EP0793439B1 - Verfahren zum geschirrwaschen ohne verwendung von bleichmitteln - Google Patents
Verfahren zum geschirrwaschen ohne verwendung von bleichmitteln Download PDFInfo
- Publication number
- EP0793439B1 EP0793439B1 EP95940999A EP95940999A EP0793439B1 EP 0793439 B1 EP0793439 B1 EP 0793439B1 EP 95940999 A EP95940999 A EP 95940999A EP 95940999 A EP95940999 A EP 95940999A EP 0793439 B1 EP0793439 B1 EP 0793439B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- component
- cleaning
- enzyme
- aqueous solution
- warewashing
- 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.)
- Revoked
Links
- 238000000034 method Methods 0.000 title claims description 25
- 239000007844 bleaching agent Substances 0.000 title claims description 23
- 238000004140 cleaning Methods 0.000 claims description 53
- 102000004190 Enzymes Human genes 0.000 claims description 44
- 108090000790 Enzymes Proteins 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 42
- 108010065511 Amylases Proteins 0.000 claims description 27
- 102000013142 Amylases Human genes 0.000 claims description 27
- 239000012459 cleaning agent Substances 0.000 claims description 24
- 239000004382 Amylase Substances 0.000 claims description 22
- 235000019418 amylase Nutrition 0.000 claims description 22
- 239000007864 aqueous solution Substances 0.000 claims description 19
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 108091005804 Peptidases Proteins 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical class OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- -1 alkyl succinate Chemical class 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 5
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000004367 Lipase Substances 0.000 claims description 3
- 102000004882 Lipase Human genes 0.000 claims description 3
- 108090001060 Lipase Proteins 0.000 claims description 3
- 239000004365 Protease Substances 0.000 claims description 3
- 235000019421 lipase Nutrition 0.000 claims description 3
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 229920005646 polycarboxylate Polymers 0.000 claims description 2
- 229920001282 polysaccharide Polymers 0.000 claims description 2
- 239000005017 polysaccharide Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 description 42
- 229920002472 Starch Polymers 0.000 description 17
- 235000019698 starch Nutrition 0.000 description 17
- 239000008107 starch Substances 0.000 description 17
- 241001122767 Theaceae Species 0.000 description 12
- 239000002689 soil Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000002255 enzymatic effect Effects 0.000 description 9
- 102000035195 Peptidases Human genes 0.000 description 8
- 230000003625 amylolytic effect Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000004851 dishwashing Methods 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 235000011118 potassium hydroxide Nutrition 0.000 description 4
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 4
- 108010075550 termamyl Proteins 0.000 description 4
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 239000003599 detergent Substances 0.000 description 3
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 description 3
- 125000003071 maltose group Chemical group 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 108090000637 alpha-Amylases Proteins 0.000 description 2
- 102000004139 alpha-Amylases Human genes 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000002366 lipolytic effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940117958 vinyl acetate Drugs 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000233866 Fungi 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- YHGREDQDBYVEOS-UHFFFAOYSA-N [acetyloxy-[2-(diacetyloxyamino)ethyl]amino] acetate Chemical class CC(=O)ON(OC(C)=O)CCN(OC(C)=O)OC(C)=O YHGREDQDBYVEOS-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- ZNFNDZCXTPWRLQ-UHFFFAOYSA-N butane-1,1,1-tricarboxylic acid Chemical compound CCCC(C(O)=O)(C(O)=O)C(O)=O ZNFNDZCXTPWRLQ-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- FRXGWNKDEMTFPL-UHFFFAOYSA-N dioctadecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCCCC FRXGWNKDEMTFPL-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 230000003861 general physiology Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 239000003752 hydrotrope Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- ATGAWOHQWWULNK-UHFFFAOYSA-I pentapotassium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O ATGAWOHQWWULNK-UHFFFAOYSA-I 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- GDJZZWYLFXAGFH-UHFFFAOYSA-M xylenesulfonate group Chemical group C1(C(C=CC=C1)C)(C)S(=O)(=O)[O-] GDJZZWYLFXAGFH-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47L—DOMESTIC WASHING OR CLEANING; SUCTION CLEANERS IN GENERAL
- A47L15/00—Washing or rinsing machines for crockery or tableware
- A47L15/42—Details
- A47L15/44—Devices for adding cleaning agents; Devices for dispensing cleaning agents, rinsing aids or deodorants
-
- 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
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/40—Specific cleaning or washing processes
- C11D2111/44—Multi-step processes
Definitions
- the present invention relates to a method of warewashing in industrial or institutional systems, as opposed to domestic automatic dishwashing machines.
- a typical conventional industrial warewashing system consists of a conveyor system separated into prewash, wash, rinse and drying stations. Wash water is typically introduced into the rinse zone of this system and is passed cascade fashion toward a prewash zone, while dishware is transported in a countercurrent direction.
- Dishwashing compositions used in such systems generally contain a chlorine bleaching agent combined with a cleaning ingredient such as an aqueous solution of a caustic agent and a sequestering agent or builder such as sodium tripolyphosphate.
- a cleaning ingredient such as an aqueous solution of a caustic agent and a sequestering agent or builder such as sodium tripolyphosphate.
- EP-A-282,214 discloses a process for cleaning dirty dishware with a non-directional mist-like spray of a strongly alkaline solution.
- a highly alkaline spray is potentially hazardous for an operator.
- DE-C-4324106 discloses a method of warewashing for industrial or institutional dishwashing machines, wherein an enzyme component Thermamyl 300L and a phosphate or NTA-based low alkaline cleaning component are added to the cleaning liquor in order to optimize the cleaning results.
- German patent specification DE-A-4 219 620 describes a domestic dishwasher in which bleach- and enzyme- containing components are dosed in different stages of the wash process.
- the enzyme is added during the prerinse or at the very beginning of the wash cycle.
- the bleach is added only during the cleaning cycle after a predetermined time after which the wash liquor reaches a desired temperature. Thus the negative interaction between the bleach and the enzyme is avoided.
- This approach is not feasible in an industrial dishwasher where a cascade flow of water occurs from one tank to another and wherein the cleaning operation is a continuous process.
- Bleach agents have been removed from warewashing detergent compositions to minimize the deactivation of enzyme ingredients. It is known in the absence of a bleach that good stain removal (e.g., tea stain removal) may be effected across a range of water hardness by utilizing a strong builder or sequestrant at a relatively high wash pH. Thus, the negative interaction between bleach and enzyme may be avoided while maintaining a good cleaning performance.
- stain removal e.g., tea stain removal
- One object of the invention is to provide an industrial or institutional warewashing process involving a chemical cleaning system which contains at least two separate components. Each component is dissolved or diluted in an aqueous solution to a concentration useful for cleaning.
- the chemical cleaning system has substantially no bleaching agents among its components.
- the present invention provides a method of warewashing in a multi-tank industrial or institutional machine, said method comprising the steps of:
- Typical industrial warewashing processes are either continuous or non-continuous and are conducted in either a single tank or a multi-tank/ conveyor type machine.
- a prewash, wash, rinse and drying zone are generally established using partitions. Wash water is introduced into the rinsing zone and is passed cascade fashion back toward the prewash zone while the dirty dishware is transported in a countercurrent direction.
- the inventive method of warewashing is especially effective in the multi-tank/ conveyor type systems.
- contact time between the cleaning composition and the articles to be washed is relatively short. Means of maximizing these contact times are constantly sought while at the same time any negative interaction time of the actives of the cleaning composition needs to be minimized to provide the best cleaning performance.
- Adequate cleaning performance has been achieved in the present invention in spite of the elimination of a bleaching agent.
- Reason is that bleaches generally create a negative interaction with other cleaning components such as enzymes.
- Amylolytic enzymes are used to remove starch stains.
- the amylolytic enzymes usable can be derived from bacteria or fungi.
- Preferred amylolytic enzymes are those prepared and described in GB-A-1 296 839 which are cultivated from the strains of Bacillus licheniformis NIB 8061 NIB 8059, ATCC 6334. ATCC 6598, ATCC 19945, ATCC 8480 and ACTT 9945 A.
- Examples of such amylolytic enzymes are those produced and supplied under the trademark Termamyl® by Novo Industri A/S, Copenhagen, Denmark.
- ⁇ -amylase enzymes which have been mutated by modifying one or more amino acid sequences as described in WO-A-94/14951 and WO-A-94/02597 and supplied by Novo Industri under the tradename Durmamyl.
- Other ⁇ -amylase enzymes useful in the invention are described in EP-A-208,491 (Genencor Int'l).
- amylolytic enzymes may be used in either granular or liquid form and have enzymatic activities of from 2 to 25 Maltose units/milligram. They may be incorporated in the cleaning system of the invention in amount such that the final composition has an amylolytic activity of from 10 3 to 10 8 Maltose units/kilograms, preferably from 10 5 to 10 8 Maltose units per kilogram(s), and more preferably 10 6 to 10 8 Maltose units per kilogram.
- amylolytic activity referred to herein can be determined by the method described by in P. Bernfeld in "Method of Enzymology", Vol 1 (1955), pg. 149.
- proteolytic enzymes may also be incorporated in the cleaning system to remove protein stains.
- Usable proteolytic enzymes include the subtilisin obtained from strains of Bacillus Subtilis licheniformis, such as the commercially available subtilisins Maxatase supplied by Gist-Brocades N.V., Delft, Holland and Alcalase supplied by Novo Industri A/S, Copenhagen, Denmark.
- Particularly suitable proteases are those obtained from a strain of Bacillus having maximum activity throughout a pH range of 8 to 12 and are commercially available from Novo Industri A/S under the tradenames of Esperase and Savinase.
- Also useful is a protease supplied under the tradename of OxP by Genencor Int'1.
- proteolytic enzymes are generally presented as granules, such as marumes, prills or p-granulates, or in liquid form.
- the proteolytic enzyme activities of these samples are from 500 to 6000 glycine units per milligram.
- proteolytic enzymes may be present in amounts such that the final composition has a proteolytic enzyme activity of from about 10 3 to 10 10 glycine units per kilogram, preferably from 10 5 to 10 10 , more preferably 10 6 to 10 9 .
- lipolytic enzymes useful to improve fat removal.
- lipolytic enzymes include Lipase YL, Amano CE, Wallerstein AW, Lipase MY and Lipolase supplied by Novo Industri.
- the enzyme containing component is dosed into the warewashing system so that upon aqueous dissolution or dilution to its use concentration, the pH value of a 1% aqueous solution is desirably less than 9, preferably 7 to 9, most preferably 8 to 9.
- the enzyme containing component should be introduced into the system separately from the other active components of the cleaning system. Generally, the component will be applied in a washing zone of the system using any conventional means such as suitable spray nozzles or jets which are directed upwards or downwards toward the dishware. In a preferred embodiment, the enzyme containing component is sprayed directly onto the dishware as it moves in a countercurrent direction from the dosed component. A thorough rinsing of the enzyme from the dishware once the contact time is completed should follow.
- the enzyme containing component is sequentially dosed into the warewashing process after the cleaning agent containing component in a separate tank from the tank in which the cleaning agent containing component is introduced.
- an aqueous solution of the component which contains the cleaning agent must have a higher alkalinity than that of the enzyme component by at least one unit, preferably more than one pH unit.
- a 1% aqueous solution of the cleaning component which results from its dissolution or dilution to its use concentration should have a pH of at least 1 pH unit more alkaline than a pH value of a 1% aqueous solution of the enzymatic component.
- the cleaning agent component solution has a pH of 9.5 or greater, preferably 9.5 to 13.
- more than one component may contain a cleaning agent so that the component which contains the greatest total amount (that is % by weight) of the cleaning agent is referred to by the phrase "that component which contains the cleaning agent or the cleaning agent containing component". It will also be appreciated that the total cleaning agent in any given component may comprise two or more different and individual cleaning agents as described below.
- the concentration of the cleaning agent following its dissolution or dilution is such that the weight of the component per volume unit of water should be in the range of 1 to 5 grams per liter, preferably from 1 to 4 grams per liter, more preferably from 1 to 3 grams per liter.
- the cleaning agent may be selected from a caustic or strongly alkaline material, a detergency builder, a surfactant or a mixture thereof.
- Suitable caustic agents include alkaline metal hydroxides such as sodium or potassium hydroxides, alkaline metal silicates such as metasilicates, preferably sodium metasilicate, and other alkaline caustic materials such as borax.
- alkaline metal hydroxides such as sodium or potassium hydroxides
- alkaline metal silicates such as metasilicates, preferably sodium metasilicate
- borax alkaline caustic materials
- sodium silicate having a mole ratio of SiO 2 :Na 2 O of from 1 to 3.3, preferably from 1.8 to 2.2 generally referred to as sodium disilicate.
- Suitable builder materials are well known in the art and many types of organic and inorganic compounds have been extensively described in the literature.
- Builder materials include both the phosphate and non-phosphate compounds. They are generally used in cleaning compositions to provide alkalinity and buffering capacity, prevent flocculation, maintain ionic strength, extract metals from soils, remove alkaline earth metal ions from washing solutions.
- the builder material usable herein can be any one or mixtures of the various phosphate and non-phosphate builder materials.
- non-phosphate builder materials can also be used, such as, for example, the alkali metal citrates carbonates and bicarbonates; and the salts of nitrilotriacetic acid (NTA); dipicolinic acid (DPA), oxydisuccinic acid (ODS), alkyl and alkenyl succinates (AKS); ethylenediamine tetraacetates, oxidized heteropolymeric polysaccharides, polycarboxylates such as polymaleates, polyacetates, polyhydroxyacrylates, polyacrylate/polymaleate and polyacrylate; polymethacrylate copolymers and the terpolymer of polyacrylate/polymaleate and vinylacetate (ex Huls), as well as zeolites; layered silicas and mixtures thereof.
- NTA nitrilotriacetic acid
- DPA dipi
- They may be present in more than one component of the system but in the only component which contains builder, or in that component which contains the most total builder material (in % by wt.), in the range of from 1 to 50, preferably from 5 to 40, more preferably from 10 to 30.
- Particularly preferred builders are citrates, DPA, ODS, alkenyl succinates, carbonates, bicarbonates, the higher molecular weight block copolymers ITA/VA having Mw greater than 60,000, maleic anhydride/(meth)acrylic acid copolymers, e.g. Sokalan CP5 ex. BASF; NTA and the terpolymer of polyacrylate/polymaleate and vinylacetate (ex. Huls).
- Scale formation on dishes and machine parts is an important problem that needs to be resolved or at least mitigated in formulating a machine warewashing product, especially in the case of low-phosphate (e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate) and phosphate-free machine warewashing compositions, particularly zero-P machine warewashing compositions.
- low-phosphate e.g. less than the equivalent of 20% by weight, particularly 10% by weight of sodium triphosphate
- phosphate-free machine warewashing compositions particularly zero-P machine warewashing compositions.
- co-builders such as polyacrylic acids or polyacrylates (PAA), and the various organic polyphosphonates, e.g. of the Dequest range, may be incorporated in one or more system components.
- PAA polyacrylic acids or polyacrylates
- the block copolymers of formula (I) as defined in published PCT patent specification WO-A-94/17170 may also be used.
- the amount of co-builder may be in the range of from 0.5 to 10, preferably from 0.5 to 5, and more preferably from 1 to 5% by weight.
- the cleaning agent may comprise one or more surfactants.
- Surfactant may also be present in one or more of components of the system. However, in the component(s) which contain the most surfactant, they may be present in the range of from 0.5 to 20, preferably from 1 to 15, and more preferably from 3 to 15% by weight. Such surfactant (if present) is of course separate from any surfactant used as rinse aid in the rinse phase, after use of a system according to the present invention.
- compositions may further include a defoamer.
- Suitable defoamers include mono- and distearyl acid phosphate, silicone oil and mineral oil.
- compositions may include 0.02 to 2% by weight of defoamer, or preferably 0.05 to 1.0%.
- silver anti-tarnish agents may also be included such as benzotriazole or 1,3-N azole compounds described in WO-A-95/10588.
- Minor amounts of various other components may be present in the chemical cleaning composition.
- These components include solvents, and hydrotropes such as ethanol, isopropanol and xylene sulfonates, flow control agents; enzyme stabilizing agents; soil suspending agents; anti-redeposition agents; anti-tarnish agents; anti-corrosion agents; colorants, bleach scavengers (e.g. sulfite) and other functional additives.
- solvents, and hydrotropes such as ethanol, isopropanol and xylene sulfonates, flow control agents; enzyme stabilizing agents; soil suspending agents; anti-redeposition agents; anti-tarnish agents; anti-corrosion agents; colorants, bleach scavengers (e.g. sulfite) and other functional additives.
- bleach scavengers e.g. sulfite
- Components used in the present invention may independently be formulated in the form of solids, (optionally to be dissolved before use), aqueous liquids or non-aqueous liquids, also to be diluted before use.
- Neither of the sample formulations contained a bleaching 30 agent or an enzyme.
- the pH value of a 1% aqueous solution of each of the samples was adjusted by the addition of either NaOH or H 2 SO 4 to a pH value of between 7 and 11.
- Porcelain cups were stained with tea three times prior to washing. Cleaning experiments were conducted in a dishwashing machine. The temperature of the water in the main wash was 55°C and the wash time was 1 min.
- Sample 1 described in Example 1 was prepared with the addition of an amylase enzyme (supplied as Termamyl 300L by Novo) to provide an enzymatic activity of 2x10 7 Maltose units per kilogram.
- a second sample was prepared with the Termamyl enzyme, but no builder was present.
- Each sample was adjusted to pH values of 8.5 and 10 and the four samples were observed for enzyme stability and starch removal as follows.
- Porcelain plates were soiled with potato starch.
- a single tank Industrial dishwashing machine was run over a period of about 30-40 minutes during which time 11 wash cycles were completed. At the end of each wash cycle, fresh product was dosed to compensate for the dilution of the wash solution by the rinse water.
- the enzyme stability of the amylase was measured by conventional means.
- Residual starch on the cleaned dishware was rated by a panel on a percentage scale with 100% indicating residual soil over the entire area of the plate and 0 indicating complete removal of the soil.
- the observed amylase stability and cleaning effectiveness in the four samples were as follows: Samples (% Loss of Amylase Activity) Elapsed time (minutes) NTA and Amylase pH 10 NTA and Amylase pH 8.5 Amylase pH 10 Amylase pH 8.5 0 0 0 0 0 5 30 15 5 5 10 30 15 0 0 15 40 10 0 0 20 40 10 0 0 25 50 10 0 0 30 50 5 0 0 0 Sample Residual Starch (% Area) NTA and Amylase pH 10 80% NTA and Amylase pH 8.5 45% Amylase pH 10 60% Amylase pH 8.5 25%
- Example 2 The significant effect of the presence of a strong builder on the amylase enzyme stability at a high alkalinity was again observed in wash solutions of 65°C. High temperature washes are conventionally used in industrial and institutional warewashing and in a multi-chamber machine are most likely to be encountered in the final wash tank.
- the four compositions of Example 2 were prepared and the amylase stability was measured at a temperature of 65°C with the following results (expressed as % residual Amylase Activity): Elapsed Time NTA & Amylase pH 10 NTA & Amylase pH 8.5 Amylase pH 10 Amylase pH 8.5 0 100 100 100 100 10 30 82 92 98 20 20 70 87 100 30 18 60 80 98 40 18 55 76 100 50 19 45 72 98 60 17 43 63 100
- amylase stability is improved significantly at pH 8.5 compared to pH 10, even at pH 8.5 there are clear benefits for not having a strong sequestrant present in the wash tank wherein the amylase enzyme is dosed.
- the cleaning efficiency of a composition as used according to the invention was compared to the cleaning of a commercial composition used in warewashing.
- the evaluation was carried out in a multi-chamber machine (ex. Hobart) to assess the real benefits to be gained from a sequential dosing of ingredients and a pH differential between the washing zones into which the cleaning and enzyme components are dosed.
- inventive composition having two (2) components and no bleaching agent was prepared as follows:
- the pH of a 1% aqueous solution of the cleaning component was adjusted to pH 9.8.
- the cleaning agent component was dosed into a wash zone in an amount of 2 grams per liter followed by a sequential dosing of an enzymatic component.
- the cleaning efficiency of the inventive composition was compared to a commercial composition of the prior art having the following cleaning and bleach components:
- Active sodium hydroxide 50%) 70 phosphono 1,2,4, butanetricarboxylic acid 6 polyacrylic acid, sodium salt 8 water to 100
- the pH of a 1% aqueous solution of the cleaning component was about 11.
- the bleach containing component was first dosed into a prewash or wash zone in an amount of 0.5 g/liter, followed by a sequential dosing of the cleaning component into a wash zone in an amount of 2 grams per liter.
- Porcelain cups were stained with tea three times prior to washing. Porcelain plates were soiled with potato starch. To mimic the gradual buildup of starch soil due to incomplete starch removal in one wash, the starch plates were resoiled after the first wash and then subjected to further consecutive wash/starch soiling procedures.
- inventive formula which does not contain a bleaching agent but does have an enzymatic component which has a pH of at least one unit less than the pH value of the cleaning component shows significantly improved cleaning performance over the performance of the commercial product with bleach.
- Sequential dosing of the cleaning agent and enzyme components into separate wash tanks gives significantly improved starch removal compared to the situation where cleaning agent and enzyme are separately dosed into the same wash tank.
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Claims (7)
- Verfahren zum Geschirrwaschen in einer industriellen Mehrbehältermaschine oder einer Mehrbehältermaschine für größere Einrichtungen, umfassend die Schritte von:a) Auswählen eines chemischen Reinigungssystems, umfassend mindestens zwei getrennte Komponenten zur wässerigen Auflösung oder Verdünnung für die entsprechende Verwendungskonzentration in zwei getrennten Zonen einer Geschirrwaschmaschine, wobei die erste Komponente ein Reinigungsmittel umfaßt und die zweite Komponente ein Enzym umfaßt, wobei das System im wesentlichen frei von zugegebenem Bleichmittel ist und eine 1%ige wässerige Lösung der ersten Komponente mindestens 1 pH-Einheit alkalischer ist als eine 1%ige wässerige Lösung der zweiten Komponente;b) Einführen der ersten Komponente in eine Waschzone zum Reinigen von schmutzigem Geschirr;c) anschließendes Einführen der zweiten Komponente in eine zweite Waschzone zum weiteren Reinigen des Geschirrs undd) Spülen des Geschirrs mit einer wässerigen Lösung, um das chemische Reinigungssystem im wesentlichen abzuspülen.
- Verfahren nach Anspruch 1, wobei die wässerige Lösung der ersten Komponente einen pH-Wert von 9,5 oder mehr aufweist.
- Verfahren nach Anspruch 1 oder 2, wobei die wässerige Lösung der zweiten Komponente einen pH-Wert von weniger als 9,0 aufweist.
- Verfahren nach einem der Ansprüche 1 - 3, wobei die erste Komponente ausgewählt ist aus der Gruppe, bestehend aus einem basischen oder stark alkalischen Material, einem Waschmittelbuilder, einem Tensid und einem Gemisch davon.
- Verfahren nach Anspruch 4, wobei der Waschmittelbuilder ein Phosphat- oder Nichtphosphatmaterial darstellt.
- Verfahren nach Anspruch 5, wobei der Nichtphosphatbuilder ausgewählt ist aus der Gruppe, bestehend aus den Salzen von Nitrilotriessigsäure, Dipicolinsäure, Oxydibernsteinsäure, Bernsteinsäurealkylester, Bernsteinsäurealkenylester, Ethylendiamintetraacetat, oxidierten heteropolymeren Polysacchariden, Polycarboxylaten, Zeolithen, Schichtsilikaten und Gemischen davon.
- Verfahren nach einem der Ansprüche 1 - 6, wobei das Enzym ausgewählt ist aus der Gruppe, bestehend aus einer Amylase, einer Protease, einer Lipase und Gemischen davon.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9423234 | 1994-11-24 | ||
GB9423234A GB9423234D0 (en) | 1994-11-24 | 1994-11-24 | Cleaning compositions and their use |
PCT/EP1995/004606 WO1996015710A1 (en) | 1994-11-24 | 1995-11-21 | A method and composition for warewashing without bleach |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0793439A1 EP0793439A1 (de) | 1997-09-10 |
EP0793439B1 true EP0793439B1 (de) | 2000-01-26 |
Family
ID=10764569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95940999A Revoked EP0793439B1 (de) | 1994-11-24 | 1995-11-21 | Verfahren zum geschirrwaschen ohne verwendung von bleichmitteln |
Country Status (10)
Country | Link |
---|---|
EP (1) | EP0793439B1 (de) |
JP (1) | JPH10509990A (de) |
AU (1) | AU713330B2 (de) |
BR (1) | BR9509918A (de) |
CA (1) | CA2202162A1 (de) |
DE (1) | DE69514824T2 (de) |
ES (1) | ES2142504T3 (de) |
GB (1) | GB9423234D0 (de) |
WO (1) | WO1996015710A1 (de) |
ZA (1) | ZA959924B (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2220312C (en) * | 1997-11-10 | 1999-11-09 | Murugesu Nandhakumaran | Radio receiver and rebroadcaster |
DE10053416A1 (de) † | 2000-10-27 | 2002-05-08 | Bsh Bosch Siemens Hausgeraete | Verfahren zum maschinellen Reinigen von Textilien oder festen Gegenständen |
GB0111618D0 (en) * | 2001-05-14 | 2001-07-04 | Procter & Gamble | Dishwashing |
PT1347039E (pt) * | 2002-03-18 | 2007-10-29 | Weigert Chem Fab | Processo para lavar louça |
EP1657297B1 (de) * | 2004-11-15 | 2009-07-22 | Chemische Fabrik Dr. Weigert GmbH & Co. KG. | Verfahren zum Reinigen von Geschirr |
CA2606817C (en) * | 2005-05-04 | 2013-10-22 | Johnsondiversey, Inc. | Warewashing system containing low levels of surfactant |
EP2014757A1 (de) | 2007-07-05 | 2009-01-14 | JohnsonDiversey, Inc. | Spülhilfe |
EP2364350B1 (de) | 2008-12-02 | 2019-09-18 | Diversey, Inc. | Geschirrspülmittel mit kationischer stärke |
US20120318303A1 (en) * | 2011-06-14 | 2012-12-20 | Ecolab Usa Inc. | Non-bleaching procedure for the removal of tea and coffee stains |
EP3741283A1 (de) * | 2019-05-22 | 2020-11-25 | The Procter & Gamble Company | Automatisches geschirrspülverfahren |
IT201900022392A1 (it) * | 2019-11-28 | 2021-05-28 | Salros S R L | Composizione di lavaggio liquida a componenti separati, per bucato in macchine lavatrici automatiche |
JP2023537336A (ja) * | 2020-08-04 | 2023-08-31 | ザ プロクター アンド ギャンブル カンパニー | 自動食器洗浄方法及びパック |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0282214A1 (de) * | 1987-03-07 | 1988-09-14 | Diversey Corporation | Verfahren zum Reinigen von Geschirr |
DE4324106C1 (de) * | 1993-05-25 | 1994-09-15 | Henkel Ecolab Gmbh & Co Ohg | Verfahren und Vorrichtung zur Zudosierung von Wirkstoffen zu einer Spülmaschine |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1296839A (de) * | 1969-05-29 | 1972-11-22 | ||
GB2189520A (en) * | 1986-03-21 | 1987-10-28 | Unilever Plc | Washing and bleaching process |
DE4219620A1 (de) * | 1992-06-16 | 1993-12-23 | Licentia Gmbh | Verfahren zur Reinigungsmittelzugabe bei Haushalt-Geschirrspülmaschinen |
TR28788A (tr) * | 1993-05-25 | 1997-03-25 | Henkel Ecolab Gmbh & Co Ohg | Makinayla bulasik temizlemege mahsus usul ve tertibat. |
-
1994
- 1994-11-24 GB GB9423234A patent/GB9423234D0/en active Pending
-
1995
- 1995-11-21 AU AU42550/96A patent/AU713330B2/en not_active Ceased
- 1995-11-21 BR BR9509918A patent/BR9509918A/pt not_active IP Right Cessation
- 1995-11-21 DE DE69514824T patent/DE69514824T2/de not_active Revoked
- 1995-11-21 EP EP95940999A patent/EP0793439B1/de not_active Revoked
- 1995-11-21 ES ES95940999T patent/ES2142504T3/es not_active Expired - Lifetime
- 1995-11-21 JP JP8516582A patent/JPH10509990A/ja not_active Ceased
- 1995-11-21 WO PCT/EP1995/004606 patent/WO1996015710A1/en not_active Application Discontinuation
- 1995-11-21 CA CA002202162A patent/CA2202162A1/en not_active Abandoned
- 1995-11-22 ZA ZA959924A patent/ZA959924B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0282214A1 (de) * | 1987-03-07 | 1988-09-14 | Diversey Corporation | Verfahren zum Reinigen von Geschirr |
DE4324106C1 (de) * | 1993-05-25 | 1994-09-15 | Henkel Ecolab Gmbh & Co Ohg | Verfahren und Vorrichtung zur Zudosierung von Wirkstoffen zu einer Spülmaschine |
Also Published As
Publication number | Publication date |
---|---|
AU4255096A (en) | 1996-06-17 |
EP0793439A1 (de) | 1997-09-10 |
DE69514824D1 (de) | 2000-03-02 |
GB9423234D0 (en) | 1995-01-04 |
CA2202162A1 (en) | 1996-05-30 |
DE69514824T2 (de) | 2000-06-15 |
AU713330B2 (en) | 1999-12-02 |
BR9509918A (pt) | 1997-09-30 |
ZA959924B (en) | 1997-05-22 |
JPH10509990A (ja) | 1998-09-29 |
WO1996015710A1 (en) | 1996-05-30 |
ES2142504T3 (es) | 2000-04-16 |
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PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20081126 Year of fee payment: 14 |
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PLAB | Opposition data, opponent's data or that of the opponent's representative modified |
Free format text: ORIGINAL CODE: 0009299OPPO |
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R26 | Opposition filed (corrected) |
Opponent name: CHEMISCHE FABRIK DR. WEIGERT (GMBH & CO.) Effective date: 20001025 Opponent name: HENKEL KGAA Effective date: 20001024 |