EP2007863B1 - Granulates for a sensitive washing- or cleaning agent containing material - Google Patents

Granulates for a sensitive washing- or cleaning agent containing material Download PDF

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Publication number
EP2007863B1
EP2007863B1 EP20070728143 EP07728143A EP2007863B1 EP 2007863 B1 EP2007863 B1 EP 2007863B1 EP 20070728143 EP20070728143 EP 20070728143 EP 07728143 A EP07728143 A EP 07728143A EP 2007863 B1 EP2007863 B1 EP 2007863B1
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EP
European Patent Office
Prior art keywords
particular
granules
weight
preferably
washing
Prior art date
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Active
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EP20070728143
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German (de)
French (fr)
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EP2007863A1 (en
Inventor
Peter Schmiedel
Petra Padurschel
Heribert Kaiser
Anette Nordskog
Wolfgang Von Rybinski
Regina Stehr
Karl-Heinz Maurer
Cornelius Bessler
Sören HÖLSKEN
Rolf Tenhaef
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication date
Family has litigation
Priority to DE200610018780 priority Critical patent/DE102006018780A1/en
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to PCT/EP2007/053678 priority patent/WO2007122126A1/en
Publication of EP2007863A1 publication Critical patent/EP2007863A1/en
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Publication of EP2007863B1 publication Critical patent/EP2007863B1/en
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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50Perfumes
    • C11D3/502Protected perfumes
    • C11D3/505Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0034Fixed on a solid conventional detergent ingredient
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials characterised by their shape or physical properties
    • C11D17/0039Coated compositions or coated components in the compositions, (micro)capsules
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/38Products with no well-defined composition, e.g. natural products
    • C11D3/386Preparations containing enzymes, e.g. protease, amylase
    • C11D3/38672Granulated or coated enzymes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3935Bleach activators; Bleach catalysts granulated, coated or protected
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40Dyes ; Pigments
    • C11D3/42Brightening agents ; Blueing agents

Abstract

The present invention relates to granulates for a material that contains a sensitive washing- or cleaning agent, containing the components (a) the material that contains the sensitive washing- or cleaning agent, (b) an individual substrate material (adsorbent), (c) a substance of content that is different from (b) as a binding agent,and (d) optional additional substances of content that are different from (b) and (c) that display a disintegration index of at least 50% after 24 hours. These granulates are particularly suited for use in liquid- or gel-forming aqueous washing- or cleaning agents. The present invention also relates to a procedure for the manufacture of such granulates, in regard to washing- and cleaning agents, as well as the use of appropriate components (a), (b), (c), and (d) for the manufacture of such granulates.

Description

  • 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, mostly solid means.
  • A fundamental alternative to this is the preparation of enzymes in liquid form, which are usually incorporated in over-flowing 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.
  • 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 by WO 99/00471 A1 and WO 99/00478 A1 disclosed. In both cases, the enzymes are formulated into so-called prills, which are also customary for use in solid compositions, that is to say without protection beyond this solid form. However, both are anhydrous. The first of these applications teaches 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 context 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 preparation of granules in which various layers are applied to an inert core or support. 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, for example, go out WO 96/38527 A1 and WO 97/39116 A1 out. The PEG-containing layer may in each case also contain titanium dioxide. A fundamental one For example, interchangeability of PEG and PVA for these purposes is disclosed WO 00/63336 A1 ,
  • A liquid applied coating system for sensitive ingredients that can also enter into aqueous media, also reveals 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. So can according to WO 01/23513 A1 Enzyme encapsulated in a wax and added in this form liquid detergents and cleaners, wherein the disclosed in this application agents are virtually free of water.
  • The registration EP 356239 A2 discloses a system according to which enzymes are uniformly 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 is revealed WO 92/20771 A1 for liquid detergent formulations with a water content of up to 60 wt .-%.
  • The registrations 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 contained enzymes 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 registration US 2005/0245418 A1 describes the encapsulation of enzymes in a water-soluble gel for use in aqueous detergents and cleaners.
  • Out EP 653485 A1 It turns out to dissolve or suspend sensitive ingredients such as enzymes in an oil and to trap 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 used WO 03/106607 A1 out. 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 according to claim 1
  • 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, granules are to be understood as 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 Form of discrete particles or granules (granules, granules) are provided. 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 the preparation of various chemical compounds, especially for use in detergents and cleaners are 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.
  • An alternative to the extrusion process, for example, from the Handbook "Fluidized Bed Spray Granulation" by H.Uhlemann and L.Mörl, Springer-Verlag, Berlin, Heidelberg, New York, 2000, Chap. 1 (Basics of Fluidized Bed Spray Granulation), pp. 69 to 126 , and Cape. 8 (process variants), p. 219 to 244 or.
  • 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) which can be converted, for example, by oxidizing ingredients into the corresponding different or non-fragrant derivatives, such as the carboxylic acids;
    • optical brighteners (for example, biphenyl derivatives with fused 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.
  • According to the invention, these are: 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 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-cross-linked, polymeric compounds selected from the group: polyacrylates, polymethacrylates, methacrylic acid-ethyl acrylate copolymers, polyvinylpyrrolidones, 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, triacetin 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 improvers make up a weight fraction of 0-50% by weight (based on the granules). Preferably, they are selected from the group consisting of water-soluble inorganic salts, monosaccharides, preferably glucose, oligosaccharides, and swelling agents, especially compounds suitable as disintegrants, 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 a reduced C-terminus, especially 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 C 8 -C 18 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 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) remaining 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 for 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, granules of the prior art, which had a structurally different structure, showed significantly worse values. including those having an inert core (of MgSO 4 ) on 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.
  • According to the invention, the components (b) and (c) are present in a weight% ratio of (b) to (c) of from 1: 5 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.
  • Granules of the invention contain the components:
  1. (a) the sensitive detergent or cleaning agent ingredient,
  2. (b) 10 to 80% by weight of a particulate carrier material (adsorbent),
  3. (c) 3-50% by weight of one of (b) different ingredients as a binder and
  4. (d) as optional further ingredients other than (b) and (c):
    • 0-50 wt .-% (based on the granules) plasticizer,
    • 0-50 wt .-% (based on the granules) Löslichkeitsverbesserer (swelling agents, disintegrants, 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.
  • Individual ingredients have already been listed above and will be listed again below. 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 .-%. component (b), 18% by weight of component (c) and under (d) a proportion of 31% by weight of plasticizer and about 10% by weight of water. A part of the particulate carrier material, namely the TiO 2 , which in itself accounts for 13% by weight of the total mass of the granulate, also serves as a color pigment in the formulation specified therein. 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 wt .-%, preferably less than 30 wt .-% and more preferably less than 20 wt .-% 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, lilial and bourgeonal, to the ketones for example the ionone, α-isomethylionone and methyl cedryl ketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include 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. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of 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-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), acylated hydroxycarboxylic acids, such as triethyl-O-acetylcitrate (TEOC), Carboxylic anhydrides, in particular phthalic anhydride, isatoic anhydride and / or succinic anhydride, carboxylic acid amides 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 their mixtures (SORMAN), acylated sugar derivatives, especially 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-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 dodecanoyloxybenzenesulfonate ( 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
    Figure imgb0001
    in the R 1 is -H, -CH 3 , a C 2-24 alkyl or alkenyl radical, a substituted C 2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2 , -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C 1-24 -alkyl group and at least one further substituent on the aromatic ring, R 2 and R 3 are 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
    Figure imgb0002
    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, 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 - 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 percent by weight, 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 ( Gornall AG, 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. From the protease from Bacillus lentus DSM 5483 ( WO 91/02792 A1 ) derive from the name under the name BLAP ® variants, which in particular in WO 92/21760 A1 . WO 95/23221 A1 . WO 02/088340 A2 and WO 03/038082 A2 to be discribed. Other useful proteases from various Bacillus sp. and B. gibsonii go out of the patent applications WO 03/054185 A1 . WO 03/056017 A2 . WO 03/055974 A2 and WO 03/054184 A1 out.
  • 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, for this purpose in the application WO 02/10356 A2 disclosed α-amylase from Bacillus sp. A 7-7 (DSM 12368) and in the application WO 02/44350 A2 described cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948). Furthermore, the amylolytic enzymes belonging to the sequence space of α-amylases can be used, which in the application WO 03/002711 A2 is defined, and the ones in the application WO 03/054177 A2 to be discribed. Likewise, fusion products of said molecules can be used, for example those from the application DE 10138753 A1 or point mutations of it.
  • In addition, the enhancements available under the trade names Fungamyl.RTM ® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. 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 sold, for example, 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 are the originally marketed by Gist-Brocades preparations 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 in terms of their various performance aspects. These performance aspects include, in particular, contributions to the primary washing performance, the secondary washing performance of the composition (anti-redeposition effect or graying inhibition) and softening (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 ®, likewise available from Novozymes, are based on the 50 kD EG and 43 kD EG from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ® and Renozyme ®. The latter is based on the registration WO 96/29397 A1 , Performance-enhanced cellulase variants go, for example, from the application WO 98/12307 A1 out. Likewise, those in the application WO 97/14804 A1 disclosed cellulases 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 in WO 96/34092 A2 disclosed, the 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 IndiAge ® 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, for example, from the application WO 99/06573 A1 out. The obtained from B. subtilis β-glucanase 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 as peroxidase at low H 2 O 2 concentrations), 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 an example of advantageous systems for an enzymatic perhydrolysis can be applied to the application WO 98/45398 A1 directed. Particularly useful for such a system For example, choline oxidases are disclosed WO 2004/058955 A2 , Modified proteases with pronounced, at this point also advantageously usable perhydrolase activity, in particular for achieving a mild bleaching in laundry detergents go from the application WO 2004/058961 A1 out. 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 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 the 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
    1. a) choline oxidases whose amino acid sequence with the 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 most preferably 100%,
    2. b) choline oxidases, whose amino acid sequence with the in the international patent application WO 2005/124012 in SEQ ID NO. At least 89%, more preferably at least 90%, 92%, 94%, 95%, 96%, 97%, 98%, 99%, and most preferably 100%, of the indicated amino acid sequence,
    3. c) choline oxidases, whose amino acid sequence with the 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,
    4. d) choline oxidases, whose amino acid sequence with the in 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 most preferably 100% matches, and
    5. e) choline oxidases according to a), b), c) or d) obtained by mono- 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) available;
      and / or the perhydrolase is selected from
    6. f) 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, 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, 235, 215, 255, 257, 261,
    7. 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,
    8. h) 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 58, 89, 96, 117, 216, 217,
    9. i) perhydrolases whose amino acid sequence is that described in the 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,
    10. j) perhydrolases, whose amino acid sequence with one of the in the 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%.
  • The disclosure of the abovementioned sequences of perhydrolases is based on the disclosure in the international patent application WO 2005/124012 directed.
  • 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. Among the above-mentioned commercial products Everlase ® and Purafect OxP as examples of such proteases and Duramyl are particular to cite 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 enzyme" preparations are also commercially available, especially proteases and amylases designed for use in detergents and cleaners. For the preparation of the granules are, for example, liquid protease preparations having an enzyme protein content of 0.1 to 50%, preferably 5 to 40%, particularly preferably 10 to 35% They may optionally by methods known in the art (for example, concentration via rotary evaporation or dilution by adding buffer) to a suitable concentration for further processing.
  • Granules according to the invention contain 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 aluminosilicate, bentonite, aluminosilicate (zeolite), sulfate, titanium dioxide and / or polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA, more 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 So 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.
  • Granules according to the invention contain as component (c) (binder) one or more of the compounds selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, substituted polysaccharide, in particular cellulose ethers, polyvinyl alcohol (PVA), in particular partially hydrolyzed PVA or ethoxylated PVA, a copolymer of the abovementioned 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: 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.
  • 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.
  • 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, p 4440) and Voigt "textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184 ) Under tablet disintegrants or disintegrants understood excipients that provide for the rapid disintegration of tablets in water or gastric juice and for the release of drugs 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 gasein derivatives.
  • Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention.
  • 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 can 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 optical image.
  • 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 also reflected in the structure of the coating. Overviews of these processes and apparatuses, for example, provide the Manuals "Fluidized Bed Spray Granulation" by H.Uhlemann and L.Mörl, Springer-Verlag, Berlin, Heidelberg, New York, 2000, Chap. 14.3 (enveloping), pp. 461 to 473 , and " Agglomeration Processes. Phenomena, Technologies, Equipment "by W. Pietsch, Verlag Wiley-VCH, Welnheim, 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: // w210.ub.unituebingen.de/dbt/volltexte/2000/134/index.html. can be viewed (accessed on 5/5/2005).
  • 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. (1) a pigment-containing coating of: (a) 5 to 70% by weight (based on the coating) of fine, inorganic, water-insoluble pigment, (b) 45 to 90% by weight of an organic substance having a melting point of 40 to 70 ° C and (c) to 20 wt .-% of a bulkiness improving agent; such a coating goes out EP 944704 B1 forth;
    2. (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 goes out WO 03/020868 A1 forth;
    3. (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 disclosed in the non-prepublished application DE 102004062326.0 described;
    4. (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. (5.) according to the non-prepublished application DE 102004062326.0 abrasion-resistant coated enzyme granules which can be produced by subjecting the granules particles to a urea-containing aqueous preparation and at least partially removing the water 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, polyhydric 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 having an average density of from 1.00 to 1.50, preferably from 1.02 to 1.30, particularly 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. Advantageously, according to the invention, an extrusion temperature of below 60 ° C and an extrusion pressure in the range of 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. Conveniently, the diameter of the holes in the perforated disc is 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 widely used in the art under the trade name Marumerizer® and, for example, in US Pat DE 2137042 and DE 2137043 described. 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 of more than 2 mm, in particular more than 1.6 mm, can be removed by sieving or air classification and optionally returned to the production 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 additional solids mixed together with the adsorbent (b) and submitted;
    • 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 liquid 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 connection with the present invention, as can be seen from the previous statements and can also be recognized from this description, the following variants of the method have also been found 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 addition of materials of higher or lower density as additional component of the adsorbent (a) or as further ingredient (d) to average densities of 1.00 to 1.50, preferably of 1.02 is adjusted to 1.30, more preferably from 1.05 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 cleaners are provided which contain sensitive ingredients, especially enzymes with good protection against other, especially 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 include, for example: extrudates, granules, tablets or pouches, packed both in large 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.
  • 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 average particle sizes Range from 0.7 to 2.0 mm. The granules according to the invention preferably contain less than 2% by weight, in particular not more than 1.4% by weight, of particles having a particle size outside the range from 0.4 to 2.0 mm. The method is not limited to these particle sizes, but covers a wide range of particle sizes corresponding to the field of application; usually the average particle diameter (d 50 ) is between 0.1 and more than 2 mm.
  • 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 detergents or cleaning agents according to the invention characterized as follows:
    • with a water content of increasingly preferred 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 .-%,
    • 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
    • at a density of 1.00 to 1.50 g / ml, preferably from 1.02 to 1.30 g / ml, more 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 composition 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 of this aspect of the invention form detergents or cleaners according to the invention, wherein the bleach is
    1. (i) H 2 O 2 or an H 2 O 2 -forming system, in particular percarbonate,
    2. (ii) H 2 O 2 or an H 2 O 2 -forming system, in each case in combination with a peroxycarboxylic acid precursor, in particular tetraacetylethylenediamine (TAED),
    3. (iii) a preformed peroxycarboxylic acid, in particular 1,12-diperdodecanedioic acid (DPDDA), phthalimidoperoxyhexanoic acid (PAP), more preferably PAP or
    4. (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 bleaching agent 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. It is in particular to the registrations WO 2004/110610 A1 . WO 2004/110612 A1 and WO2004 / 110611 A1 directed. 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.
  • 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, enzyme and substrate can be at least largely separated from one another in this way, 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 Reinigungsmiltelinhaltsstoffe in the form of granules comparatively stable.
  • Therefore, according to the invention is the use according to claim 13.
  • 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: No. Quantity [g] ingredient 1 80 Polyvinyl alcohol (viscosity of 4.5 ± 0.5; Saponifikations number 270-310 mg KOH / g; commercial product Erkol ® M05 / 290 Fa Erkol, Tarragona, Spain.) 2 140 Sodium stearate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 3 20 Sodium aluminum silicate (average particle size 3.5 microns; commercially available product ® Wessalith P = Wessalith ® 4000;. Degussa, Frankfurt / M, Germany) 4 80 Aluminum oxide (commercial product Disperal P3 ®; Sasol, Hamburg, Germany.) 5 60 Titanium dioxide (Kronos, Leverkusen, Germany) 6 456 Liquid protease preparation (commercial product containing 95% water, balance: pure enzyme stabilized by point mutagenesis against oxidation and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g)
  • For this purpose, all powdery and dry substances 1 to 5 were premixed and introduced with a powder metering into a twin screw extruder Type 20 / 40D 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: No. Quantity [g] ingredient 1 110 Polyvinyl alcohol (Erkol ® M05 / 290) 2 120 Sodium stearate (Riedel / Fluka) 3 40 Sodium aluminum silicate (Wessalith ® 4000) 4 40 glucose 5 80 Alumina (Disperal P3 ®) 6 40 Titanium dioxide (Kronos) 7 516 Liquid protease preparation (as in Example 1)
  • The granulation took place with the following deviations as in example 1:
    • All powdered 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 for liquid metering was 15: 0.6-0.4;
    • as pressure 5 to 15 bar were set and
    • as torque 23 Nm.
  • 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
  • The following carrier material components were used for three further granules:
  • (E3)
    Sodium aluminum silicate (trade name Wessalith® ® 4000, manufactured by Degussa, Frankfurt / M., Germany),
    (E4)
    partially hydrolyzed PVA (Trade name Mowiol ® 4-88;.. manufacturer Clariant, Frankfurt / M, Germany) and
    (E5)
    sodium sulphate
  • 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;. meanwhile Degussa, Frankfurt / M), which has been previously adjusted to pH 7.2 with concentrated sodium hydroxide solution at 60 ° C. sprayed. The granules thus obtained 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 11: 1.
  • Example 4 Production of coated fluidized bed granules E3c, E4c and E5c
  • In each case 900 g of the enzyme granules E3, E4 and E5 produced according to Example 3 were 100-55 with 1,800 ml of a 10% solution of Eudragit ® L (see above), which has been previously adjusted to pH 7.2 with concentrated sodium hydroxide and 5% triethyl citrate (based on the polymer content) had been added as plasticizer, sprayed in the fluid bed unit used in Example 3 at 60 ° C. As a result, the coated enzyme granules were obtained, which were screened 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 in each case about 1.29 g / ml.
  • 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: No. amount ingredient [% By weight of active substance] 1 16.5 Sodium linear alkyl benzene sulfonate (commercial product Maranil ®, from Cognis, Dusseldorf). 2 10 Nonionic surfactant (C 12-18 fatty alcohol ethoxylate (7 EO); commercial product Dehydol ® LT 7; Cognis). 3 1 Hydroxyethane-1,1-diphosphonic acid Na4 salt (HEDP; Sequion ® 10 H 60; Fa Polygon Chemie, Olten, Switzerland). 4 3 sodium citrate 5 8th sodium sulphate 6 3 Phthalimidoperoxyhexanoic acid (PAP) as granules (400-1200 microns; commercial product Eureco ® W; Solvay Solexis; Bussi, Italy.) 7 3.5 Enzyme granules E1, E2, E3c, E4c or E5c 8th 0.25 Xanthan gum; Commercial product TGCS; Fa. Jungbunzlauer Xanthan, Pernhofen, Austria) 9 1 Perfume 10 0.1 Silicone antifoam (commercial product DC 2-3910, Wacker, Munich) 11 ad 100 water
  • 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
  • Liquid heavy-duty detergents of the composition given in Example 5 were prepared, with the difference that the commercially available formulations of the protease were used as component 7, in each case the protease Everlase from Novozymes A / S, Bagsværd, 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 recipe: water
  • It can be assumed that the coating of this granulate in accordance with numerous descriptions from the prior art, for example the application WO 97/39116 A1 as essential ingredients PEG and titanium dioxide contained.
  • 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 using 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. In principle, any other protease activity determination method which is not impaired by surfactants present can also be used.
  • 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: sample 1 week 2 weeks 4 weeks 8 weeks V1 45 30 15 0 V2 0 0 0 0 F1 96 89 77 55 F2 94 87 75 48 F3c 92 87 69 40 F4c 95 88 68 45 F5C 100 89 77 56
  • 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) resulted in an additional stability increase.
  • Example 8 Preparation of Enzyme Granules E6
  • The following constituents were used to prepare an extrudate (granulate E6) as described in Example 1: No. amount amount ingredient [G] [Wt .-%] 1 80 13 Polyvinyl alcohol (viscosity 4.5 ± 0.5, saponification number 270-310 mg KOH / g, commercial product Erkol M05 / 290 from Erkol, Tarragona, Spain) 2 80 13 Sodium oleate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 3 60 9.7 Sodium stearate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 4 60 9.7 Sodium sulfate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 5 80 13 crosslinked polyvinylpyrrolidone (commercial product Collidon ® CL of the Fa. BASF, Ludwigshafen, Germany) 6 260 42 Liquid protease preparation (commercial product containing about 10% by weight of pure enzyme protein stabilized by point mutagenesis against oxidation, balance: water and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g)
  • 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: No. amount amount ingredient [G] [Wt .-%] 1 80 16 Polyvinyl alcohol (viscosity 4.5 ± 0.5, saponification number 270-310 mg KOH / g, commercial product Erkol M05 / 290 from Erkol, Tarragona, Spain) 2 60 12 Sodium stearate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 3 80 16 Sodium sulfate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 4 80 16 cross-linked polyvinylpyrrolidone (commercial product Collidon CL from BASF, Ludwigshafen) 5 200 40 Liquid protease preparation (commercial product containing about 10% by weight of pure enzyme protein stabilized by point mutagenesis against oxidation, balance: water and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g)
  • 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: No. amount amount ingredient [Wt .-%] [Wt .-%] 1 80 16 Polyvinyl alcohol (viscosity of 4.5 ± 0.5; Saponifikations number 270-310 mg KOH / g; commercial product Erkol ® M05 / 290 Fa Erkol, Tarragona, Spain.) 2 60 12 Sodium stearate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 3 60 12 Sodium sulfate (Riedel-de Haën / Sigma-Aldrich, Seelze, Germany) 4 20 4 Methacrylic acid-ethyl acrylate copolymer (commercial product Eudragit ® L100. From Degussa, Frankfurt / M) 5 80 16 crosslinked polyvinylpyrrolidone (commercial product Collidon ® CL of the Fa. BASF, Ludwigshafen, Germany) 6 200 40 Liquid protease preparation (commercial product containing about 10% by weight of pure enzyme protein stabilized by point mutagenesis against oxidation, balance: water and 1,2-ethylene glycol as stabilizer, about 160,000 HPU / g)
  • 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
  • (Novozymes Everlase ® 12T.), For determining the disintegration rate of the enzyme granules, the granules produced according to the previous examples E7, E7c, E8, E8c and E5c have been well as to control the two commercial products K1 (Purafect ® OX4000E Fa Genencor.) And K2 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 moved 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: granules Residue [% by weight] K1 45 K2 7 E7 60 E7c 70 E8 66 E8c 70 E5c 89
  • 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 well 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 (13)

    1. Granulate of a sensitive washing or cleaning agent ingredient, containing the components:
      (a) the sensitive washing or cleaning agent ingredient,
      (b) 10 to 80% by weight of a particulate carrier material selected from the group: talc, silicic acid, aluminium oxide, silicate, in particular phyllosilicates and/or sodium aluminium silicate, bentonite, aluminosilicate, sulfate, titanium dioxide and/or polyvinyl alcohol, in particular partly hydrolyzed polyvinyl alcohol, more preferably a combination of two or three of these compounds,
      (c) 3 to 50% by weight of an ingredient different from (b) as a binder, selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, substituted polysaccharide, in particular cellulose ether, polyvinyl alcohol, in particular partly hydrolyzed polyvinyl alcohol or ethoxylated polyvinyl alcohol, methacrylic acid-ethyl acrylate copolymer, more preferably a combination of two or three of these compounds, and
      (d) optionally further ingredients different from (b) and (c):
      0 to 50% by weight of plasticizer,
      0 to 50% by weight of solubility enhancing agent and/or
      0 to 40% by weight of water, enzyme stabilizers, coloring agents, color pigments, pH buffer substances, antioxidants, density regulating compounds and/or further ingredients,
      which has a disintegration index of at least 50% after 24 hours, determined with a sieve with a mesh size of 280µm, and in which the components (b) and (c) are present in a weight % ratio of (b) to (c) from 1:5 to 20:1, more preferably from 1:5 to 5:1.
    2. The granulate according to claim 1, containing as part of the component (d) (solubility enhancing agent) one or several compounds selected from the group: water-soluble inorganic salt, monosaccharide, in particular glucose, oligosaccharide, polysaccharide, in particular cellulose, compacted cellulose or cellulose derivative, cross-linked organic polymer, in particular cross-linked polyvinylpyrrolidone or cross-linked polyacrylate.
    3. The granulate according to any of claims 1 or 2, which is additionally coated with a single or multiple coating, in particular, one in which the coating consists of more than 50% by weight of one or more of the following compounds: water-dispersible substances, a water-dispersible and/or water-soluble polymer, a fatty acid, a fatty acid salt, a fatty alcohol, a paraffin, polyvinyl acetate, polyacrylate, polymethacrylate, methacrylic acid-ethyl acrylate copolymer, polyvinylpyrrolidone, cellulose ether, polyvinyl alcohol and ethoxylated polyvinyl alcohol, in particular, one with an average density from 1.00 to 1.50, preferably from 1.02 to 1.30, more preferably from 1.05 to 1.15g/mL.
    4. A method for preparing a granulate according to any of claims 1 to 3, in particular one in which the adsorbent (b) is placed as an essentially dry substance and the enzyme component (a) is incorporated as a liquid preparation.
    5. A washing or cleaning agent, containing a sensitive ingredient as a granulate according to any of claims 1 to 3.
    6. The washing or cleaning agent according to claim 5, which is essentially a liquid, a gel or a slurry and preferably aqueous, in particular, one with a water content increasingly preferred from 5 to 95, 10 to 90, 20 to 80, 30 to 70, 40 to 60, 45 to 55% by weight and most preferably with a water content of 50% by weight.
    7. The washing or cleaning agent according to claim 6 with a content of an inorganic salt from 3 to 30% by weight, preferably from 5 to 20% by weight, more preferably from 7 to 10% by weight in the liquid, gel, respectively slurry phase.
    8. The washing or cleaning agent according to any of claims 6 to 7, with a specific gravity from 1.00 to 1.50 g/mL, preferably from 1.02 to 1.30 g/mL, more preferably from 1.05 to 1.15 g/mL.
    9. The washing or cleaning agent according to any of claims 5 to 8, containing a bleaching agent, selected from the group: an enzymatic bleaching system, an inorganic bleaching system, an organic bleaching system, or a mixture thereof.
    10. The washing or cleaning agent according to claim 9, wherein as for the bleaching agent, this is
      (i) H2O2 or a H2O2 forming system, in particular a percarbonate,
      (ii) H2O2 or a H2O2 forming system, each in combination with a peroxycarboxylic acid precursor, in particular tetraacetylethylene-diamine (TAED),
      (iii) a preformed peroxycarboxylic acid, in particular 1,12-diperdodecanedioic acid (DPDDA), phthalimidoperoxyhexanoic acid (PAP), more preferably PAP or
      (iv) a combination of (a), (b) and/or (c).
    11. The washing or cleaning agent according to claim 9 or 10, wherein the bleaching agent is present as a particle in the liquid or gel agent, preferably as a coated particle.
    12. The washing or cleaning agent according to any of claims 5 to 11, wherein the sensitive ingredient is an oxidative enzyme.
    13. The use of the components:
      (b) 10 to 80% by weight of a particulate carrier material, selected from the group: talc are, silicic acid, aluminium oxide, silicate, in particular phyllosilicates and/or sodium aluminium silicate, bentonite, aluminosilicate, sulfate, titanium dioxide and/or polyvinyl alcohol, in particular partly hydrolyzed polyvinyl alcohol, more preferably a combination of two or three of these compounds.
      (c) 3 to 50% by weight of an ingredient different from (b) as a binder, selected from the group: polyacrylate, polymethacrylate, polyvinylpyrrolidone, substituted polysaccharide, in particular cellulose ether, polyvinyl alcohol, in particular partly hydrolyzed polyvinyl alcohol or ethoxylated polyvinyl alcohol, and
      (d) optionally further ingredients different from (b) and (c):
      0 to 50% by weight of plasticizer,
      0 to 50% by weight of solubility enhancing agent and/or
      0 to 40% by weight of water, enzyme stabilizers, coloring agents, color pigments, pH buffer substances, antioxidants, density regulating compounds and/or further ingredients, in order to prepare a granulate of this sensitive washing and cleaning agent ingredient in an intimate mixture of these components with a sensitive washing or cleaning agent ingredient, which has a disintegration index of at least 50% after 24 hours, and in which the components (b) and (c) are present in a weight % ratio of (b) to (c) from 1:5 to 20:1, more preferably from 1:5 to 5:1.
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    WO2007122126A1 (en) 2007-11-01
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    JP2009534493A (en) 2009-09-24
    US20090156454A1 (en) 2009-06-18

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