EP0870007A1 - Granules enzymatiques contenant des agents anticorrosion pour l'argent - Google Patents

Granules enzymatiques contenant des agents anticorrosion pour l'argent

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Publication number
EP0870007A1
EP0870007A1 EP96920771A EP96920771A EP0870007A1 EP 0870007 A1 EP0870007 A1 EP 0870007A1 EP 96920771 A EP96920771 A EP 96920771A EP 96920771 A EP96920771 A EP 96920771A EP 0870007 A1 EP0870007 A1 EP 0870007A1
Authority
EP
European Patent Office
Prior art keywords
weight
enzyme
corrosion inhibitor
silver corrosion
silver
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96920771A
Other languages
German (de)
English (en)
Inventor
Kathleen Paatz
Wilfried Rähse
Werner Pichler
Jürgen Härer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0870007A1 publication Critical patent/EP0870007A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38672—Granulated or coated enzymes

Definitions

  • the invention relates to an enzyme granulate which contains a silver corrosion inhibitor, a process for its production and the use of the granulate in solid cleaning agents, in particular for machine dishwashing.
  • Enzymes are used extensively in detergents, washing aids 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 admixed with conventional detergents or cleaning agents, a considerable reduction in the enzyme activity can occur during storage, especially if bleach-active compounds are present.
  • 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 Offenlegungsschrift DT 20 32 768, and the German interpretations DE 21 37 042 and DE 21 37 043.
  • Such enzyme preparations only have poor solubility properties. The undissolved particles can get caught in the material to be cleaned and contaminate it, or they can be discharged into the waste water unused.
  • Embedding agents known from German patent specification DT 18 03 099 which consist of a mixture of solid acids or acidic salts and carbonates or bicarbonates and which disintegrate when water is added, improve the solvency, but are themselves very sensitive to moisture and therefore require additional protective measures.
  • enzyme granules for use in granular detergents and cleaning agents 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 Granuherellosxnittel, 10 wt .-% to 35 wt .-% cereal and 3 wt .-% to 12 wt .-% water.
  • Such an additive mixture enables enzyme processing without major loss of activity, and the storage stability of the enzymes in the granules is also satisfactory.
  • Silver can react when cleaning with sulfur-containing substances that are dissolved or dispersed in the rinsing water, because when cleaning dishes in household dishwashers, food residues and thus, among other things, mustard, peas, egg and other sulfur-containing compounds such as mercaptoamino acids are introduced into the washing liquor .
  • the much higher temperatures during machine rinsing and the longer contact times with the sulfur-containing food residues also favor the tarnishing of silver compared to manual rinsing. Due to the intensive cleaning process in the dishwashing
  • the silver surface is also completely degreased, making it more sensitive to chemical influences.
  • Such active oxygen bleaching agents are used, generally together with bleach activators, especially in modern, low-alkaline machine dishwashing detergents of the new generation of cleaners.
  • These agents generally consist of the following functional components: builder component (complexing agent dispersant), alkali carrier, bleaching system (combination of bleaching agent and bleach activator), enzyme and surfactant.
  • EP 135 226 and EP 135 227 describe weakly alkaline machine dishwashing detergents containing peroxy compounds and activators, which may contain benzotriazoles and fatty acids as silver preservatives. Finally, it is known from German published patent application DE 41 28 672 that peroxy compounds, which are activated by the addition of known organic bleach activators, prevent the tarnishing of silver parts in strongly alkaline cleaning agents.
  • German patent applications DE 43 25 922 and DE 43 15 397 describe the use of titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes in which the metals in one of the oxidation stages ⁇ , HL IV, V or VI are present, or of manganese (II) salts or complexes to prevent silver corrosion.
  • the international patent application WO 94/19445 describes the use of certain manganese (i ⁇ ) or manganese (TV) complexes as silver corrosion inhibitors in mechanical dishwashing detergents.
  • International patent application WO 94/07981 discloses the use of cysteine as a silver protection agent.
  • German patent application 195 18 693.1 describes the supercorrosion-inhibiting action of cystine, alone or in particular in combination with isocyanuric acid.
  • the unpublished German patent application DE 43 44 215 relates to enzyme granules suitable for incorporation into particulate cleaning agents in particular, containing enzyme and inorganic and / or organic carrier material in the core and optionally granulating aids onto which a uniform coating layer has been applied, which in particular applies a coating layer contains inorganic silver corrosion inhibitor.
  • These enzyme granules can be produced in particular by applying an aqueous solution or dispersion which contains the silver corrosion inhibitor to an enzyme-containing core.
  • Such a manufacturing process creates difficulties in the processing of water-insoluble or sparingly water-soluble silver corrosion inhibitors.
  • additional energy is required for the evaporation of the water applied with the silver corrosion inhibitor.
  • corrosion is to be interpreted in its broadest meaning in chemistry, in particular “corrosion” here should stand for any visually just recognizable change in a metal surface, here silver, be it for example a selective discoloration or be it for example large start-up.
  • this object is achieved by enzyme granulate containing silver corrosion inhibitor which is suitable for incorporation into particulate cleaning agents and which contains enzyme, inorganic and / or organic carrier material for the enzyme and silver corrosion inhibitor and optionally granulation aids in an intimate, so to say homogeneous mixture.
  • the organic silver corrosion inhibitors include compounds with a trivalent N atom, such as pyrazole, thionalide, morpholine, melamine, cysteine, 2-mercaptobenzodiazole, distearylamine, isocyanuric acid, bezotriazole, aminotriazole, aminotetrazole, indazole and imidazole and its derivatives, for example organic benzimidazole Disulfides, for example cystine, and di- and trihydric phenols and their derivatives, for example hydroquinone, pyrocatechol, phloroglucinol, gallic acid, hydroxyhydroquinone and pyrogallol.
  • a trivalent N atom such as pyrazole, thionalide, morpholine, melamine, cysteine, 2-mercaptobenzodiazole, distearylamine, isocyanuric acid, bezotriazole, aminotriazole, aminotetrazole, indazole and imid
  • inorganic silver corrosion inhibitors are manganese, titanium, zirconium, hafnium, vanadium, cobalt or cerium salts and / or complexes in which the metals mentioned are present in one of the oxidation states II, HI, IV, V or VI.
  • the counterions suitable for salt formation include all customary single, double or triple negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.
  • metal complexes are compounds which consist of a central atom and one or more ligands and, if appropriate, additionally one or more of the above-mentioned anions.
  • the central atom is one of the metals mentioned above in one of the oxidation states mentioned above. fen.
  • the ligands are neutral molecules or anions, which can be monodentate or multidentate; the term “ligand” in the sense of the invention is explained in more detail, for example, in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507”.
  • Preferred metal salts or metal complexes are MnSO 4 , V 2 O 5 , V 2 O 4 , VO 2 , TiOSO 4 , K 2 TiF 6 , K 2 ZrF 6 , CoSO 4 , Co (NO 3 ) 2 , Ce (NO 3 ) 3 as well as their mixtures.
  • salts or complexes are commercially available substances that can generally be used for the purpose of protecting against silver corrosion without prior cleaning.
  • the oxidic mixture of tetravalent and pentavalent vanadium (V 2 O 5 , VO 2 , V 2 O 4 ) known from SO 3 production (contact process) is suitable, as is that by diluting a Ti (SO) 2 - Solution with titanyl sulfate TiOSO 4 .
  • 0.5% by weight to 40% by weight in particular 1% by weight to 30% by weight and particularly preferably 2.5% by weight to 25% by weight, is preferably enzymatic Protein, 30% by weight to 95% by weight, in particular 40% by weight to 80% by weight of carrier material for the enzyme, optionally 3% by weight to 12% by weight of water and 0.5 % By weight to 50% by weight, in particular 5% by weight to 30% by weight, of silver corrosion inhibitor.
  • Enzymes primarily include the proteases, lipases, cutinases, amylases, pullulanases, hemicellulases, cellulases, oxidases and / or peroxidases obtained from microorganisms, such as bacteria or fungi, proteases produced by Bacillus species and their mixtures with amylases are preferred. They are obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 1940488, DE 2044 161, DE 22 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and 4264 738 and European patent application EP 006638.
  • the method according to the invention for the formulation of very active proteases which are known, for example, from international patent application WO 91/02792 or US Pat. No. 5,340,735, are used because their storage-stable incorporation into detergents and cleaning agents often causes problems.
  • the enzyme granulate according to the invention is a protease-containing formulation
  • the protease activity is preferably 50,000 protease units (PE, determined by the method described in Tenside 7 (1970), 125) to 350,000 PE, in particular 100,000 PE up to 300,000 PE, per gram of enzyme granulate.
  • the particularly preferred enzyme granules according to the invention include those in which the enzyme protease and the silver corrosion inhibitor is MnSO, or in which the enzyme protease and the silver corrosion inhibitor is cystine, or in which the enzyme is amylase and the silver corrosion inhibitor cystine.
  • 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 which is 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 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% 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 which has not been fully ground and 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 odor reduction in 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 5% by weight to 35% by weight, in particular from 10% by weight to 25% by weight.
  • the enzyme granules according to the invention preferably contain, as a further component of the carrier material, 1% by weight to 50% by weight, preferably 5% by weight to 25% by weight, based on the total granulate, of a granulation aid system, the alkali carboxymethyl cellulose contains with degrees of substitution from 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate.
  • This granulation aid system preferably contains, based in each case on finished enzyme granules, 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 Contain 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 than 2% by weight of alkali carboxymethyl cellulose is contained.
  • 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 others can also be used as additional constituents of the granulation aid system
  • Water-soluble or readily dispersible oligomers 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.
  • 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 granulation aids 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 that is to say those with an average molecular weight of more than 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but it is precisely the higher molecular weight polyethylene glycols which cause an undesirable increase in the granule dissolution time required, so that these substances can be used in the invention
  • Enzyme granules are preferably completely absent.
  • the enzyme granules have a uniform outer coating layer.
  • a coating system which contains 10% by weight to 30% by weight of finely divided inorganic pigment, 45% by weight to 80% by weight of an alcohol or alcohol mixture with a melting point in the range of 35 ° C. is particularly suitable for the coating layer up to 75 ° C, up to 15 wt .-% emulsifier for the alcohol, up to 5 wt .-% dispersant for the pigment and up to 5 wt .-% water.
  • the alcohol component of the coating system 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 appropriate chain length, it being essential that the alcohol component of the coating system mentioned has a melting point in the range from 35 ° C. to 75 ° C, in particular from 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.
  • Suitable emulsifiers for the alcohol component are substances which are able to emulsify the alcohol component in water so that a mixture which can be sprayed at temperatures of up to 95 ° C. is obtained and / or which allow the coating system to be as homogeneous as possible to transfer meltable sprayable at temperatures up to 120 ° C.
  • it can serve as a point of reference that liquids with viscosities of up to about 10,000 mPa.s can generally be sprayed without any problems at the temperatures mentioned by means of devices provided for this purpose and applied to enzyme granules.
  • the emulsifiers for the alcohol component of the coating system include, for example, the ethoxylation products of the alcohols mentioned, their reaction products with an average of 25 to 80, in particular 30 to 45, molar equivalents of ethylene oxide being preferred. If the coating system is applied to the enzyme granulate as an aqueous dispersion, preferred among the compounds mentioned are those with degrees of ethoxylation of 25 to 50, that is to say reaction products with 25 to 50 molar equivalents of ethylene oxide.
  • ethoxylated fatty acids the degree of ethoxylation preferably being 3 to 9, ethoxylated fatty acid amides, the degree of ethoxylation preferably being 4 to 11, and / or ethoxylation products of hydroxy fatty acid esters having 1 to 6 C- Atoms in the alcohol part of the ester, for example ricinoleic acid glyceride, where the degree of ethoxylation is preferably 5 to 80, in particular 20 to 40, can be used as the emulsifier component in the coating system.
  • the fatty acid component of the substances mentioned preferably has 12 to 22 carbon atoms. If desired, the ethoxy groups in the emulsifiers mentioned can be at least partially replaced by propoxy groups.
  • the inorganic pigments with which possible disruptive coloring of the enzyme granulate 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, anti-monoxide, 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 organic constituents of the coating system or in water.
  • the average particle size of such pigments is usually in the range from 0.004 ⁇ m to 50 ⁇ m.
  • this dispersion contains dispersing agents for the pigment and / or, as described below, the additional silver corrosion inhibitor which is optionally present in the coating system.
  • dispersants can be inorganic, for example aluminum oxide or silicon oxide, which can also serve as pigments, or organic, for example diethylene glycol or dipropylene glycol. Use with dispersants of surface-modified pigments is also possible.
  • Titanium dioxide pigment which is surface-modified with Al, Si, Zr or polyol compounds is preferred, in particular in rutile form, as is sold, for example, under the trade names Kronos® 2132 (Kronos-Titan) or Hombitan® R 522 (Sachtleben Chemie GmbH) , used.
  • the Tiona® RLL, AG and VC types from Solvay and the Bayertitan® RD, R-KB and AZ types from Bayer AG can also be used.
  • the coating system preferably has a content of at least 25% by weight of a silver corrosion inhibitor, in particular a silver corrosion inhibitor which is not identical to the silver corrosion inhibitor contained in the enzyme core, up to 30% by weight, in particular 5% by weight to 25% by weight.
  • % finely divided inorganic pigment 5% by weight to 75% by weight at room temperature solid alcohol with a melting point in the range from 35 ° C.
  • the enzyme granules containing silver corrosion inhibitor are preferably produced, at least in part, based on the processes of international patent application WO 92/11347 comprising an extrusion step or German patent application DE 43 10 506 using swellable starch, water-soluble organic polymer and cereal flour .
  • Another object of the invention thus relates to a method for producing an enzyme granulate containing silver corrosion inhibitor suitable for incorporation into particulate cleaning agents by mixing an aqueous liquid containing the enzyme, which liquid can optionally be a fermentation broth freed from insoluble constituents and concentrated. with inorganic and / or organic carrier material and the silver corrosion inhibitor, subsequent extrusion of the mixture obtained in this way through a perforated plate with subsequent cutting device, optionally spheronization of the extrudate in a rounding device and drying, and, if appropriate, application of a dye and / or pigment-containing coating, if desired train
  • Such a method has the advantage over known methods that it also makes it possible to process silver corrosion inhibitors which are insoluble or only slightly water-soluble.
  • the enzyme granules according to the invention are preferably prepared from fermentation broths which are freed of insoluble accompanying substances, for example by microfiltration.
  • the microfiltration is preferably carried out as a cross-flow microfiltration using porous tubes with micropores larger than 0.1 ⁇ m, 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 expediently prepared beforehand in a dry, powdery to granular mixture of the additives described above. Impact substances, including the silver corrosion inhibitor, metered in and mixed in.
  • 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 Can heat 55 ° C.
  • the material leaving the extruder is passed through a perforated disk with a subsequent knock-off knife and is thereby reduced to cylindrical particles of a defined size.
  • the diameter of the bores in the perforated disk is expediently 0.7 mm to 1.6 mm, preferably 0.8 mm to 1.4 mm.
  • the particles in this form can then be dried and coated with a coating system.
  • a device 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 widely used in technology under the Marumerizer® product name and are described, for example, in the German specifications 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, in the Manufacturing process can be traced.
  • the beads can be added 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. up to the desired residual moisture content of, for example, 4% by weight. % to 10% by weight, in particular 5% by weight to 8% by weight, based on the total granulate, are dried.
  • the coating system which optionally contains additional silver corrosion inhibitor, can be applied as an outer covering.
  • the coating system is in the form of an aqueous solution or dispersion which preferably contains 30% by weight to 65% by weight of water and 35% by weight to 70% by weight of the coating system, in particular 1 % By weight to 2.5% by weight, based on the entire coating system, of dispersant for the pigment and / or the silver corrosion inhibitor, is introduced into the fluidized bed of enzyme extrudate.
  • the water supplied via the aqueous dispersion is removed during the drying which is carried out simultaneously or is subsequently necessary again.
  • the coating system optionally with cooling, is applied to the enzyme-containing extrudate as a heated liquid at a temperature of 5 ° C. to 45 ° C.
  • a further embodiment of this method comprises the production of enzyme granules which contain two or more different enzymes.
  • the procedure is preferably such that an enzyme core containing super-anticorrosive agents, prepared as described by extrusion, is mixed with a second enzyme which has been made up in particulate form and, if appropriate, further enzymes made up in particulate form, under agglomeration conditions, a binder optionally being used, and the coating material is then used or applies simultaneously, the average particle size of the extrudate core containing the first enzyme preferably being 1.1 to 3 times, in particular 1.3 to 2 times that of the second or further enzyme-shaped enzyme.
  • This variant is based on the production method for multi-enzyme granules disclosed in German patent application DE 43 29463.
  • the enzyme in the extrudate core is preferably Protease and in the enzyme contained in the separately produced, smaller particles which agglomerate to the extrudate or in the enzymes, if several different smaller particles are used, to amylase, pullulanase, lipase, cutinase, hemicellulase, cellulase, peroxidase and / or Oxidase.
  • multi-enzyme granules containing silver corrosion inhibitor which contain protease in the extrudate core and amylase and / or lipase in the separately produced, smaller particles, are particularly preferred.
  • the enzyme 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 good dissolution behavior in the detergent liquor.
  • the enzyme 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 cleaning agents which can be obtained by simply mixing the enzyme granules with other powder components customary in such agents.
  • the enzyme granules preferably have average grain sizes in the range from 0.8 mm to 1.6 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.
  • a further subject of the invention is a lower-alkaline agent for machine cleaning of dishes whose 1% by weight solution has a pH of 8 to 11.5, preferably 9 to 10.5, containing enzyme, silver corrosion inhibitor, 15% by weight to 60% by weight, preferably 30% by weight to 50% by weight of water-soluble builder component, 5% by weight % up to 25% by weight, preferably 10% by weight to 15% by weight of oxygen-based bleach, 1% by weight to 10% by weight, preferably 2% by weight to 6% by weight of bleach activator, in each case based on the total agent, which is characterized in that it contains 0.1% by weight to 10% by weight, in particular 0.5% by weight to 5% by weight, of enzyme granules, which enzyme, inorganic and / or contains organic carrier material for the enzyme and silver corrosion protection agent and optionally granulation aids in intimate mixture.
  • organic disulfides dihydric phenols, trihydric phenols, manganese, titanium, zirconium, hafiiium, vanadium, cobalt or cerium salts and / or - complexes in which the metals mentioned are in one of the oxidation states ⁇ , IQ, IV, V or VI are present, preferred silver corrosion inhibitors.
  • all builders typically used in machine dishwashing detergents for example polymeric alkali metal phosphates, which can be present in the form of their alkaline neutral or acidic sodium or potassium salts, are suitable as water-soluble builder components in such low-alkaline cleaning agents.
  • examples of this are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium tri-phosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Their amounts can range up to about 35% by weight, based on the total agent; however, the agents according to the invention are preferably free of such phosphates.
  • water-soluble builder components are, for example, organic polymers of native or synthetic origin, especially polycarboxylates, which act as co-builders, in particular in hard water regions.
  • polyacrylic acids and copolymers of maleic anhydride and acrylic acid and the sodium salts of these polymer acids are suitable.
  • Commercial products are, for example, Sokalan® CP 5 and PA 30 from BASF.
  • Polymers of native origin that can be used as co-builders include, for example, oxidized starch, as known, for example, from international patent application WO 94/05762, and polyamino acids such as polyglutamic acid or polyaspartic acid.
  • hydroxycarboxylic acids such as, for example, mono-, dihydroxysuccinic acid, ⁇ -hydroxypropionic acid and gluconic acid.
  • the preferred builder components include the salts of the citro- Nenoic acid, especially sodium citrate.
  • Anhydrous trisodium citrate and preferably trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder.
  • the acids corresponding to the co-builder salts mentioned can also be present.
  • Suitable oxygen-based bleaches are primarily sodium perborate mono- or tetrahydrate and / or sodium percarbonate.
  • the use of sodium percarbonate has advantages, since this has a particularly favorable effect on the corrosion behavior on glasses.
  • the oxygen-based bleach is therefore preferably a percarbonate salt, especially sodium percarbonate. Since bleaching agents based on oxygen generally only develop their full effect at elevated temperatures, so-called bleach activators are used to activate them at about 60 ° C. and below, that is to say the approximate temperatures of the cleaning process in the dishwasher.
  • Pentaacetylglucose, l, 5-diacetyl-2,2-dioxo-hexahydro-l, 3,5-triazine (DADHT) and / or isatoic anhydride can be used as bleach activators, but preferably N, N, N ', tetraacetylethylenediamine (TAED).
  • TAED tetraacetylethylenediamine
  • known peroxycarboxylic acids for example dodecanediperic acid or phthalimidopercarboxylic acids, which can optionally be substituted on the aromatic, can also be present.
  • bleach stabilizers such as, for example, phosphonates, borates or metaborates " and metasilicates and magnesium salts such as magnesium sulfate can also be useful.
  • the agents according to the invention preferably contain the alkali carriers, such as, for example, alkali silicates, alkali carbonates and / or alkali bicarbonates, contained in customary low-alkaline machine dishwashing detergents.
  • Alkali silicates can be used in amounts of up to 30% by weight .-%, based on the total agent, may be included.
  • the use of the highly alkaline metasilicates as alkali carriers is preferably avoided entirely.
  • the alkali carrier system preferably used in the agents according to the invention is a mixture of carbonate and bicarbonate, preferably sodium carbonate and bicarbonate, which is contained in an amount of up to 60% by weight, preferably 10% by weight to 40% by weight.
  • carbonate and bicarbonate preferably sodium carbonate and bicarbonate
  • the ratio of carbonate and hydrogen carbonate used varies, but an excess of sodium hydrogen carbonate is usually used, so that the weight ratio between hydrogen carbonate and carbonate is generally 1: 1 to 15: 1 is.
  • the agents according to the invention can contain ready-made enzymes such as proteases, amylases, lipases and cellulases which are not in the form of the granules according to the invention, for example proteases such as BLAP®, Optiase®, Opticlean®, Maxacal®, Maxapem®, Esperase ® and / or Savinase®, amylases like Termamyl®, Amylase-LT® and / or Maxamyl®, lipases like Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases like Celluzym® and / or KAC®.
  • proteases such as BLAP®, Optiase®, Opticlean®, Maxacal®, Maxapem®, Esperase ® and / or Savinase®, amylases like Termamyl®, Amylase-LT® and / or Maxamyl®, lipa
  • surfactants in particular low-foaming nonionic surfactants, can also be added to the agents according to the invention, which serve to better detach fatty food residues, as wetting agents and, if appropriate, as granulating aids in the course of the preparation of the cleaning agents.
  • Their amount can be up to 5% by weight, preferably up to 2% by weight.
  • Extremely low-foaming compounds are usually used in particular in cleaning agents for use in machine dishwashing processes. These preferably include C 2 -C alkyl polyglycol-propylene glycol ether, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • C ⁇ -Cis-alkylpolyethylene glycol-polybutylene glycol ether each with up to 8 moles of ethylene oxide and butylene oxide units in the molecule
  • end-capped alkylpolyalkylene glycol mixed ethers and the foaming but ecologically attractive Cg- C H alkyl polyglucosides with a degree of polymerization of about 1 to 4 (eg APG® 225 and APG® 600 from Henkel) and / or C 2 -C 14 alkyl polyethyleneglycols with 3 to 8 ethylene oxide units in the molecule.
  • surfactants from the family of glucamides such as, for example, alkyl-N-methyl-glucamides, in which the alkyl part preferably comes from a fatty alcohol with the C chain length C ⁇ -Cu. It is sometimes advantageous if the surfactants described are used as mixtures den, for example the combination of alkyl polyglycoside with fatty alcohol ethoxylates or glucamide with alkyl polyglycosides.
  • the cleaning agents foam too much during use, they can still contain up to 6% by weight, preferably about 0.5% by weight to 4% by weight, of a foam-suppressing compound, preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bisfatty acid amides, and other other known commercially available defoamers.
  • a foam-suppressing compound preferably from the group of silicone oils, mixtures of silicone oil and hydrophobicized silica, paraffins, paraffin-alcohol combinations, hydrophobicized silica, the bisfatty acid amides, and other other known commercially available defoamers.
  • Other optional ingredients in the agents according to the invention are, for example, perfume oils.
  • the dishwashing detergents according to the invention are preferably in the form of powdery, granular or tablet-like preparations which, in a manner known per se, for example by mixing, granulating, roller compacting and / or by spray drying the thermally loadable components and admixing the more sensitive components, to which in particular the enzyme granulate according to the invention is to be expected, can be produced.
  • the procedure is preferably such that all constituents are mixed with one another in a mixer and the mixture by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing pressures in the range from 200 • 10 5 Pa to 1 500 • 10 5 Pa pressed.
  • a tablet produced in this way preferably has a weight of 15 g to 40 g, in particular 20 g to 30 g, with a diameter from 35 mm to 40 mm.
  • Dishwashing detergents according to the invention in the form of non-dusting, storage-stable, free-flowing powders and / or granules with high bulk densities in the range from 800 to 1000 g / 1 can be carried out by adding the builder components with at least a proportion of liquid mixture components in a first process stage Increase in the bulk density of this premixed mixture and subsequently - if desired after an intermediate drying - the other constituents of the agent, including the enzyme granules containing silver corrosion inhibitor, combined with the premix obtained in this way.
  • the agents can be used both in household dishwashers and in commercial dishwashers. It is added by hand or using suitable dosing devices.
  • the application concentrations in the cleaning liquor are generally about 1 to 8 g / 1, preferably 2 to 5 g / 1.
  • a machine wash program is generally supplemented and ended by a few intermediate rinse cycles with clear water and a rinse cycle with a customary rinse aid after the cleaning cycle. After drying, when using the agents according to the invention, not only are completely clean dishes which are an from a hygienic point of view, but above all also bright silver cutlery items.
  • aqueous protease concentrate obtained after fermentation, removal of the fermentation residues by decanting, microfiltration in an ultrafiltration system and further concentration by means of vacuum evaporation as described in international patent application WO 91/02792 was mixed with the additives listed in the table below in a laboratory mixer from Lödige® homogeneously mixed and converted into granules with the aid of an extruder with a cutting device.
  • the hole diameter of the perforated plate of the extruder was 0.8 mm.
  • the ratio of length to thickness of the granules was 1.
  • the grain fraction between 0.4 mm and 1.6 mm was in a ball coater with Turbojet system from Wilsontlin with a coating layer coated, a melt of 70% by weight technical stearyl alcohol, 6% by weight 40 times ethoxylated tallow fatty alcohol and 24% by weight titanium dioxide being used.
  • the enzyme granulate containing silver protective agent obtained had a protease activity of 145,600 PE / g.

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  • Wood Science & Technology (AREA)
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Abstract

L'invention vise à mettre au point un procédé permettant de produire le plus aisément possible des granulés contenant des enzymes, aptes à être intégrés dans des nettoyants particulaires et contenant en outre des agents anticorrosion pour l'argent, par exemple sous forme de substances redox organiques déterminées, les constituants mentionnés, notamment l'enzyme, étant stables au stockage. A cet effet, on produit des granulés contenant en mélange intime l'enzyme, l'excipient organique et/ou inorganique destiné à l'enzyme et l'inhibiteur de corrosion de l'argent, ainsi qu'éventuellement des auxiliaires de granulation. Ces granulés enzymatiques s'utilisent pour produire des nettoyants solides, notamment particulaires.
EP96920771A 1995-06-12 1996-06-03 Granules enzymatiques contenant des agents anticorrosion pour l'argent Withdrawn EP0870007A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1995121371 DE19521371A1 (de) 1995-06-12 1995-06-12 Silberkorrosionsschutzmittelhaltige Enzymgranulate
DE19521371 1995-06-12
PCT/EP1996/002386 WO1996041860A1 (fr) 1995-06-12 1996-06-03 Granules enzymatiques contenant des agents anticorrosion pour l'argent

Publications (1)

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EP0870007A1 true EP0870007A1 (fr) 1998-10-14

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EP96920771A Withdrawn EP0870007A1 (fr) 1995-06-12 1996-06-03 Granules enzymatiques contenant des agents anticorrosion pour l'argent

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EP (1) EP0870007A1 (fr)
DE (1) DE19521371A1 (fr)
WO (1) WO1996041860A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6204236B1 (en) 1996-06-01 2001-03-20 Genencor International, Inc. Enzyme granulates comprising an enzyme and an organic disulfide core
DE19622131A1 (de) * 1996-06-01 1997-12-04 Solvay Enzymes Gmbh & Co Kg Neue Enzymgranulate
CN100378218C (zh) * 1999-10-01 2008-04-02 诺沃奇梅兹有限公司 喷雾干燥的酶产品
DE10258869A1 (de) * 2002-12-17 2004-07-15 Henkel Kgaa Silberschutz beim maschinellen Geschirrspülen
EP1571198A1 (fr) * 2004-03-02 2005-09-07 Dalli-Werke GmbH & Co. KG. Composés au manganèse liés à des polymères dans des compositions détergentes
DE102015217816A1 (de) 2015-09-17 2017-03-23 Henkel Ag & Co. Kgaa Verwendung hochkonzentrierter Enzymgranulate zur Erhöhung der Lagerstabilität von Enzymen

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Publication number Priority date Publication date Assignee Title
BE792940A (fr) * 1971-12-21 1973-06-18 Unilever Nv Compositions detergentes enzymatiques
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
DE4041752A1 (de) * 1990-12-24 1992-06-25 Henkel Kgaa Enzymzubereitung fuer wasch- und reinigungsmittel
DE4344215A1 (de) * 1993-12-23 1995-06-29 Cognis Bio Umwelt Silberkorrosionsschutzmittelhaltige Enzymzubereitung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9641860A1 *

Also Published As

Publication number Publication date
DE19521371A1 (de) 1996-12-19
WO1996041860A1 (fr) 1996-12-27

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