EP0741776B1 - Co-granules and detergent tablets formed therefrom - Google Patents
Co-granules and detergent tablets formed therefrom Download PDFInfo
- Publication number
- EP0741776B1 EP0741776B1 EP95907583A EP95907583A EP0741776B1 EP 0741776 B1 EP0741776 B1 EP 0741776B1 EP 95907583 A EP95907583 A EP 95907583A EP 95907583 A EP95907583 A EP 95907583A EP 0741776 B1 EP0741776 B1 EP 0741776B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- alkali metal
- granule
- granules
- detergent
- 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.)
- Expired - Lifetime
Links
- 239000008187 granular material Substances 0.000 title claims description 120
- 239000003599 detergent Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 claims description 86
- 102000004190 Enzymes Human genes 0.000 claims description 39
- 108090000790 Enzymes Proteins 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 32
- -1 alkali metal salt Chemical class 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000002002 slurry Substances 0.000 claims description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims description 25
- 239000007844 bleaching agent Substances 0.000 claims description 25
- 239000004615 ingredient Substances 0.000 claims description 25
- 230000008569 process Effects 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 14
- 108091005804 Peptidases Proteins 0.000 claims description 13
- 238000004851 dishwashing Methods 0.000 claims description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 9
- 229940071207 sesquicarbonate Drugs 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- 239000004365 Protease Substances 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 6
- 229910052906 cristobalite Inorganic materials 0.000 claims description 6
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 6
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 229910052682 stishovite Inorganic materials 0.000 claims description 6
- 229910052905 tridymite Inorganic materials 0.000 claims description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 4
- 238000004061 bleaching Methods 0.000 claims description 4
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical group [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 239000002085 irritant Substances 0.000 claims description 4
- 231100000021 irritant Toxicity 0.000 claims description 4
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 4
- 229920001184 polypeptide Polymers 0.000 claims description 4
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 4
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical group [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 claims description 3
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 claims description 3
- 150000004973 alkali metal peroxides Chemical class 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 150000001451 organic peroxides Chemical class 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N noncarboxylic acid Natural products CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 claims description 2
- 229940117958 vinyl acetate Drugs 0.000 claims description 2
- 150000003628 tricarboxylic acids Chemical class 0.000 claims 5
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- 239000007858 starting material Substances 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 description 35
- 239000000843 powder Substances 0.000 description 16
- 108090001060 Lipase Proteins 0.000 description 14
- 102000004882 Lipase Human genes 0.000 description 12
- 239000004367 Lipase Substances 0.000 description 12
- 238000005469 granulation Methods 0.000 description 12
- 230000003179 granulation Effects 0.000 description 12
- 235000019421 lipase Nutrition 0.000 description 12
- 102000035195 Peptidases Human genes 0.000 description 11
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 description 10
- 230000003625 amylolytic effect Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002689 soil Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000001509 sodium citrate Substances 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical group NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 238000004140 cleaning Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000004760 silicates Chemical class 0.000 description 5
- 108010065511 Amylases Proteins 0.000 description 4
- 102000013142 Amylases Human genes 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 108010056079 Subtilisins Proteins 0.000 description 4
- 102000005158 Subtilisins Human genes 0.000 description 4
- 235000019418 amylase Nutrition 0.000 description 4
- 229940025131 amylases Drugs 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 159000000001 potassium salts Chemical class 0.000 description 4
- 235000019419 proteases Nutrition 0.000 description 4
- 230000009897 systematic effect Effects 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 229920002257 Plurafac® Polymers 0.000 description 3
- 150000002484 inorganic compounds Chemical class 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 150000004965 peroxy acids Chemical class 0.000 description 3
- 239000002243 precursor 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
- 241000194108 Bacillus licheniformis Species 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- 102000004157 Hydrolases Human genes 0.000 description 2
- 108090000604 Hydrolases Proteins 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
- 241000282320 Panthera leo Species 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005842 biochemical reaction Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
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- 238000005056 compaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical class ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Chemical compound Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
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- QSKQNALVHFTOQX-UHFFFAOYSA-M sodium nonanoyloxybenzenesulfonate Chemical compound [Na+].CCCCCCCCC(=O)OC1=CC=CC=C1S([O-])(=O)=O QSKQNALVHFTOQX-UHFFFAOYSA-M 0.000 description 2
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- LYOKOJQBUZRTMX-UHFFFAOYSA-N 1,3-bis[[1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl]oxy]-2,2-bis[[1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-yl]oxymethyl]propane Chemical compound FC(F)(F)C(C(F)(F)F)(C(F)(F)F)OCC(COC(C(F)(F)F)(C(F)(F)F)C(F)(F)F)(COC(C(F)(F)F)(C(F)(F)F)C(F)(F)F)COC(C(F)(F)F)(C(F)(F)F)C(F)(F)F LYOKOJQBUZRTMX-UHFFFAOYSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
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- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 241000187479 Mycobacterium tuberculosis Species 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000019280 Pancreatic lipases Human genes 0.000 description 1
- 108050006759 Pancreatic lipases Proteins 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 108010020346 Polyglutamic Acid Proteins 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241000589516 Pseudomonas Species 0.000 description 1
- 108020004511 Recombinant DNA Proteins 0.000 description 1
- 241000221662 Sclerotinia Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- BGRWYDHXPHLNKA-UHFFFAOYSA-N Tetraacetylethylenediamine Chemical compound CC(=O)N(C(C)=O)CCN(C(C)=O)C(C)=O BGRWYDHXPHLNKA-UHFFFAOYSA-N 0.000 description 1
- 241000235015 Yarrowia lipolytica Species 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 108090000637 alpha-Amylases Proteins 0.000 description 1
- 102000004139 alpha-Amylases Human genes 0.000 description 1
- 229940024171 alpha-amylase Drugs 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 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
- 108010019077 beta-Amylase Proteins 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical class C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- UNWDCFHEVIWFCW-UHFFFAOYSA-N decanediperoxoic acid Chemical compound OOC(=O)CCCCCCCCC(=O)OO UNWDCFHEVIWFCW-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000004683 dihydrates Chemical group 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 1
- BRDYCNFHFWUBCZ-UHFFFAOYSA-N dodecaneperoxoic acid Chemical compound CCCCCCCCCCCC(=O)OO BRDYCNFHFWUBCZ-UHFFFAOYSA-N 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229960004585 etidronic acid Drugs 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000370 gamma-poly(glutamate) polymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003861 general physiology Effects 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000001469 hydantoins Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 108010003855 mesentericopeptidase Proteins 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229940116369 pancreatic lipase Drugs 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 125000005342 perphosphate group Chemical group 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 108010064470 polyaspartate Proteins 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 235000019833 protease Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000002797 proteolythic effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- MIKSWWHQLZYKGU-UHFFFAOYSA-M sodium;2-benzoyloxybenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1OC(=O)C1=CC=CC=C1 MIKSWWHQLZYKGU-UHFFFAOYSA-M 0.000 description 1
- IBDSNZLUHYKHQP-UHFFFAOYSA-N sodium;3-oxidodioxaborirane;tetrahydrate Chemical compound O.O.O.O.[Na+].[O-]B1OO1 IBDSNZLUHYKHQP-UHFFFAOYSA-N 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 108010075550 termamyl Proteins 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XGMYMWYPSYIPQB-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethoxy)butanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)OC(C([O-])=O)CC([O-])=O XGMYMWYPSYIPQB-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000003053 toxin Substances 0.000 description 1
- 231100000765 toxin Toxicity 0.000 description 1
- 108700012359 toxins Proteins 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- AQLJVWUFPCUVLO-UHFFFAOYSA-N urea hydrogen peroxide Chemical compound OO.NC(N)=O AQLJVWUFPCUVLO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/02—Preparation in the form of powder by spray drying
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2082—Polycarboxylic acids-salts thereof
-
- 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
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
- C11D3/2086—Hydroxy carboxylic acids-salts thereof
-
- 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
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
-
- 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
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
- C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
Definitions
- This invention relates to co-granules useful in detergent compositions, and to the preparation of such co-granules.
- the invention further relates to compacted forms of product produced from the granules, e.g. detergent tablets. More particularly, the invention relates to co-granules and tablets formed therefrom, especially of and for the use in automatic dishwashing compositions.
- co-granules means granules comprising more than one compound or component of an overall cleaning system.
- granule is to be interpreted broadly and is intended to embrace various particulate forms such as granulate, coarse powder, tablets and noodles.
- tablette is to be construed as meaning a discretely shaped solid body of material, of which the shape and dimensions may vary with the application envisaged, and which may for example have a weight in the range of from about 1 to about 100 grams, preferably from about 10 to about 50 grams.
- Dishwashing compositions are frequently made up from granules of one particular inorganic compound such as e.g. alkali silicate and these compositions often contain other ingredients, especially organic compounds for example, in the form of different particles.
- the silicate granules for instance often dissolve only with difficulty and they lead to the formation of fines (dust).
- the dissolution problem is aggravated by the fact that silicate granules having a SiO 2 :Na 2 O molar ratio between 1.8 and 3.0 and a moisture content of below about 18% dissolve only with considerable difficulty.
- alkali silicate granules with a homogeneous distribution of moisture are difficult to obtain, often as a consequence of the drying process, since less moisture tends to be present in the outer skin and more in the inside of the granules. This also reduces the solubility of the granules during use.
- the preparation of granules of builder materials e.g. phosphate-replacing builders like di-, tri- or tetracarboxylic acid and salts thereof, is difficult and therefore relatively expensive. The economics of granule manufacturing processes are therefore important.
- Co-granules useful in detergent compositions are known inter alia from EP-A-0421664 (Rohm and Haas Company), which discloses a polymer-containing granulate containing at least 20% by weight of polymer and at least 20% by weight of a water-soluble inorganic compound. Such compounds are preferably sulphates, carbonates or silicates.
- other phosphate-replacing builders may also be present, such as zeolites, carbonates, nitrilotriacetic acid, citric acid, tartaric acid, salts thereof, phosphonates etc.
- the examples in the reference disclose granules containing polymer and sodium sulphate or sodium carbonate.
- EP-A-0561452 discloses phosphate-free machine dishwashing compositions comprising a polyamino acid and an anti-scaling agent.
- Various builder salts may be included in the disclosed compositions, including preferably citrates, alkenylsuccinates, carbonates, bicarbonates, zeolites and mixtures thereof, but the amount of a carbonate and/or bicarbonate builder in the composition is limited to 50% by weight.
- CH-A-673033 discloses phosphate- and trisodiumnitriloacetate-freealkalinemachinedishwashing compositions comprising sodium citrate, at least one sodium salt of hydroxyethanediphosphonic acid and at least one sodium silicate.
- JP-A-49076905 discloses spray-dried powder detergents comprising, inter alia, inorganic and organic builder salts.
- a salt selected from a polyphosphate, carbonate, sulphate, silicate and/or sodium citrate.
- JP-A-54106509 discloses the preparation of spray-dried granulated detergent compositions comprising a surfactant, an alkali metal silicate salt and a phosphate salt.
- a surfactant an alkali metal silicate salt
- a phosphate salt a surfactant that is added to the silicate.
- the SiO 2 :M 2 O molar ratio in the silicate is controlled using an acid type surfactant or an organic acid such as citric acid.
- EP-A-0526978 for instance is disclosed the simultaneous drying and granulation of silicates in a turbine dryer, e.g. a turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
- a turbine dryer e.g. a turbogranulation dryer ex. Vomm-Turbo Technology, VOMM IMPIANTI E PROCESSI S.r.l., Milan, Italy.
- this dryer is less suited for the combined drying and granulation to produce co-granules containing substantial quantities of organic ingredients in conjunction with silicate. Due to the high attrition between the rotating blades and the film formed on the wall during the granulation phase, local overheating can cause partial decomposition of the organic ingredients, leading to (local-) colouring.
- Drying can also conveniently be achieved by spray drying a slurry by a conventional technique using a spray tower in which the slurry is atomized and dried in a hot air stream.
- spray drying must be followed by a granulation step (e.g. using a Lödige Ploughshare mixer), optionally after milling.
- a granulation step e.g. using a Lödige Ploughshare mixer
- For granulation usually a small amount of moisture is added.
- the powders obtained in a turbine dryer generally have a wider particle size distribution as part of the product gathers at the walls, creating larger particles. Furthermore powder particles obtained in a turbine dryer are less homogeneously dried as a result of the larger particles being more effectively dried at the outside than on the inside and as a result of the difference in residence time between particles remaining in the gas stream and those sticking on the (heated) wall of the dryer.
- Dishwashing tablets are frequently produced from a mixture containing granules of one particular inorganic compound, such as e.g. alkali metal silicate, and additionally other ingredients, such as organic builder salts, as separate particles.
- one particular inorganic compound such as e.g. alkali metal silicate
- other ingredients such as organic builder salts, as separate particles.
- binder material that can hold the tablet ingredients together so as to obtain stronger tablets.
- binding material has a negative influence on the rate of tablet dissolution such that cleaning performance during the washing cycle may be deteriorated.
- detergent tablets can more easily be formed if a fine grade or powder-form builder salt, such as sodium citrate, is used instead of the granular grades of sodium citrate that are normally used in machine dishwashing powders.
- a fine grade or powder-form builder salt such as sodium citrate
- increasing the level of fine citrate leads to poor flow properties of the base powder and, thus to poor die filling during the tabletting process. As a consequence of this, a large variation in individual tablet weights is obtained.
- the present invention provides.
- a homogeneous co-granule comprising:
- the invention also provides a process for the preparation of the above-defined co-granules, comprising preparing a slurry or solution of the ingredients of the co-granules, drying the mixture using any of various suitable known techniques, and granulating the resulting material.
- the present invention provides a detergent composition comprising at least 25% by weight, preferably at least 40% by weight, more preferably at least 50% by weight, of co-granules according to the first aspect of the invention.
- the detergent composition comprises a bleach system and/or an enzyme system.
- the detergent composition is formed from the co-granules, with or without other ingredients.
- the present invention provides a detergent tablet comprising from about 25 to about 100% by weight, preferably from about 25 to about 90% by weight, of co-granules according to the first aspect of the invention.
- the tablet includes a bleaching system and/or an enzyme system.
- the present invention further provides the use of a co-granule containing granular detergent composition or detergent tablet according to the invention, in a machine dishwashing process.
- the salt of a di-, tri- or tetracarboxylic acid is an alkali metal salt of citric acid, mellitic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, malonic acid, dipicolinic acid or alkenyl succinic acid.
- Part of the di-, tri- and tetracarboxylic acid component e.g. up to about 30%, may if desired be replaced by a lower hydroxy monocarboxylic acid, e.g. lactic acid.
- Partial salts of the di-, tri- or tetracarboxylic acid in which one or more of the hydrogen ions of the carboxylic groups are replaced by metal ions are particularly useful. Especially sodium and potassium salts can be used with good results for the purpose of the invention. Potassium salts are sometimes preferred because of their higher solubility.
- alkali metal citrate, especially sodium citrate, in the co-granules according to the present invention is preferred.
- the use of sodium oxydisuccinate is also preferred.
- the inorganic salt component of the co-granule of the invention is selected from alkali metal silicate, alkali metal carbonate or bicarbonate, alkali metal sesquicarbonate, alkali metal sulphate, alkali metal tripolyphosphate and mixtures thereof.
- Alkali metal disilicates, in particular sodium disilicate, are especially preferred.
- the co-granule material also comprises at least one polymeric compound, being either acid and/or salt, selected from the group consisting of polycarboxylic acid polymers and polypeptides.
- Suitable polycarboxylic acid polymers comprise e.g. a water-soluble homopolymer or copolymer having a molecular weight of at least 500. It may be derived from a monocarboxylic acid or from a di-, tri- or polycarboxylic acid. The polymer will normally be used in the form of its water-soluble alkali metal salt.
- One group of polymer materials found to be of value comprises homopolymers derived from a monomer of the formula: wherein R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM; R 2 is hydrogen, C 1 -C 4 alkyl or -COOM and M is an alkali metal.
- R 1 is hydrogen, hydroxyl, C 1 -C 4 alkyl or alkoxy, acetoxy, or -CH 2 COOM
- R 2 is hydrogen, C 1 -C 4 alkyl or -COOM
- M is an alkali metal.
- this group include the sodium and potassium salts of polyacrylic, polymethacrylic, polyitaconic, polymaleic and polyhydroxyacrylic acids and also the hydrolysis products of the corresponding polymerised acid anhydrides.
- the polymer obtained by hydrolysis of maleic anhydride falls within this group.
- a second group of suitable polymeric materials comprises the copolymers of two or more carboxylic monomers of the above formula.
- this group include the sodium and potassium salts of copolymers of maleic anhydride with acrylic acid, methacrylic acid, crotonic acids, itaconic acid and its anhydride and/or aconitic acid.
- a third group of suitable polymeric materials comprises the copolymers of one carboxylic monomer of the above formula and two or more non-carboxylic acid monomers such as ethylene, propylene, styrene, alpha-methylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
- non-carboxylic acid monomers such as ethylene, propylene, styrene, alpha-methylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers such as ethyl acrylate and methacrylate.
- Suitable polypeptides which can be incorporated in the co-granules according to the present invention include for example poly-aspartate and polyglutamate.
- One of the advantages of incorporating such an inorganic salt as mentioned above into the co-granule of the invention is that it increases the solubility of the co-granule, especially if the co-granule contains silicates with SiO 2 :Na 2 O >2.4, because these salts dissolve rapidly and thereby convert the co-granule into an open sponge-like structure so that the surface area of the co-granule is increased. This leads to an increase of the solubility of the remaining solid material of the co-granule.
- Most of the salts also act as a builder, reinforcing detergent activity.
- Non-phosphate inorganic salts such as various carbonates, especially alkali metal carbonate/bicarbonate/sesquicarbonate are preferred.
- the inorganic salts are usually present in the form of their lower stable hydrate(s).
- the co-granule has the following composition (I) or alternatively the following compositions (II) or (III) (all amounts being approximate):
- the organic phosphonates which can be present in the co-granule include for example those of the Dequest R range, which are especially added as builders to phosphate-free machine dishwashing compositions.
- a drawback of these polymers however is that some of them are not quite biodegradable and are therefore environmentally less acceptable. Therefore some of the polyphosphonates, whilst being effective, are less acceptable as being P-containing products.
- adjunct materials commonly found in cleaning compositions, such as: enzyme stabilizers, such as the poly-alcohols, e.g. glycerol, and borax; anti-scaling agents; corrosion inhibitors, e.g. zinc salts, aluminium salts, benzotriazole, etc; crystal-growth inhibitors; threshold agents; thickening agents; anionic surfactants; perfumes and dyestuffs; preservatives.
- enzyme stabilizers such as the poly-alcohols, e.g. glycerol, and borax
- anti-scaling agents such as the poly-alcohols, e.g. glycerol, and borax
- corrosion inhibitors e.g. zinc salts, aluminium salts, benzotriazole, etc
- crystal-growth inhibitors e.g. zinc salts, aluminium salts, benzotriazole, etc
- threshold agents e.g. zinc salts, aluminium salts, benzotriazole, etc
- a small amount of preferably low- to non-foaming nonionic surfactant which includes any alkoxylated nonionic surface-active agent wherein the alkoxy moiety is selected from the group consisting of ethylene oxide, propylene oxide and mixtures thereof, is preferably used to improve the detergency and to suppress excessive foaming due to protein soil.
- an excessive proportion of nonionic surfactant should be avoided.
- an amount of up to 7% by weight e.g. 0.1 to 5% by weight, preferably from 0.5 to 4% by weight, is quite sufficient.
- nonionic surfactants for use in the co-granule material of the invention are the low- and non-foaming ethoxylated straight-chain alcohols of the Plurafac R RA series, supplied by the Eurane Company; of the Lutensol R LF series, supplied by the BASF Company and of the Triton R DF series, supplied by the Rohm & Haas Company.
- co-granules are preferred which have an average particle size of from about 100 to about 1500 ⁇ m. More particularly there is a preference for co-granules having an average particle size of from about 300 to about 900 ⁇ m especially from about 500 to about 700 ⁇ m, and a Rosen Rammler N-value above about 2.5. Particle size determination and the definition and determination of the Rosen Rammler N-value are described in detail in "Small Particle Statistics" by Herdan, E; second revised edition; Butterworth, London 1960, in particular pp 86-101. Graph paper according to DIN 1171 (new) is often used to determine the N-value.
- the present invention also provides, within its first aspect, a process for the preparation of the co-granules, which process comprises preparing a slurry of the ingredients of the co-granule and drying the mixture by means of suitable equipment, e.g. a turbine dryer such as a turbogranulation drier ex Vomm-Turbo Technology, Vomm Impianti E Processi S.r.l., Milan, Italy.
- suitable equipment e.g. a turbine dryer such as a turbogranulation drier ex Vomm-Turbo Technology, Vomm Impianti E Processi S.r.l., Milan, Italy.
- An alternative to drying using a turbine drier, and especially preferred, is spray-drying the slurry by a conventional technique using a spray tower in which the slurry is atomized and dried in a hot air stream.
- the resulting particles may be milled and/or restructured, for example in a granulation process, e.g. using a Lödige recycler, a Lödige plough share mixer, or any other suitable apparatus, such as a twin roll compactor. Any restructuring stage does not need to be limited to the material produced by spray-drying and optionally then milled, which is used as an example only.
- the granulation process involves combining fine solid particles like citrate, carbonates, sulphate, silicates, tripolyphosphate or co-granules as described above.
- Heat sensitive components of the granules e.g. sodium bicarbonate
- Minor ingredients that are used in the final powder or granulate formulation that are available in liquid or fine powder form e.g. surfactant, perfume, dyes, organic phosphonate, corrosion inhibitors, may also be added as required.
- Turbine driers usually operate at around 300°C.
- the slurry is sprayed onto fine (recycled) particles and dried to form gradually growing co-granules.
- Particularly favoured are processes that separate fine particles from the coarser ones, preferably continuously, and recirculate the fines to the fluidized bed for further spraying-on. Particles of the desired size can then be separated from the process at the appropriate time.
- Suitable equipment for continuous drying and granulation is e.g. an AGT-unit ex Glatt-GmbH/Process Technology, Binzen, Lorrach, Germany.
- the co-granules of this aspect of the invention have a bulk density of at least about 700 g/dm 3 , more preferably above about 800 g/dm 3 , and most preferably a bulk density between about 900 g/dm 3 and about 1200 g/dm 3 .
- High bulk densities are desirable at present, to be able to provide final detergent compositions with a relatively high specific weight.
- the present invention also provides, in a second aspect, a detergent composition which comprises at least about 25% by weight, preferably at least about 40% by weight, more preferably at least about 50% by weight of co-granules according to the first aspect of the invention.
- the composition includes a bleach system and/or an enzyme system, which usually may be added to the co-granules in the form of separate particles which may have the same particle size distribution as the co-granules. Also it is usually advantageous if the bulk density of the bleach/enzyme particles is comparable to that of the co-granules.
- Preferred forms of detergent composition consist of at least about 50% by weight of the co-granules and less than about 30% by weight of a bleach system and an enzyme system.
- the detergent composition is non-irritant.
- Enzymes are used for many purposes in various fields where biochemical reactions occur.
- an enzyme can be described as a catalyst capable of permitting a biochemical reaction to quickly occur and can be classified according to the type of reaction they catalyze.
- Enzymes are characterized by high specificity; that is to say, each enzyme can catalyze a single reaction of one substance or a very small number of closely related substances.
- enzymes suitable for use in the cleaning compositions of this invention include lipases, peptidases, amylases (amylolytic enzymes) and others which degrade, alter or facilitate the degradation or alteration of biochemical soils and stains encountered in cleansing situations so as to remove more easily the soil or stain from the object being washed or to make the soil or stain more removable in a subsequent cleansing step. Both degradation and alteration can improve soil removability.
- lipases are classified as EC class 3, hydrolases subclass EC 3.1, preferably carboxylic ester hydrolases EC 3.1.1.
- lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases are lipases EC 3.1.1.3 with the systematic name glycerol ester hydrolases.
- Amylases belong to the same general class as lipases, subclass EC 3.2, especially EC 3.2.1 glycose hydrolases such as 3.2.1.1. alpha-amylase with the systematic name alpha-1,4-glucan-4-glucanohydrolase; and also 3.2.1.2, beta-amylase with the systematic name alpha-1,4-glucan maltohydrolase.
- Proteases belong to the same class as lipases and amylases, subclass EC 3.4, particularly EC 3.4.4 peptide peptido-hydrolases such as EC 3.4.4.16 with the systematic name subtilopeptidase A.
- enzyme-containing embodiments of compositions according to the invention Enzymes serving different functions can also be used in the practice of this aspect of the invention, the selection depending upon the composition of biochemical soil, intended purpose of a particular composition, and the availability of an enzyme to degrade or alter the soil.
- Lipases sometimes called esterases, hydrolyze fatty soils.
- Lipases suitable for use herein include those of animal, plant and microbiological origin. Suitable lipases are also found in many strain of bacteria and fungi.
- lipases suitable for use herein can be derived from Pseudomonas, Aspergillus, Pneumococcus, Staphylococcus, Toxins, Mycobacterium Tuberculosis, Mycotorula Lipolytica, and Sclerotinia microorganisms, and can be made using recombinant DNA manufacturing techniques.
- Suitable animal lipases are found in the body fluids and organs of many species.
- a preferred class of animal lipase herein is the pancreatic lipase.
- Lipase may be employed in the present cleaning compositions in an amount of from about 0.005% to about 10%, preferably from about 0.01 to about 5% by weight of the composition, on a pure enzyme basis.
- the enzyme most commonly used in machine dishwashing compositions are amylolytic enzymes.
- amyloltic enzymes for use in the present invention can be those derived from bacteria or fungi.
- Preferred amylolytic enzymes are those prepared and described in GB-A-1,296,839, cultivated from the strains of Bacillus licheniformis NCIB 8061, NCIB 8059, ATCC 6334, ATCC 6598, ATCC 11 945, ATCC 8480 and ATCC 9945 A.
- Examples of such amylolytic enzymes are amylolytic enzymes produced and distributed under the trade name of SO-95 R or Termamyl R by Novo Industria A/S, Copenhagen, Denmark. These amylolytic enzymes are generally presented as granules and may have enzyme activities of from about 2 to 10 Maltose units/milligram.
- amylolytic activity can be determined by the method as described by P.Bernfeld in "Method of Enzymology", Vol. I (1955), page 149.
- composition of this aspect of the invention preferably also contains a proteolytic enzyme.
- subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis, such as the commercially available subtilisins Maxatase R , supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase R , supplied by Novo Industri A/S, Copenhagen, Denmark.
- protease obtained from a strain of Bacillus having maximum activity throughout the pH range of 8-12, being commercially available from Novo Industri A/S under the registered trade names of Esperase R and Savinase R .
- the preparation of these and analogous enzymes is described in GB-A-1243784.
- protease useful herein is a fairly recent commercial product sold by Novo Industri A/S under the trade name Durazym R , as described in WO-A-89/06279.
- the enzymes are generally presented as granules, e.g. marumes, prills, T-granules etc., and may have enzyme activities of from about 500 to 1700 glycine units/milligram.
- All of these enzymes may each be present in a weight percentage amount of from about 0.2 to about 5% by weight, such that for amylolytic enzymes the final composition may have amylolytic activity of from about 10 2 to about 10 6 Maltose units/kg, and for proteolytic enzymes the final composition may have proteolytic enzyme activity of from about 10 6 to about 10 9 Glycine Units/kg.
- enzyme material is present in the compositions of the invention in a total amount of up to about 10% by weight.
- the detergent composition may also comprise a bleach system, which may or may not be encapsulated.
- the bleach system may be a chlorine- or bromine-releasing agent or a peroxygen compound.
- a peroxygen-based bleaching system is preferred.
- Suitable peroxygen compounds may be selected from alkali metal peroxides, organic peroxides such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonate, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
- Particularly preferred peroxygen compounds are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
- Sodium perborate monhydrate is preferred because of its high active oxygen content.
- Sodium percarbonate may also be preferred for environmental reasons.
- peroxyacids usable in the present invention are solid and, preferably, substantially water-insoluble compounds.
- substantially water-insoluble is meant herein a water-solubility of less than about 1% by weight at ambient temperature.
- peroxyacids containing at least about 7 carbon atoms are sufficiently insoluble in water for use herein.
- Typical monoperoxy acids useful herein include alkyl peroxy acids and aryl peroxyacids such as:
- Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
- Peroxyacid bleach precursors are well known in the art. As non-limiting examples can be named N,N,N'N'-tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulphonate (SNOBS), sodium benzoyloxybenzene sulphonate (SBOBS) and the cationic peroxyacid precursor (SPCC) as described in US-A-4751015.
- TAED N,N,N'N'-tetraacetyl ethylene diamine
- SNOBS sodium nonanoyloxybenzene sulphonate
- SBOBS sodium benzoyloxybenzene sulphonate
- SPCC cationic peroxyacid precursor
- suitable reactive chlorine- or bromine-oxidizing materials are heterocyclic N-bromo- and N-chloro imides such as tri-chloroisocyanuric, tribromoisocyanuric, dibromoisocyanuric and dichloroisocyanuric acids, and salts thereof with water-solubilizing cations such as potassium and sodium.
- Hydantoin compounds such as 1,3-dichloro-5,5- dimethyl-hydantoin are also quite suitable.
- Dry, particulate, water-soluble anhydrous inorganic salts are likewise suitable for use herein such as lithium, sodium or calcium hypochlorite and hypobromite.
- Chlorinated trisodium phosphate is another suitable material.
- Chloroisocyanurates are, however, the preferred bleaching agents.
- Potassium dichlorosocyanurate is sold by Monsanto Company as ACL-59 R .
- Sodium dichloroisocyanurates are also available from Monsanto as ACL-60 R , and in the dihydrate form, from the Olin Corporation as Clearon CDB-56 R , available in powder form (particle diameter of less than 150 microns); medium particle size (about 50 to 400 microns); and coarse particle size (150-850 microns). Very large particles (850-1700 microns) are also found to be suitable also for encapsulation.
- a bleach catalyst such as the manganese complex, e.g. Mn-Me TACN, as described in EP-A-0458397, or the sulphonimines of US Patents 5,041,232 and 5,047,163, may be incorporated in the composition.
- Such bleach catalysts may suitably be presented in the form of a second encapsulate separately from the bleach capsule component.
- the amount of encapsulates used in the compositions of the invention may vary preferably within the range of from about 0.1 to about 10%, especially from about 0.5 to about 3% as available chlorine (Av Cl).
- a suitable preferred range will be from about 0.1 to about 20%, especially from about 0.1 to about 10%, preferably from about 0.5 to about 3 or 5% Av O (available oxygen).
- the amount of peroxygen bleach, silicate and, carbonate, protease and surfactant taken together is at most about 20% by weight, more especially preferably between about 10 and 19.95% by weight of the composition.
- a detergent tablet comprising from about 25 to about 100%, preferably from about 25 to about 90% by weight, more preferably from about 40 to about 90% by weight, of co-granules according to the first aspect of the invention.
- the co-granules used to form the tablet are made by any of the processes described above.
- the tablet of the invention preferably contains less than 35% by weight, preferably less than 20% by weight, of irritant material selected from peroxygen bleach, silicate, carbonate, protease and surfactant.
- the strength of the tablet of the invention should preferably be high enough to allow handling without the need for individual wrapping.
- the tablet strength is defined as the force, expressed in Newtons, needed to break the tablet, as measured using a Chatillon type UTSM (remote 500) instrument in a direction perpendicular to the direction of compression.
- the tablet strength should preferably be at least about 150 Newton, more preferably at least about 200 Newton, so as to be sufficient for the tablet concerned to survive handling and packing. On the other hand, the tablet strength should not be too high, since in such a case the dissolution characteristics of the tablet concerned may not be adequate.
- the tablet strength should generally be below about 1000 Newton, preferably below about 800 Newton, more preferably below about 600 Newton, for round tablets. For rectangular tablets, the tablet strength should generally be below about 2000 Newton, preferably below about 1600 Newton, more preferably below about 1400 Newton.
- the tablets of the invention preferably have a density of at least about 1300 kg/m 3 .
- the tablets of this aspect of the invention preferably comprise more than about 20% by weight, preferably from about 25 to about 50% by weight, of the salt of di-, tri-, or tetracarboxylic acid, as builder salt.
- the detergent tablet of this aspect of the present invention comprises (in approximate amounts):
- the tablet of the invention may be effectively produced by a process involving the steps of mixing the co-granule material with the other ingredients of the tablet, and compacting the resulting detergent mixture using a pressure of at least 10 KN/cm 2 .
- Example 1 Example 2 Alkaline silicate solution (45%) 302 1209 Sodium hyroxide solution (46%) 190 763 Citric acid solution (48%) 292 1170 Copolymer maleate/acrylate (Sokalan CP-5 ex BASF) solution (40%) 56 225 Nonionic surfactant (Plurafac LF403) 8.5 - Synthetic clay (Laponite powder) 8.5 34
- the slurries of Examples 1 and 2 had a water content of 55% (w/w), with a low viscosity.
- the slurries were dried using a laboratory scale spray tower, followed by restructing (milling and spraying-on a few percent of a 45% alkaline silicate solution) and redrying.
- the co-granules so obtained showed an excellent whiteness due to citrate which was translucent bound up in a white co-granule.
- the co-granules were easily soluble in water and showed an excellent dish washing performance.
- a slurry was prepared on a tonne scale having the following composition by adding the ingredients one after another: parts per weight Citric acid solution (48%) 90 Sodium hydroxide solution (45%) 58 Copolymer maleate/acrylate solution (40%) 12.5 Alkaline silicate solution (45%) 75.6
- the moisture content of the slurry was 55% (w/w). It had a low viscosity.
- the slurry was dried using a pilot scale spray tower, yielding a powder with a moisture content of 12% (w/w), a bulk density of 400g/l and an average particle diameter of 400 ⁇ m.
- the powder was partly broken and restructured using a Lödige recycler and plough share mixer, yielding co-granules with a bulk density of 750 g/l and an average particle diameter of 550 ⁇ m.
- the appearance of the final product was pleasant. It dissolved and dispensed well in automatic dishwashing machines with a dissolution time of 1 minute at 20°C and a dispensing time of 4 minutes at 20°C. When compared with a product of the same composition obtained by dry mixing of components, these data were 3 minutes and 10 minutes, respectively.
- the strength of detergent tablets produced from a detergent mixture not containing co-granules was compared with the strength of tablets according to the invention produced from a mixture having the same composition but containing co-granules.
- composition (parts by weight)
- Example 4A Sodium citrate 40 30
- Maleate/acrylate copolymer 6 6
- Sodium disilicate 26.2 5
- detergent tablets having a weight of 20 grams were made from mixtures containing the co-granules, by compacting these mixtures using a Fette Perfecta 3 tabletting machine fitted with a 41 mm round die and optionally plastic inserts.
- the compaction pressure was 30 kN/cm 2 .
- 20 gram tablets (Comparative Examples 4C and 4D, respectively) were also made from mixtures not containing these co-granules but instead comprising the individual, non-co-granulated constituents thereof at concentrations equal to their respective concentrations in the co-granules-containing mixtures.
- compositions of the mixtures from which the tablets were produced were as follows (in % by weight):
- Example Example no 4A 4C (Comparative) 4B 4D (Comparative) Co-granules 72.2 - 77.7 - Sodium citrate - 40 - 30
- Acrylate/maleate copolymer - 6 - 6 Sodium disilicate - 26.2 - 5
- Nonionic surfactant Plurafac LF403
- the tablets of the invention took about 8 minutes to dissolve during a dishwashing cycle in a Bauknecht GSF 1161 automatic dishwashing machine.
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Description
Another possibility is to spray slurry in a rotary drum granulator onto fines to build up coarser particles, followed by, or in conjunction with, drying. Such spray-on techniques lead to granules with a more homogeneous distribution of moisture and consequently a better solubility.
The tablets of the invention preferably have a density of at least about 1300 kg/m3.
Composition (grams) | ||
Example 1 | Example 2 | |
Alkaline silicate solution (45%) | 302 | 1209 |
Sodium hyroxide solution (46%) | 190 | 763 |
Citric acid solution (48%) | 292 | 1170 |
Copolymer maleate/acrylate (Sokalan CP-5 ex BASF) solution (40%) | 56 | 225 |
Nonionic surfactant (Plurafac LF403) | 8.5 | - |
Synthetic clay (Laponite powder) | 8.5 | 34 |
The co-granules so obtained showed an excellent whiteness due to citrate which was translucent bound up in a white co-granule. Moreover the co-granules were easily soluble in water and showed an excellent dish washing performance.
parts per weight | |
Citric acid solution (48%) | 90 |
Sodium hydroxide solution (45%) | 58 |
Copolymer maleate/acrylate solution (40%) | 12.5 |
Alkaline silicate solution (45%) | 75.6 |
Composition (parts by weight) | ||
Example 4A | Example 4B | |
Sodium citrate | 40 | 30 |
Maleate/acrylate copolymer | 6 | 6 |
Sodium disilicate | 26.2 | 5 |
Sodium bicarbonate | 0 | 36.7 |
Example | ||||
Example no | 4A | 4C (Comparative) | 4B | 4D (Comparative) |
Co-granules | 72.2 | - | 77.7 | - |
Sodium citrate | - | 40 | - | 30 |
Acrylate/maleate copolymer | - | 6 | - | 6 |
Sodium disilicate | - | 26.2 | - | 5 |
Sodium bicarbonate | - | - | - | 36.7 |
perborate mono | 18 | 18 | 16 | 16 |
Bleach catalyst granules | 2.8 | 2.8 | 2.4 | 2.4 |
Enzymes | 5.4 | 5.4 | 3.3 | 3.3 |
Nonionic surfactant (Plurafac LF403) | 1.5 | 1.5 | 1.5 | 1.5 |
Perfume | 0.1 | 0.1 | 0.1 | 0.1 |
Example no | 4A | 4C (Comparative) | 4B | 4D (Comparative) |
Tablet strength | 808 | 45 | 448 | 115 |
Claims (32)
- A homogeneous co-granule comprising(i) a salt of a di-, tri-, or tetracarboxylic acid which is an alkali metal salt of citric acid, mellitic acid, oxydisuccinic acid, carboxymethoxysuccinic acid, malonic acid, dipicolinic acid or alkenyl succcinic acid; and(ii) an inorganic salt which is selected from alkali metal silicate, alkali metal carbonate, alkali metal bicarbonate, alkali metal sesquicarbonate, alkali metal sulphate, alkali metal tripolyphosphate, and mixtures thereof,
- A co-granule according to claim 1, wherein up to 30% of the di-, tri- or tetracarboxylic acid salt component is replaced by a lower hydroxy monocarboxylic acid.
- A co-granule according to claim 1, wherein the inorganic salt is sodium silicate with a composition satisfying SiO2: Na2O = 1.0 - 3.3.
- A co-granule according to claim 3, wherein the sodium silicate has a composition satisfying SiO2: Na2O = 1.8 - 2.8.
- A co-granule according to claim 1 wherein the inorganic salt is sodium disilicate.
- A co-granule according to claim 1, wherein the polymeric compound is an alkali metal salt of a water-soluble homopolymer or copolymer having a molecular weight of at least 500 and derived from a mono-, di-, tri- or polycarboxylic acid.
- A co-granule according to claim 6, wherein the polymeric compound is selected from the group consisting of:-(i) homopolymers derived from a monomer of the formula: wherein R1 is hydrogen, hydroxyl, C1-C4 alkyl or alkoxy, acetoxy, or -CH2COOM; R2 is hydrogen, C1-C4 alkyl or -COOM; and M is an alkali metal;(ii) copolymers of two or more carboxylic monomers of the above formula (i); and(iii) copolymers of one carboxylic monomer of the above formula (i) and two or more non-carboxylic acid monomers selected from ethylene, propylene, styrene, alphamethylstyrene, acrylonitrile, acrylamide, vinylacetate, methylvinylketone, acrolein and esters of carboxylic acid monomers.
- A co-granule according to any preceding claim, which further comprises up to 7% by weight of a low- to non-foaming nonionic surfactant.
- A co-granule according to any preceding claim, which has the following composition (II):20 - 75% (w/w) alkali metal silicate, carbonate, bicarbonate or sesquicarbonate;25 - 75% (w/w) alkali metal salt of di-, tri- or tetracarboxylic acid;1 - 9% (w/w) polymer;1 - 36% (w/w) alkali metal tripolyphosphate;0 - 60% (w/w) alkali metal sulphate;0 - 9% (w/w) organic phosphonate;0 - 5% (w/w) of minor ingredients;3 - 20% (w/w) moisture.
- A co-granule according to any preceding claim, which has an average particle size of from 100 to 1500 µm.
- A co-granule according to claim 10, which has an average particle size of 500 to 700 µm and a Rosen Rammler N-value above 2.5.
- A co-granule according to any preceding claim, which has a bulk density of at least 700 g/dm3.
- A process for preparing a co-granule according to any preceding claim, which process comprises preparing a slurry or solution of the ingredients of the co-granule, drying the mixture, and granulating the resulting material.
- A process according to claim 13, wherein the drying step is carried out using a turbine drier or a spray drying apparatus.
- A process for preparing a co-granule according to any of claims 1-12, wherein material prepared by the process of claim 13 or claim 14, or fine solid starting material comprising the ingredients of the co-granule is restructured.
- A process according to any one of claims 13 to 15, which process comprises preparing a slurry or solution by neutralizing the di-, tri- or tetracarboxylic acid with alkali, adding the inorganic salt, optionally adding further ingredients, so as to obtain a slurry with a water content of 30 - 60% (w/w), and converting the slurry into co-granules.
- A detergent composition comprising at least 25% of co-granules according to any one of claims 1 to 12.
- A detergent composition according to claim 17, which further comprises a bleach system and/or an enzyme system.
- A detergent composition according to claim 18, comprising at least 50% of the co-granules and less than 30% of the bleach system and/or enzyme system.
- A detergent composition according to claim 18 or 19, wherein the bleach system is a peroxygen bleaching system.
- A detergent composition according to claim 20, wherein the amount of peroxygen bleach, silicate, carbonate, protease and surfactant taken together in the composition is at most 30%, preferably at most 20% by weight.
- A method of making a detergent composition according to any of claims 17-21, wherein the composition is subjected to a tabletting operation in a tabletting apparatus.
- A detergent tablet comprising from 25 to 100% by weight of co-granules according to any one of claims 1 to 12.
- A detergent tablet according to claim 23, comprising from 40 to 90% by weight of the co-granule material.
- A detergent tablet according to claim 23 or 24, which further comprises a bleaching system and/or an enzyme system.
- A detergent tablet according to claim 25, which comprises less than 35%, preferably less than 20% by weight of irritant material selected from peroxygen bleach, silicate, carbonate, protease and surfactant.
- A detergent tablet according to any one of claims 23 to 26, which has a strength of from 150 to 2000 Newton, being the force needed to break the tablet, as measured using a Chatillon type UTSM (remote 500) instrument in a direction perpendicular to the direction of compression.
- A detergent tablet according to any one of claims 23 to 27, which has a density of at least 1300 Kg/m3.
- A detergent tablet according to any one of claims 23 to 28, which comprises more than 20% by weight of the salt of a di-, tri- or tetracarboxylic acid.
- A detergent tablet according to any one of claims 23 to 29, which has the following composition:25-90 %wt of the cogranule material;5-20 %wt of a hydrogen peroxide source selected from alkali metal peroxides, organic peroxides, inorganic persalts, and mixtures thereof;0-5 %wt of a bleach catalyst;0-10 %wt of enzyme material;0-5 %wt of tabletting aids;0-10 %wt of minor ingredients.
- A process for preparing a detergent tablet according to any one of claims 23 to 30, the process comprising the steps of mixing the cogranule material with the other ingredients of the tablet, and compressing the resulting mixture under a pressure of at least 10 kN/cm2.
- Use of a co-granule according to any one of claims 1 to 12, or a detergent composition according to any one of claims 17 to 21, or a detergent tablet according to any one of claims 23 to 30, in a machine dishwashing process.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP95907583A EP0741776B2 (en) | 1994-01-25 | 1995-01-23 | Process for the preparation of detergent tablets |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP94200165 | 1994-01-25 | ||
EP94200165 | 1994-01-25 | ||
EP94202818 | 1994-09-29 | ||
EP94202818 | 1994-09-29 | ||
PCT/EP1995/000226 WO1995020030A1 (en) | 1994-01-25 | 1995-01-23 | Co-granules and detergent tablets formed therefrom |
EP95907583A EP0741776B2 (en) | 1994-01-25 | 1995-01-23 | Process for the preparation of detergent tablets |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0741776A1 EP0741776A1 (en) | 1996-11-13 |
EP0741776B1 true EP0741776B1 (en) | 1998-05-27 |
EP0741776B2 EP0741776B2 (en) | 2001-10-24 |
Family
ID=26136022
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP95907583A Expired - Lifetime EP0741776B2 (en) | 1994-01-25 | 1995-01-23 | Process for the preparation of detergent tablets |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0741776B2 (en) |
AU (1) | AU702040B2 (en) |
BR (1) | BR9506561A (en) |
CA (1) | CA2180433C (en) |
DE (1) | DE69502701T3 (en) |
ES (1) | ES2118561T5 (en) |
WO (1) | WO1995020030A1 (en) |
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US9242879B2 (en) | 2012-03-30 | 2016-01-26 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
US9676711B2 (en) | 2008-03-28 | 2017-06-13 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
US10893674B2 (en) | 2013-03-05 | 2021-01-19 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
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GB9414576D0 (en) * | 1994-07-19 | 1994-09-07 | Unilever Plc | Method for preparing cogranules by compaction |
DK173111B1 (en) * | 1996-04-03 | 2000-01-31 | Cleantabs As | Laundry Tablets |
IL120992A0 (en) * | 1996-06-14 | 1997-11-20 | Rohm & Haas | Detergent tablets |
MA24525A1 (en) | 1997-04-14 | 1998-12-31 | Procter & Gamble | DETERGENT PARTICLE |
CN1260827A (en) * | 1997-04-14 | 2000-07-19 | 普罗格特-甘布尔公司 | Foaming component |
EP0872544A1 (en) * | 1997-04-14 | 1998-10-21 | The Procter & Gamble Company | Dry effervescent granules and granular compositions comprising the same |
GB2332442A (en) * | 1997-12-17 | 1999-06-23 | Procter & Gamble | Detergent tablet |
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US6410500B1 (en) | 1997-12-30 | 2002-06-25 | Henkel Kommanditgesellschaft Auf Aktien | Moulded body dishwasher detergents with soil release polymers |
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EP1076686B1 (en) * | 1998-04-27 | 2004-03-03 | The Procter & Gamble Company | A process for producing a water-dispersable non-particulate detergent product from low-density particulate detergent particles |
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FI106958B (en) * | 1998-11-25 | 2001-05-15 | Kemira Chemicals Oy | Method for Stabilizing Peroxy Compounds |
AU2110500A (en) * | 1999-02-05 | 2000-08-25 | Unilever Plc | Dish washing process and compositions relating thereto |
GB2347431A (en) * | 1999-03-04 | 2000-09-06 | Procter & Gamble | Detergent tablet |
US6770616B1 (en) | 1999-03-04 | 2004-08-03 | The Procter & Gamble Company | Detergent tablet |
US7084102B1 (en) | 1999-03-12 | 2006-08-01 | The Procter & Gamble Company | Perfumed detergent tablet |
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AU3290300A (en) * | 1999-03-25 | 2000-10-16 | Henkel Kommanditgesellschaft Auf Aktien | Tablet containing a builder |
DE19918722A1 (en) * | 1999-04-24 | 2000-10-26 | Henkel Kgaa | Detergent formed bodies, e.g. tablets, include percarbamide which acts both as a bleach and as an agent to improve the hardness and decomposition properties |
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EP1203809A1 (en) * | 2000-11-06 | 2002-05-08 | The Procter & Gamble Company | Polymer containing granules and compositions thereof |
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US9624119B2 (en) | 2014-06-13 | 2017-04-18 | Ecolab Usa Inc. | Enhanced catalyst stability in activated peroxygen and/or alkaline detergent formulations |
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US20230062299A1 (en) * | 2019-12-18 | 2023-03-02 | Basf Se | Powders and granules and process for making such powders and granules |
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US4379080A (en) † | 1981-04-22 | 1983-04-05 | The Procter & Gamble Company | Granular detergent compositions containing film-forming polymers |
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GB9015503D0 (en) † | 1990-07-13 | 1990-08-29 | Unilever Plc | Detergent composition |
DK166548B1 (en) * | 1991-03-15 | 1993-06-07 | Cleantabs As | PHOSPHATE-FREE MACHINE DISHWASH |
EP0508034B1 (en) † | 1991-04-12 | 1996-02-28 | The Procter & Gamble Company | Compact detergent composition containing polyvinylpyrrolidone |
DK167363B1 (en) † | 1991-04-12 | 1993-10-18 | Cleantabs As | CLOTHING DETERGENT |
DE4112075A1 (en) † | 1991-04-12 | 1992-10-15 | Henkel Kgaa | METHOD FOR PRODUCING STABLE, BIFUNCTIONAL, PHOSPATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
DE4114956A1 (en) * | 1991-05-02 | 1992-11-05 | Dispo Kommerz Ag Huenenberg | GRANULAR PHOSPHATE-FREE AGENT FOR MACHINE DISHWASHER |
DE4121307A1 (en) † | 1991-06-27 | 1993-01-07 | Henkel Kgaa | METHOD FOR THE PRODUCTION OF STABLE, BIFUNCTIONAL, PHOSPHATE AND METASILICATE-FREE LOW-ALKALINE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
EP0561452A1 (en) * | 1992-03-20 | 1993-09-22 | Unilever N.V. | Machine dishwashing composition containing polyaminoacids as builders |
US5458799A (en) † | 1993-08-03 | 1995-10-17 | Amway Corporation | Mix process for formulating detergents |
US5366652A (en) † | 1993-08-27 | 1994-11-22 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
US5486303A (en) † | 1993-08-27 | 1996-01-23 | The Procter & Gamble Company | Process for making high density detergent agglomerates using an anhydrous powder additive |
-
1995
- 1995-01-23 AU AU15756/95A patent/AU702040B2/en not_active Ceased
- 1995-01-23 EP EP95907583A patent/EP0741776B2/en not_active Expired - Lifetime
- 1995-01-23 DE DE69502701T patent/DE69502701T3/en not_active Expired - Fee Related
- 1995-01-23 BR BR9506561A patent/BR9506561A/en active Search and Examination
- 1995-01-23 WO PCT/EP1995/000226 patent/WO1995020030A1/en active IP Right Grant
- 1995-01-23 ES ES95907583T patent/ES2118561T5/en not_active Expired - Lifetime
- 1995-01-23 CA CA002180433A patent/CA2180433C/en not_active Expired - Fee Related
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US11015151B2 (en) | 2008-03-28 | 2021-05-25 | Ecolab Usa Inc. | Sulfoperoxycarboxylic acids, their preparation and methods of use as bleaching and antimicrobial agents |
US9926214B2 (en) | 2012-03-30 | 2018-03-27 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
US10023484B2 (en) | 2012-03-30 | 2018-07-17 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
US9242879B2 (en) | 2012-03-30 | 2016-01-26 | Ecolab Usa Inc. | Use of peracetic acid/hydrogen peroxide and peroxide-reducing agents for treatment of drilling fluids, frac fluids, flowback water and disposal water |
US11939241B2 (en) | 2012-10-05 | 2024-03-26 | Ecolab Usa Inc. | Stable percarboxylic acid compositions and uses thereof |
US10165774B2 (en) | 2013-03-05 | 2019-01-01 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
US10893674B2 (en) | 2013-03-05 | 2021-01-19 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
US8822719B1 (en) | 2013-03-05 | 2014-09-02 | Ecolab Usa Inc. | Peroxycarboxylic acid compositions suitable for inline optical or conductivity monitoring |
US11026421B2 (en) | 2013-03-05 | 2021-06-08 | Ecolab Usa Inc. | Efficient stabilizer in controlling self accelerated decomposition temperature of peroxycarboxylic acid compositions with mineral acids |
US11206826B2 (en) | 2013-03-05 | 2021-12-28 | Ecolab Usa Inc. | Defoamer useful in a peracid composition with anionic surfactants |
Also Published As
Publication number | Publication date |
---|---|
ES2118561T3 (en) | 1998-09-16 |
AU1575695A (en) | 1995-08-08 |
WO1995020030A1 (en) | 1995-07-27 |
DE69502701T3 (en) | 2002-05-29 |
DE69502701T2 (en) | 1998-11-26 |
CA2180433C (en) | 2000-04-25 |
CA2180433A1 (en) | 1995-07-27 |
EP0741776B2 (en) | 2001-10-24 |
AU702040B2 (en) | 1999-02-11 |
DE69502701D1 (en) | 1998-07-02 |
ES2118561T5 (en) | 2002-03-16 |
EP0741776A1 (en) | 1996-11-13 |
BR9506561A (en) | 1997-10-28 |
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