.Mörl, Springer-Verlag, Berlin, Heidelberg, New York, 2000, chapter 14.3 (enveloping), pages 461 to 473. and "Agglomeration Processes, Phenomena, Technologies, Equipment" by W. Pietsch, Verlag Wiley-VCH, Weinheim, 2002.

For the production of granules according to the invention, for example, a ball coater (turbojet) can be used, described in the dissertation by Karin Wöstheinrich, "Possible applications of the Hüttlin-Kugelcoaters HKC 05-TJ including simulations", as an online dissertation under the URL http: // can be viewed (accessed on April 5, 2005). In a suitable coating process, the granules particles, preferably enzyme particles, are introduced into the hot air stream and the coating material is sprayed on via a top sprayer. This is done under drying conditions, ie 40-45 ° C, so that the product has about 35-38 ° C and remains dry.

Preferred such methods and process products are characterized in that the enzyme granules particles are coated with an aqueous emulsion based on silicone oil.

No less preferred such processes and process products are characterized in that the enzyme granules particles are coated with a polymer solution containing inorganic pigment.

These are, for example, processes and process products with the polymer component PEG, PVA, PVP, starch, starch derivative, cellulose, cellulose derivative or mixtures thereof or their copolymers and kaolin, TiO ₂ and / or antioxidants as inorganic pigment.

It may be advantageous to use the polymer in the form of an aqueous solution, for example as an aqueous PEG solution. Optionally, the coating and surfactant, such as nonionic surfactant with about 80 EO can be used.

The following coating methods and coating granules according to the invention obtainable thereby are particularly preferred:

(1) a pigment-containing coating of: (a) 5 to 70 wt .-% (based on the

Coating) of fine, inorganic, water-insoluble pigment, (b) 45 to

90 wt .-% of an organic substance having a melting point of 40 to 70 ° C and

(c) up to 20% by weight of a bulkiness improving agent; such a

Coating is evident from EP 944704 B1;

(2) a coating containing a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated

Fatty acid having at least 12 carbon atoms is applied; such a

Coating is evident from WO 03/020868 A1; (3) applying a mixture of TiO ₂ , urea and polyethylene glycol having a water content of less than 50% by weight; such a coating is described in the non-prepublished application DE 102004062326.0; (4.) Silicone oil-based emulsions in the form of water-in-oil emulsions (W / O), oil-in-water emulsions (O / W), multiple emulsions (W / O / W) and nano and microemulsions are applied;

(5.) according to the non-prepublished application DE 102004062326.0 abrasion-resistant coated enzyme granules, which can be prepared by subjecting the granules particles with a urea-containing aqueous preparation and the water at least partially removed by drying. Advantageously, according to this application, first the fines of the unbrided granules presented are removed via a two-stage air classification and then the very abrasion-resistant urea / PEG / TiO ₂ layer having a water content of less than 50% is applied.

In a preferred embodiment of the present invention is a granules coated according to the invention, wherein the coating consists of more than 50 wt .-% of one or more of the following compounds: water-dispersible substances, water-dispersible and / or water-soluble polymer, fatty acid, salt Fatty acid, fatty alcohol, paraffin, polyvinyl acetate, polyacrylate, polymethacrylate, methacrylic acid-ethyl acrylate copolymer, polyvinyl pyrrolidone, cellulose ethers, polyvinyl alcohol and ethoxylated polyvinyl alcohol.

As is apparent from the examples for the present application, granules according to the invention having an additional polymer coating have increased stability values.

In a preferred embodiment, it is a polymer-coated granules according to the invention, wherein the water-soluble polymer is polyacrylate or a methacrylic acid-ethyl acrylate copolymer and / or the cellulose ether is methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) or carboxymethylcellulose (CMC). As is apparent from the examples for the present application, granules according to the invention having an additional polymer coating have increased stability values. Concretely, in Example 4, a coating was made with a commercially available polyacrylate (methacrylic acid-ethyl acrylate copolymer (1: 1)), which gave excellent stability values. Likewise suitable for this purpose is the commercially available polymer Kollicoat MEA from BASF.

In a preferred embodiment, it is an inventive coated granules, wherein the coating additionally contains one or more fillers selected from the group of inorganic particles, preferably silicate or alumina, more preferably talc.

Such fillers may be used, for example, to influence the overall plasticity of the coating in question and / or of the particles obtained in order to improve their diffusion-tightness or to regulate the bulk density of the particles.

In a preferred embodiment, it is a coated granules according to the invention, wherein the coating additionally contains one or more plasticizers selected from the group: triethyl citrate, triacetin, polyfunctional alcohol, in particular 1,2-propanediol, and polyethylene glycol.

As is apparent from the examples for the present application, granules according to the invention having an additional polymer coating have increased stability values. Concretely, in Example 4, the coating was carried out with a commercially available polyacrylate (methacrylic acid-ethyl acrylate copolymer (1: 1)) to which 5% (based on the coating polymer) was further added as a plasticizer. This has had a positive effect on the processability of the material and thus ultimately on the advantageous properties of the resulting coated granules. In a preferred embodiment, it is an inventive coated granules, wherein the coating additionally contains color pigment, preferably titanium dioxide.

As described above, color pigments according to the invention serve to improve the optical appearance of the granules and can also have an overall positive effect on the plasticity of the respective material. Analogously, it is within the scope of the present invention to impart these properties to the coating or the coating material.

In a preferred embodiment, it is an inventive coated granules, wherein the coating additionally contains one or more compounds acting as antioxidants.

In connection with the present invention, where in particular the task has been to protect ingredients against bleach, that is to protect against oxidation, it makes sense and of the present application, this protective function of the granules to an additional, applied through the coating protection too complete. It therefore advantageously contains antioxidants.

Antioxidants are known per se to the person skilled in the art. For example, it is common to increase the stability of enzymes to oxidative degradation by sulfur-containing reducing agents, sodium sulfite and reducing sugars to antioxidants (see above). Further compounds which may be mentioned as being suitable at this point are, for example, ascorbic acid, tocopherol, gallates, thiosulfate-substituted phenols, hydroquinones, catechols and aromatic amines, and also organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

In a preferred embodiment, it is a coated granules according to the invention, wherein the coating is 5 to 100 wt .-%, preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% of the uncoated granules. This information refers to the ready-made granules. At the moment of manufacture, these values may still be slightly different because granules, even after their coating, are usually subjected to a drying step. This reduces the water content of both the core and the coating, which may also result in differences in the ratio of water to each other. This is the case, for example, when comparatively dilute, that is to say particularly water-containing, enzyme preparations have been incorporated into the core or when it has been coated with an aqueous suspension of a per se hydrophobic coating material. In the latter case, the water content of the finally obtained coating is significantly lower than that of the core.

In a preferred embodiment of the present invention is an inventive uncoated or coated granules, having an average particle diameter of 100 to 3000 microns, preferably 200 to 2500 microns, more preferably 400 to 2000 microns.

This size depends on the one hand after the manufacturing process, after which coated granules usually have a slightly larger diameter than uncoated. On the other hand, it depends on the field of application. Furthermore, these size ranges have been found to be advantageous to achieve a rapid disintegration and release of the ingredients at the moment of use of the funds in question and also to give the product a special aesthetic impression.

In addition, it is visually appealing and also advantageous in terms of manageability and to achieve a consistent profile of action to submit the granules in a uniform size distribution as possible, depending on the manufacturing process certain fluctuation ranges are taken into account. The size of the particles can be regulated according to variations known per se to those skilled in the art for the preparation of the particles, in particular the uncoated particles. Thus, those granules obtainable by extrusion in which 90% of all particles are within a range of ± 20% of the mean size are preferred. This can be controlled via the nozzle plate. In the case of the fluidized bed granules, those in which 90% of all particles are within a range of ± 50% of the mean size are preferred. This can be ensured as ultimately for the extrudates via screening.

A preferred embodiment of the present invention is an uncoated or coated granulate according to the invention with an average density of from 1.00 to 1.50, preferably from 1.02 to 1.30, more preferably from 1.05 to 1.15 g / ml.

Possibilities for regulating the density are known per se to the person skilled in the art and have already been mentioned above. The regulation of the density according to the invention is advantageous for matching the granules to the density of the agent intended for use. Thus, liquid or gel compositions of the present invention (see below) contain granules of virtually the same density as the surrounding matrix to avoid both sedimentation and creaming.

The density of the granules described in example 4 of the present application is in each case about 1.29 g / ml.

A further subject of the present invention are processes for the preparation of each granulate according to the invention.

Processes for the production of granules of sensitive washing or cleaning agent ingredients are known per se to a person skilled in the art. For this purpose, remember the manuals and illustrations already mentioned above. In particular, for the preparation of enzyme granules is an extensive state of the art.

An advantageous procedure, based on a liquid, concentrated aqueous enzyme preparation can be described as follows: The enzyme concentrate is added to the advantageously previously prepared dry, powdery to granular mixture of a composition relevant to the invention. The water content of the mixture should be chosen so that when working with stirring and impact tools in granular, at room temperature not Transfer adhesive particles and plastically deform and extrude using higher pressure. The free-flowing premix is then processed in a known manner in a kneader and a connected extruder to a plastic, homogeneous as possible mass, the mass as a result of mechanical processing to temperatures between 15 and 80 ° C, in particular 40 ° C and 60 ° C, in particular to 45 ° C to 55 ° C can heat. It is advantageous according to the invention, an extrusion temperature of below 6O ⁰ C and an extrusion pressure in the range from 30 to 130 bar, in particular in the range of 50 to 90 bar.

The material leaving the extruder is passed through a perforated disc with subsequent doctor blade and thereby comminuted to form cylindrical particles of defined size. Appropriately, the diameter of the holes in the perforated disc 0.7 to 1, 2 mm, preferably 0.8 to 1, 0 mm. It may also be advantageous not to cut off the mass emerging from the nozzle plate of the extruder immediately at the nozzle head, but to interpose a cooling section, after which the granulation takes place in a cutting device.

The particles present in this form can then be dried, rounded and / or coated. It has proven to be advantageous to spheronize the cylindrical particles leaving the extruder and chopper prior to wrapping, that is to round and deburr them in suitable apparatus. For this purpose, a device is used which consists of a cylindrical container with stationary, solid side walls and a base plate rotatably mounted friction plate. Devices of this type are common in the art under the trade name Marumerizer® and described for example in DE 2137042 and DE 2137043. Subsequently, possibly occurring dust-like fractions with a particle size of less than 0.1 mm, in particular less than 0.4 mm, and any coarse fractions with a particle size greater than 2 mm, in particular about 1, 6 mm removed by sieving or air classification and optionally returned to the manufacturing process. After spheronization, the beads are continuously or batchwise, preferably using a fluidized bed dryer, at inlet air temperatures of preferably 35 ° C to 70 ° C and in particular in a Product temperature of not more than 60 ° C to the desired residual moisture content of, for example, 2 wt .-% to 10 wt .-%, in particular 3 wt .-% to 8 wt .-%, based on total granules, dried, if they previously had higher water contents have shown.

Processes for coating granules have already been mentioned above. For this purpose, methods are known in the art, according to which the coating materials, in particular those with a waxy structure (that is lying above the room temperature melting points) are applied in the form of a melt, or those, according to which in particular organic coating materials as a solution in an organic solvent be applied. All of these methods are possible implementations of the present invention. However, preferred are those according to which the coating materials are applied in the form of an aqueous solution or suspension and the excess water is then optionally evaporated. Because this reduces the risk of denaturation of enzymes contained in the Granulatpatzikeln at elevated temperature or contact with the solvents in question. Even contained perfumes could be dissolved out of the particles with organic solvents. Also in terms of environmental protection, the coating using water as the solvent is preferred.

In connection with the present invention, as can be seen from the previous explanations and can also be recognized from this description, the following variants of the method have proven to be advantageous in each case and in particular in combination with one another:

Process according to the invention, wherein the adsorbent (b) is introduced as a predominantly dry substance and the enzyme component (a) is incorporated as a liquid preparation;

Process according to the invention, wherein the binder (c) is incorporated simultaneously with the liquid enzyme component (a), preferably in the form of a prior mixing of these two components with one another; Inventive method, wherein the adsorbent (b) presented in a mixer or a fluidized bed apparatus and the binder (b) and the liquid enzyme component (a) are sprayed individually or with prior mixing, resulting in a per se homogeneous agglomerate;

Process according to the invention, optionally containing further

Solids together with the adsorbent (b) are mixed and charged;

Process according to the invention, optionally containing further liquid substances being incorporated as liquid preparation (s), optionally with prior mixing or emulsification with one of the other liquids

components;

Process according to the invention, wherein the ingredients are extruded and optionally spheronized and / or optionally coated.

In a preferred embodiment, it is inventive method, wherein at least one liquid under process conditions ingredient is supplied separately during the extrusion process.

This applies, for example, to a liquid preparation of the sensitive ingredient (a) to be incorporated, in particular a liquid enzyme preparation. It can be added by a separate liquid metering device at any point of the process length of the extruder, while the components (b), (c) and (d) are supplied at the beginning of the process length as free-flowing granules or as a powder.

In the context of the present invention, as can be seen from the previous statements and can also be recognized from this description, the following process variants have also proven to be advantageous, in each case and in particular in combination with one another and with those already mentioned: Process according to the invention, wherein the density of the granulate particles obtained by adding substances of higher or lower density as additional component of the adsorbent (a) or as further ingredient (d) to average densities of from 1, 00 to 1, 50, preferably from 1, 02 to 1, 30, particularly preferably from 1 , Is adjusted to 05 to 1, 15 g / ml; Inventive method for producing a coated enzyme granules, wherein the coating material in a Fluidized bed apparatus is sprayed from an aqueous solution / suspension on the particles to be coated;

Inventive method for producing a coated enzyme granules, wherein the total mass of the coating material is 5 to 100 wt .-%, preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% of the initially introduced mass of the particles to be coated.

Another object of the present invention are detergents or cleaners containing a sensitive ingredient in the form of granules of the invention.

According to the invention, solid, liquid or gel detergents and cleaning agents are provided which contain sensitive ingredients, in particular enzymes with good protection against other, in particular bleaching, ingredients. This form of packaging is physically largely stable to perform its protective function. On the other hand, it shows in the application, that is at the moment of dilution by the aqueous wash liquor a good release behavior, so that the enzymes are readily available in an active form, and leave virtually no residue on the laundry.

For the purposes of the present invention, a washing or cleaning agent is to be understood as meaning every conceivable type of detergent, both concentrates and undiluted agents, for use on a commercial scale, in the washing machine or in hand washing or cleaning. These include, for example, detergents for textiles, carpets, or natural fibers, for which according to the present invention the term laundry detergent is used. These include, for example, dishwashing detergents for dishwashers or manual dishwashing detergents or cleaners for hard surfaces such as metal, glass, porcelain, ceramics, tiles, stone, painted surfaces, plastics, wood or leather; for such according to the present invention, the term cleaning agent is used.

Embodiments of the present invention include all known in the art and / or all appropriate dosage forms of Detergents or cleaning agents according to the invention. These include in particular solid, pulverulent, means, possibly also of several phases, compressed or uncompressed; Further examples include: extrudates, granules, tablets or pouches, packed both in bulk containers and in portions.

In addition to granules, preferably of enzymes (see above), a washing or cleaning agent according to the invention optionally contains further ingredients such as enzyme stabilizers (see above), surfactants, for example nonionic, anionic and / or amphoteric surfactants, and / or bleaching agents, and / or builders and optionally further customary ingredients, among which are the following: other, in particular the enzymes already mentioned above, sequestering agents, electrolytes, optical brighteners, grayness inhibitors, silver corrosion inhibitors, dye transfer inhibitors, foam inhibitors, abrasives, dyes and / or fragrances, as well as microbial Active ingredients and / or UV absorbents.

For the preparation and composition of detergents and / or cleaning agents there is a comprehensive state of the art, to which reference is made here. Usually, the funds are tailored to specific problems, such as the stains, use temperatures and media or Applizierungsmöglichkeiten concerns. In such optimizations Granualte invention are included, for example, in terms of their dissolution behavior or tuning of the components contained.

According to these statements, the use of the granules described as being in accordance with the invention as admixing component in detergents or cleaners constitutes a further subject matter of the present invention.

The enzyme granules according to the invention or produced by the process according to the invention is used for the production of solid, in particular particulate detergents or cleaners, which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents. For incorporation into particulate detergents and cleaners, the enzyme granules preferably have mean particle sizes in Range from 0.7 to 2.0 mm. The granules according to the invention preferably contain less than 2% by weight, in particular at most 1.4% by weight, of particles having particle sizes outside the range from 0.4 to 2.0 mm. However, the method is not limited to these particle sizes, but covers a field of application corresponding broad particle size spectrum, usually the average particle diameter (dso) is between 0.1 to more than 2 mm.

A washing or cleaning agent according to the invention contains, in addition to the granules according to the invention, surfactant (s), it being possible to use anionic, nonionic, zwitterionic and / or amphoteric surfactants. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants. The total surfactant content of the liquid washing or cleaning agent is preferably below 40% by weight and more preferably below 35% by weight, based on the total liquid detergent.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, 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 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C-ι ₂ --ι ₄ alcohols containing 3 EO, 7 EO or 4 EO, C ₉ H -alcohol with 7 EO, C ₃ -i ₅ alcohols containing 3 EO, 5 EO , 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ₂ - ₁₄ -alcohol with 3 EO and Ci ₂ -is-alcohol with 7 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 be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are available by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched 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 degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4. Alkyl glycosides are known, mild surfactants.

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.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl N, N-dimethylamine oxide and N-tallow alkyl N, N-dihydroxyethyl amine 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 (I)

R ¹

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

in which RCO 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. 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 (II)

R ¹ -OR ²

I R-CO-N- [Z] (II)

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 is or an oxyalkyl group having 1 to 8 carbon atoms, Ci _-4 alkyl or phenyl groups being preferred, and [Z] is a linear polyhydroxyalkyl residue, whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or pro- polyoxylated derivatives of this residue. [Z] is preferably obtained by reductive amination of a 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.

The content of nonionic surfactants in the washing or cleaning agent is preferably 5 to 30 wt .-%, preferably 7 to 20 wt .-% and in particular 9 to 15 wt .-%, each based on the detergent or cleaning agent.

In addition to the nonionic surfactants, the washing or cleaning agent may also contain anionic surfactants. As anionic surfactants, for example, those of the sulfonate type and sulfates are used. As surfactants of the sulfonate type preferably come here C ₉ -i ₃ -alkylbenzenesulfonates, olefinsulfonates, that is mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from Ci ₂ -i ₈ monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from d ₂ -i ₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of .alpha.-sulfo fatty acids (ester sulfonates), for example the .alpha.-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

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

Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelsäurehalbester C ₂ -C ₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or Cio-C ₂ o-oxoalcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the Ci ₂ -Ci ₆ alkyl sulfates and Ci ₂ -Ci ₅ alkyl sulfates and Ci ₄ -Ci ₅ 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 Schwefelsäuremonoester of linear or branched C ethoxylated with 1 to 6 mol ethylene oxide ₇ - ₂ i-alcohols such as 2-methyl-branched C ₉ n-alcohols containing on average 3.5 mol ethylene oxide (EO) or C _{_2-18} Fatty alcohols containing 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 Cs-is fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Again, sulfosuccinates, whose Fatty alcohol residues derived from ethoxylated fatty alcohols with restricted homolog distribution, 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.

Particularly preferred anionic surfactants are soaps. Suitable are saturated and unsaturated 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, olive oil or tallow fatty acids.

When used in PAP-containing agents, it has been found to be advantageous due to the reactivity of this oxidizing agent to keep the content of surfactants with simple and especially polyunsaturated C-chains low.

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.

The content of a washing or cleaning agent in anionic surfactants is advantageously from 0.1 to 30 wt .-% based on the total detergent or cleaning agent.

In addition to the surfactant (s), the washing or cleaning agent may contain further ingredients which further improve the performance and / or aesthetic properties of the washing or cleaning agent. In the context of the present invention, the washing or cleaning agent preferably additionally contains one or more substances from the group of builders, bleaching agents, bleach activators, enzymes, electrolytes, nonaqueous solvents, pH adjusters, perfumes, perfume carriers, fluorescers, dyes, hydrotopes, foam inhibitors, Silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, anti-crease agents, further color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, repellents and impregnating agents, swelling and anti-slip agents, neutral filler salts, coagulating components as well as UV absorbers.

The washing or cleaning agent may also contain a second, preferably nitrogen-containing, color transfer inhibitor. Examples of second color transfer inhibitors are: polymers or copolymers of cyclic amines such as vinylpyrrolidone and / or vinylimidazole, polyvinylpyrrolidone (PVP), polyvinylimidazole (PVI), copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI), polyvinylpyridine-N-oxide, poly-N carboxymethyl-4-vinylpyridium chloride and mixtures thereof.

The polyvinylpyrrolidones (PVP) used preferably have an average molecular weight of 2,500 to 400,000 and are commercially available from ISP Chemicals as PVP K 15, PVP K 30, PVP K 60 or PVP K 90 or from BASF as Sokalan® HP 50 or Sokalan® HP 53 available.

The copolymers of vinylpyrrolidone and vinylimidazole (PVP / PVI) used preferably have a molecular weight in the range from 5,000 to 100,000. Commercially available is a PVP / PVI copolymer, for example from BASF under the name Sokalan® HP 56th

The amount of the second color transfer inhibitor, if any, based on the total amount of detergent or cleaning agent is preferably from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, and more preferably from 0.1 to 2% by weight. Suitable builders which may be present in the washing or cleaning agent are in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x +} IH 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-radiation, which have 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, with values of up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates. 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, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by SASOL under the brand name VEGOBOND AX ^® and 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 n = 0.90-1.0

can be described. The zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation. In the case that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₂ -Cis fatty alcohols having 2 to 5 ethylene oxide groups, C ₁₂ -d ₄ -fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Organic builders which may be present in the washing or cleaning agent are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning such carboxylic acids which carry more than one acidity 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) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the 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 useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

As builders further polymeric polycarboxylates are suitable. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of from 2,000 to 20,000 g / mol. Because of their superior Solubility may again be preferred from this group, the short-chain polyacrylates having molecular weights of 2,000 to 10,000 g / mol, and more preferably from 3,000 to 5,000 g / mol.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.

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 relative molecular weight, based on free acids, is generally from 2,000 to 70,000 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 an aqueous solution or, preferably, as a powder.

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.

Further preferred copolymers are those which have as monomers preferably 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. Particularly preferred Polyaspartic acids or their salts and derivatives, which in addition to builder properties also have a bleach-stabilizing effect.

Further suitable builders are polyacetals which can be obtained by reacting dialdehydes with polyol carboxylic 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 builders 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 of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.

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. Also suitable is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylene diamine disuccinate, are also other suitable builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), preferably in the form of its sodium or magnesium salts used. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates.

Other useful organic builders 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.

For liquid formulations particularly suitable and thus particularly preferred within the scope of the present invention are builders such as citric acid / citrates, polycarboxylates and phosphonates.

Among the compounds serving as bleaches 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, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-N H ₂ - H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-Phthalimidoperoxycapronsäure (Phthalimidoperoxyhexansäure, PAP), o-carboxy benzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamido-persuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxy- brassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1, 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.

It is particularly advantageous to use perborate monohydrate, percarbonate or PAP, preferably PAP.

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

The content of bleaching agent content may be 0.1 to 40% by weight, preferably 0.5 to 30% by weight, more preferably 1 to 25% by weight and especially 2 to 20% by weight. The active oxygen content of the washing or cleaning agents, in particular the automatic dishwashing agents, is in each case based on the total weight of the composition, preferably between 0.3 and 15 wt .-%, particularly preferably between 0.5 and 10 wt .-% and in particular between 0.6 and 8 wt .-%, for example, 5 wt .-%. Particularly preferred compositions have an active oxygen content above 0.7% by weight, more preferably above 0.8% by weight and in particular above 1.0% by weight. PAP as a particularly suitable bleach with only about 5% active oxygen (based on the molecule) a nominal comparatively low active oxygen content, but has such a high reactivity, that PAP contents of 1 to 5 wt .-%, preferably 2 to 4 wt .-%, more preferably 2.5 to 3 wt .-%, based on the total formulation, according to the invention.

In order to achieve a good bleaching effect when washing at temperatures of 60 ° C and below, and especially in the laundry pre-treatment, the means may also contain bleach activators. Suitable bleach activators are compounds which, under perhydrolysis conditions, have aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or, where appropriate substituted perbenzoic acid, can be used. 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 alkylene diamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular 1, 3,4 , 6-tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetyl citrate (TEOC ), Carboxylic acid anhydrides, in particular phthalic anhydride, isoic anhydride and / or succinic anhydride, carboxamides, such as N-methyldiacetamide, glycolide, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, isopropenyl acetate, 2,5-diacetoxy-2,5-dihydrofuran and those from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 describes mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine or gluconolactone, triazole or triazole derivatives and / or particulate caprolactams and / or caprolactam derivatives, preferably N-acylated lactams, for example N-benzoyl-caprolactam and N-acetyl-caprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Likewise, nitrile derivatives such as cyanopyridines, nitrile quats, for example N-alkylammonium acetonitriles, and / or cyanamide derivatives can be used. Preferred bleach activators are sodium 4- (octanoyloxy) benzenesulfonate, n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzene sulfonate (OBS 12), as well as N-methylmorpholinum acetonitrile (MMA). Such bleach activators can in the usual amount range of 0.01 to

20 wt .-%, preferably in amounts of 0.1 to 15 wt .-%, in particular 1 wt .-% to 10 wt .-%, based on the total composition, be contained.

in the R ^{1 is} -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 Ci- ₂₄ alkyl group, or a substituted alkyl or Alkenylaryl radical having 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.

Particularly preferred is a cationic nitrile of the formula

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 (CHs) -CH ₃ , wherein R ⁴ additionally also -H and X is an anion, preferably 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₎₎ 3 N ⁽⁺⁾ CH ₂ -CN ^X", or (HO-CH ₂ - CH ₂₎ ₃ N ⁽⁺⁾ CH ₂ -CN X ^"are particularly preferred, wherein from the group of these substances turn the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^" , in which X ^"is an anion which is selected from the group chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be included. 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 amine complexes are also suitable as bleach catalysts.

It is particularly preferred to use complexes of manganese in the oxidation state II, III, 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). Suitable manganese complexes are, for example, [Mn " ¹ 2 (μ-O) ₁ (μ-OAc) ₂ (TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ^MI Mn ^lv (μ-O) ₂ (μ-OAc) i ( TACN) ₂ ] (BPh ₄ ) ₂ , [Mn ^ιv ₄ (μ-O) ₆ (TACN) ₄ ] (CIO ₄ ) ₄ , [Mn ^MI ₂ (μ-O) i (μ-OAc) ₂ (MeOH)]. TACN) ₂ ] (CIO ₄ ) ₂ , [Mn ^IM Mn ^lv (μ-O) i (μ-OAc) ₂ (Me-TACN) ₂ ] (CIO ₄ ) S, [Mn ^lv ₂ (μ-O) ₃ (Me-TACN) ₂ ] (PF ₆ ) ₂ and [Mn ^lv ₂ ( _μ- O) ₃ (Me / Me-TACN) ₂ ] (PF ₆ ) ₂ (OAc = OC (O) CH ₃ ).

Bleach catalysts may be used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt. -%, in each case based on the total weight of bleach activator-containing agents are used. In special cases, however, more bleach catalyst can be used.

It may also be preferred that the detergent or cleaning agent is a softening detergent ("2in1") For this purpose, the detergent or cleaning agent contains, in addition to the dye transfer inhibitor and the surfactants, also a softening component.

The softening component includes, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.

Suitable examples of quaternary ammonium compounds are shown, for example, in the formulas (IM) and (IV):

wherein in (III) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{1 is} a saturated CrC ₄ alkyl or hydroxyalkyl radical, R ² and R ^{3 are} either R or R ¹ or are an aromatic radical. X ^" is either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these Examples of cationic compounds of the formula (III) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of the formula (IV), (V) and (VI) are so-called ester quats. Esterquats are characterized by excellent biodegradability. In formula (IV) R ^{4 is} an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is, independently of R ^5, H, OH or O (CO) R ⁸ , where R ⁷ and R ⁸ are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with O, 1, 2 or 3 double bonds, m, n and p may each independently have the value 1, 2 or 3 have. X ^~ may be either a halide, methosulfate, methophosphate or phosphate ion as well as mixtures of these anions. Preference is given to compounds in which R ^{5 represents} the group 0 (CO) R ⁷ . Particularly preferred are compounds in which R ^{5 is} the group 0 (CO) R ⁷ and R ⁴ and R ^{7 are} alk (en) yl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallow acyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1, 2-bis [tallowloxy] -3-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.

If quaternized compounds of the formula (IV) are used which have unsaturated alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular equal to or greater than 60:40. Commercial examples are sold by Stepan under the trade name Stepantex® ^® methylhydroxyalkyldialkoyloxyalkylammonium or known by Dehyquart® ^® products from Cognis known under Rewoquat ^® products from Degussa or known by Tetranyl® products from Kao. Further preferred compounds are the diester quats of the formula (V) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.

R ²¹ and R ²² are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

Instead of the ester group 0 (CO) R, where R is a long-chain alk (en) yl radical, it is possible to use softening compounds which have the following groups: RO (CO), N (CO) R or RN (CO), where of these groups, N (CO) R groups are preferred.

In addition to the quaternary compounds described above, it is also possible to use other compounds as the softening component, for example quaternary imidazolinium compounds of the formula (VI)

10 wherein R is H or a saturated alkyl radical having 1 to 4 carbon atoms, R and

R, 11 independently of one another may each represent an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{10 may} alternatively also stand for 0 (CO) R ²⁰ , where R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms and Z is an NH group or oxygen and X ^"is an anion, q can take integer values between 1 and 4.

Further particularly preferred plasticizing compounds are described by formula (VII), R13 H

R12 NU (CH ₂₎ r CI O (CO) R15 X (VN);

R14 CH ₂ - O (CO) R16

wherein R ^12, R ¹³ and R ¹⁴ independently of one another stands for a Ci _-4 alkyl, alkenyl or hydroxyalkyl group, R ¹⁵ and R ¹⁶ are each independently selected a Cs ₂₈ - represents alkyl group, X ^"is an anion and R is an Number between 0 and 5. A preferred example of a cationic deposition aid according to formula (VII) is 2,3-bis [tallowloxy] -3-trimethylammonium propane chloride.

Further plasticizing components which can be used according to the invention are quaternized protein hydrolyzates or protonated amines.

Furthermore, cationic polymers are also suitable softening component. Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats. 10 polymers (Polymer JR, LR and KG series of Amerchol), polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyl triammonium chloride, and the like quaternized guar derivatives (for example Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride" , Copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and Vinyl pyrrolidone, aminosilicone polymers and copolymers. Also suitable are polyquaternized polymers (for example Luviquat® Care from BASF) and also cationic biopolymers based on chitin and derivatives thereof, for example the polymer available under the trade name Chitosan® (manufacturer: Cognis).

Some of the cited cationic polymers additionally have skin and / or texturing properties.

It is likewise possible to use compounds of the formula (VIII)

R ¹⁷ can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5. R ¹⁸ and R ¹⁹ are each independently H, Ci _-4 alkyl or hydroxyalkyl, and X ^~ is an anion.

Other suitable softening components include protonated or quaternized polyamines.

Particularly preferred plasticizing components are alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group. Very particularly preferred are N-methyl-N- (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) hydroxyethyl-methyl-ammonium methosulfate.

The washing or cleaning agent may contain a thickening agent. The thickener may, for example, be a polyacrylate thickener, xanthan gum, Gellan gum, guar gum, alginate, carrageenan, carboxymethyl cellulose, bentonites, wellan gum, locust bean gum, agar, tragacanth, gum arabic, pectins, polyoses, starch, dextrins, gelatin and casein. However, modified natural substances such as modified starches and celluloses, examples which may be mentioned here include carboxymethylcellulose and other cellulose ethers, hydroxyethyl and -propylcellulose and core flour ethers, can be used as thickeners.

Examples of polyacrylic and polymethacrylic thickeners include the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the International Dictionary of Cosmetic Ingredients of The Cosmetic, Toiletry and Fragrance Association (CTFA) ": carbomer), also referred to as carboxyvinyl polymers. Such polyacrylic acids are available, inter alia, from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon (formerly BF Goodrich) under the trade name Carbopol®, for example Carbopol 940 (molecular weight about 4,000,000). , Carbopol 941 (molecular weight about 1. 250,000) or Carbopol 934 (molecular weight about 3,000,000). Furthermore include the following acrylic acid copolymers: (i) copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably formed with Ci _-4 alkanols (INCI Acrylates Copolymer), which include for instance the copolymers of Methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and, for example, the company Rohm & Haas under the trade names Aculyn® and Acusol® and from the company Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (cross-linked), Acusol 810, Acusol 820, Acusol 823 and Acusol 830 (CAS 25852-37-3); (ii) crosslinked high molecular weight acrylic acid copolymers, such as those with an allyl ether of sucrose or pentaerythritol crosslinked copolymers of C-ιo-30- Alkyl acrylates having one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably with Ci _-4 -alkanols formed ester (INCI acrylates / Cio _-3O alkyl acrylate crosspolymer) include and which are available, for example, from the company Noveon (formerly BF Goodrich) are available under the trade name Carbopol®, for example the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C-ιo-30 alkyl acrylate crosspolymer) and Carbopol Aqua 30 (former Carbopol EX 473).

Another preferred polymeric thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million daltons. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

As thickening agent, a fatty alcohol is also suitable. Fatty alcohols may be branched or unbranched, of native origin or of petrochemical origin. Preferred fatty alcohols have a C chain length of 10 to 20 C atoms, preferably 12 to 18. Preference is given to using mixtures of different C chain lengths, such as tallow fatty alcohol or coconut oil fatty alcohol. Examples are Lorol® Spezial (Ci ₂ - ₁₄ -ROH) or Lorol® Technical (C- ₁₂ - ₁ 8-ROH) (both ex Cognis).

Another suitable class of thickeners are silicate particles, such as those offered under the trade name Optigel or Thixogel (Südchemie) or silica. Particularly preferred is Optigel WX (Südchemie).

The washing or cleaning agent may contain from 0.01 to 3% by weight and preferably from 0.1 to 1% by weight of thickener. The amount of thickener used depends on the type of thickener and the desired degree of thickening.

The washing or cleaning agent may contain further, not according to the invention granulated enzymes. Suitable enzymes are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases, hemicellulases, cutinases, .beta.-glucanases, oxidases, peroxidases, perhydrolases and / or laccases and mixtures of the abovementioned Enzymes in question. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens. 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 especially 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 α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which also Cellobiases are called, or mixtures thereof used. 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 encapsulated or adsorbed to carriers to protect against premature degradation. The proportion of the enzymes, of the enzyme liquid formulation (s) or of the enzyme granules in a washing or cleaning agent can be, for example, about 0.01 to 5% by weight, preferably 0.12 to about 3.5% by weight.

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, particularly suitable anions are the sulfates. The proportion of electrolytes in the washing or cleaning agent is usually 0.1 to 5 wt .-%.

Non-aqueous solvents that can be used in the washing or cleaning agent, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. Preferably, the solvents are selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl -, -ethyl or -propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or Butoxytriglykol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol -t-butyl ether, di-n-octyl ether and mixtures of these solvents. Non-aqueous solvents can be used in the Detergents or cleaning agents in amounts between 0.5 and 15 wt .-%, but preferably below 12 wt .-% and in particular below 9 wt .-% are used.

In order to bring the pH of the washing or cleaning agent in the desired range, the use of pH adjusters may be indicated. Applicable here are all known acids or alkalis, unless their use prohibits application-related or environmental reasons or for reasons of consumer protection. Usually, the amount of these adjusting agents does not exceed 10% by weight of the total formulation.

The pH of the washing or cleaning agent is suitably between 3 and 7, preferably between 3.5 and 6.5, more preferably between 4.0 and 5.5.

In a preferred embodiment, the washing or cleaning agent contains one or more (optionally additional) perfumes in an amount of usually up to 10 wt .-%, preferably 0.01 to 5 wt .-%, in particular 0.3 to 3 wt. %. For this purpose, in principle, all perfumes described in the prior art for this application, in particular the perfumes already described above as ready for manufacture according to the invention come into question.

As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance gemi see, as they are available from plant sources.

In order to improve the aesthetic impression of the washing or cleaning agent, they can be dyed with suitable dyes. Preferred dyestuffs, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the Textile treatment agents and against light and no pronounced substantivity to textile fibers so as not to stain them. For this purpose, in particular phthalocyanine dyes are suitable.

Suitable foam inhibitors which can be used in the detergents or cleaners are, for example, soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Suitable soil-release polymers, which are also referred to as "anti-redeposition agents", are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a methoxy group content of 15 to 30% by weight and hydroxypropyl groups of 1 to 15% by weight, respectively based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene and / or polypropylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof Derivatives include the sulfonated derivatives of the phthalic and terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the fabric treatment agents to eliminate graying and yellowing of the treated fabrics, which will attract the fiber and cause lightening and fake bleaching by converting invisible ultraviolet radiation to visible longer wavelength light. wherein the absorbed from sunlight ultraviolet light is radiated as pale bluish fluorescence and pure for the yellow shade of the grayed or yellowed laundry White results. Suitable compounds originate for example from the substance classes of the 4,4 ^{^{'diamino-2,2-stilbenedisulfonic}} acids (flavonic ), 4,4 ^{'-Distyryl-biphenylene,} Methylumbelliferone, coumarins, dihydroquinolinones, 1, 3- diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole and benzimidazole systems, and pyrene derivatives substituted by heterocycles. the optical Brighteners are usually used in amounts of between 0% and 0.3% by weight, based on the total amount of detergent or cleaning agent.

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. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, 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. However, preference is given to using cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof in amounts of from 0.1 to 5% by weight, based on the total amount of detergent or cleaning agent ,

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 squeezing transverse to the fiber direction, the detergents or cleaning agents may contain synthetic crease inhibitors. 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.

For controlling microorganisms, the textile treatment agents may contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatic agents and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and Phenolmercuriacetat, wherein in the inventive washing or cleaning agents can be completely dispensed with these compounds.

The textile treatment agents according to the invention may contain preservatives, it being preferred to use only those which have no or only a slight skin-sensitizing potential. Examples are sorbic acid and its salts, benzoic acid and its salts, salicylic acid and its salts, phenoxyethanol, formic acid and its salts, 3-iodo-2-propynyl butylcarbamate, sodium N- (hydroxymethyl) glycinate, biphenyl-2-ol and mixtures thereof. A suitable preservative is the solvent-free, aqueous combination of diazolidinyl urea, sodium benzoate and potassium sorbate (available as Euxyl® K 500 ex Schuelke & Mayr), which can be used in a pH range up to 7.

To prevent undesirable changes to the fabric treatment agents and / or the treated fabrics caused by oxygen and other oxidative processes, the detergents or cleaners may contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites, phosphonates and vitamin E.

An increased wearing comfort can result from the additional use of antistatic agents, which are additionally added to the detergents or cleaning agents. Antistatic agents increase the surface conductivity and thus allow an improved drainage 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 (respectively Stearyl) dimethylbenzylammonium chlorides are suitable as antistatic agents for textile fabrics or as an additive to textile treatment agents, wherein additionally a finishing effect is achieved.

To improve the rewettability of the treated fabrics and to facilitate the ironing of the treated fabrics, for example, silicone derivatives may be used in the fabric treatment agents. These additionally improve the rinsing out of the 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. The viscosities of the preferred silicones are in the range between 100 and 100,000 mPas at 25 ° C., wherein the silicones can be used in amounts of between 0.2 and 5% by weight, based on the total amount of detergent or cleaning agent.

Finally, the washing or cleaning agent may also contain UV absorbers, which are applied to the treated fabrics and improve the light resistance of the fibers. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. Also suitable are substituted benzotriazoles, phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

In order to avoid the catalyzed by heavy metals decomposition of certain detergent ingredients, substances that complex heavy metals can be used. Suitable heavy metal complexing agents are, for example, the Alkali metal salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA), methylglycinediacetic acid trisodium salt (MGDA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates present in the detergent or cleaning agent in amounts of 0.01 to 2.5% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1, 5 wt .-% are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1, 1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriaminepenta- (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.

The washing or cleaning agents according to the invention can be used for washing and / or cleaning textile fabrics, in particular dyed textile fabrics.

For the preparation of the washing or cleaning agent, a base formulation is first prepared by conventional methods and methods in which, for example, the ingredients of the base formulation are simply mixed in stirred tanks, water, non-aqueous solvents and surfactants are conveniently presented and the other ingredients, Fettalkyldialkylhydroxyethyl - Ammonium salt as a color transfer inhibitor, added in portions. Separate heating in the preparation is not required, if desired, the temperature of the mixture should not exceed 80 ° C.

In a preferred embodiment of this subject matter of the invention is a washing or cleaning agent, which is predominantly liquid, gel or pasty and preferably hydrous. The bleach-containing liquid or gel-containing compositions according to the invention are preferably heavy-duty detergents for textile cleaning, which have a flow behavior which the user perceives as aesthetically pleasing and / or good manufacturability.

Preferred embodiments of this subject matter are washing or cleaning agents according to the invention characterized as follows: having a water content of increasingly preferably 5 to 95, 10 to 90, 20 to 80, 30 to 70, 40 to 60, 45 to 55% by weight. % and very particularly preferably with a water content of 50 wt .-%, with a content of an inorganic salt, preferably a sulfate, particularly preferably sodium sulfate, from 3 to 30 wt .-%, preferably 5 to 20 wt .-%, particularly preferably 7 to 10 wt .-% in the liquid, gel or pasty phase and / or having a density of 1, 00 to 1, 50 g / ml, preferably from 1, 02 to 1, 30 g / ml, particularly preferably from 1 , 05 to 1, 15 g / ml.

Because the regulation of the water and / or electrolyte content of these agents and (possibly associated) their density - which are known in the art per se - they can be adapted in terms of their physico-chemical properties of the granules. The optimum of density, nature and dissolution behavior of the particles and water and / or electrolyte content and density of the funds is to be determined experimentally in individual cases. Particular care should be taken to ensure that the particles do not prematurely disintegrate. Advantageously, often desired and achievable in this way is also a floating of the particles in a liquid medium.

The density of the agent described in Example 5 of the present application is about 1.094 g / ml while that of the particles incorporated therein is about 1.29 g / ml. This shows that both densities do not necessarily have to be identical, but can differ within a certain range. Because there are other surface effects (charges, hydrophobicity / hydrophilicity effects, etc.) added, which are to be compensated experimentally in detail. Furthermore, a stabilization of the particles takes place in suspension the flow behavior of the agents. In particular, in liquid or gel compositions, the presence of a flow limit provides effective stabilization of the particle phase.

Preferred embodiments of this subject matter are detergents or cleaning compositions according to the invention containing a bleaching agent selected from the group: enzymatic bleaching system, inorganic bleaching system, organic bleaching system or a mixture thereof.

Bleaching systems for use in detergents and cleaners are known per se and have already been described above. Enzymatic systems have also been described above and can be added in inventive compositions in granulated form according to the invention or in another way, as long as at least one granule according to the invention is present. This may, for example, also be the substrate of such a bleaching enzyme (see above).

According to these explanations, preferred embodiments form this

Invention invention detergent or cleaning agent, wherein the bleach to

(i) H ₂ O ₂ or an H ₂ θ ₂ -generating system, particularly percarbonate,

(ii) H ₂ O ₂ or an H ₂ O ₂ -forming system, each in combination with a

Peroxycarboxylic acid precursor, in particular tetraacetylethylenediamine (TAED),

(iii) a preformed peroxycarboxylic acid, especially 1, 12-

Diperdodecanedioic acid (DPDDA), phthalimidoperoxyhexanoic acid (PAP), more preferably PAP or

(iv) is a combination of (a), (b) and / or (c).

Because this is on the one hand to particularly powerful bleaching agents (see above). On the other hand, in the examples for the present application, a formulation according to the invention which has been admixed with corresponding particles and additionally contains PAP is shown. These examples show the superiority of the present invention. Preferred embodiments of this aspect of the invention are detergents and cleaners according to the invention, wherein the bleach is present in the liquid or gel agent as particles, preferably as coated particles.

Possibilities for the realization of this idea have already been presented in the introduction. Reference may be made in particular to the applications WO 2004/110610 A1, WO 2004/1 10612 A1 and WO 2004/1 10611 A1. Although the coatings described therein alone were not sufficient to stabilize enzymes incorporated in liquid form, it is advantageous to combine these possibilities of encapsulating the bleaching agent with the granules of sensitive ingredients according to the invention. It comes in this way to an additionally improved protection of the sensitive ingredients.

Preferred embodiments of this aspect of the invention are detergents and cleaners according to the invention, wherein the sensitive ingredient is an oxidative enzyme.

In this way, on the one hand, the oxidative enzyme is protected against acting compounds, for example against the highly concentrated surfactants of a liquid detergent formulation. On the other hand, the enzyme and the substrate can be separated from one another in this manner, so that it comes to a reaction between the two only at the moment of use, that is the bursting of the granular particles at high dilution with water. In this way, the substrate is not prematurely consumed and is almost completely available for the desired use.

According to the previous embodiments, the present invention is also realized by suitable uses to make sensitive detergent or cleaning agent ingredients in the form of granules comparatively stable.

The use of the components is therefore according to the invention:

(b) particulate carrier material (adsorbent),

(c) one of (b) a different ingredient as a binder and (d) optionally further ingredients other than (b) and (c) to produce, in intimate mixture of these components with a sensitive detergent or detergency ingredient (component a), granules of this sensitive detergent or detergency ingredient which exhibits a disintegration index of at least 50% 24 hours.

In a use preferred according to the previous explanations, components (b) and (c) are in a weight% ratio of (b) to (c) of 1:50 to 50: 1, preferably of 1:20:20 : 1, more preferably from 1: 5 to 5: 1.

Accordingly preferred is the use according to the invention with the following components:

(a) the sensitive detergent or cleaning agent ingredient,

(b) 10 to 80% by weight of a particulate carrier material (adsorbent),

(c) 3 to 50% by weight of one of (b) a different ingredient as a binder, and

0 - 50 wt .-% (based on the granules) Löslichkeitsverbesserer (swelling agents, disintegration aids, disintegrants) and / or 0 - 40 wt .-% (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, antioxidants , the density regulating compounds and / or other ingredients.

Accordingly preferred is the use according to the invention, wherein the sensitive detergent or cleaning agent ingredient is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme.

Further embodiments of this aspect of the invention result in a corresponding manner from the previous representations of the granules according to the invention, their production process and / or detergents and cleaners. Further embodiments of all aspects of the invention will become apparent from the following examples.

Examples

example 1

Production of Enzyme Granules E1

An extrudate (granules E1) was prepared from the following constituents:

For this purpose, all pulverulent and dry substances 1 to 5 were premixed and introduced with a powder metering into a twin screw extruder type 20 / 4OD from Brabender (Duisburg, Germany) (screw diameter D: 20 mm; process length of the extruder: 40 × D, ie 800 mm) ). In this case, a temperature of 50 ° C and a pressure of 30 bar prevailed at the nozzle feeder; Furthermore, a torque of 37 Nm and a screw speed of 100 rpm were set at the extruder. After 12D, the liquid component 6 was added using a laboratory metering pump type M5 Lewa Lab (Hermann Ott AG, Leonberg). The mixture was then homogenized and plasticized on a process length of 28 × D. For the preparation, the enzyme mass was discharged through a round-strand die (diameter 1 mm) onto a conveyor belt and, after a cooling distance of 1 m, passed into a granulator type 881203 (from Brabender). The resulting cylindrical extrudate particles were mechanically rounded.

These granules consisted of (a) about 5% pure enzyme; the remaining components are thus contained in the following quantities: (b) 36% by weight of particulate carrier material consisting of Wessalith, Dispersal and TiO ₂ , (c) 18% by weight of binder, consisting of PVA, (d) 31% by weight. -% plasticizer, consisting of sodium stearate, and about 10% water. A portion of the particulate carrier material, namely the TiO ₂ , which in itself accounts for 13% of the total mass of the granules, also serves as a color pigment. The weight ratio of (b) to (c) was about 2: 1.

Example 2

Production of Enzyme Granules E2

An extrudate (granulate E2) was prepared from the following constituents:

The granulation took place except for the following deviations as in Example 1: All powdery and dry substances, that is to say components 1 to 6, were premixed and introduced into the extruder; the delivery ratio of the powder metering to the liquid metering was 15: 0.6

0.4; 5 to 15 bar were set as pressure and 23 Nm as torque.

These granules consist of about 5% pure enzyme; the remaining components are thus contained in the following quantities: (b) 31% by weight of particulate carrier material consisting of Wessalith, Dispersal and TiO ₂ , (c) 22% by weight of binder, consisting of PVA, (d) 24% by weight. % Plasticizer, consisting of sodium stearate, 8% by weight solubility improver, consisting of glucose and about 10% water. A portion of the particulate carrier material, namely the TiO ₂ , which in itself accounts for 8% of the total mass of the granules, also serves as a color pigment. The weight ratio of (b) to (c) was about 1.4: 1.

Example 3

Production of fluidized bed granules E3, E4 and E5

Manufacturer (E3) of sodium aluminum silicate (trade name Wessalith® ^® 4000: Degussa, for three more granules following carrier material components were used

Frankfurt / Main, Germany), (E4) partially hydrolyzed PVA (Trade name Mowiol ^® 4-88;.. Manufacturer Clariant,

Frankfurt / M., Germany) and (E5) sodium sulfate

For each of the three granules E3, E4 and E5, 600 g thereof were initially charged in the fluidized-bed system from Fielder-Aeromatic (Bubendorf, Switzerland). They were then treated with a mixture of 500 ml of protease solution (Everlase ^® 16 L, Novozymes A / S.) And with 500 ml of a 10% solution of a polyacrylate (methacrylic acid-ethyl acrylate copolymer (1: 1); , commercial product Eudragit ^® L 100-55 of Rohm, Darmstadt Germany; now, which has been previously adjusted with concentrated sodium hydroxide to pH 7.2 Degussa Frankfurt / M), at 60 ° C.. sprayed. The resulting granules were screened to a particle size of 0.6 mm - 1, 2 mm.

In addition to the protease component (about 5% by weight) and water (about 10% by weight), these granules also contained 78% by weight of the particulate carrier material (b) (sodium aluminum silicate, PVA or sodium sulfate) and 7% by weight. % of the binder (c) (polyacrylate). The weight ratio of (b) to (c) was about 1 1: 1.

Example 4

Production of coated fluidized bed granules E3c, E4c and E5c

In each case 900 g of the enzyme granules E3 prepared according to Example 3, E4 and E5 were mixed with 1.800 ml of a 10% solution of Eudragit ^® L 100-55 (see above), which has been previously adjusted with concentrated sodium hydroxide solution to pH 7.2 and 5% triethyl citrate (based on the polymer content) had been added as plasticizer, sprayed at 60 ^° C. in the fluidized bed system used in Example 3. As a result, the coated enzyme granules were obtained, which were sieved through a 2,000 micron sieve. They now carry the designations E3c, E4c and E5c.

The ready-made granules E3c, E4c and E5c thus contained a coating which in each case constituted about 21% of the mass of the granule core. The density of the coated granules was approximately 1.29 g / ml in each case.

Example 5

Production of liquid detergent formulations

Liquid heavy-duty detergents of the following compositions were prepared, the amount in% by weight being based on the active ingredient content in each case:

The preparation was carried out by the water was placed in a stirred tank and to the xanthan was added. After swelling the xanthan (30 min), the sulfate was added. Thereafter, the addition of the surfactants and the other raw materials in the order listed, with stirring. The pH was adjusted to 5.0 ± 0.2 by concentrated NaOH.

This gave the liquid detergent formulations F1 (with E1), F2 (with E2), F3c (with E3c), F4c (with E4c) and F5c (with E5c).

Their density of the liquid phase was determined to be about 1.094 g / ml. Example 6

Preparation of comparison formulations according to the prior art

There were liquid heavy duty detergents of the composition given in Example 5 were prepared, but with the difference that were used as component 7 commercially available forms of the protease, in each case the protease Everlase from. Novozymes A / S, Bagsvaerd, Denmark. As a result, the following comparative formulations were obtained:

V1: with 3.5% Everlase ^® 12 T (granules)

V2: with 2% Everlase ^® 16 L (liquid enzyme), weight balance in the formula:

water

It can be assumed that the coating of these granules in accordance with numerous descriptions of the prior art, for example the application WO 97/39116 A1 as essential ingredients PEG and titanium dioxide.

Example 7

Determination of storage stabilities

The formulations F1, F2, F3c, F4c, F5c and V1 and V2 prepared according to the preceding example were stored at a storage temperature of 25 ° C in gas-tight glass bottles. After periods of 1, 2, 4 and 8 weeks, the enzyme activity was determined by means of a "continuous flow apparatus" (Skalar, Erkelenz) The method is based on the cleavage of casein, staining of the hydrolysis products with trinitrobenzenesulfonic acid and their photometric determination Any other protease activity assay method which is not adversely affected by surfactants present is also applicable.

In the following table, the percentage residual activity of the protease, based on the starting activity immediately after the preparation of the samples, is given after the respective storage times:

It is observed that the enzyme presented in liquid form in sample V2 is presumably completely inactivated by the bleach contained within a very short time.

The commercially available enzyme granules in V1 show a higher but by no means satisfactory stability. The granulation and coating has therefore been insufficient to prevent exposure to the bleaching agent during storage. Further, it was observed in V1 that its granules disintegrate over time.

In contrast, the uncoated granules E1 and E2 are already characterized by a significantly longer lasting high enzyme activity, which in fact means a higher enzyme stability. This is particularly noteworthy because the recipe in question contains more than 50 wt .-% water. Both granules remained unchanged in shape, that is they did not disintegrate.

The results of the formulations E3c, E4c and E5c show that a considerable stabilization can also be achieved with the aid of the chosen coating agent. E5c with sodium sulfate as the particulate carrier material of the core shows in each case the absolute best values, followed by E4c with PVA as carrier material of the core. These granules also remained unchanged in their shape, that is they did not disintegrate. A combination of E1 (granule core with PVA, sodium stearate, sodium aluminum silicate, aluminum oxide and titanium dioxide) with a coating according to Example 4 (polyacrylate / triethyl citrate) gave an additional increase in stability.

Example 8

Preparation of Enzyme Granules E6

The following constituents were used to prepare an extrudate (granulate E6) as described in Example 1:

Thus, this formulation contained, with No. 6, approximately 4.2% by weight of enzyme as the sensitive ingredient (a), with Nos. 1 and 4 together, 22.7% by weight of component (b), with No. 5 13 wt .-% of component (c), with Nos. 2 and 3 together 22.7 wt .-% plasticizer as part of component (d) and as the predominant remainder water.

A portion of E6 was then coated as described in Example 4 to yield the coated granules E6c.

Example 9

Preparation of Enzyme Granules E7

The following constituents were used to prepare an extrudate (granulate E7) as described in Example 1:

Thus, this formulation contained, with No. 5, approximately 4% by weight of enzyme as component (a), with Nos. 1 and 3 together, 32% by weight of component (b), with No. 4 16% by weight of component ( c), with No. 2 12 wt .-% plasticizer as part of component (d) and as the predominant remainder water. A portion of E7 was then coated as described in Example 4 to give the coated granules E7c.

Example 10

Preparation of the enzyme granules E8

The following constituents were used to prepare an extrudate (granulate E8) as described in Example 1:

Thus, this formulation contained, with No. 6, approximately 4% by weight of enzyme as component (a), with Nos. 1 and 3 together 28% by weight of component (b), with Nos. 4 and 5 20% by weight. Component (c), with No. 2 12 wt .-% plasticizer as part of component (d) and as the predominant remainder water.

A portion of E8 was then coated as described in Example 4 to give the coated granule E8c.

Example 11

Disintegration test of enzyme granules

(Fa Genencor Purafect ^® OX4000E.) And K2 (Everlase ^® 12T; Novozymes Fa.) To determine the disintegration rate of the enzyme granules, the granules to the preceding examples prepared according to E7, E7c, E8, E8c and E5c and to control the two commercial products K1 were subjected to the following disintegration test:

1 g each of the respective enzyme preparation were weighed into a 50 ml glass bottle and with 30 ml of a 16% Na sulfate / 3% Na citrate solution, which had been adjusted to pH 5.0 by means of 10% sulfuric acid, added. This mixture was agitated for 24 hours at 23 ° C on a laboratory shaker (Certomat ^® U, Fa. Braun, Melsungen) at 100 revolutions per minute. Subsequently, this dispersion thus treated was filtered through an ED fast sieve, mesh size 0.28 mm without applying a pressure and with 50 ml of dist. Rinsed with water.

The sieve was dried for 48 h at 35 ° C. and the granules remaining in the sieve were weighed out and related to the initial value. In each case duplicate determinations were carried out.

The following values were obtained:

It can be seen that the state of the art granules K2 provides by far the worst value, that is largely disintegrated.

The granule K1 disintegrates significantly more than 50%. In addition, it has been observed that in these granules, the majority of the enzyme-containing active layer peels off.

The granules E7, E7c, E8, E8c, E5c according to the invention show values significantly above 50%, which means that the majority of the granules are not disintegrated in the test solution during storage (and even with shaking). So they meet the requirements of the invention.

Furthermore, a further stabilization by the application of a coating (coating) can be observed on the granules according to the invention.

Claims

claims

1. Granules of a sensitive detergent or cleaner ingredient containing the components

(a) the sensitive detergent or cleaning agent ingredient,

(b) a particulate carrier material (adsorbent),

(c) one of (b) different ingredient as binder and

2. Granules according to claim 1, wherein the components (b) and (c) in a wt .-% ratio of (b) to (c) from 1:50 to 50: 1, preferably from 1:20 to 20: 1, more preferably from 1: 5 to 5: 1.

3. Granules according to claim 1 or 2, comprising the following components:

(a) the sensitive detergent or cleaning agent ingredient,

(b) 10 to 80% by weight of a particulate carrier material (adsorbent),

(c) 3-50% by weight of one of (b) different ingredients as a binder and

0-50 wt .-% (based on the granules) Löslichkeitsverbesserer (swelling agents, disintegration aids, disintegrants), and / or 0 - 40 wt .-% (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, Antioxidants, density regulating compounds and / or other ingredients.

4. Granules according to one of claims 1 to 3, wherein it is the sensitive detergent or cleaning agent ingredient (a) to a perfume, an optical Brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme.

5. Granules according to claim 4, wherein the enzyme is one or a mixture of the following enzymes: protease, amylase, cellulase, hemicellulase, oxidase and perhydrolase, preferably an oxidation stabilized of these respective enzymes.

6. Granules according to one of claims 1 to 5, comprising as component (b) (adsorbent) one or more of the compounds selected from the group: talc, silica, alumina, silicate, in particular phyllosilicate and / or sodium aluminosilicate, bentonite, aluminosilicate ( Zeolite), sulfate, titanium dioxide and / or polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA, particularly preferably a combination of two or three of these compounds.

7. Granules according to one of claims 1 to 6, containing as component (c) (binder) one or more of the compounds selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, polysaccharide or substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of said compounds, in particular methacrylic acid-ethyl acrylate copolymer, more preferably a combination of two or three of these compounds.

8. Granules according to one of claims 1 to 7, comprising as part of component (d) (plasticizer), one or more compounds selected from the group: water-dispersible organic compound or water-dispersible organic polymer, in particular polyethylene glycol (PEG), especially short-chain PEG, fatty acid or salt of a fatty acid, triacetin, triethyl citrate and / or polyhydric alcohol, preferably fatty acid or salt of a fatty acid, more preferably sodium stearate and / or sodium oleate.

9. Granules according to one of claims 1 to 8, comprising as part of component (d) (solubility improver), one or more compounds selected from the group: water-soluble inorganic salt, monosaccharide, in particular glucose, oligosaccharide, polysaccharide, in particular cellulose, compacted Cellulose or cellulose derivative, crosslinked organic polymer, in particular crosslinked polyvinylpyrrolidone or crosslinked polyacrylate.

10. Granules according to one of claims 1 to 9, which is additionally coated with a single or multiple coating (coating).

11. Granules according to claim 10, wherein the coating consists of more than 50 wt .-% of one or more of the following compounds: water-dispersible substances, water-dispersible and / or water-soluble polymer, fatty acid, salt of a fatty acid, fatty alcohol, paraffin, polyvinyl acetate, polyacrylate , Polymethacrylate, methacrylic acid-ethyl acrylate copolymer, polyvinylpyrrolidone, cellulose ether, polyvinyl alcohol and ethoxylated polyvinyl alcohol.

12. Granules according to claim 11, wherein the water-soluble polymer is polyacrylate or a methacrylic acid-ethyl acrylate copolymer and / or the cellulose ether is methylcellulose (MC), hydroxyethylcellulose (HEC), hydroxypropylcellulose (HPC), hydroxypropylmethylcellulose (HPMC) or carboxymethylcellulose (CMC).

13. Granules according to any one of claims 10 to 12, wherein the coating additionally contains one or more fillers selected from the group of inorganic particles, preferably silicate or alumina, more preferably talc.

14. Granules according to any one of claims 10 to 13, wherein the coating additionally contains one or more plasticizers selected from the group: triethyl citrate, triacetin, polyhydric alcohol, in particular 1, 2-propanediol, and polyethylene glycol.

15. Granules according to any one of claims 10 to 14, wherein the coating additionally contains color pigment, preferably titanium dioxide.

16. Granules according to any one of claims 10 to 15, wherein the coating additionally contains one or more compounds acting as antioxidants.

17. Granules according to one of claims 10 to 16, wherein the coating is 5 to 100 wt .-%, preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% of the uncoated granules.

18. Granules according to one of claims 1 to 17, with an average particle diameter of 100 to 3000 microns, preferably 200 to 2500 microns, more preferably 400 to 2000 microns.

19. Granules according to one of claims 1 to 18, with an average density of 1, 00 to 1, 50, preferably from 1, 02 to 1, 30, particularly preferably from 1, 05 to 1, 15 g / ml.

20. A process for producing a granulate according to any one of claims 1 to 19.

21. The method according to claim 20, wherein the adsorbent (b) is presented as predominantly dry substance and the enzyme component (a) is incorporated as a liquid preparation.

22. The method according to claim 20 or 21, wherein the binder (c) is incorporated simultaneously with the liquid enzyme component (a), preferably in the form of a prior mixing of these two components together.

23. The method according to any one of claims 20 to 22, wherein the adsorbent (b) presented in a mixer or a fluidized bed apparatus and the binder (b) and / or the liquid enzyme component (a) are sprayed individually or with prior mixing, whereby it a per se homogeneous agglomerate comes.

24. The method according to any one of claims 20 to 23, optionally contained further solids together with the adsorbent (b) are mixed and submitted.

25. The method according to any one of claims 20 to 24, optionally incorporated further liquid substances are incorporated as a liquid preparation (s), optionally with prior mixing or emulsification with one or more of the other liquid components.

26. The method according to any one of claims 20 or 21, wherein the ingredients are extruded and optionally spheronized and / or optionally coated.

27. The method of claim 26, wherein at least one liquid under process conditions ingredient is fed separately during the extrusion process.

28. The method according to any one of claims 20 to 27, wherein the density of the granules obtained by adding higher or lower density substances as an additional component of the adsorbent (a) or as further ingredient (d) to average densities of 1, 00 to 1 , 50, preferably from 1, 02 to 1, 30, more preferably from 1, 05 to 1, 15 g / ml is set.

29. A process for producing a coated enzyme granulate according to any one of claims 20 to 28, wherein the coating material is sprayed in a fluidized bed apparatus from an aqueous solution / suspension on the particles to be coated.

30. A method for producing a coated enzyme granules according to any one of claims 20 to 29, wherein the total mass of the coating material 5 to 100 wt .-%, preferably 10 to 80 wt .-%, particularly preferably 15 to 60 wt .-% of the initially introduced mass the particle to be coated is.

31. Washing or cleaning agent containing a sensitive ingredient in the form of granules according to one of claims 1 to 19.

32. Washing or cleaning agent according to claim 31, which is predominantly liquid, gel or pasty and preferably hydrous.

33. Washing or cleaning agent according to claim 31 or 32 having a water content of increasingly preferably 5 to 95, 10 to 90, 20 to 80, 30 to 70, 40 to 60, 45 to 55 wt .-% and most preferably with a Water content of 50 wt .-%.

34. Washing or cleaning agent according to claim 32 or 33, with an inorganic salt content of 3 to 30 wt .-%, preferably 5 to 20 wt .-%, particularly preferably 7 to 10 wt .-% in the liquid, gel-like or pasty phase.

35. Washing or cleaning agent according to one of claims 32 to 34, having a density of 1, 00 to 1, 50 g / ml, preferably from 1, 02 to 1, 30 g / ml, particularly preferably from 1, 05 to 1 , 15 g / ml.

36. A washing or cleaning agent according to any one of claims 31 to 35, containing a bleaching agent selected from the group: enzymatic bleaching system, inorganic bleaching system, organic bleaching system or a mixture thereof.

37. Washing or cleaning agent according to claim 36, wherein the bleaching agent to

(i) H ₂ O ₂ or a hbCV-forming system, in particular percarbonate,

(ii) H ₂ O ₂ or a hbCV-forming system, each in combination with a

(iii) a preformed peroxycarboxylic acid, especially 1, 12-

(iv) is a combination of (a), (b) and / or (c).

38. Washing or cleaning agent according to claim 36 or 37, wherein the bleaching agent is present in the liquid or gel-like agent as a particle, preferably as a coated particle.

39. Washing or cleaning agent according to one of claims 31 to 38, wherein the sensitive ingredient is an oxidative enzyme.

40. Use of the components:

(b) particulate carrier material (adsorbent),

(c) one of (b) a different ingredient as a binder and

(d) optionally further ingredients other than (b) and (c) to produce, in intimate mixture of these components with a sensitive detergent or detergency ingredient (component a), granules of this sensitive detergent or detergency ingredient having a disintegration index of at least 50% after 24 hours.

41. Use according to claim 40, wherein the components (b) and (c) in a wt .-% ratio of (b) to (c) from 1:50 to 50: 1, preferably from 1:20 to 20: 1, more preferably from 1: 5 to 5: 1.

42. Use according to claim 40 or 41, with the following components:

(a) the sensitive detergent or cleaning agent ingredient,

(b) 10 to 80% by weight of a particulate carrier material (adsorbent),

(c) 3 to 50% by weight of one of (b) a different ingredient as a binder, and

0-50 wt .-% (based on the granules) Löslichkeitsverbesserer (swelling agents, disintegration aids, disintegrants) and / or 0- 40 wt .-% (based on the granules) of water, enzyme stabilizers, dyes, color pigments, pH buffer substances, Antioxidants, density regulating compounds and / or other ingredients.

43. Use according to any one of claims 40 to 42, wherein it is the sensitive detergent or cleaning agent ingredient is a perfume, an optical brightener, a bleach activator or an enzyme, preferably an enzyme, more preferably an oxidation-stabilized enzyme.