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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • 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
• • C—CHEMISTRY; METALLURGY
  • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
  • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
  • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
  • C12N9/98—Preparation of granular or free-flowing enzyme compositions

Definitions

• the present invention relates to an enzyme granulate, a process for its preparation and the use of the granulate in solid washing and cleaning agents.
• Enzymes 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 DT 16 17 190 or by sticking with nonionic surfactants in accordance with German Offenlegungsschrift DT 16 17 188 does not lead to any appreciable improvement in storage stability, since the sensitive enzymes are found in such mixtures in the Usually located 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 marbling, as described, for example, in German patent DE 16 17232, the German publication DT 20 32 768 and the German interpretations DE 21 37 042 and DE 21 37 043.
• Such enzyme preparations have poor solubility properties. The undissolved particles can get caught in the laundry and contaminate it, or they can be discharged unused into the wastewater.
• Embedding agents known from German Offenlegungsschrift 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 .
• European patent EP 168 526 enzyme granules are known which contain starch which swells in water, zeolite and water-soluble granulation aid.
• 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.
• 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.
• 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 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.
• an enzyme-containing granulate 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.
• coated enzyme granules are known, the coating layer of which consists of a coating system which contains 30% by weight to 50% by weight of finely divided inorganic pigment, 45% by weight to 60% by weight of one at room temperature solid alcohol with a melting point in the range from 45 ° C. to 65 ° C., up to 15% by weight emulsifier for the alcohol, up to 5% by weight Contains dispersant for the pigment and up to 3 wt .-% water. Due to the presence of relatively large amounts of water-insoluble fatty alcohol, such enzyme granules can lead to residue problems when dissolved in water, since the presence of the emulsifier is often not sufficient to dissolve the organic components of the coating system.
• the coating compositions used in the documents mentioned for the outermost coating layer are normally applied to the enzyme granules in the form of an aqueous dispersion in a fluidized bed dryer.
• the risk of at least superficial destruction of the granules by dust abrasion in the fluidized bed which leads to an increased proportion of extremely fine-grained material in the enzyme granules, which is unusable for admixture with conventional particulate detergents or cleaning agents, since it is not homogeneous in the
• the resulting mixture is distributed and, moreover, enzyme-containing fine dust can lead to allergenic reactions among detergent users.
• the invention further relates to a method for producing an enzyme granulate suitable for incorporation into particulate detergents or cleaning agents and having an average grain size of 0.8 mm to 1.4 mm by extruding one by mixing an aqueous enzyme liquid, one of which is insoluble, if appropriate by microfiltration
• Ingredients can be freed, concentrated fermentation broth, with an inorganic and / or organic carrier material as an additive, an enzyme premix obtained, spheronization of the extrudate in a rounding machine, optionally drying and application of an outer coating layer, an outer coating layer of a coating system being applied in a fluidized bed of extrudate , the 5 wt .-% to 70 wt .-%, in particular 10 wt .-% to 50 wt .-% of finely divided inorganic water-insoluble pigment, 45 wt .-% to 90 wt .-%, in particular 50 wt .-% to 85 wt% waterl solid at room temperature s
• water-soluble substances are understood to mean substances which dissolve in water at a temperature of 30 ° C. to at least 50 g / 1, in particular at least 80 g / 1. Fatty alcohols are therefore not water-soluble substances.
• the main component of the coating system is selected in particular from alkoxylated alcohols, fatty acid esters, fatty acid amides and / or hydroxy fatty acid esters. It is preferably an alcohol, in particular a primary linear alcohol, with 16 to 22 carbon atoms, which is etherified with 45 to 120, in particular 60 to 110 molar equivalents of alkylene oxide, in particular ethylene oxide.
• the alcohols mentioned include, in particular, stearyl alcohol, arachidyl alcohol, behenyl alcohol and mono- to tri-unsaturated alcohols of corresponding chain length, it being essential that the alkoxylated alcohol component mentioned has a melting point in the range from 40 ° C to 70 ° C, in particular from 50 ° C to 60 ° C, which is to be understood here as the temperature at which 100% of the substance is in liquid form when heated.
• ethoxylated fatty acid amides and / or ethoxylation products of fatty acid esters or hydroxy fatty acid esters with 1 to 6 carbon atoms in the alcohol part of the ester for example ricinoleic acid glyceride, the degree of ethoxylation in each case preferably being 45 to 120, in particular 60 to 110, can be used .
• the fatty acid component of the substances mentioned preferably has 12 to 22, in particular 16 to 18, carbon atoms.
• the preferred alkoxylates in this context include ethoxylation products with what is known as a narrow homolog distribution (nre, "narrow range ethoxylates"), as obtained in accordance with the process of European patent EP 339 426 or international patent application WO 90/13533.
• the ethoxy groups in the alkoxylation products mentioned can be at least partially replaced by propoxy groups
• the solidification point is the temperature at which hardened material cools to a temperature above the melting point
• a rotating thermometers can be determined according to the method of DIN ISO 2207.
• Particularly suitable for the production process according to the invention are substances which, when mixed with the other components of the coating system, are as homogeneous as possible Temperatures up to 120 ° C result in sprayable melt. In this context, it can serve as a guide that liquids with viscosities of up to about 500 mPas can generally be sprayed without problems at the temperatures mentioned by means of devices provided for this purpose, as known, for example, from German patent application DE 196 44 244, and applied to enzyme granules .
• Subordinate amounts, preferably 3% by weight to 45% by weight, in particular 4% by weight to 35% by weight, of a compound of the general formula I are preferably used as an additional component of the coating material,
• R is an organic radical having at least 2 C atoms, preferably 3 to 12 C atoms and in particular 4 to 10 C atoms, n 2 or 3 , m is 1 to 15 and x is 2 or 3.
• Such components can be produced in a known manner by reacting alcohols R [OH] x with ethylene oxide and / or propylene oxide and can be part of the above-mentioned portion which is liquid at room temperature.
• those are preferably used in the production of which the alcohol mentioned has first been reacted with propylene oxide and then with ethylene oxide.
• Preferred alcohols R [OH] x include 1,6-hexylene glycol, glycerol and trimethylolpropane, although 1,2-hydroxyethane is also useful.
• the water-insoluble inorganic pigments with which any disruptive coloring of the enzyme 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, talc 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 coating system.
• the average particle size of such pigments is usually in the range from 0.004 ⁇ m to 50 ⁇ m.
• Free-flowing improvers are another component of the coating system. These are to be understood as active ingredients, the absence of which leads to a deterioration in the free-flowing properties of the coated granules.
• aluminum silicates, zeolites, sodium silicates or silicas can be used which, in finely divided form for application to the enzyme granulate, are homogeneously mixed with the other constituents of the encapsulation system or can be applied separately after application of the other constituents of the encapsulation system.
• the primary enzymes which can be used are the proteases, lipases, amylases and / or cellulases obtained from microorganisms, such as bacteria or fungi, proteases produced by Bacillus species, alone or in combination 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 21 01 803 and DE 21 21 397, US Pat. Nos. 3,632,957 and US 4,264,738 and European patent application EP 006 638.
• 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 are.
• a carrier material mixture is preferably used which contains starch which is swellable in water and, if appropriate, cereal flour, cellulose powder and / or alkali carbonate.
• 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 cereal flour optionally contained 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.
• Preferred Commercially available wheat flour qualities such as Type 450 or Type 550 are 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 of up to 35% by weight, in particular from 15% 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, in particular 5% by weight to 25% by weight, based on the total granulate, of a granulation aid system which contains alkali carboxymethyl cellulose with degrees of substitution of Contains 0.5 to 1 and polyethylene glycol and / or alkyl polyethoxylate.
• This granulation aid system preferably contains, in each case 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.
• Phosphated, optionally partially hydrolyzed starches are also suitable as granulation aids.
• Phosphated starch is understood to mean a starch derivative in which the hydroxyl groups of the starch anhydroglucose units are replaced by the group -OP (O) (OH) 2 or its water-soluble salts, in particular alkali metal salts such as sodium and / or potassium salts.
• the average degree of phosphatization of the starch is to be understood as the number of esterified oxygen atoms bearing a phosphate group per saccharide monomer of the starch, averaged over all saccharide units.
• the average degree of phosphating in the case of preferably used phosphated starches is in Range from 1.5 to 2.5, since especially when using them, much smaller amounts are required to achieve a certain granule strength than when using carboxymethyl cellulose.
• partially hydrolyzed starches are to be understood as meaning oligomers or polymers of carbohydrates which are accessible by conventional hydrolysis of starch, for example by acid or enzyme-catalyzed processes. They are preferably hydrolysis products with average molecular weights in the range from 440 to 500,000.
• DE dextrose equivalent
• DE 3 - 20 maltodextrins
• DE 20 - 37 dry glucose syrups
• yellow dextrins and white dextrins with higher average molecular weights in the range from about 2,000 to 30,000 can be used.
• Relative to finished granules are contents of 0.1 % By weight to 20% by weight, in particular 0.5% by weight to 15% by weight of phosphated starch is preferred.
• 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.
• 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 i.e. those with an average molecular weight above 1000, can be used as synthetic water-soluble polymers with a dust-binding effect, but the higher molecular weight polyethylene glycols have the effect undesirable increase in the required granule dissolution time, so that these substances are preferably completely absent in the enzyme granules according to the invention.
• microfiltration is preferably carried out as crossflow microfiltration using porous tubes with micropores larger than 0.1 mm, 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 a known manner, subsequently processed in a kneader and a connected extruder to give 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 system according to the invention.
• 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.
• the coating system according to the invention is applied as an outer covering.
• the coating system optionally with cooling, is applied to the extrudate as a heated liquid at a temperature of 5 ° C. to 45 ° C. above the melting point of the organic water-soluble component which is solid at room temperature.
• 5% by weight to 25% by weight of the coating system is applied to the enzyme-containing extrudate as an outer coating layer.
• 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 for rapid and complete dissolution behavior in the wash liquor.
• the granules according to the invention preferably set 100% of them Free enzyme activity within 3 minutes, especially within 90 seconds to 2 minutes, in water at 25 ° C.
• 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 detergents or 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 1.2 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 grain sizes outside the range from 0.4 mm to 1.6 mm.
• This protease concentrate was mixed with additives (6% by weight sucrose, 4% by weight cellulose, 5% by weight carboxymethyl cellulose with a degree of substitution 0.65-0.75, 16% by weight wheat flour, 36% by weight corn starch and 3% by weight of polyethylene glycol with an average molecular weight of 2000, quantities given in each case based 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 0.85 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 rotor granulator of the type GPCG-5 from Glatt with a coating layer, a coating melt of 70% by weight 80 times ethoxylated C 6/18 fatty alcohol (Lutensol ® AT 80; manufacturer BASF) and 30 wt .-% titanium dioxide was used. 16% by weight, based on the resulting enzyme granules, of the melt kept at 120 ° C. was sprayed onto the enzyme granules under the following operating conditions:
• Amount of enzyme granulate used 10 kg
• Air volume 150 m 3 / h
• Dual-substance spray air temperature 120 ° C
• Dosing rate for coating melt 50 g / minute.
• the coating material formed a uniform, non-porous film on the granulate surface.
• 60 g of the granulate P1 thus produced were placed in a fluidized bed.
• the exhaust air from the fluidized bed passed through a filter.
• the amount of dust collected after 40 minutes of residence time of the enzyme granules corresponds to the amount of dust abrasion.
• the dust abrasion was negligibly low at under 10 mg per filter.
• Example 1 was repeated, a coating melt now consisting of 20% by weight of titanium dioxide, 48% by weight of 80 times ethoxylated C 6 6 fatty alcohol, 25% by weight of polyethylene glycol and 7% by weight of trimethylolpropane, which has 3 equivalents Propylene oxide and 7 equivalents of ethylene oxide per hydroxyl group had been used.
• granules (P2) with negligible dust abrasion were obtained

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Zoology (AREA)
• Genetics & Genomics (AREA)
• Bioinformatics & Cheminformatics (AREA)
• Biotechnology (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Microbiology (AREA)
• Medicinal Chemistry (AREA)
• Biochemistry (AREA)
• General Engineering & Computer Science (AREA)
• Biomedical Technology (AREA)
• Detergent Compositions (AREA)
• Enzymes And Modification Thereof (AREA)
• Medicinal Preparation (AREA)
• Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
• Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)
• Paints Or Removers (AREA)
• Cosmetics (AREA)

Priority Applications (6)

Applications Claiming Priority (2)

Publications (2)

Family

ID=7814338

Family Applications (1)

Country Status (9)

Cited By (8)

Families Citing this family (19)

Family Cites Families (31)

• 1996
  • 1996-12-11 DE DE19651446A patent/DE19651446A1/de not_active Ceased
• 1997
  • 1997-12-02 CN CN97180522A patent/CN1117143C/zh not_active Expired - Fee Related
  • 1997-12-02 WO PCT/EP1997/006744 patent/WO1998026037A2/de not_active Ceased
  • 1997-12-02 DK DK97952858T patent/DK0944704T3/da active
  • 1997-12-02 ES ES97952858T patent/ES2195193T3/es not_active Expired - Lifetime
  • 1997-12-02 JP JP52617398A patent/JP2001505946A/ja active Pending
  • 1997-12-02 AT AT97952858T patent/ATE234351T1/de not_active IP Right Cessation
  • 1997-12-02 DE DE59709528T patent/DE59709528D1/de not_active Expired - Lifetime
  • 1997-12-02 EP EP97952858A patent/EP0944704B1/de not_active Expired - Lifetime
  • 1997-12-02 US US09/319,714 patent/US6350728B1/en not_active Expired - Lifetime

Also Published As

Similar Documents

Legal Events