EP0629692A1 - Liquid enzyme preparations - Google Patents
Liquid enzyme preparations Download PDFInfo
- Publication number
- EP0629692A1 EP0629692A1 EP94108755A EP94108755A EP0629692A1 EP 0629692 A1 EP0629692 A1 EP 0629692A1 EP 94108755 A EP94108755 A EP 94108755A EP 94108755 A EP94108755 A EP 94108755A EP 0629692 A1 EP0629692 A1 EP 0629692A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- liquid
- enzyme
- weight
- enzyme preparation
- preparation according
- 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.)
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- 239000007788 liquid Substances 0.000 title claims abstract description 78
- 229940079919 digestives enzyme preparation Drugs 0.000 title abstract description 33
- 102000004190 Enzymes Human genes 0.000 claims abstract description 85
- 108090000790 Enzymes Proteins 0.000 claims abstract description 85
- 229940088598 enzyme Drugs 0.000 claims abstract description 85
- 239000000725 suspension Substances 0.000 claims abstract description 32
- 229920000642 polymer Polymers 0.000 claims abstract description 25
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000003599 detergent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000945 filler Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 108091005804 Peptidases Proteins 0.000 claims description 23
- 239000004365 Protease Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 14
- 239000012459 cleaning agent Substances 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 108010065511 Amylases Proteins 0.000 claims description 9
- 102000013142 Amylases Human genes 0.000 claims description 9
- 235000019418 amylase Nutrition 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 7
- 239000004382 Amylase Substances 0.000 claims description 6
- 102000004882 Lipase Human genes 0.000 claims description 4
- 108090001060 Lipase Proteins 0.000 claims description 4
- 239000004367 Lipase Substances 0.000 claims description 4
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 4
- 235000019421 lipase Nutrition 0.000 claims description 4
- 102000004316 Oxidoreductases Human genes 0.000 claims description 2
- 108090000854 Oxidoreductases Proteins 0.000 claims description 2
- 102000004020 Oxygenases Human genes 0.000 claims description 2
- 108090000417 Oxygenases Proteins 0.000 claims description 2
- 108010002430 hemicellulase Proteins 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 108010059892 Cellulase Proteins 0.000 claims 1
- 229940106157 cellulase Drugs 0.000 claims 1
- 229940059442 hemicellulase Drugs 0.000 claims 1
- 235000019419 proteases Nutrition 0.000 claims 1
- 108091005658 Basic proteases Proteins 0.000 abstract description 10
- 238000004140 cleaning Methods 0.000 abstract description 3
- 102000035195 Peptidases Human genes 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229920001983 poloxamer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229910002016 AerosilĀ® 200 Inorganic materials 0.000 description 5
- 108010056079 Subtilisins Proteins 0.000 description 5
- 102000005158 Subtilisins Human genes 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 229940025131 amylases Drugs 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 241000193375 Bacillus alcalophilus Species 0.000 description 2
- 244000063299 Bacillus subtilis Species 0.000 description 2
- 102000005575 Cellulases Human genes 0.000 description 2
- 108010084185 Cellulases Proteins 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 235000010633 broth Nutrition 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002797 proteolythic effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910002012 AerosilĀ® Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000193744 Bacillus amyloliquefaciens Species 0.000 description 1
- 241000193422 Bacillus lentus Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108010083608 Durazym Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004851 dishwashing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 125000003607 serino group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C(O[H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38663—Stabilised liquid enzyme compositions
Definitions
- the present invention relates to liquid enzyme preparations, a process for their preparation and their use in liquid detergent and cleaning agent compositions.
- liquid detergent and cleaning agent compositions e.g. B. for cleaning textiles or dishes
- enzymes are used to increase the washing effectiveness.
- Proteases, lipases, amylases or cellulases are usually used as enzymes.
- the enzyme stability can be severely impaired by the other detergent components present.
- Another problem with these enzyme-containing liquid compositions is often their sedimentation stability.
- the object was therefore to provide liquid enzyme preparations which are stable to sedimentation and have high enzyme stability and are therefore well suited for use in liquid detergent and cleaning agent compositions.
- Liquid enzyme preparations have now been found which show the required properties.
- the invention therefore relates to a liquid enzyme preparation which comprises 3 to 25% by weight of an enzyme particle suspension, optionally 0.5 to 30% by weight of water, 1 to 10% by weight of a highly disperse filler and 65 to 95.5% by weight. -% of a liquid alkylene oxide polymer based on ethylenediamine having a molecular weight in the range from 500 to 8,200.
- All the enzymes customary in detergent and cleaning agent compositions for example proteases, lipases, amylases, glucanases such as cellulases, hemicellulases, oxidases or oxygenases, can be present as enzymes in the liquid enzyme preparations according to the invention.
- the enzymes can be present individually or as an enzyme mixture, for example as a protease / amylase mixture or protease / lipase mixture.
- the liquid enzyme preparations according to the invention preferably contain proteases and / or amylases.
- the liquid enzyme preparations according to the invention advantageously contain a heat-stable amylase such as, for. B. Optitherm R.
- the liquid enzyme preparations according to the invention contain proteases, in particular alkaline proteases.
- the so-called subtilisins are particularly advantageous as alkaline proteases.
- Subtilisins are alkaline proteases with a pH optimum in the alkaline pH range and an essential serine residue in the active center.
- Optimized proteases which have improved properties such as increased washing performance or improved stability due to known biotechnological mutagenesis can also be used in an advantageous manner.
- Proteases can be obtained in a manner known per se from Gram-positive bacteria or fungi.
- proteases obtained from Bacillus strains, for example subtilisins such as Subtilisin BPN ', Subtilisin Carlsberg and proteases derived from Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus or Bacillus alcalophilus can be isolated.
- proteases which have a pH optimum in the range from 7 to 13 and which, for. B. as Savinase R , Maxacal R , Durazym R , Maxapem R or Opticlean R are commercially available.
- the enzymes suitable for the liquid enzyme preparations according to the invention can be obtained in a manner known per se by fermentation processes from suitable microorganisms, in particular from bacteria or fungi.
- the fermentation broths obtained during the fermentation are made of insoluble accompanying substances, e.g. B. by filtration, and then freed in a conventional manner, for. B. by membrane filtration processes or by thin-layer evaporation, whereby so-called enzyme concentrates are obtained, which usually contain the enzyme or enzyme mixture in an amount of 2 to 50 wt .-%, based on the dry matter.
- the enzymes are in the form of a so-called aqueous enzyme particle suspension (enzyme slurry).
- aqueous enzyme particle suspension is obtained by, for example, from the aforementioned enzyme concentrates in a manner known per se. B. by precipitation processes, spray drying or crystallization, the enzymes precipitated and the precipitate thus obtained again in a known manner in liquid, for. B. the mother liquor or a suitable buffer solution, saline or amino acid solution.
- Suitable precipitation processes according to which the enzymes can be precipitated from the enzyme concentrates are e.g. B. the known methods according to which the enzymes by means of the addition of salts, for. B.
- a concentrated sodium or ammonium sulfate solution or by the addition of an organic solvent such as.
- an organic solvent such as ethanol, acetone, octanol or decanol can be precipitated from the enzyme concentrates obtained after the fermentation.
- An enzyme crystal suspension (enzyme crystal slurry) is preferably used as the enzyme particle suspension in the liquid enzyme preparations according to the invention. This is obtained by adding an aqueous, e.g. B. 5 to 20% solution of an alkali or alkaline earth metal halide salt, optionally heated to 20 to 35 Ā° C and awaiting crystallization of the enzyme.
- An aqueous 10% alkali metal chloride solution in particular a 10% sodium chloride solution, is preferably added.
- the enzyme crystal suspension of a protease in particular an alkaline protease such as, for example, is preferably processed in the liquid enzyme preparations according to the invention.
- the main constituent of the liquid enzyme preparations according to the invention contains 65 to 95.5% by weight, preferably 80 to 90% by weight, of a liquid alkylene oxide polymer based on ethylenediamine with a molecular weight in the range from 500 to 8,200.
- a liquid alkylene oxide polymer based on ethylenediamine with a molecular weight in the range from 500 to 8,200.
- Such compounds are obtained in a manner known per se by the addition of alkylene oxide units, for. B. ethylene oxide or propylene oxide units, on ethylenediamine.
- alkylene oxide block or mixed polymers are obtained. Both the alkylene block and the copolymers based on ethylenediamine can be used in the liquid enzyme preparations according to the invention.
- the block polymers are preferably used.
- alkylene oxide polymers based on a lower alkylenediamine other than ethylenediamine e.g. B. based on propylenediamine.
- the alkylene oxide polymers are used in liquid form in the enzyme preparations according to the invention. Since the flowability of the alkylene oxide polymers depends on the number of alkylene oxide units present in the polymer changed, "liquid" in the sense of the invention should be understood to mean both low viscosity and viscous to pasty alkylene oxide polymers.
- the liquid enzyme preparations according to the invention preferably contain an ethylene oxide-propylene oxide polymer based on ethylenediamine.
- the molecular weight of this polymer should preferably be in the range from 1,500 to 7,500.
- the ethylene oxide content in such a preferred polymer should advantageously be about 40% by weight.
- Such polymers that contain ethylene oxide and propylene oxide units as block polymers added to ethylenediamine are, for. B. commercially available under the trade name Synperonic T R (from ICI).
- the liquid enzyme preparations according to the invention contain a highly disperse filler in an amount of 1 to 10% by weight, preferably 1 to 5% by weight.
- a highly disperse filler in an amount of 1 to 10% by weight, preferably 1 to 5% by weight.
- highly disperse inorganic compounds from the group consisting of silicas, aluminosilicates, aluminum oxides and titanium dioxide are suitable as highly disperse fillers.
- Such highly disperse products are generally known and commercially available. Preference is given to using highly disperse silicas such.
- B. the products available from Degussa under the trade name Aerosil R , e.g. B. Aerosil 200 R.
- a liquid enzyme preparation according to the invention contains 3 to 10% by weight of an enzyme crystal suspension of a highly alkaline protease, 5 to 10% by weight of water, 1 to 5% by weight of Aerosil R 200 and 80 to 90% by weight of Synperonic T304 R.
- 1,000 DU correspond to a proteolytic activity which, with a volume of 1 ml of a 2% enzyme solution (w / w) after degradation of casein, results in an extinction difference (1 cm light path; 275 nm; determination against blind sample test) of 0.400.
- the invention further comprises a process for the preparation of liquid enzyme preparations, in which 3 to 25% by weight of an enzyme particle suspension, optionally 0.5 to 30% by weight of water, 1 to 10% by weight of a highly disperse filler and 65 to 95.5% by weight of a liquid alkylene oxide polymer based on ethylenediamine with a molecular weight in the range from 500 to 8,200 are mixed with one another, the percentages by weight relating to the finished overall preparation.
- the process is expediently carried out by placing the liquid alkylene oxide polymer based on ethylenediamine in a vessel and then slowly adding the highly disperse filler with vigorous stirring, and then adding the corresponding enzyme particle suspension homogenized by stirring.
- An ethylene oxide-propylene oxide polymer based on ethylene diamine is preferably used. This polymer should preferably have a molecular weight in the range from 1,500 to 7,500.
- Synperonic R e.g. B. Use Synperonic T304 R with a molecular weight of approx. 1,650.
- the enzyme particle suspension the appropriate amount of water is usually also added due to the water content of the enzyme particle suspension added.
- An enzyme crystal suspension of a highly alkaline protease is preferably used as the enzyme particle suspension, the enzyme activity of which has been concentrated to 2 million to 6 million DU / ml in a manner known per se.
- the invention further relates to liquid washing and cleaning agents which contain the liquid enzyme preparations according to the invention.
- the liquid enzyme preparations according to the invention are preferably used in liquid detergents for cleaning textiles or in liquid dishwashing detergents. Except for the liquid enzyme preparations
- the detergent or cleaning agent formulations can contain all the ingredients and auxiliaries which are customary in the prior art for the formulation of liquid washing and cleaning agents, for. B. surfactants, builders (builder) and optionally bleach or bleach precursors in conventional amounts.
- the auxiliaries include e.g. B. enzyme stabilizers, complexing and chelating agents, foam regulators and additives such as corrosion inhibitors, antistatic agents, dyes, fragrances, bactericides, fungicides and activators.
- the liquid enzyme preparations according to the invention show surprisingly good properties which are particularly suitable for use in liquid detergent and cleaning agent formulations.
- the liquid enzyme preparations according to the invention have a very high storage stability, the enzyme activity of the enzymes processed in these liquid enzyme preparations remaining virtually unchanged even over a relatively long period.
- the liquid enzyme preparations according to the invention are very stable to sedimentation. Due to their low viscosity, the liquid enzyme preparations according to the invention can be easily metered and are therefore very well suited for processing in liquid washing or cleaning agents.
- the activity of the protease processed in the liquid enzyme preparations was determined in Delft Units (DU).
- 1,000 DU correspond to the proteolytic activity, which results in an extinction difference (1 cm light path; 275 nm; determination against blind sample test) of 0.400 with a volume of 1 ml of a 2% enzyme solution (w / w) after degradation of casein.
- a Bacillus alcalophilus (DSM No. 5466) was fermented in a manner known per se. Insoluble accompanying substances were separated from the fermenter broth by filtration using filter aids and flocculants. The pH in the filtrate was adjusted to 5.2 and concentrated by ultrafiltration by a factor of about 4 to a protease activity of about 750,000 DU / ml. After ultrafiltration, a 10% saline solution was added, the mixture was warmed to about 30 Ā° C. and the crystallization of the enzyme was awaited. An enzyme crystal suspension was obtained which, in a manner known per se, was concentrated to a protease activity of about 3.6 million DU / ml while removing the mother liquor.
- the enzyme crystal suspension of the highly alkaline protease was then processed into the liquid enzyme preparations according to the invention using the following recipe: 5% by weight enzyme crystal suspension 7.0% by weight of water (also introduced via the enzyme crystal suspension) 2.6% by weight Aerosil 200 R (highly disperse silica) 85.4% by weight Synperonic T304 R (liquid ethylene oxide-propylene oxide polymer based on ethylenediamine, MW: approx.1,650).
- the liquid enzyme preparations according to the invention were prepared by placing the specified amount of Synperonic T304 R in a vessel to which the specified amount of Aerosil 200 R was slowly added with vigorous stirring. Then the enzyme crystal suspension previously homogenized by stirring was added with stirring. You got a sedimentation-stable liquid enzyme preparation of the highly alkaline protease with a protease activity of approx. 678,000 DU / g.
- An enzyme crystal suspension of a protease obtained in the same way as in Example 1 was processed in the same manner according to the following recipe: 10% by weight enzyme crystal suspension 7% by weight of water (also introduced via the enzyme crystal suspension) 5.2% by weight Aerosil 200 R 77.8% by weight Synperonic T304 R A sedimentation-stable liquid enzyme preparation with a protease activity of approx. 960,000 DU / g was obtained.
- a liquid enzyme preparation of a protease was produced according to the following recipe: 25% by weight enzyme crystal suspension 7.4% by weight of water (also introduced via the enzyme crystal suspension) 2.6% by weight of Aerosil 200 R. 65% by weight Synperonic T 304 R A sedimentation-stable liquid enzyme preparation with a protease activity of approximately 1.8 million DU / g was obtained.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Enzymes And Modification Thereof (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft flĆ¼ssige Enzymzubereitungen, ein Verfahren zu deren Herstellung sowie deren Verwendung in flĆ¼ssigen Wasch- und Reinigungsmittelzusammensetzungen.The present invention relates to liquid enzyme preparations, a process for their preparation and their use in liquid detergent and cleaning agent compositions.
In zahlreichen flĆ¼ssigen Wasch- und Reinigungsmittelzusammensetzungen, z. B. zur Reinigung von Textilien oder Geschirr werden Enzyme zur Erhƶhung der Waschwirksamkeit eingesetzt. Ćblicherweise verwendet man dabei als Enzyme Proteasen, Lipasen, Amylasen oder Cellulasen. Hierbei kann in derartigen FlĆ¼ssigzusammensetzungen die EnzymstabilitƤt durch die anderen vorhandenen Waschmittelbestandteile stark beeintrƤchtigt sein. Ein weiteres Problem dieser enzymhaltigen flĆ¼ssigen Zusammensetzungen ist oft deren SedimentationsstabilitƤt.In numerous liquid detergent and cleaning agent compositions, e.g. B. for cleaning textiles or dishes, enzymes are used to increase the washing effectiveness. Proteases, lipases, amylases or cellulases are usually used as enzymes. In such liquid compositions, the enzyme stability can be severely impaired by the other detergent components present. Another problem with these enzyme-containing liquid compositions is often their sedimentation stability.
Es besteht weiterhin Bedarf an flĆ¼ssigen Enzymzubereitungen, welche sich gut in flĆ¼ssigen Wasch- und Reinigungsmittelzusammensetzungen mit einer hohen EnzymstabilitƤt verarbeiten lassen.There is still a need for liquid enzyme preparations which can be processed well in liquid detergent and cleaning agent compositions with a high enzyme stability.
Es bestand daher die Aufgabe, flĆ¼ssige Enzymzubereitungen zur VerfĆ¼gung zu stellen, die sedimentationsstabil sind und eine hohe EnzymstabilitƤt besitzen und sich daher gut fĆ¼r die Verwendung in flĆ¼ssigen Wasch- und Reinigungsmittelzusammensetzungen eignen.The object was therefore to provide liquid enzyme preparations which are stable to sedimentation and have high enzyme stability and are therefore well suited for use in liquid detergent and cleaning agent compositions.
Es wurden nun flĆ¼ssige Enzymzubereitungen gefunden, die die geforderten Eigenschaften zeigen.Liquid enzyme preparations have now been found which show the required properties.
Gegenstand der Erfindung ist daher eine flĆ¼ssige Enzymzubereitung, welche 3 bis 25 Gew.-% einer Enzympartikelsuspension, gegebenenfalls 0,5 bis 30 Gew.-% Wasser, 1 bis 10 Gew.-% eines hochdispersen FĆ¼llstoffes und 65 bis 95,5 Gew.-% eines flĆ¼ssigen Alkylenoxidpolymerisats auf Basis Ethylendiamin mit einem Molekulargewicht im Bereich von 500 bis 8.200 enthƤlt.The invention therefore relates to a liquid enzyme preparation which comprises 3 to 25% by weight of an enzyme particle suspension, optionally 0.5 to 30% by weight of water, 1 to 10% by weight of a highly disperse filler and 65 to 95.5% by weight. -% of a liquid alkylene oxide polymer based on ethylenediamine having a molecular weight in the range from 500 to 8,200.
Als Enzyme kƶnnen in den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen alle in Wasch- und Reinigungsmittelzusammensetzungen Ć¼blichen Enzyme, beispielsweise Proteasen, Lipasen, Amylasen, Glucanasen wie Cellulasen, Hemicellulasen, Oxydasen oder Oxygenasen enthalten sein. Die Enzyme kƶnnen dabei einzeln oder auch als Enzymgemisch, beispielsweise als Protease/Amylase-Gemisch oder Protease/Lipase-Gemisch vorliegen. Bevorzugt enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen Proteasen und/oder Amylasen.All the enzymes customary in detergent and cleaning agent compositions, for example proteases, lipases, amylases, glucanases such as cellulases, hemicellulases, oxidases or oxygenases, can be present as enzymes in the liquid enzyme preparations according to the invention. The enzymes can be present individually or as an enzyme mixture, for example as a protease / amylase mixture or protease / lipase mixture. The liquid enzyme preparations according to the invention preferably contain proteases and / or amylases.
Als Amylase enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen vorteilhaft eine hitzestabile Amylase wie z. B. OptithermR.As the amylase, the liquid enzyme preparations according to the invention advantageously contain a heat-stable amylase such as, for. B. Optitherm R.
In einer besonders bevorzugten Ausgestaltung enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen Proteasen, insbesondere alkalische Proteasen. Hierbei sind als alkalische Proteasen insbesondere die sogenannten Subtilisine vorteilhaft. Subtilisine sind alkalische Proteasen mit einem pH-Optimum im alkalischen pH-Bereich und einen essentiellen Serinrest im aktiven Zentrum. In vorteilhafter Weise kƶnnen dabei besonders auch optimierte Proteasen eingesetzt werden, die verbesserte Eigenschaften wie gesteigerte Waschleistung oder verbesserte StabilitƤt aufgrund an sich bekannter biotechnologischer Mutagenese besitzen. Proteasen kƶnnen auf an sich bekannte Weise aus Gram-Positiven Bakterien oder Pilzen gewonnen werden. Bevorzugt sind dabei die aus Bacillus-StƤmmen gewonnenen Proteasen, beispielsweise Subtilisine wie Subtilisin BPN', Subtilisin Carlsberg und Proteasen, die aus Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus oder Bacillus alcalophilus isoliert werden kƶnnen. Besonders bevorzugt sind Proteasen, die ein pH-Optimum im Bereich von 7 bis 13 haben und die z. B. als SavinaseR, MaxacalR, DurazymR, MaxapemR oder OpticleanR kommerziell erhƤltlich sind.In a particularly preferred embodiment, the liquid enzyme preparations according to the invention contain proteases, in particular alkaline proteases. The so-called subtilisins are particularly advantageous as alkaline proteases. Subtilisins are alkaline proteases with a pH optimum in the alkaline pH range and an essential serine residue in the active center. Optimized proteases which have improved properties such as increased washing performance or improved stability due to known biotechnological mutagenesis can also be used in an advantageous manner. Proteases can be obtained in a manner known per se from Gram-positive bacteria or fungi. Preferred are the proteases obtained from Bacillus strains, for example subtilisins such as Subtilisin BPN ', Subtilisin Carlsberg and proteases derived from Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus or Bacillus alcalophilus can be isolated. Proteases which have a pH optimum in the range from 7 to 13 and which, for. B. as Savinase R , Maxacal R , Durazym R , Maxapem R or Opticlean R are commercially available.
Die fĆ¼r die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen geeigneten Enzyme kƶnnen auf an sich bekannte Weise durch Fermentationsprozesse aus geeigneten Mikroorganismen, insbesondere aus Bakterien oder Pilzen, gewonnen werden. Die bei der Fermentation erhaltenen FermenterbrĆ¼hen werden von unlƶslichen Begleitstoffen, z. B. durch Filtration, befreit und anschlieĆend auf an sich bekannte Weise, z. B. durch Membranfiltrationsverfahren oder durch DĆ¼nnschichtverdampfung eingeengt, wodurch man sogenannte Enzymkonzentrate erhƤlt, die Ć¼blicherweise das Enzym bzw. Enzymgemisch in einer Menge von 2 bis 50 Gew.-%, bezogen auf die Trockensubstanz, enthalten.The enzymes suitable for the liquid enzyme preparations according to the invention can be obtained in a manner known per se by fermentation processes from suitable microorganisms, in particular from bacteria or fungi. The fermentation broths obtained during the fermentation are made of insoluble accompanying substances, e.g. B. by filtration, and then freed in a conventional manner, for. B. by membrane filtration processes or by thin-layer evaporation, whereby so-called enzyme concentrates are obtained, which usually contain the enzyme or enzyme mixture in an amount of 2 to 50 wt .-%, based on the dry matter.
In den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen liegen die Enzyme in Form einer sogenannten wƤĆrigen Enzympartikelsuspension (Enzyme slurry) vor. Eine derartige wƤĆrige Enzympartikelsuspension wird erhalten, indem man aus den vorgenannten Enzymkonzentraten auf an sich bekannte Weise z. B. durch FƤllungsverfahren, SprĆ¼htrocknung oder Kristallisation die Enzyme prƤzipitiert und das so erhaltene PrƤzipitat auf an sich bekannte Weise wieder in FlĆ¼ssigkeit, z. B. der Mutterlauge oder einer geeigneten Pufferlƶsung, Salzlƶsung oder AminosƤurelƶsung, suspendiert. Geeignete FƤllungsverfahren, nach denen sich die Enzyme aus den Enzymkonzentraten prƤzipitieren lassen, sind z. B. die an sich bekannten Verfahren, nach denen die Enzyme mittels der Zugabe von Salzen, z. B. durch die Zugabe einer konzentrierten Natrium- oder Ammoniumsulfat-Lƶsung, oder durch die Zugabe eines organischen Lƶsungsmittels wie z. B. Ethanol, Aceton, Octanol oder Dekanol aus den nach der Fermentation gewonnenen Enzymkonzentraten ausgefƤllt werden.In the liquid enzyme preparations according to the invention, the enzymes are in the form of a so-called aqueous enzyme particle suspension (enzyme slurry). Such an aqueous enzyme particle suspension is obtained by, for example, from the aforementioned enzyme concentrates in a manner known per se. B. by precipitation processes, spray drying or crystallization, the enzymes precipitated and the precipitate thus obtained again in a known manner in liquid, for. B. the mother liquor or a suitable buffer solution, saline or amino acid solution. Suitable precipitation processes according to which the enzymes can be precipitated from the enzyme concentrates are e.g. B. the known methods according to which the enzymes by means of the addition of salts, for. B. by the addition of a concentrated sodium or ammonium sulfate solution, or by the addition of an organic solvent such as. As ethanol, acetone, octanol or decanol can be precipitated from the enzyme concentrates obtained after the fermentation.
Bevorzugt setzt man in den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen als Enzympartikelsuspension eine Enzymkristallsuspension (Enzyme crystal slurry) ein. Diese wird erhalten, indem man dem Enzymkonzentrat auf an sich bekannte Weise eine wƤĆrige, z. B. 5 bis 20 %ige, Lƶsung eines Alkali- oder Erdalkalihalogenid-Salzes zufĆ¼gt, gegebenenfalls auf 20 bis 35 Ā°C erwƤrmt und die Kristallisation des Enzyms abwartet. Vorzugsweise setzt man eine wƤĆrige 10 %ige Alkalichloridlƶsung, insbesondere eine 10 %ige Kochsalzlƶsung, zu.An enzyme crystal suspension (enzyme crystal slurry) is preferably used as the enzyme particle suspension in the liquid enzyme preparations according to the invention. This is obtained by adding an aqueous, e.g. B. 5 to 20% solution of an alkali or alkaline earth metal halide salt, optionally heated to 20 to 35 Ā° C and awaiting crystallization of the enzyme. An aqueous 10% alkali metal chloride solution, in particular a 10% sodium chloride solution, is preferably added.
Bevorzugt verarbeitet man in den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen die Enzymkristallsuspension einer Protease, insbesondere einer alkalischen Protease wie z. B. OpticleanR und/oder die Enzymkristallsuspension einer hitzestabilen Amylase wie z. B. OptithermR.The enzyme crystal suspension of a protease, in particular an alkaline protease such as, for example, is preferably processed in the liquid enzyme preparations according to the invention. B. Opticlean R and / or the enzyme crystal suspension of a heat-stable amylase such as. B. Optitherm R.
Als Hauptbestandteil enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen 65 bis 95,5 Gew.-%, vorzugsweise 80 bis 90 Gew.-% eines flĆ¼ssigen Alkylenoxidpolymerisats auf Basis Ethylendiamin mit einem Molekulargewicht im Bereich von 500 bis 8.200. Erhalten werden derartige Verbindungen auf an sich bekannte Weise durch die Addition von Alkylenoxid-Einheiten, z. B. Ethylenoxid- oder Propylenoxid-Einheiten, an Ethylendiamin. Je nach ReaktionsfĆ¼hrung werden dabei Alkylenoxid-Block- oder Mischpolymerisate erhalten. Sowohl die Alkylen-Block- als auch die Mischpolymerisate auf Basis Ethylendiamin kƶnnen in den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen eingesetzt werden. Bevorzugt verwendet man die Blockpolymerisate. SelbstverstƤndlich kƶnnen in den erfindungsgemƤĆen Enzymzubereitungen auch Alkylenoxidpolymerisate auf der Basis eines anderen Niederalkylendiamins als Ethylendiamin, z. B. auf der Basis von Propylendiamin, verwendet werden.The main constituent of the liquid enzyme preparations according to the invention contains 65 to 95.5% by weight, preferably 80 to 90% by weight, of a liquid alkylene oxide polymer based on ethylenediamine with a molecular weight in the range from 500 to 8,200. Such compounds are obtained in a manner known per se by the addition of alkylene oxide units, for. B. ethylene oxide or propylene oxide units, on ethylenediamine. Depending on the reaction procedure, alkylene oxide block or mixed polymers are obtained. Both the alkylene block and the copolymers based on ethylenediamine can be used in the liquid enzyme preparations according to the invention. The block polymers are preferably used. Of course, alkylene oxide polymers based on a lower alkylenediamine other than ethylenediamine, e.g. B. based on propylenediamine.
Die Alkylenoxidpolymerisate werden in den erfindungsgemƤĆen Enzymzubereitungen in flĆ¼ssiger Form eingesetzt. Da sich die FlieĆfƤhigkeit der Alkylenoxidpolymerisate in AbhƤngigkeit von der Anzahl der im Polymerisat vorhandenen Alkylenoxid-Einheiten verƤndert, sollen unter "flĆ¼ssig" im Sinne der Erfindung sowohl dĆ¼nnflĆ¼ssige als auch zƤhflĆ¼ssige bis pastenfƶrmige Alkylenoxidpolymerisate verstanden werden.The alkylene oxide polymers are used in liquid form in the enzyme preparations according to the invention. Since the flowability of the alkylene oxide polymers depends on the number of alkylene oxide units present in the polymer changed, "liquid" in the sense of the invention should be understood to mean both low viscosity and viscous to pasty alkylene oxide polymers.
Bevorzugt enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen ein Ethylenoxid-Propylenoxidpolymerisat auf der Basis von Ethylendiamin. Vorzugsweise sollte dabei das Molekulargewicht dieses Polymerisates im Bereich von 1.500 bis 7.500 liegen. Vorteilhaft sollte dabei der Ethylenoxid-Anteil in einem solchen bevorzugten Polymerisat ca. 40 Gew.-% betragen. Derartige Polymerisate, die Ethylenoxid- und Propylenoxideinheiten als Blockpolymerisate addiert an Ethylendiamin enthalten, sind z. B. unter dem Handelsnamen Synperonic TR (von der Fa. ICI) kommerziell erhƤltlich.The liquid enzyme preparations according to the invention preferably contain an ethylene oxide-propylene oxide polymer based on ethylenediamine. The molecular weight of this polymer should preferably be in the range from 1,500 to 7,500. The ethylene oxide content in such a preferred polymer should advantageously be about 40% by weight. Such polymers that contain ethylene oxide and propylene oxide units as block polymers added to ethylenediamine are, for. B. commercially available under the trade name Synperonic T R (from ICI).
Weiterhin enthalten die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen einen hochdispersen FĆ¼llstoff in einer Menge von 1 bis 10 Gew.-%, vorzugsweise 1 bis 5 Gew.-%. Als hochdisperse FĆ¼llstoffe sind dabei insbesondere hochdisperse anorganische Verbindungen aus der Gruppe KieselsƤuren, Alumosilikate, Aluminiumoxide und Titandioxid geeignet. Derartige hochdisperse Produkte sind allgemein bekannt und kommerziell erhƤltlich. Vorzugsweise setzt man hochdisperse KieselsƤuren wie z. B. die von der Firma Degussa unter dem Handelsnamen AerosilR erhƤltlichen Produkte, z. B. Aerosil 200R, ein.Furthermore, the liquid enzyme preparations according to the invention contain a highly disperse filler in an amount of 1 to 10% by weight, preferably 1 to 5% by weight. In particular, highly disperse inorganic compounds from the group consisting of silicas, aluminosilicates, aluminum oxides and titanium dioxide are suitable as highly disperse fillers. Such highly disperse products are generally known and commercially available. Preference is given to using highly disperse silicas such. B. the products available from Degussa under the trade name Aerosil R , e.g. B. Aerosil 200 R.
In einer bevorzugten Ausgestaltung enthƤlt eine erfindungsgemƤĆe flĆ¼ssige Enzymzubereitung 3 bis 10 Gew.-% einer Enzymkristallsuspension einer hochalkalischen Protease, 5 bis 10 Gew.-% Wasser, 1 bis 5 Gew.-% AerosilR 200 sowie 80 bis 90 Gew.-% Synperonic T304R. Die Protease-AktivitƤt einer derartigen erfindungsgemƤĆen Zubereitung kann dabei 500.000 bis 800.000 DU/g (DU = Delft Units) betragen. 1.000 DU entsprechen dabei einer proteolytischen AktivitƤt, die bei einem Volumen von 1 ml einer 2 %igen Enzymlƶsung (w/w) nach Abbau von Casein eine Extinktionsdifferenz (1 cm Lichtweg; 275 nm; Bestimmung gegen Blindprobentest) von 0,400 ergibt.In a preferred embodiment, a liquid enzyme preparation according to the invention contains 3 to 10% by weight of an enzyme crystal suspension of a highly alkaline protease, 5 to 10% by weight of water, 1 to 5% by weight of Aerosil R 200 and 80 to 90% by weight of Synperonic T304 R. The protease activity of such a preparation according to the invention can be 500,000 to 800,000 DU / g (DU = Delft Units). 1,000 DU correspond to a proteolytic activity which, with a volume of 1 ml of a 2% enzyme solution (w / w) after degradation of casein, results in an extinction difference (1 cm light path; 275 nm; determination against blind sample test) of 0.400.
Weiterhin umfaĆt die Erfindung ein Verfahren zur Herstellung von flĆ¼ssigen Enzymzubereitungen, bei dem man unter RĆ¼hren 3 bis 25 Gew.-% einer Enzympartikelsuspension, gegebenenfalls 0,5 bis 30 Gew.-% Wasser, 1 bis 10 Gew.-% eines hochdispersen FĆ¼llstoffes und 65 bis 95,5 Gew.-% eines flĆ¼ssigen Alkylenoxidpolymerisats auf Basis Ethylendiamin mit einem Molekulargewicht im Bereich von 500 bis 8.200 miteinander vermischt, wobei die Gewichtsprozent-Angaben sich auf die fertige Gesamtzubereitung beziehen.The invention further comprises a process for the preparation of liquid enzyme preparations, in which 3 to 25% by weight of an enzyme particle suspension, optionally 0.5 to 30% by weight of water, 1 to 10% by weight of a highly disperse filler and 65 to 95.5% by weight of a liquid alkylene oxide polymer based on ethylenediamine with a molecular weight in the range from 500 to 8,200 are mixed with one another, the percentages by weight relating to the finished overall preparation.
ZweckmƤĆigerweise wird das Verfahren so durchgefĆ¼hrt, daĆ man das flĆ¼ssige Alkylenoxidpolymerisat auf Basis Ethylendiamin in einem GefĆ¤Ć vorlegt und dann langsam unter intensivem RĆ¼hren den hochdispersen FĆ¼llstoff zufĆ¼gt, und dann die entsprechende durch AufrĆ¼hren homogenisierte Enzympartikelsuspension unter RĆ¼hren zusetzt. Bevorzugt verwendet man dabei ein Ethylenoxid-Propylenoxid-Polymerisat auf der Basis von Ethylendiamin. Vorzugsweise sollte dieses Polymerisat ein Molekulargewicht im Bereich von 1.500 bis 7.500 aufweisen. Beispielsweise kann man hierfĆ¼r eine unter dem Handelsnamen SynperonicR kommerziell erhƤltliche Verbindung, z. B. Synperonic T304R mit einem Molekulargewicht von ca. 1.650, einsetzen. Mit der Enzympartikelsuspension wird zumeist bereits auch die entsprechende Menge Wasser aufgrund des Wassergehaltes der zugefĆ¼gten Enzympartikelsuspension zugegeben. Falls notwendig, kann die entsprechende fehlende Menge Wasser noch zusƤtzlich zugefĆ¼gt werden. Als Enzympartikelsuspension wird vorzugsweise eine Enzymkristallsuspension einer hochalkalischen Protease eingesetzt, deren EnzymaktivitƤt auf an sich bekannte Weise auf 2 Millionen bis 6 Millionen DU/ml aufkonzentriert wurde.The process is expediently carried out by placing the liquid alkylene oxide polymer based on ethylenediamine in a vessel and then slowly adding the highly disperse filler with vigorous stirring, and then adding the corresponding enzyme particle suspension homogenized by stirring. An ethylene oxide-propylene oxide polymer based on ethylene diamine is preferably used. This polymer should preferably have a molecular weight in the range from 1,500 to 7,500. For example, a compound commercially available under the trade name Synperonic R , e.g. B. Use Synperonic T304 R with a molecular weight of approx. 1,650. With the enzyme particle suspension, the appropriate amount of water is usually also added due to the water content of the enzyme particle suspension added. If necessary, the corresponding missing amount of water can also be added. An enzyme crystal suspension of a highly alkaline protease is preferably used as the enzyme particle suspension, the enzyme activity of which has been concentrated to 2 million to 6 million DU / ml in a manner known per se.
Ein weiterer Gegenstand der Erfindung sind flĆ¼ssige Wasch- und Reinigungsmittel, die die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen enthalten. Bevorzugt werden die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen in FlĆ¼ssigwaschmitteln zur Reinigung von Textilien oder in flĆ¼ssigen Geschirreinigungsmitteln eingesetzt. AuĆer den flĆ¼ssigen Enzymzubereitungen kƶnnen die Wasch- bzw. Reinigungsmittelformulierungen dabei alle an sich im Stand der Technik Ć¼blichen Inhaltsstoffe und Hilfsstoffe fĆ¼r die Formulierung von flĆ¼ssigen Wasch- und Reinigungsmitteln z. B. Tenside, GerĆ¼ststoffe (Builder) sowie gegebenenfalls Bleichmittel oder Bleichmittelvorstufen in an sich gebrƤuchlichen Mengen enthalten. Zu den Hilfsstoffen gehƶren z. B. Enzymstabilisatoren, Komplex- und Chelatbildner, Schaumregulatoren und Zusatzstoffe wie Korrosionsinhibitoren, Antielektrostatika, Farbstoffe, Duftstoffe, Bakterizide, Fungizide und Aktivatoren.The invention further relates to liquid washing and cleaning agents which contain the liquid enzyme preparations according to the invention. The liquid enzyme preparations according to the invention are preferably used in liquid detergents for cleaning textiles or in liquid dishwashing detergents. Except for the liquid enzyme preparations The detergent or cleaning agent formulations can contain all the ingredients and auxiliaries which are customary in the prior art for the formulation of liquid washing and cleaning agents, for. B. surfactants, builders (builder) and optionally bleach or bleach precursors in conventional amounts. The auxiliaries include e.g. B. enzyme stabilizers, complexing and chelating agents, foam regulators and additives such as corrosion inhibitors, antistatic agents, dyes, fragrances, bactericides, fungicides and activators.
Die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen zeigen Ć¼berraschend gute, fĆ¼r die Verwendung in flĆ¼ssigen Wasch- und Reinigungsmittelformulierungen besonders geeignete Eigenschaften. So haben die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen eine sehr hohe LagerstabilitƤt, wobei auch Ć¼ber einen lƤngeren Zeitraum die EnzymaktivitƤt der in diesen flĆ¼ssigen Enzymzubereitungen verarbeiteten Enzyme praktisch unverƤndert bleibt. DarĆ¼ber hinaus sind die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen sehr sedimentationsstabil. Durch ihre niedrige ViskositƤt sind die erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen leicht dosierbar und damit sehr gut fĆ¼r die Verarbeitung in flĆ¼ssigen Wasch- oder Reinigungsmitteln geeignet.The liquid enzyme preparations according to the invention show surprisingly good properties which are particularly suitable for use in liquid detergent and cleaning agent formulations. Thus, the liquid enzyme preparations according to the invention have a very high storage stability, the enzyme activity of the enzymes processed in these liquid enzyme preparations remaining virtually unchanged even over a relatively long period. In addition, the liquid enzyme preparations according to the invention are very stable to sedimentation. Due to their low viscosity, the liquid enzyme preparations according to the invention can be easily metered and are therefore very well suited for processing in liquid washing or cleaning agents.
Die nachfolgenden Beispiele sollen die Erfindung weiter erlƤutern, ohne sie jedoch in ihrem Umfang zu begrenzen.The following examples are intended to explain the invention further, but without restricting its scope.
Im folgenden wird die Herstellung einer flĆ¼ssigen Enzymzubereitung, welche als Enzymbestandteil eine hochalkalische Protease enthƤlt, beschrieben.The production of a liquid enzyme preparation which contains a highly alkaline protease as an enzyme component is described below.
Die AktivitƤt der in den flĆ¼ssigen Enzymzubereitungen verarbeiteten Protease wurde in Delft Units (DU) bestimmt. 1.000 DU entsprechen der proteolytischen AktivitƤt, die bei einem Volumen von 1 ml einer 2 %igen Enzymlƶsung (w/w) nach Abbau von Kasein eine Extinktionsdifferenz (1 cm Lichtweg; 275 nm; Bestimmung gegen Blindprobentest) von 0,400 ergibt.The activity of the protease processed in the liquid enzyme preparations was determined in Delft Units (DU). 1,000 DU correspond to the proteolytic activity, which results in an extinction difference (1 cm light path; 275 nm; determination against blind sample test) of 0.400 with a volume of 1 ml of a 2% enzyme solution (w / w) after degradation of casein.
Auf an sich bekannte Weise wurde ein Bacillus alcalophilus (DSM-Nr. 5466) fermentiert. Aus der FermenterbrĆ¼he wurde durch Filtration unter Verwendung von Filterhilfsmitteln und Flockungsmitteln unlƶsliche Begleitstoffe abgetrennt. Im Filtrat wurde der pH-Wert auf 5,2 eingestellt und durch Ultrafiltration etwa um den Faktor 4 auf eine Protease-AktivitƤt von ca. 750.000 DU/ml auf- konzentriert. Nach der Ultrafiltration wurde eine 10 %ige Kochsalzlƶsung zugefĆ¼gt, auf ca. 30 Ā°C erwƤrmt und die Kristallisation des Enzyms abgewartet. Man erhielt eine Enzymkristallsuspension, die auf an sich bekannte Weise unter Entfernung der Mutterlauge auf eine Protease-AktivitƤt von ca. 3,6 Millionen DU/ml aufkonzentriert wurde.A Bacillus alcalophilus (DSM No. 5466) was fermented in a manner known per se. Insoluble accompanying substances were separated from the fermenter broth by filtration using filter aids and flocculants. The pH in the filtrate was adjusted to 5.2 and concentrated by ultrafiltration by a factor of about 4 to a protease activity of about 750,000 DU / ml. After ultrafiltration, a 10% saline solution was added, the mixture was warmed to about 30 Ā° C. and the crystallization of the enzyme was awaited. An enzyme crystal suspension was obtained which, in a manner known per se, was concentrated to a protease activity of about 3.6 million DU / ml while removing the mother liquor.
Die Enzymkristallsuspension der hochalkalischen Protease wurde anschlieĆend zu den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen nach folgender Rezeptur verarbeitet:
5 Gew.-% Enzymkristallsuspension
7,0 Gew.-% Wasser (Ć¼ber die Enzymkristallsuspension mit eingebracht)
2,6 Gew.-% Aerosil 200R (hochdisperse KieselsƤure)
85,4 Gew.-% Synperonic T304R (flĆ¼ssiges Ethylenoxid-Propylenoxidpolymerisat auf Basis Ethylendiamin, MW: ca. 1.650).The enzyme crystal suspension of the highly alkaline protease was then processed into the liquid enzyme preparations according to the invention using the following recipe:
5% by weight enzyme crystal suspension
7.0% by weight of water (also introduced via the enzyme crystal suspension)
2.6% by weight Aerosil 200 R (highly disperse silica)
85.4% by weight Synperonic T304 R (liquid ethylene oxide-propylene oxide polymer based on ethylenediamine, MW: approx.1,650).
Die Herstellung zu den erfindungsgemƤĆen flĆ¼ssigen Enzymzubereitungen erfolgte, indem man die angegebene Menge an Synperonic T304R in einem GefĆ¤Ć vorlegte, zu dem man langsam unter intensiven RĆ¼hren die angegebene Menge Aerosil 200R zufĆ¼gte. AnschlieĆend wurde die durch AufrĆ¼hren zuvor homogenisierte Enzymkristallsuspenion unter RĆ¼hren zugegeben. Man erhielt eine sedimentationsstabile flĆ¼ssige Enzymzubereitung der hochalkalischen Protease mit einer Protease-AktivitƤt von ca. 678.000 DU/g.The liquid enzyme preparations according to the invention were prepared by placing the specified amount of Synperonic T304 R in a vessel to which the specified amount of Aerosil 200 R was slowly added with vigorous stirring. Then the enzyme crystal suspension previously homogenized by stirring was added with stirring. You got a sedimentation-stable liquid enzyme preparation of the highly alkaline protease with a protease activity of approx. 678,000 DU / g.
Es wurde eine analog Beispiel 1 erhaltene Enzymkristallsuspension einer Protease in gleicher Herstellungsweise nach folgender Rezeptur verarbeitet:
10 Gew.-% Enzymkristallsuspenision
7 Gew.-% Wasser (Ć¼ber die Enzymkristallsuspension mit eingebracht)
5,2 Gew.-% Aerosil 200R
77,8 Gew.-% Synperonic T304R
Man erhielt eine sedimentationsstabile flĆ¼ssige Enzymzubereitung mit einer Protease-AktivitƤt von ca. 960.000 DU/g.An enzyme crystal suspension of a protease obtained in the same way as in Example 1 was processed in the same manner according to the following recipe:
10% by weight enzyme crystal suspension
7% by weight of water (also introduced via the enzyme crystal suspension)
5.2% by weight Aerosil 200 R
77.8% by weight Synperonic T304 R
A sedimentation-stable liquid enzyme preparation with a protease activity of approx. 960,000 DU / g was obtained.
Wie in Beispiel 1 und 2 beschrieben, wurde nach folgender Rezeptur eine flĆ¼ssige Enzymzubereitung einer Protease hergestellt:
25 Gew.-% Enzymkristallsuspension
7,4 Gew.-% Wasser (Ć¼ber die Enzymkristallsuspension mit eingebracht)
2,6 Gew.-% Aerosil 200R
65 Gew.-% Synperonic T 304R
Man erhielt eine sedimentationsstabile flĆ¼ssige Enzymzubereitung mit einer Protease-AktivitƤt von ca 1,8 Mio. DU/g.As described in Examples 1 and 2, a liquid enzyme preparation of a protease was produced according to the following recipe:
25% by weight enzyme crystal suspension
7.4% by weight of water (also introduced via the enzyme crystal suspension)
2.6% by weight of Aerosil 200 R.
65% by weight Synperonic T 304 R
A sedimentation-stable liquid enzyme preparation with a protease activity of approximately 1.8 million DU / g was obtained.
Claims (12)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4319908A DE4319908A1 (en) | 1993-06-16 | 1993-06-16 | Liquid enzyme preparations |
| DE4319908 | 1993-06-16 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0629692A1 true EP0629692A1 (en) | 1994-12-21 |
| EP0629692B1 EP0629692B1 (en) | 2001-11-28 |
Family
ID=6490438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94108755A Expired - Lifetime EP0629692B1 (en) | 1993-06-16 | 1994-06-08 | Liquid enzyme preparations |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5558812A (en) |
| EP (1) | EP0629692B1 (en) |
| JP (1) | JPH078277A (en) |
| CN (1) | CN1102436A (en) |
| AT (1) | ATE209675T1 (en) |
| AU (1) | AU688312B2 (en) |
| BR (1) | BR9402425A (en) |
| CA (1) | CA2125945A1 (en) |
| DE (2) | DE4319908A1 (en) |
| DK (1) | DK0629692T3 (en) |
| ES (1) | ES2169052T3 (en) |
| FI (1) | FI942847A (en) |
| PT (1) | PT629692E (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995015371A1 (en) * | 1993-12-03 | 1995-06-08 | Buckman Laboratories International, Inc. | Enzyme stabilization by block-copolymers |
| WO2014087011A1 (en) * | 2012-12-07 | 2014-06-12 | Novozymes A/S | Preventing adhesion of bacteria |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117842C (en) * | 1996-12-20 | 2003-08-13 | 尤尼å©å¼å ¬åø | Enzymatic bleach composition |
| US6251845B1 (en) | 1997-07-09 | 2001-06-26 | The Procter & Gamble Company | Detergent compositions comprising an oxygenase enzyme and cofactor to remove body soils |
| AU3667797A (en) * | 1997-07-09 | 1999-02-08 | Procter & Gamble Company, The | Cleaning compositions comprising a specific oxygenase |
| JP2002508027A (en) * | 1997-07-09 | 2002-03-12 | ć¶ććććÆćæć¼ććØć³ććć®ć£ć³ćć«ćć«ć³ććć¼ | Detergent composition containing specific oxygenase |
| US6541606B2 (en) * | 1997-12-31 | 2003-04-01 | Altus Biologics Inc. | Stabilized protein crystals formulations containing them and methods of making them |
| GB2477914B (en) | 2010-02-12 | 2012-01-04 | Univ Newcastle | Compounds and methods for biofilm disruption and prevention |
| EP2831215B1 (en) | 2012-03-29 | 2018-08-08 | Novozymes A/S | Use of enzymes for preparing water soluble films |
| JP6186821B2 (en) * | 2013-04-10 | 2017-08-30 | ę„ę²¹ę Ŗå¼ä¼ē¤¾ | Aqueous dispersant and aqueous dispersion composition |
| MX2016005852A (en) | 2013-11-11 | 2016-07-13 | Ecolab Usa Inc | High alkaline warewash detergent with enhanced scale control and soil dispersion. |
| MX2016005941A (en) | 2013-11-11 | 2016-07-13 | Ecolab Usa Inc | Multiuse, enzymatic detergent and methods of stabilizing a use solution. |
| US20160312157A1 (en) * | 2013-12-11 | 2016-10-27 | Novozymes A/S | Use of Enzyme Particles in Water-Soluble Films |
| CN107197877B (en) * | 2017-07-12 | 2020-04-21 | å®æčæē ē¾ēē©ē§ęęéå ¬åø | Biological compound enzyme virus scavenger (disinfectant) |
| CN115322846A (en) * | 2022-08-23 | 2022-11-11 | å¹æč„æēµē½ęéč“£ä»»å ¬åøé¦å·ä¾ēµå± | Multienzyme-containing cleaning agent for cleaning biological membrane and production method thereof |
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| DD286181A5 (en) * | 1988-12-28 | 1991-01-17 | Adw Der Ddr,Zi Fuer Organische Chemie,De | LIQUID, ENZYMETHIC DETERGENT |
| JPH0465494A (en) * | 1990-07-04 | 1992-03-02 | Kao Corp | Cleaner composition for automatic dish washer |
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| US3553139A (en) * | 1966-04-25 | 1971-01-05 | Procter & Gamble | Enzyme containing detergent composition and a process for conglutination of enzymes and detergent composition |
| US3717550A (en) * | 1970-09-25 | 1973-02-20 | Pabst Brewing Co | Liquid compositions of bacterial protease and/or amylase and preparation thereof |
| US3950277A (en) * | 1973-07-25 | 1976-04-13 | The Procter & Gamble Company | Laundry pre-soak compositions |
| US4889652A (en) * | 1988-05-02 | 1989-12-26 | Colgate-Palmolive Company | Non-aqueous, nonionic heavy duty laundry detergent with improved stability using microsperes and/or vicinal-hydroxy compounds |
| ES2044718T3 (en) * | 1989-12-21 | 1994-01-01 | Novo Nordisk As | PREPARATION CONTAINING ENZYMES AND DETERGENT CONTAINING SUCH PREPARATION. |
-
1993
- 1993-06-16 DE DE4319908A patent/DE4319908A1/en not_active Withdrawn
-
1994
- 1994-06-08 DE DE59409972T patent/DE59409972D1/en not_active Expired - Lifetime
- 1994-06-08 AT AT94108755T patent/ATE209675T1/en active
- 1994-06-08 EP EP94108755A patent/EP0629692B1/en not_active Expired - Lifetime
- 1994-06-08 ES ES94108755T patent/ES2169052T3/en not_active Expired - Lifetime
- 1994-06-08 PT PT94108755T patent/PT629692E/en unknown
- 1994-06-08 DK DK94108755T patent/DK0629692T3/en active
- 1994-06-09 US US08/257,826 patent/US5558812A/en not_active Expired - Lifetime
- 1994-06-14 AU AU64734/94A patent/AU688312B2/en not_active Ceased
- 1994-06-15 CN CN94108904A patent/CN1102436A/en active Pending
- 1994-06-15 JP JP6133320A patent/JPH078277A/en active Pending
- 1994-06-15 FI FI942847A patent/FI942847A/en unknown
- 1994-06-15 CA CA002125945A patent/CA2125945A1/en not_active Abandoned
- 1994-06-15 BR BR9402425A patent/BR9402425A/en not_active Application Discontinuation
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| DD286181A5 (en) * | 1988-12-28 | 1991-01-17 | Adw Der Ddr,Zi Fuer Organische Chemie,De | LIQUID, ENZYMETHIC DETERGENT |
| JPH0465494A (en) * | 1990-07-04 | 1992-03-02 | Kao Corp | Cleaner composition for automatic dish washer |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995015371A1 (en) * | 1993-12-03 | 1995-06-08 | Buckman Laboratories International, Inc. | Enzyme stabilization by block-copolymers |
| US5780283A (en) * | 1993-12-03 | 1998-07-14 | Buckman Laboratories International, Inc. | Enzyme stabilization by oxygen-containing block copolymers |
| WO2014087011A1 (en) * | 2012-12-07 | 2014-06-12 | Novozymes A/S | Preventing adhesion of bacteria |
| CN110628528A (en) * | 2012-12-07 | 2019-12-31 | čÆŗē»“äæ”å ¬åø | Preventing adhesion of bacteria |
| CN110628528B (en) * | 2012-12-07 | 2021-09-14 | čÆŗē»“äæ”å ¬åø | Preventing adhesion of bacteria |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE209675T1 (en) | 2001-12-15 |
| EP0629692B1 (en) | 2001-11-28 |
| AU6473494A (en) | 1994-12-22 |
| US5558812A (en) | 1996-09-24 |
| JPH078277A (en) | 1995-01-13 |
| PT629692E (en) | 2002-03-28 |
| ES2169052T3 (en) | 2002-07-01 |
| FI942847A (en) | 1994-12-17 |
| DE59409972D1 (en) | 2002-01-10 |
| BR9402425A (en) | 1995-01-17 |
| CA2125945A1 (en) | 1994-12-17 |
| DK0629692T3 (en) | 2002-04-02 |
| FI942847A0 (en) | 1994-06-15 |
| AU688312B2 (en) | 1998-03-12 |
| DE4319908A1 (en) | 1994-12-22 |
| CN1102436A (en) | 1995-05-10 |
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