EP1421169A1

EP1421169A1 - Encapsulated active ingredient preparation for use in particulate detergents and cleaning agents

Info

Publication number: EP1421169A1
Application number: EP02797546A
Authority: EP
Inventors: Wilfried Rähse; Dieter Baur; Werner Pichler
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2001-08-30
Filing date: 2002-08-21
Publication date: 2004-05-26
Anticipated expiration: 2022-08-21
Also published as: DE50207660D1; CN1549855A; DK1421169T3; US20040198629A1; ATE334184T1; HK1067890A1; CN1260341C; ES2268150T3; EP1421169B1; DE10142124A1; JP2005501958A; WO2003020868A1; US6979669B2

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

Coated active ingredient preparation for use in particulate washing and

detergents

The invention relates to coated granules which contain 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 cleaning agents.

In addition to good washing and cleaning performance, consumers expect modern washing and cleaning agents to have a positive aesthetic impression, which is particularly evident in a fragrance that can be associated with freshness and cleanliness. In order to comply with this, the agents normally contain appropriate fragrances. However, a not insignificant proportion of consumers reject this, among other things with the argument that fragrances do not contribute to the washing or cleaning result, so that when they are used, only the price of the means increases. These consumers prefer completely odorless washing and cleaning agents. However, some ingredients of such agents have a more or less strong intrinsic odor, which can also be based on the minor components contained in these ingredients. The use of such ingredients is unpleasant with fragrance-free agents and can increase the fragrance concentration in fragrance-containing agents in order to compensate for their own odor.

In connection with this problem, the German patent application DE 17 92 074 discloses agents which contain zinc ricinoleate as a deodorant active substance, the deodorant effect of which is obtained by adding other salts or esters of other saturated or unsaturated even or odd numbered hydroxylated fatty acids with 17 or more carbon atoms, for example Salts and esters of trioxystearic acids, synergistically supported. German patent application DE 25 48 344 discloses the deodorization activity of metal salts of an unsaturated fatty acid, in particular of metal ricinoleates. Metals from Group II of the Periodic Table of the Elements and rare earths such as cerium, lanthanum or neodymium are preferred. Zinc ricinoleate is particularly emphasized.

German patent application DE 38 08 114 relates to deodorising active substance mixtures, the zinc ricinoleate and optionally the zinc salt of abietic acid and / or further zinc salts of other saturated or unsaturated hydroxylated fatty acids with 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 with at least monounsaturated carboxylic acids with a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140 and optionally contain amino and / or amido compounds and in preparations with water contents of up to 50% by weight. -% remain clearly resolved.

Active ingredients which are usually used in detergents and cleaning agents and in which the occurrence of a more or less unpleasant odor cannot always be excluded include enzymes and bleach activators.

Enzymes, especially proteases, are used extensively in washing, auxiliary washing and cleaning agents. The enzymes are usually not used as concentrates, but in mixtures with a dilution and carrier material. If such enzyme preparations are mixed in with conventional detergents, a considerable reduction in the enzyme activity can occur during storage, especially if bleach-active compounds are present. The application of the enzymes to carrier salts with simultaneous granulation in accordance with German Offenlegungsschrift DE 16 17 190 or by sticking with nonionic surfactants in accordance with German Offenlegungsschrift DE 16 17 118 or aqueous solutions of cellulose ethers in accordance with German Offenlegungsschrift DE 17 87 568 does not lead to any noteworthy ver - Improvement of storage stability, since the sensitive enzymes in such mixtures are usually on the surface of the carrier. The storage stability of the enzymes can be significantly increased if the enzymes are encased or embedded in the carrier material and then converted into the desired particle shape by extrusion, pressing and marumerization, as described, for example, in German patent DE 16 17 232, German DE 20 32 768, and the German advanced DE 21 37 042 and DE 21 37 043 described. However, such enzyme preparations have poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it, or they can be transferred to the wastewater unused. Embedding agents known from German published patent application DE 18 03 099, which consist of a mixture of solid acids or acidic salts and carbonates or bicarbonates and disintegrate when water is added, improve the solvency but are themselves very sensitive to moisture and therefore require additional protective measures.

From the European patent EP 0 168 526, enzyme granules are known which contain starch which can swell in water, zeolite and water-soluble granulation aid. In this document, a manufacturing process for such formulations is proposed, which essentially consists of concentrating a fermenter solution freed from insoluble constituents, adding the additives mentioned, granulating the resulting mixture and, if appropriate, coating 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 so produced have such a high dissolution or disintegration rate under washing conditions that the granules disintegrate relatively quickly even during storage and the enzymes are deactivated. From international patent application WO 92/11347, enzyme granules for use in granular detergents and cleaning agents are known which contain 2% by weight to 20% by weight of enzyme, 10% by weight to 50% by weight of swellable starch, 5% by weight .-% to 50 wt .-% water-soluble organic polymer as a granulating aid, 10 wt .-% to 35 wt .-% cereal and 3 wt .-% to 12 wt .-% water. Such additives enable enzyme processing without major loss of activity.

From the international patent application WO 93/07263, an enzyme-containing granulate is known, which consists of a water-soluble or -dispersible core, which is coated with a vinyl polymer, on which there is a layer of enzyme and vinyl polymer, the granules having an outer coating Has vinyl polymer. The outer coating can also contain pigments. Due to the multi-layer structure, such an enzyme granulate is relatively complex to manufacture.

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

The international patent application WO 95/02031 relates to an enzyme granulate 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 comprises 30% by weight to 50% by weight % fine-particle inorganic pigment, 45% by weight to 60% by weight of an alcohol solid at room temperature with a melting point in the range from 45 ° C. to 65 ° C., up to 15% by weight, in particular 5% by weight % to 15% by weight emulsifier for the alcohol, up to 5% by weight, in particular 0.2% by weight to 3% by weight of dispersant for the pigment and up to 3% by weight of water.

Even if the above-mentioned cladding systems are generally suitable for stably enclosing enzyme granules in such a way that no odor escapes from them one nevertheless strives to find alternatives whose application is as simple as possible and / or leads to cost advantages.

The present invention, which wants to make a contribution to this, relates to a granulate which is suitable for incorporation into particulate detergents or cleaning agents and which contains a detergent and / or detergent active ingredient and has an outer coating layer, which is characterized in that the outer coating layer contains a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 12, in particular 16 to 24 carbon atoms or mixtures thereof. Among them, ricinoleic acid is particularly preferred. The granules can be undyed or, for example due to the presence of pigment in the coating layer, white or colored.

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

The wrapping layer contains one or more of the deodorant active ingredients mentioned 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% by weight. It is preferred to apply so much of the coating material forming the coating layer to the granules that the resulting coated granules 0.02% by weight to 1% by weight, in particular 0.05% by weight to 0.2% by weight. % of said deodorant ingredient. For the solubilization of the deodorizing active ingredient, the wrapping material forming the wrapping layer can contain one or more solubilizers, in particular in amounts from 0.05 wt.% To 5 wt.%, Preferably from 0.3 wt.% To 1 wt. contain. Preferred solubilizers are anionic, nonionic, cationic and / or amphoteric or zwitterionic surfactants, in particular anionic and / or nonionic surfactants with solubilizing, hydrotropic and / or emulsifying action. Nonionic solubilizers include ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C _{10.22 alcohols} with an average degree of alkoxylation of up to 30, preferably ethoxylated C ₁₀ . ₁₈ fatty alcohols with an average degree of ethoxylation of 1 to 20, in particular 1 to 12, particularly preferably 1 to 8, extremely preferably 2 to 5, for example C _12-1 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 with at least monounsaturated carboxylic acids with a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140, which in the German patent application DE 38 08 114 and European patent application EP 0 046 070, to which reference is made in this regard. In addition to an unbranched or branched, saturated or unsaturated, aliphatic or aromatic, acylclic or cyclic, optionally alkoxylated alkyl radical, preferred anionic solubilizers have 4 to 28, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, very preferably 12 to 14 carbon atoms, two or more anionic, in particular two, acid groups, preferably carboxylate, sulfonate and / or sulfate groups, in particular one carboxylate and one sulfate group. Examples of these compounds are the alpha-sulfofatty acid salts, the acylglutamates, the monoglyceride disulfates and the alkyl ethers of glycerol disulfate as well as the sulfosuccinamates, sulfosuccina ide and sulfosuccinates. at the latter are the salts of the mono- and diesters of sulfosuccinic acid HOOCCH (SO ₃ H) CH ₂ COOH, while sulfosuccinamates are taken to mean the salts of monoamides of sulfosuccinic acid and sulfosuccinamides are 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 the anionic to the nonionic surfactants of 10 to 1 to 1 to 10, in particular 3 to 1 to 1 to 5, particularly preferably 1: 1 to 1: 3, most preferably from 1 to 1.5 to 1 to 2, wherein the anionic and nonionic surfactants mentioned above, in particular the sulfosuccinates, especially the Monoester, and alkoxylated C preferably ₁₀ _ ₂₂ alcohols, can be combined with each other.

In a further particular embodiment, the wrapping material contains one or more solubilizers and one or more of the deodorising active substances mentioned in a weight ratio of not more than 14 to 1, preferably from 10 to 1 to 1 to 10, in particular 5 to 1 to 1 to 5, particularly preferably 2 to 1 to 1 to 2, extremely 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.

In a preferred embodiment, the covering material forming the covering layer additionally contains one or more complexing agents. Chelating agents, usually also called sequestering agents, are ingredients which can complex and inactivate metal ions in order to prevent their adverse effects on the stability or the appearance of the agents. On the one hand, it is important that to complex incompatible calcium and magnesium ions of water hardness with numerous ingredients of washing and cleaning agents. The complexation of the ions of heavy metals such as iron or copper on the other hand delays the oxidative decomposition of the finished agent. For example, are suitable

Aminotrimethylenephosphonic acid, beta-alaninediacetic acid,

Ethylenediaminetetraacetic acid, citric acid, cyclohexanediaminetetraacetic acid, diethylenetriaminepentamethylenephosphonic acid, etidronic acid, gluconic acid, glucuronic acid, tetrahydroxyethylethylenediamine, tetrahydroxypropylethylenediamine, nitrilo triacetic acid and mixtures thereof, wherein the acids under these can also be used in form of their alkali and / or ammonium salts. Preferred complexing agents are tertiary amines, especially tertiary alkanolamines (amino alcohols). These compounds have both amino and hydroxyl and / or ether groups as functional groups. Particularly preferred tertiary alkanolamines are triethanolamine and tetra- (2-hydroxypropyl) ethylenediamine. Combinations of tertiary amines or tertiary alkanolamines with zinc ricinoleate and one or more ethoxylated fatty alcohols as nonionic solubilizers and, if appropriate, solvents, which are particularly preferred in the context of the present invention, are described in German patent DE 40 14 055, to which reference is made in this regard. If desired, the coating material can 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 with a melting point in the range from 45 ° C. to 65 ° C., which may, if desired, be present in amounts of up to 60% by weight in the wrapping material forming the wrapping layer. This alcohol component is preferably a primary linear alcohol with 14 to 22 carbon atoms or a mixture of these. The alcohols mentioned include in particular myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol and mono- to tri-unsaturated alcohols of the appropriate chain length, it being essential that the alcohol component of the coating system mentioned has a melting point in the range from 45 ° C. to 65 ° C., in particular from 50 ° C to 60 ° C has what is to be understood here as the temperature at which 100% of the alcohol component is in liquid form when heated. When alcohol mixtures are used, it is also possible to use those which contain small proportions, normally below 15% by weight, based on the alcohol mixture, of fractions which are liquid at room temperature, as long as the entire alcohol mixture appears solid at room temperature and has a solidification point in the range from 45 ° C. to 65 ° ° C, in particular from 50 ° C to 60 ° C. The solidification point is the temperature at which solidification occurs when the material which has been heated to a temperature above the melting point cools down. It can be determined with the help of a rotating thermometer according to the procedure of DIN ISO 2207. The use of polymeric diols with the stated melting or solidification behavior is also possible, with polyethylene glycols in particular being preferred.

In addition, the coating layer can contain inorganic pigment. The inorganic pigments, with which possible disruptive coloring of the granules can be covered, include, for example, calcium carbonate, titanium dioxide, which can 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 a finely divided form that they can be dispersed in a melt of the other constituents of the wrapping material or in water. The average particle size of such pigments is usually in the range from 0.004 μm to 50 μm. In particular, if the pigment or the entire coating material is to be used in the form of an aqueous dispersion in the course of the production of the coated granules, it is preferred that this dispersion contains dispersants for the pigment. Such dispersants can be inorganic, for example aluminum oxide or silicon oxide, which can also serve as pigments, or organic, for example alkali metal carboxymethyl cellulose, diethylene glycol or dipropylene glycol. The use of surface-modified pigments with dispersants is also possible. Titanium dioxide pigment which is surface-modified with Al, Si, Zr or polyol compounds, in particular in rutile form, is preferred for example, sold under the trade names Kronos® 2132 (from Kronos-Titan) or Hombitan® R 522 (Sachtleben Chemie GmbH). The Tiona® RLL, AG or VC types from Solvay and the Bayertitan® RD, R-KB and AZ types from Bayer AG can also be used.

Another object of the invention is a process for the production of granules suitable for incorporation into particulate detergents or cleaning agents, which contains a detergent and / or cleaning agent active ingredient and has an outer coating layer, which is characterized in that an encasing material is applied to the granules as an outer coating layer, which contains a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 12 carbon atoms. The proportion of said deodorant active ingredient in the coating material to be applied is preferably 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 process for a granulate according to the invention, the coating material is introduced as an aqueous dispersion, which if desired contains up to 70% by weight, preferably 40% by weight to 60% by weight, of water into a fluidized bed of granules to be coated , The water supplied via the aqueous dispersion is removed during the drying which is carried out simultaneously or is subsequently necessary again. In a further embodiment of the manufacturing 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, consisting in 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 the finished granules, 6% by weight to 15% by weight of the coating material is applied to the granules as the outer coating layer. The detergent and / or cleaning agent active ingredient contained in the granulate to be encased is, in particular, one which has a perceptible own odor. The coating with the deodorizing active ingredient mentioned is used with particular advantage in the case of granules which contain enzyme and / or bleach activator.

The primary enzymes that can be used are the proteases, lipases, amylases and / or cellulases obtained from microorganisms such as bacteria or fungi, 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 patent applications 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 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 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 surfactants 7 (1970), 125) to 350,000 PE, in particular 160,000 PE to 300,000 PE, per gram of enzyme granulate.

A preferred embodiment of the invention relates to a method for producing an enzyme granulate suitable for incorporation into particulate washing or cleaning agents with an average grain 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, optionally previously freed from insoluble constituents by microfiltration, with inorganic and / or organic carrier material, optionally spinning the extrudate in a rounding machine, drying and applying an outer coating layer, wherein an outer coating layer is applied in a fluidized bed of extrudate, which contains a polyvalent metal salt of an unbranched or contains branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 16 carbon atoms.

In principle, all organic or inorganic powdery substances which do not destroy or deactivate the enzymes to be granulated, or tolerably little, and which are stable under granulation conditions, can be used as carrier materials for the enzyme. Such substances include, for example, starch, cereal flour, cellulose powder, alkali alumosilicate, in particular zeolite, layered silicate, for example bentonite or smectite, and water-soluble inorganic or organic salts, for example alkali metal chloride, alkali metal sulfate, alkali metal carbonate or alkali metal acetate, sodium or potassium being the preferred alkali metals. A carrier material mixture of starch swellable in water, cereal flour and optionally cellulose powder and alkali carbonate is preferably used. The starch which is swellable in water is preferably corn starch, rice starch, potato starch or mixtures thereof, the use of corn starch being particularly preferred. Swellable starch is contained in the enzyme granules according to the invention preferably in amounts of 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% by weight, in particular 32% by weight to 65% by weight. The cereal flour is in particular a product which can be produced from wheat, rye, barley or oats or a mixture of these flours, wholemeal flours being preferred. A wholemeal flour is understood to mean a flour that is not fully ground, which has been produced from whole, unpeeled grains or at least predominantly consists of such a product, the rest consisting of fully ground flour or starch. Commercial wheat flour qualities, such as Type 450 or Type 550, are preferably used. It is also possible to use flour products from the cereals leading to the aforementioned swellable starches, provided that care is taken to ensure that the flours have been produced from the whole grains. The flour component of the additive mixture is known to achieve a substantial reduction in odor of the enzyme preparation, which far exceeds the reduction in odor by incorporating the same amounts of corresponding starch types. Such cereal flour is contained in the enzyme granules according to the invention preferably in amounts from 10% by weight to 35% by weight, in particular from 15% by weight to 25% by weight. The enzyme granules according to the invention may contain, as a further component of the carrier material, preferably 1% by weight to 50% by weight, preferably 5% by weight to 25% by weight, based on the total amount of granules, of a granulation aid system which contains alkali carboxymethyl cellulose with degrees of substitution contains from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate. This granulation aid system preferably contains, based on the finished enzyme granulate, 0.5% by weight to 5% by weight of alkali carboxymethyl cellulose with degrees of substitution from 0.5 to 1 and up to 3% by weight of polyethylene glycol and / or alkyl polyethoxylate , it being particularly preferred if at least 0.5% by weight, in particular 0.8% by weight to 2% by weight, of polyethylene glycol with an average molecular weight below 1000 and / or alkyl polyethoxylate with at least 30 ethoxy groups is present, if more is contained as 2 wt .-% alkali carboxymethyl cellulose. Highly substituted carboxymethyl cellulose, with degrees of substitution up to 3, is preferably not contained in the granulation aid system. If necessary, additional cellulose or starch ethers, such as carboxymethyl starch, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and corresponding cellulose mixed ethers, gelatin, casein, tragacanth, maltodextrose, sucrose, invert sugar, glucose syrup or other water-soluble or readily dispersible olefin can also be used as additional constituents of the granulation aid system or polymers of natural or synthetic origin can be used. Usable synthetic water-soluble polymers are polyacrylates, polymethacrylates, copolymers of acrylic acid with maleic acid or compounds containing vinyl groups, furthermore polyvinyl alcohol, partially saponified polyvinyl acetate and polyvinyl pyrrolidone. Insofar as the aforementioned compounds are those with free carboxyl groups, they are normally in the form of their alkali metal salts, in particular their sodium salts. Such additional granulating agents can be contained 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. Higher molecular weight polyethylene glycols, i.e. those with an average molecular weight of over 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but they do just that higher molecular weight polyethylene glycols an undesirable increase in the required granule dissolution time, so that these substances are preferably completely absent in enzyme granules to be coated according to the invention.

Fermentation broths are preferably used for the production of the enzyme granules, which are freed of insoluble accompanying substances, for example by microfiltration. The microfiltration is preferably carried out as cross-flow microfiltration using porous tubes with micropores larger than 0.1 μm, 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, as for example in the European patent application EP 200 032. The microfiltration permeate is then concentrated, preferably by ultrafiltration, if appropriate with subsequent vacuum evaporation. The concentration can, as described in international patent application WO 92/11347, be carried out in such a way that only relatively low dry matter contents of preferably 5% by weight to 50% by weight, in particular 10% by weight up to 40% by weight. The concentrate is metered into a suitably previously prepared dry, powdery to granular mixture of the additives described above. The water content of the mixture should be selected so that it can be converted into granular particles which do not stick at room temperature when processed with stirring and striking tools and plastically deformed and extruded when using higher pressures. The free-flowing premix is, in principle, subsequently processed in a kneader and a connected extruder to form a plastic mass which is as homogeneous as possible, the mass being at temperatures between 40 ° C. and 60 ° C., in particular 45 ° C. to, as a result of the mechanical processing Can heat 55 ° C. The material leaving the extruder is passed through a perforated disc with a subsequent knock-off knife and is thereby crushed into cylindrical particles of a defined size. The diameter of the bores in the perforated disk is expediently 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 coating material described above. However, it has proven advantageous to leave the extruder and chopper Spheronize cylindrical particles before coating, i.e. round them off and deburr them in suitable devices. For this purpose, a device is used which consists of a cylindrical container with stationary, fixed side walls and a friction plate rotatably mounted on the bottom. Devices of this type are widespread in technology under the Marumerizer® product name and are described, for example, in German specification DE 21 37 042 and DE 21 37 043. Any dusty particles with a grain size of less than 0.1 mm, in particular less than 0.4 mm and any coarse particles with a grain size of more than 2 mm, in particular more than 1.6 mm, can then be removed by sieving or air separation and, if necessary, returned to the manufacturing process. After spheronization, the beads are continuously or in batches, preferably using a fluidized bed drying unit, 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% by weight 10% by weight, in particular 5% by weight to 8% by weight, based on the total granules, are dried.

Further preferred detergent or cleaning agent ingredients that can be contained in the granules to be coated are bleach activators, especially from the classes of the N- or O-acyl compounds, for example polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated Hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfurylamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate, and acylated sugar derivatives. In this connection, particularly preferred detergent or cleaning agent ingredients are bleach activators of the quaternized aminoalkyl nitrile type of the general formula (I),

R ¹

R ² -N ⁽⁺⁾ - (CR ⁴ R ⁵ ) -CN X ° (I)

R ³ in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ _ ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br, -OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C ^ alkyl group, or for a substituted alkyl or alkenylaryl radical with 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 for R ¹ , R above ² or R ³ have the meaning given and X is a charge-balancing anion. If appropriate, the radicals R ² and R ^{3 can} also be part of a heterocycle which includes the N atom and, if appropriate, further hetero atoms, in particular a morpholine ring.

Compounds according to formula I can be prepared according to known procedures or based on these, 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), pp. Lff, or from Arnett in J. Am. Chem. Soc. 102 (1980), p. 5892ff. Compounds of the formula I in which R ¹ , R ² and R ^{3 are} identical are preferred. Among these, those compounds are particularly preferred in which the said radicals denote methyl groups. On the other hand, preference is also given to those compounds in which at least 1 or 2 of the radicals mentioned are methyl groups and the others have more than one carbon atom. 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, hydrogen carbonate, sulfate, hydrogen sulfate, C _μ20 -alkyl sulfate, C ^ o Alkyl sulfonate, optionally C _1-1S -alkyl-substituted aryl sulfonate, chlorate, perchlorate and / or the anions of _. ^ - carboxylic acids such as formate, acetate, laurate, benzoate or citrate, alone or in any mixtures. Bleach activators according to formula I are preferred which X ^" chloride, sulfate, hydrogen sulfate, ethosulfate, C _12/18 -, C _12/16 - or C _13/15 alkyl sulfate, lauryl sulfate, Is dodecylbenzenesulfonate, toluenesulfonate, cumene sulfonate, xylene sulfonate or methosulfate or mixtures thereof. Toluene sulfonate or cumene sulfonate means the anion of the ortho, meta or αrα isomer of methylbenzenesulfonic acid or isopropylbenzenesulfonic acid and any mixtures thereof. Rαrα-isopropylbenzenesulfonic acid is particularly preferred.

The bleach activators can, if desired, be converted into granular form before the encapsulation step essential to the invention, as described above for enzyme, with an aqueous preparation of the bleach activator that occurs as a result of the production taking the place of the fermenter broth. Bleach activator granules coated according to the invention have a bleach activator content 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 largely rounded, uniformly coated and dust-free particles which generally have a bulk density of approximately 500 to 900 grams per liter, in particular 650 to 880 grams per liter. The granules according to the invention are notable for very high storage stability, in particular at temperatures above room temperature and high atmospheric humidity, and for rapid dissolution behavior in the wash liquor. The granules according to the invention preferably release 100% of the activity of the active ingredient contained in them, in particular if this is an enzyme, in water at 25 ° C. within 3 minutes, in particular within 90 seconds to 2 minutes.

The coated granulate according to the invention or produced by the method according to the invention is preferably used for the production of solid, in particular particulate detergents or cleaning agents which can be obtained by simply mixing the granules with other particulate components customary in such compositions. For incorporation into particulate detergents and cleaning agents, the granules preferably have average grain sizes in the range from 0.8 mm to 1.2 mm. The granules according to the invention preferably contain less than 2% by weight, in particular at most 1.4% by weight, of particles with particle sizes outside the range from 0.4 mm to 1.6 mm. If desired, it is also possible to shape-coat the coated granules according to the invention or produced by the process according to the invention, if appropriate together with other ingredients of such agents, and to produce detergents and cleaning agents in tablet form or in the form of other shaped articles, for example.

Examples

example 1

A harvest pulp obtained after fermentation with 75,000 protease units per g (PE / g), as described in international patent application WO 91/2792, was concentrated in an ultrafiltration system after removal of the fermentation residues by decanting and microfiltration. 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.% Carboxymethyl cellulose with a degree of substitution 0.65-0.75, 19 wt.% Wheat flour, 35 wt. % Corn starch and 3% by weight polyethylene glycol, based in each case on the resulting mixture), homogenized and then converted into granules in an extruder with a 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 rounding and drying the granules, the particles with a particle size smaller than 0.4 mm and larger 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 type STREA-1 from Aeromatic in the fluidized bed. The following operating parameters were set during coating:

Supply air temperature: 85 ° C

Product temperature: 36 ° C

Exhaust air temperature: 33 ° C

Air volume: 90 m ³ / h

Throughput rate at coating suspension: 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 triple ethoxylated lauryl alcohol and 15% by weight . Parts Tetra- (2-hydroxyρropyl) ethylenediamine (Tegosorb® conc 50), 0.5% by weight sodium carboxymethyl cellulose and the rest to 100% by weight 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 on about 285 g of coating suspension per kg of enzyme granules, the extrudates were uniformly coated with a white coloring and protective layer. In comparison to an otherwise unchanged granulate which was produced by spraying on a coating suspension and which lacked the mixture containing zinc ricinoleate, the odor was significantly lower, in particular the onion note of the odor was missing.

Example 2:

A coating suspension consisting of titanium dioxide, polyethylene glycol and water was first applied to the enzyme extrudate prepared as in Example 1 and then the mixture of 50 parts by weight of zinc ricinoleate, 35 parts by weight of 3-fold ethoxylated lauryl alcohol and 15 parts by weight mentioned in Example 1. Parts of tetra- (2-hydroxypropyl) ethylenediamine were each sprayed on in such amounts that the ratios of Example 1 resulted in the gross composition. Here, too, the smell after spraying on the zinc ricinoleate was significantly lower.

Claims

claims

1. Granules suitable for incorporation into particulate detergents or cleaning agents which contain a detergent and / or cleaning agent active ingredient and have an outer coating layer (coating), characterized in that the outer coating layer is a polyvalent metal salt of an unbranched or branched, unsaturated or saturated , contains one or more hydroxylated fatty acids with at least 12 carbon atoms or mixtures thereof.

2. Granules according to claim 1, characterized in that the polyvalent metals are selected from the transition metals and the lanthanoids and in particular are the transition metals of groups IIB, VIIIB and optionally IB of the periodic table.

3. Granules according to claim 1 or 2, characterized in that the polyvalent metal is cobalt, nickel, copper or zinc, in particular zinc.

4. Granules according to one of claims 1 to 3, characterized in that the fatty acid is ricinoleic acid.

5. Granules according to one of claims 1 to 4, characterized in that the coating layer polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polydroxyated fatty acid with at least 12 carbon atoms in an amount of 0.05 wt .-% to Contains 5 wt .-%.

6. Granules according to one of claims 1 to 5, characterized in that it contains polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or polydroxyated fatty acid with at least 12 carbon atoms in an amount of 0.02% by weight to 1 % By weight, in particular from 0.05% by weight to 0.2% by weight.

7. Granules according to one of claims 1 to 6, characterized in that the covering material forming the covering layer for solubilizing the deodorant active ingredient is one or more solubilizers in amounts of 0.05% by weight to 5% by weight, in particular of 0, Contains 3 wt .-% to 1 wt .-%.

8. Granules according to claim 7, characterized in that the solubilizer is an alkoxylated with ethylene oxide (EO) and / or propylene oxide (PO), unbranched or branched, saturated or unsaturated C ₁₀ . ₂₂ -alcohol with an average degree of alkoxylation up to 30, in particular an ethoxylated C _10.ls -fatty alcohol with an average degree of ethoxylation from 1 to 20, in particular from 2 to 5.

9. Granules according to claim 7, characterized in that the solubilizer is an alpha-sulfofatty acid salt, acylglutamate, monoglyceride disulfate, an alkyl ether of glycerol disulfate, a sulfosuccinamate, sulfosuccinamide and / or sulfosuccinate.

10. Granules according to one of claims 1 to 9, characterized in that the coating material forming the coating layer additionally contains one or more complexing agents, in particular tertiary alkanolamines.

11. Granules according to one of claims 1 to 10, characterized in that the coating material forming the coating layer additionally contains inorganic pigment.

12. Granules according to one of claims 1 to 11, characterized in that it contains enzyme, in particular in amounts of 4% by weight to 20% by weight.

13. Granules according to claim 12, characterized in that the enzyme is protease, lipase, amylase and / or cellulase obtained from microorganisms.

14. Granules according to one of claims 1 to 13, characterized in that it has a bleach activator content of at least 40% by weight and in particular from 50% by weight to 92% by weight.

15. Granules according to claim 14, characterized in that it is bleach activator of the quaternized aminoalkyl nitrile type of the general formula (I),

R ¹

R ² -N ⁽⁺⁾ - (CR ⁴ R ⁵ ) -CN X ^Θ (I)

R ³

in the R ¹ for -H, -CH ₃ , a C ₂ . ₂₄ alkyl or alkenyl radical, a substituted C ₂ . ₂₄ alkyl or alkenyl radical with at least one substituent from the group -Cl, -Br,

-OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical with a C ₁ . ₂₄ alkyl group, or for a substituted alkyl or alkenylaryl radical with a and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH ( CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH ) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have a meaning given above for R ¹ , R ² or R ³ , optionally radicals R ² and R ^{3 are} also part of a heterocycle which includes the N atom and optionally further hetero atoms, in particular a morpholine ring and X is a charge-balancing anion ,

16. A process for the preparation of granules suitable for incorporation into particulate detergents or cleaning agents which contains a detergent and / or cleaning agent active ingredient and which has an outer coating layer, characterized in that an encapsulation material is applied to the granules as the outer coating layer, which a polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 12 carbon atoms.

17. The method according to claim 16, characterized in that as much of the coating material forming the coating layer is applied to the granules that the resulting coated granules 0.02 wt .-% to 1 wt .-%, in particular 0.05 wt .-% % to 0.15% by weight of polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 16 carbon atoms.

18. The method according to claim 16 or 17, characterized in that the proportion of the polyvalent metal salt of an unbranched or branched, unsaturated or saturated, mono- or poly-hydroxylated fatty acid with at least 12 carbon atoms in the coating material to be applied 0.05 wt .-% to 5 wt .-%, in particular 0.3 wt .-% to 1 wt .-%.

19. The method according to any one of claims 16 to 18, characterized in that the coating material as an aqueous dispersion, which optionally contains up to 70 wt .-%, in particular 40 wt .-% to 60 wt .-% water, in a fluidized bed from the granules to be coated.

20. The method according to any one of claims 16 to 19, characterized in that the granules to be coated contains enzyme and / or bleach activator.