EP1421169B1 - Encapsulated active ingredient preparation for use in particulate detergents and cleaning agents - Google Patents

Abstract

A granulate for particulate detergents or cleaning agents, the granulate containing a detergent or cleaning agent active ingredient and an outer encapsulation layer formed of polyvalent metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms or a mixture of the salts. Also, a process for making the granulate by applying to the granules an encapsulation material that comprises one or more polyvalent metal salt or salts, preferably in the form of an aqueous dispersion in a fluidized bed process.

Description

The invention relates to a coated granules containing a detergent or cleaning agent ingredient, in particular an enzyme and / or a bleach activator, a process for its preparation and the use of the granules in solid detergents and cleaners.

In addition to good washing and cleaning performance, the consumer also expects modern laundry detergents and cleaners to have a positive aesthetic impression, which manifests itself, in particular, in a fragrance that is associated with freshness and cleanliness. To comply with this, the agents usually contain appropriate fragrances. However, a not insignificant proportion of consumers rejects this, inter alia, arguing that fragrances do not contribute to the washing or cleaning results, so that their use merely increases the price of the funds. These consumers prefer completely odorless detergents and cleaners. Some ingredients of such agents, however, have a more or less strong odor, which may also be based on minor components contained in these ingredients. The use of such ingredients is unpleasant in perfume-free agents and may cause an increase in perfume concentration in fragrance-containing agents to compensate for the inherent odor.

In connection with this problem, the German patent application DE 17 92 074 discloses agents containing zinc ricinoleate as a deodorizing agent whose deodorizing effect by addition of other salts or esters of other saturated or unsaturated even or odd-numbered hydroxylated fatty acids having 17 or more carbon atoms, for example Salts and esters of trioxystearic acids, is synergistically supported.

German patent application DE 25 48 344 discloses the deodorization efficiency of metal salts of an unsaturated fatty acid, in particular of metallic ricinoleates. Metals from Group II of the Periodic Table of the Elements and of the rare earths such as cerium, lanthanum or neodymium are preferred. Especially highlighted is zinc ricinoleate.

German patent application DE 38 08 114 relates to deodorizing mixtures of active substances, the zinc ricinoleate and optionally the zinc salt of abietic acid and / or further zinc salts of other saturated or unsaturated hydroxylated fatty acids having 17 or more carbon atoms, partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, Polyethylene glycols or alkanolamines with the ene adducts of maleic anhydride to at least monounsaturated carboxylic acids having a chain length of 10 to 25 carbon atoms having an acid number of 10 to 140 and optionally amino and / or amido compounds and in preparations with water contents of up to 50 wt. -% stay clear.

Active ingredients which are customarily used in detergents and cleaning agents and in which the occurrence of a more or less unpleasant odor can not always be excluded include, in particular, enzymes and bleach activators.

Enzymes, in particular proteases, find extensive use in detergents, detergents and cleaners. Usually, the enzymes are not used as concentrates, but in mixtures with a diluent and carrier material. If such enzyme preparations are mixed with customary detergents, a considerable reduction in enzyme activity may occur during storage, especially when bleach-active compounds are present. The application of the enzymes to carrier salts with simultaneous granulation according to the German patent application DE 16 17 190 or by sticking with nonionic surfactants according to the German patent application DE 16 17 118 or aqueous solutions of cellulose ethers according to the German patent document DE 17 87 568 does not lead to a significant improvement storage stability, since the sensitive enzymes in such Aufinischungen are usually on the surface of the vehicle. Although the storage stability of the enzymes can be substantially increased by enveloping the enzymes with the support material or embedded in this and then converted by extrusion, pressing and Marumerisieren in the desired particle shape, such as in German Patent DE 16 17 232, the German Laid-open publication DE 20 32 768, and the German Auslegeschriften DE 21 37 042 and DE 21 37 043 described. However, such enzyme preparations have only poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it or they are transferred unused to the wastewater. Although known from the German patent application DE 18 03 099 embedding agents consisting of a mixture of solid acids or acidic salts and carbonates or bicarbonates and decompose when added to water, although improve the Lösimgsvelvermögen, but in turn are very sensitive to moisture and therefore require additional protection measures.

European patent specification EP 0 168 526 discloses enzyme granules which contain water-swellable starch, zeolite and water-soluble granulation assistant. In this document, a production method for such formulations is proposed, which consists essentially of concentrating a fermenter solution freed from insoluble constituents, to be mixed with said additives, to granulate the resulting mixture and optionally to coat the granules with film-forming polymers and dyes. The process with the additive mixture proposed there is advantageously carried out with fermentation solutions which have been concentrated to a relatively high dry matter content, for example 55% by weight. In addition, the granules produced in this way have such a high rate of dissolution or disintegration under washing conditions that some of the granules disintegrate relatively quickly during storage and the enzymes are deactivated.

In the non-prepublished European patent application EP 1 213 344 A2, a process for the preparation of particulate detergent components by applying a melt of 30 to 70 wt .-% shell substance (s) having a melting point above 50 ° C, 0 to 65 wt .-% Fettstoff (s), 0 to 50 wt .-% of other active ingredients and / or excipients 0.1 to 70 wt .-% of metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 8 carbon atoms and or a rosin acid with the exception of the alkali metal salts, and then shaping the resulting mixture.

From the international patent application WO 92/11347 enzyme granules for use in granular detergents and cleaners are known, the 2 wt .-% to 20 wt .-% enzyme, 10 wt .-% to 50 wt .-% swellable starch, 5 wt % to 50% by weight of water-soluble organic polymer as granulating agent, 10% by weight to 35% by weight of cereal flour and 3% by weight to 12% by weight of water. Such aggregates make enzyme processing possible without major loss of activity.

International Patent Application WO 93/07263 discloses an enzyme-containing granule which consists of a water-soluble or -dispersible core coated with a vinyl polymer having thereon a layer of enzyme and vinyl polymer, the granules forming an outer coating Vinyl polymer. The outer cover may also contain pigments. Due to the multi-layer structure, however, such enzyme granules are relatively expensive to produce.

International patent application WO 93/07260 mentions various coating materials for dust-free enzyme granules which are produced by spraying a fermentation broth onto a hydratable carrier material. Among others, fatty acid esters, alkoxylated alcohols, polyvinyl alcohol, polyethylene glycol, sugar and starch are listed as suitable.

International Patent Application WO 95/02031 relates to an enzyme granule containing enzyme and inorganic and / or organic carrier material and a uniform outer pigment-containing coating layer, which is characterized in that the outer coating layer consists of a coating system, which 30 wt .-% to 50 wt .-% finely divided inorganic pigment, 45 wt .-% to 60 wt .-% of a solid at room temperature alcohol having a melting point in the range of 45 ° C to 65 ° C, up to 15 wt .-%, in particular 5 wt. % to 15 wt .-% emulsifier for the alcohol, up to 5 wt .-%, in particular 0.2 wt .-% to 3 wt .-% dispersant for the pigment and up to 3 wt .-% water.

Although the above-described coating systems are generally suitable for stably enclosing enzyme granules so that no odor escapes from them Nevertheless, one strives to find alternatives whose application is as simple as possible and / or leads to cost advantages:

The present invention, which seeks to contribute to this, relates to a suitable for incorporation into particulate detergents or cleaning granules containing a detergent and / or detergent active ingredient and having an outer coating layer (coating), which is characterized in that outer coating layer complexing agent and a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12, in particular 16 to 24 carbon atoms or mixtures thereof. Among these, ricinoleic acid is particularly preferred. The granules may be undyed or, for example by the presence of pigment in the coating layer, white or colored.

Preferred polyvalent metals are selected from the transition metals and the lanthanides and are especially the transition metals of groups IIB, VIIIB and optionally IB of the periodic table and lanthanum, cerium and neodymium, more preferably cobalt, nickel, copper and zinc, with zinc being the most preferred metal is. The cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred. In a preferred embodiment, the coating layer accordingly contains one or more metal salts of ricinoleic acid, in particular zinc ricinoleate.

The coating layer contains one or more of the said deodorizing agents in an amount of usually 0.05% by weight to 5% by weight, preferably 0.1% by weight to 2.5% by weight, in particular 0.5% by weight. -% to 2 wt .-%. It is preferred to apply as much of the coating material forming the coating layer to the granules that the resulting coated granules 0.02 wt .-% to 1 wt.%, In particular 0.05 wt .-% to 0.2 wt .-% containing said deodorant agent.

The coating material forming the coating layer may comprise one or more solubilizers for solubilizing the deodorizing agent, in particular in amounts of from 0.05% by weight to 5% by weight, preferably from 0.3% by weight to 1% by weight. contain. Preferred solubilizers are anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, in particular anionic and / or nonionic surfactants having a solubilizing, hydrotroping and / or emulsifying action. The nonionic solubilizers include ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C _10-22 alcohols having a mean degree of alkoxylation up to 30, preferably ethoxylated C _10-18 fatty alcohols with a average degree of ethoxylation of 1 to 20, in particular 1 to 12, more preferably 1 to 8, most preferably 2 to 5, for example C _12-14 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of C _12-14 fatty alcohol ethoxylates with 3 and 4 EO in a weight ratio of 1 to 1 or isotridecyl alcohol ethoxylate with 5, 8 or 12 EO, as described, for example, in German Patent DE 40 14 055, to which reference is made in this regard. Suitable anionic solubilizers are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the ene-adducts of maleic anhydride to at least monounsaturated carboxylic acids having a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140, which are described in US Pat German patent application DE 38 08 114 and the European patent application EP 0 046 070, to which reference is made in this regard will be described. Preferred anionic solubilizers comprise, in addition to an unbranched or branched, saturated or unsaturated, aliphatic or aromatic, acylclic or cyclic, optionally alkoxylated alkyl radical having 4 to 28, preferably 6 to 20, especially 8 to 18, particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms, two or more anionic, in particular two, acid groups, preferably carboxylate, sulfonate and / or sulfate groups, in particular a carboxylate and a sulfate group on. Examples of these compounds are the alpha-sulfofatty acid salts, the acylglutamates, the monoglyceride disulfates and the alkyl ethers of the glycerol disulfate, as well as the sulfosuccinamates, sulfosuccinamides and sulfosuccinates. at the latter are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, while the sulfosuccinamates mean the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides the salts of diamides of sulfosuccinic acid. The salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts , most preferably sodium salts. A preferred sulfosuccinate is sulfosuccinic acid lauryl polyglycol ester di sodium salt.

In a particular embodiment, the coating material contains as solubilizer one or more anionic and one or more nonionic surfactants, preferably in a weight ratio of anionic to nonionic surfactants of from 10 to 1 to 1 to 10, in particular 3 to 1 to 1 to 5, particularly preferably 1 to 1 to 1 to 3, more preferably from 1 to 1.5 to 1 to 2, preferably the abovementioned anionic and nonionic surfactants, in particular the sulfosuccinates, especially the monoesters, and the alkoxylated C _10-22 alcohols, be combined with each other.

In a further particular embodiment, the wrapping material contains one or more solubilizers and one or more of said deodorizing agents in a weight ratio of not more than 14: 1, preferably 10: 1 to 1: 10, especially 5: 1 to 1: 5, more preferably 2 to 1 to 1 to 2, most preferably from 1.5 to 1 to 1 to 1.5, for example 1.3 to 1, 1.1 to 1, 1 to 1 or 1 to 1.1.

The coating material forming the coating layer contains one or more complexing agents. Chelating agents, also commonly called sequestering agents, are ingredients that are capable of complexing and inactivating metal ions to prevent their adverse effects on the stability or appearance of the agents. On the one hand, it is important that the Complex with calcium and magnesium ions of water hardness incompatible with numerous ingredients of detergents and cleaners. On the other hand, the complexation of the ions of heavy metals such as iron or copper delays the oxidative decomposition of the finished agents. Suitable examples are aminotrimethylenephosphonic acid, beta-alaninediacetic acid, ethylenediaminetetraacetic acid, citric acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentamethylenephosphonic acid, etidronic acid, gluconic acid, glucuronic acid, tetrahydroxyethylethylenediamine, tetrahydroxypropylethylenediamine, nitrilotriacetic acid and mixtures thereof, the acids being used among these also in the form of their alkali metal and / or ammonium salts can. Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (amino alcohols). These compounds have both amino and hydroxy and / or ether groups as functional groups. Particularly preferred tertiary alkanolamines are triethanolamine and tetra (2-hydroxypropyl) ethylenediamine. In the context of the present invention particularly preferred combinations of tertiary amines or tertiary alkanolamines with Zinkricinoleat and one or more ethoxylated fatty alcohols as nonionic solubilizers and optionally solvents are described in German Patent DE 40 14 055, to which reference is made in this regard. If desired, the coating material may contain complexing agents in an amount of usually up to 20% by weight, preferably 0.1 to 15% by weight, in particular 0.5 to 10% by weight.

Another preferred component of the wrapping material is an alcohol having a melting point in the range of from 45 ° C to 65 ° C, which may optionally be present in amounts up to 60% by weight in the wrapping layer-forming wrapping material. This alcohol component is preferably a primary linear alcohol having 14 to 22 C atoms or a mixture of these. The alcohols mentioned include, in particular, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and monosubstituted to triunsaturated alcohols of corresponding chain length, it being essential that said alcohol component of the coating system has a melting point in the range from 45 ° C to 65 ° C, especially 50 ° C to 60 ° C which is to be understood here as the temperature at which 100% of the alcohol component is present in liquid form when heated. When alcohol mixtures are used, those which contain small proportions, normally less than 15% by weight, based on the alcohol mixture, of liquid fractions at room temperature, as long as the entire alcohol mixture appears solid at room temperature and a solidification point in the range of 45 ° C. to 65 ° C. ° C, in particular from 50 ° C to 60 ° C. The solidification point is the temperature at which solidification occurs upon cooling to a temperature above the melting point. It can be determined with the aid of a rotating thermometer according to the method of DIN ISO 2207. The use of polymeric diols with the stated melting or solidification behavior is possible, in particular polyethylene glycols are preferred.

In addition, the coating layer may contain inorganic pigment. The inorganic pigments which may be used to mask any troublesome dyeings of the granules include, for example, calcium carbonate, titanium dioxide, which may be in rutile or anatase crystal modification, zinc oxide, zinc sulfide, lead white (basic lead carbonate), barium sulfate, aluminum hydroxide, antimony oxide, lithopone (Zinc sulfide barium sulfate), kaolin, chalk and / or mica. These are in such finely divided form that they can be dispersed in a melt of the remaining constituents of the coating material or in water. Usually, the average particle size of such pigments in the range of 0.004 microns to 50 microns. In particular, when the pigment or the entire coating material is to be used in the form of an aqueous dispersion in the production of the coated granules, it is preferred that this dispersion contains dispersants for the pigment. Such dispersants may be inorganic, for example alumina or silica, which may also serve as pigments, or organic, for example, alkali metal carboxymethyl cellulose, diethylene glycol or dipropylene glycol. The use with dispersants of surface-modified pigments is also possible. Preferably, with Al, Si, Zr or polyol compounds surface-modified titanium dioxide pigment, in particular in rutile form, as it for example, under the trade names Kronos® 2132 (Kronos-Titan) or Hombitan® R 522 (Sachtleben Chemie GmbH) is used. The Tiona® RLL, AG or VC grades from Solvay and the Bayertitan® RD, R-KB and AZ grades from Bayer AG are also suitable.

Another object of the invention is a process for the preparation of suitable for incorporation into particulate detergents or cleaning granules containing a detergent and / or detergent active ingredient and having an outer coating layer, which is characterized in that on the granules, a wrapping material as an outer coating layer, the complexing agent and a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms. Preferably, the proportion of said deodorizing agent in the coating material to be applied is 0.05% by weight to 5% by weight, in particular 0.3% by weight to 1% by weight.

In a preferred embodiment of the production method for a granulate according to the invention, the wrapping material is introduced as an aqueous dispersion, which optionally contains up to 70% by weight, preferably 40% by weight to 60% by weight, of water in a fluidized bed of granules to be coated , The water fed in via the aqueous dispersion is removed again during the drying which is carried out simultaneously or subsequently again. In a further embodiment of the production method according to the invention, the wrapping material, optionally with cooling, is applied to the granules as a heated liquid. In addition, a combination of these procedures, which consists of applying part of the coating material in the form of an aqueous dispersion and a second part as a melt, is possible. Preferably, based on finished granules, 6 wt .-% to 15 wt .-% of the coating material as an outer coating layer on the granules.

The washing and / or cleaning agent active ingredient contained in the granules to be coated is, in particular, one which has a perceptible odor. With particular advantage, the coating with the mentioned deodorizing agent is used in granules containing enzyme and / or bleach activator.

Suitable enzymes are primarily those derived from microorganisms, such as bacteria or fungi, proteases, lipases, amylases and / or cellulases, with proteases produced by Bacillus species and their mixtures with amylases being preferred. They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US Pat 4,264,738, European Patent Application EP 006 638 and international patent application WO 91/2792. Enzymes are preferably contained in the granules coated according to the invention in amounts of from 4% by weight to 20% by weight. If the enzyme granulate coated according to the invention is a protease-containing formulation, the protease activity is preferably 150,000 protease units (PE, determined by the method described in Tenside 7 (1970), 125) to 350,000 PE, in particular 160,000 PE to 300,000 PE, per gram of enzyme granules.

A preferred embodiment of the invention relates to a process for preparing an enzyme granulate suitable for incorporation into particulate detergents or detergents having a mean particle size in the range from 0.4 mm to 1.2 mm, in particular from 0.8 mm to 1.2 mm by extruding an enzyme premix obtained by mixing a concentrated fermentation broth previously liberated by microfiltration from insoluble constituents with inorganic and / or organic carrier material as an additive, optionally spheronising the extrudate in a rounder, drying and applying an outer coating layer, wherein a fluidized layer of extrudate applies an outer coating layer containing a polyvalent metal salt of a straight or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms.

Suitable support materials for the enzyme are, in principle, all organic or inorganic powdery substances which do not destroy or deactivate the enzymes to be granulated, or tolerable, and are stable under granulation conditions. Such substances include, for example, starch, cornmeal, cellulose powder, alkali aluminosilicate, especially zeolite, phyllosilicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali chloride, alkali metal sulfate, alkali metal carbonate or alkali acetate, with sodium or potassium being the preferred alkali metals. Preference is given to using a carrier material mixture of starch which is swellable in water, cereal flour and optionally cellulose powder and also alkali metal carbonate. The water-swellable starch is preferably corn starch, rice starch, potato starch or mixtures thereof, the use of corn starch being particularly preferred. Swellable starch is preferably present in the enzyme granules according to the invention in amounts of from 20% by weight to 50% by weight, in particular from 25% by weight to 45% by weight. The sum of the amounts of the swellable starch and the flour is preferably not more than 80 wt .-%, in particular 32 wt .-% to 65 wt .-%. The cereal flour is, in particular, a product that can be produced from wheat, rye, barley or oats or a mixture of these flours, preference being given to full meals. Under a wholemeal flour is understood that not fully ground flour that has been made from whole, unpeeled grains or at least predominantly consists of such a product, the remainder of fully ground flour or starch. Commercially available wheat flour qualities, such as Type 450 or Type 550, are preferably used. The use of flour products of the above-mentioned swellable starches leading crops is possible if care is taken that the flours have been made from whole grains. The flour component of the aggregate mixture is known to achieve a substantial odor reduction of the enzyme preparation, which far exceeds the odor reduction by the incorporation of equal amounts of appropriate types of starch.

Such cereal flour is preferably present in the enzyme granules according to the invention in amounts of from 10% by weight to 35% by weight, in particular from 15% by weight to 25% by weight. The enzyme granules of the invention may contain as further component of the support material preferably 1 wt .-% to 50 wt .-%, preferably 5 wt .-% to 25 wt .-%, based on total granules, of a Granulierhilfsmittelsystems containing the alkali carboxymethylcellulose with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate. In this granulation auxiliary system are preferably, in each case based on finished enzyme granules, 0.5 wt .-% to 5 wt .-% alkali carboxymethylcellulose with degrees of substitution of 0.5 to 1 and up to 3 wt .-% polyethylene glycol and / or alkyl polyethoxylate , wherein it is particularly preferred if at least 0.5 wt .-%, in particular 0.8 wt .-% to 2 wt .-% polyethylene glycol having an average molecular weight below 1000 and / or alkyl polyethoxylate is present with at least 30 ethoxy groups, if more contained as 2 wt .-% alkali carboxymethyl cellulose. Higher substituted carboxymethylcellulose, with degrees of substitution up to 3, is preferably not included in the granulation aid system. Optionally, additional cellulose or starch ethers, such as carboxymethyl starch, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, Maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible oligomers or polymers as additional components of Granulierhilfsmittelsystems natural or synthetic origin. Useful synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers of acrylic acid with maleic acid or vinyl group-containing compounds, furthermore polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinylpyrrolidone. Insofar as the abovementioned compounds are those having free carboxyl groups, they are normally present in the form of their alkali metal salts, in particular their sodium salts. Such additional granulation aids may be present in the enzyme granules according to the invention in amounts of up to 10% by weight, in particular from 0.5% by weight to 8% by weight. Although higher molecular weight polyethylene glycols, that is those having an average molecular weight of more than 1000, are useful as synthetic water-soluble polymers having a dust-binding effect, the effect is precisely those higher molecular weight polyethylene glycols an undesirable increase in the required granule dissolution time, so that these substances are preferably completely absent in accordance with the invention to be enveloped enzyme granules.

For the preparation of the enzyme granules are preferably from fermented broths, which are freed, for example by microfiltration of insoluble impurities. The microfiltration is preferably carried out as a cross-flow microfiltration using porous tubes with micropores greater than 0.1 microns, flow rates of the concentrate solution of more than 2 m / s and a pressure difference to the permeate side of less than 5 bar, such as in the European patent application EP 200th 032 described. Subsequently, the microfiltration permeate is preferably concentrated by ultrafiltration, optionally followed by vacuum evaporation. The concentration may, as described in international patent application WO 92/11347, be conducted in such a way that only relatively low contents of dry substance of preferably 5% by weight to 50% by weight, in particular 10% by weight, are obtained. reaches 40 wt .-%. The concentrate is added to a suitably previously prepared dry, powdery to granular mixture of the above-described additives. The water content of the mixture should be chosen so that it can be converted into granular, non-sticking at room temperature particles when working with stirring and impact tools and plastically deform and apply at higher pressures. The free-flowing premix is in principle known manner then processed in a kneader and a connected extruder to a plastic, homogeneous as possible mass, as a result of mechanical processing, the mass to temperatures between 40 ° C and 60 ° C, especially 45 ° C to Can heat 55 ° C. The material leaving the extruder is passed through a perforated disc with subsequent doctor blade and thereby zerldeinert to cylindrical particles of defined size. Conveniently, the diameter of the holes in the perforated disc is 0.7 mm to 1.2 mm, preferably 0.8 mm to 1.0 mm. The particles present in this form can then be dried and coated with the wrapping material described above. However, it has proven to be advantageous to leave the extruder and chopper To spheronize cylindrical particles before wrapping, that is to round them in suitable devices and deburr. For this purpose, a device is used which consists of a cylindrical container with stationary, solid side walls and a base plate rotatably mounted friction plate. Devices of this type are common in the art under the trade name Marumerizer® and described for example in German Auslegeschriften DE 21 37 042 and DE 21 37 043. 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 supply air temperatures of preferably 35 ° C to 50 ° C and in particular at a product temperature of not more than 42 ° C to the desired residual moisture content of, for example, 4 wt .-% to 10 wt .-%, in particular 5 wt .-% to 8 wt .-%, based on the total granules, dried.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃,
-CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben und X ein ladungsausgleichendes Anion ist. Gegebenenfalls können die Reste R² und R³ auch Teil eines das N-Atom und gegebenenfalls weitere Heteroratome einschließenden Heterocyclusses, insbesondere eines Morpholinrings, sein.Further preferred detergent or cleaner ingredients which may be present in the granules to be coated are bleach activators, especially from the classes of N- or O-Acylverbindimgen, for example, polyacylated alkylene diamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated Hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfuryl amides and cyanurates, as well as carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose. Detergent ingredients particularly preferred in this context are bleach activators of the quaternized aminoalkyl nitrile type of the general formula (I),

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} 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 with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another above for R ¹ , R ² or R ³ have the meaning given and X is a charge-balancing anion. Optionally, the radicals R ² and R ^{3 may} also be part of a heterocycle comprising the N atom and optionally further hetero atoms, in particular a morpholine ring.

The preparation of compounds of the formula I can be carried out by known processes or by analogy thereto, as described, for example, in European Patent Application EP 0 464 880, International Patent Application WO 98/23719, by Abraham in Progr. Phys. Org. Chem. 11 (1974), p. 1ff, or Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. Preference is given to compounds of the formula I in which R ¹ , R ² and R ^{3 are} identical. Among these, particular preference is given to those compounds in which the radicals mentioned are methyl groups. On the other hand, those compounds are preferred in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have a plurality of carbon atoms. The anions X ^- include in particular the halides such as chloride, fluoride, iodide and bromide, nitrate, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, metaphosphate, hexafluorophosphate, carbonate, bicarbonate, sulfate, hydrogen sulfate, C _1-20 alkyl sulfate, C _1-20 -alkyl sulfonate, optionally C _1-18 alkyl-substituted arylsulfonate, chlorate, perchlorate and / or the anions of C _1-24 carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures. Bleach activators according to formula I are preferred in which X ^- chloride, sulfate, hydrogensulfate, ethosulfate, C _12/18 , C _12/16 or C _13/15 -alkyl sulfate, lauryl sulfate, Dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylenesulfonate or methosulfate or mixtures thereof. In this context, toluenesulfonate or cumene sulfonate is understood as meaning the anion of the ortho, meta or para isomers of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof. Para- isopropylbenzenesulfonic acid is particularly preferred.

If desired, the bleach activators can be converted into granular form, as described above for enzyme, before the coating step essential to the invention, wherein an aqueous preparation of the bleach activator which occurs as a result of the preparation takes the place of the fermenter broth. Bleach activator granules coated according to the invention have a content of bleach activator of preferably at least 40% by weight and in particular from 50% by weight to 92% by weight.

A preparation obtained by the process according to the invention consists of substantially rounded, uniformly coated and dust-free particles, which generally have a bulk density of about 500 to 900 grams per liter, in particular 650 to 880 grams per liter. The granules of the invention are characterized by a very high storage stability, especially at temperatures above room temperature and high humidity, and a rapid dissolution behavior in the wash liquor. Preferably, the granules according to the invention release 100% of the activity of the active substance contained in them, in particular if this is an enzyme, within 3 minutes, in particular within 90 seconds to 2 minutes, in water at 25 ° C.

The coated granules according to the invention or produced by the process according to the invention is preferably used for the production of solid, in particular particulate detergents or cleaners, which can be obtained by simply mixing the granules with other particulate components customary in such agents. For incorporation into particulate detergents and cleaners, the granules preferably have mean particle sizes in the range of 0.8 mm to 1.2 mm. The granules according to the invention preferably contain less than 2 wt .-%, in particular at most 1.4 wt .-% of particles with grain sizes outside the range of 0.4 mm to 1.6 mm. If desired, it is also possible to mold the coated granules according to the invention or prepared by the process according to the invention, optionally together with other ingredients of such agents, shaping and to produce, for example, detergents and cleaners in tablet form or in the form of other moldings.

Examples example 1

A harvested pulp obtained after fermentation with 75,000 protease units per g (PE / g), as described in international patent application WO 91/2792, was concentrated after removal of the fermentation residues by decantation and microfiltration in an ultrafiltration unit. After further concentration by means of vacuum evaporation, the aqueous enzyme suspension contained 700 000 PE / g. This protease concentrate was mixed with additives (3.5 wt .-% sucrose, 4.5 wt .-% cellulose, 3 wt .-% carboxymethylcellulose with degree of substitution 0.65-0.75, 19 wt .-% wheat flour, 35 wt. % Corn starch and 3 wt .-% polyethylene glycol, based in each case based on the resulting mixture), homogenized and then converted into granules in an extruder with cutting device. The hole diameter of the perforated plate of the extruder was 0.9 mm. The ratio of length to thickness of the granules was 1. After the rounding and drying of the granules, the particles with particle size less than 0.4 mm and greater than 1.6 mm were sieved. The grain fraction between 0.4 mm and 1.6 mm was coated in a fluidized bed spray granulator of the STREA-1 type from Aeromatic in the fluidized bed. During the coating, the following operating parameters were set: supply air temperature: 85 ° C Product temperature: 36 ° C Exhaust air temperature: 33 ° C Air flow: 90 m ³ / h Throughput rate of coating supension: 8 g / min

The coating suspension consisted of 16% by weight of titanium dioxide, 16% by weight of polyethylene glycol (PEG 12000), 1.5% by weight of a mixture of 50 parts by weight of zinc ricinoleate, 35 parts by weight of 3-ethoxylated lauryl alcohol and 15% by weight Parts tetra- (2-hydroxypropyl) ethylenediamine (Tegosorb® conc 50), 0.5 wt .-% sodium carboxymethylcellulose and the remainder to 100 wt .-% water.

The coating suspension was sprayed onto the enzyme extrudate at the operating parameters given above. The water of the coating suspension evaporated and was discharged with the exhaust air. After spraying about 285 g of coating suspension per kg of enzyme granules, the extrudates were completely coated with a white color and protective layer. Compared to otherwise unchanged granules made by spraying a coating suspension lacking the zinc ricinoleate-containing mixture, the odor was markedly lower, in particular lacking the onion note of the odor.

Example 2:

To the enzyme extrudate produced as in Example 1 was first a coating suspension consisting of titanium dioxide, polyethylene glycol and water, and then the mixture mentioned in Example 1 of 50 parts by weight Zinkricinoleat, 35 parts by weight of 3-ethoxylated lauryl alcohol and 15 wt. Parts of tetra- (2-hydroxypropyl) ethylenediamine each spotted in such amounts that gave the proportions of Example 1 in the gross composition. Again, the odor after spraying the Zinkricinoleats was significantly lower.

Claims (20)

1. Granulate suitable for incorporation into particulate detergents or cleaning agents which comprises a detergent and/or cleaning agent active ingredient and has an outer encapsulation layer (coating), characterized in that the outer encapsulation layer comprises complexing agents and a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms or mixtures thereof.
2. Granulate according to Claim 1, characterized in that the polyvalent metals are chosen from the transition metals and the lanthanoids and in particular are the transition metals of groups IIB, VIIIB and in some cases IB of the Periodic Table of the Elements.
3. Granulate according to Claim 1 or 2, characterized in that the polyvalent metal is cobalt, nickel, copper or zinc, in particular zinc.
4. Granulate according to one of Claims 1 to 3, characterized in that the fatty acid is ricinoleic acid.
5. Granulate according to one of Claims 1 to 4, characterized in that the encapsulation layer comprises polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms in an amount of from 0.05% by weight to 5% by weight.
6. Granulate according to one of Claims 1 to 5, characterized in that it comprises polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms in an amount of from 0.02% by weight to 1% by weight, in particular from 0.05% by weight to 0.2% by weight.
7. Granulate according to one of Claims 1 to 6, characterized in that the encapsulation material forming the encapsulation layer comprises, to solubilize the deodorizing active ingredient, one or more solubility promoters in amounts of from 0.05% by weight to 5% by weight, in particular from 0.3% by weight to 1% by weight.
8. Granulate according to Claim 7, characterized in that the solubility promoter is an unbranched or branched, saturated or unsaturated C_10-22-alcohol alkoxylated with ethylene oxide (EO) and/or propylene oxide (PO) and having an average degree of alkoxylation up to 30, in particular an ethoxylated C_10-18-fatty alcohol with an average degree of ethoxylation of from 1 to 20, in particular from 2 to 5.
9. Granulate according to Claim 7, characterized in that the solubility promoter is an α-sulpho fatty acid salt, acyl glutamate, monoglyceride disulphate, an alkyl ether of glycerol disulphate, a sulphosuccinamate, sulphosuccinamide and/or sulphosuccinate.
10. Granulate according to one of Claims 1 to 9,
    characterized in that the encapsulation material forming the encapsulation layer comprises up to 20% by weight, in particular 0.1 to 15% by weight, of complexing agents, in particular tertiary alkanolamines.
11. Granulate according to one of Claims 1 to 10, characterized in that the encapsulation material forming the encapsulation layer additionally comprises inorganic pigment.
12. Granulate according to one of Claims 1 to 11, characterized in that it comprises enzyme, in particular in amounts of from 4% by weight to 20% by weight.
13. Granulate according to Claim 12, characterized in that the enzyme is protease, lipase, amylase and/or cellulase obtained from microorganisms.
14. Granulate according to one of Claims 1 to 13, characterized in that it has a content of bleach activator of at least 40% by weight and in particular of from 50% by weight to 92% by weight.
15. Granulate according to Claim 14, characterized in that it comprises bleach activator of the quaternized aminoalkylnitrile type of the general formula (I),

    

    in which R¹ is -H, -CH₃, 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, -NH₂, -CN, an alkyl or alkenylaryl radical with a C_1-24-alkyl group, or is a substituted alkyl or alkenylaryl radical with a C_1-24-alkyl group and at least one further substituent on the aromatic ring, R² and R³, independently of one another, are chosen from -CH_2-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH (CH₃) -CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH (OH) -CH₃, -CH(OH)-CH₂-CH₃, - (CH₂CH₂-O) _nH where n = 1, 2, 3, 4, 5 or 6, R⁴ and R⁵, independently of one another, have a meaning given above for R¹, R² or R³, in some cases radicals R² and R³ are also part of a heterocycle which includes the N atom and optionally further heteroatoms, in particular a morpholine ring, and X is a charge-balancing anion.
16. Process for the preparation of granulate suitable for incorporation into particulate detergents or cleaning agents which comprises a detergent and/or cleaning agent active ingredient and has an outer encapsulation layer, characterized in that an encapsulation material is applied to the granulate as outer encapsulation layer which comprises complexing agents and a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms.
17. Process according to Claim 16, characterized in that the amount of encapsulation material forming the encapsulation layer applied to the granulate is such that the resulting encapsulated granulate comprises 0.02% by weight to 1% by weight, in particular 0.05% by weight to 0.15% by weight, of polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms.
18. Process according to Claim 16 or 17, characterized in that the content of polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 12 carbon atoms in the encapsulation material to be applied is 0.05% by weight to 5% by weight, in particular 0.3% by weight to 1% by weight.
19. Process according to one of Claims 16 to 18, characterized in that the encapsulation material is applied in the form of an aqueous dispersion, which, if desired, comprises up to 70% by weight, in particular 40% by weight to 60% by weight, of water, in a fluidized bed of granulate to be encapsulated.
20. Process according to one of Claims 16 to 19, characterized in that the granulate to be encapsulated comprises enzyme and/or bleach activator.