EP1418224B1 - Verfahren zur Herstellung einer Reinigungsmitteltablette - Google Patents
Verfahren zur Herstellung einer Reinigungsmitteltablette Download PDFInfo
- Publication number
- EP1418224B1 EP1418224B1 EP02079186A EP02079186A EP1418224B1 EP 1418224 B1 EP1418224 B1 EP 1418224B1 EP 02079186 A EP02079186 A EP 02079186A EP 02079186 A EP02079186 A EP 02079186A EP 1418224 B1 EP1418224 B1 EP 1418224B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- tablet
- smooth
- preferred
- cutting
- region
- 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
- 238000004140 cleaning Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011538 cleaning material Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000344 soap Substances 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000003826 tablet Substances 0.000 description 93
- 239000000203 mixture Substances 0.000 description 54
- 239000012071 phase Substances 0.000 description 49
- 239000007844 bleaching agent Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 239000003599 detergent Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- -1 builders Substances 0.000 description 10
- 238000007906 compression Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 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 9
- 239000003945 anionic surfactant Substances 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 230000006835 compression Effects 0.000 description 7
- 238000004851 dishwashing Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 108090000790 Enzymes Proteins 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229940088598 enzyme Drugs 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 239000002736 nonionic surfactant Substances 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011236 particulate material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000007916 tablet composition Substances 0.000 description 3
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 108091005804 Peptidases Proteins 0.000 description 2
- 102000035195 Peptidases Human genes 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 239000004365 Protease Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 108010056079 Subtilisins Proteins 0.000 description 2
- 102000005158 Subtilisins Human genes 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 229940113120 dipropylene glycol Drugs 0.000 description 2
- PMPJQLCPEQFEJW-GNTLFSRWSA-L disodium;2-[(z)-2-[4-[4-[(z)-2-(2-sulfonatophenyl)ethenyl]phenyl]phenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC=C1\C=C/C1=CC=C(C=2C=CC(\C=C/C=3C(=CC=CC=3)S([O-])(=O)=O)=CC=2)C=C1 PMPJQLCPEQFEJW-GNTLFSRWSA-L 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229960004063 propylene glycol Drugs 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 229910009112 xH2O Inorganic materials 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical class OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LVVZBNKWTVZSIU-UHFFFAOYSA-N 2-(carboxymethoxy)propanedioic acid Chemical class OC(=O)COC(C(O)=O)C(O)=O LVVZBNKWTVZSIU-UHFFFAOYSA-N 0.000 description 1
- ZTGKHKPZSMMHNM-UHFFFAOYSA-N 3-(2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1S(O)(=O)=O ZTGKHKPZSMMHNM-UHFFFAOYSA-N 0.000 description 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 description 1
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical compound CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 description 1
- YGUMVDWOQQJBGA-VAWYXSNFSA-N 5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S(O)(=O)=O)C(S(=O)(=O)O)=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 YGUMVDWOQQJBGA-VAWYXSNFSA-N 0.000 description 1
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical class [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical class OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N OS(c1ccccc1)(=O)=O Chemical compound OS(c1ccccc1)(=O)=O SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 1
- WFRXSOIFNFJAFL-UHFFFAOYSA-N P1(OCCCCO1)=O.C(CN)N Chemical compound P1(OCCCCO1)=O.C(CN)N WFRXSOIFNFJAFL-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- GBFLZEXEOZUWRN-VKHMYHEASA-N S-carboxymethyl-L-cysteine Chemical compound OC(=O)[C@@H](N)CSCC(O)=O GBFLZEXEOZUWRN-VKHMYHEASA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000007891 compressed tablet Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- VUJGKADZTYCLIL-YHPRVSEPSA-L disodium;5-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-[(e)-2-[4-[(4-anilino-6-morpholin-4-yl-1,3,5-triazin-2-yl)amino]-2-sulfonatophenyl]ethenyl]benzenesulfonate Chemical compound [Na+].[Na+].C=1C=C(\C=C\C=2C(=CC(NC=3N=C(N=C(NC=4C=CC=CC=4)N=3)N3CCOCC3)=CC=2)S([O-])(=O)=O)C(S(=O)(=O)[O-])=CC=1NC(N=C(N=1)N2CCOCC2)=NC=1NC1=CC=CC=C1 VUJGKADZTYCLIL-YHPRVSEPSA-L 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
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 229940012017 ethylenediamine Drugs 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Chemical group 0.000 description 1
- 229910052739 hydrogen Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000003698 laser cutting Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 108010020132 microbial serine proteinases Proteins 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000019271 petrolatum Nutrition 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 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 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- 229940045872 sodium percarbonate Drugs 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
- 239000007790 solid phase Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- 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
Definitions
- This invention relates to cleaning compositions in the form of tablets for example, for use in fabric washing or machine dishwashing.
- Detergent compositions in tablet form have advantages over powdered products in that they do not require measuring and are thus easier to handle and dispense into the washload.
- Tablets of a cleaning composition are generally made by compressing or compacting a quantity of the composition in particulate form.
- WO 01/42416 describes the production of multi-phase moulded bodies comprising a combination of core moulded bodies and a particulate premix.
- WO 00/61717 describes a detergent tablet which is characterised in that at least part of its outer surface is smooth.
- WO 00/04129 describes a multi-phase detergent tablet comprising a first phase in the form of a shaped body having at least one mould therein and a second phase in the form of a particulate solid compressed within said mould.
- a further objective of the present invention is to.provide a method to produce a smooth tablet or phase thereof wherein the choice of materials and the manufacturing method allows the low cost production of tablets of good performance and of good consistency and texture.
- a cleaning tablet which has a plurality of discrete regions with differing compositions, characterised in that at least one first region of the tablet is a smooth region and at least one second region of the tablet is a solid region of compacted particulate material.
- One method of producing smooth phases which can be used in cleaning tablets is first to produce a large quantity e.g. an extruded strand or a log of the material, followed by partitioning this quantity into smaller quantities for example by cutting.
- the smooth composition can advantageously be divided into smooth parts for use in cleaning tablets by using a high frequency or jet cutting process.
- the invention relates to a method of producing a cleaning tablet comprising a smooth phase wherein the preparation of the smooth phase comprises the step of high-frequency cutting or jet cutting of a cleaning material.
- the cleaning material comprises from 10 to 90 wt% of non-soap surfactants and from 0 to 20 wt% of water.
- tablets (and the smooth phases) of the invention are of cylindrical shape wherein the two main surfaces (upper side and bottom side) are substantially flat.
- the smooth phases are slices of cleaning material, for example having a diameter of from 1 to 10 cm (preferably 2 to 6 cm) and a height of from 0.1 to 5 cm (preferably 0.3 to 1.5 cm).
- tablets of the invention can be single phase tablets, which are predominantly constituted by the smooth phase as described above.
- a preferred embodiment of the invention relates to a multiphase tablet wherein the smooth phase is present and additionally one or more other phases are present.
- these additional phases can be smooth or solid.
- Particularly suitable are solid phases composed of compacted particulate solids.
- the regions of a multi-phase tablet are possibly separate layers within a tablet. However, a discrete region of a tablet could also have other forms for example one or more core(s) or insert(s).
- the first region is a smooth layer and the second region is a layer of compacted particulate material.
- the first region is a core or insert of smooth material embedded in the second region which is a layer of compacted particulate material.
- the weight of this tablet will be from 5 to 200 g, more preferably from 10 to 100 g, most preferably from 15 to 50 g.
- the smooth phase is present as a distinctive region preferably having a weight of from 2 to 20 grammes, more preferred from 3 to 10 grammes.
- the other phases together have a weight of 10 to 50 grammes, more preferred 15 to 40 grammes.
- smooth phase refers to compositions which are on the one hand solid enough to retain their shape at ambient temperature and on the other hand smooth in appearance. Smooth textures are generally of low or no porosity and have -at normal viewing distance- the appearance of a continuous phase for example as opposed to porous and particulate appearance of a compacted particulate material.
- the smooth phase is transparent or translucent.
- this means that the composition has an optical transmissivity of at least 10%, most preferably 20%, still more preferably 30%, through a path length of 0.5 cm at 25° C.
- These measurements may be obtained using a Perkin Elmer UV/VIS Spectrometer Lambda 12 or a Brinkman PC801 Colorimeter at a wavelength of 520nm, using water as the 100% standard.
- compositions according to the invention does not preclude the composition being coloured, e.g. by addition of a dye, provided that it does not detract substantially from clarity.
- the smooth phase comprises from 20-80 wt% of non-soap surfactants (based on the total weight of said smooth phase), more preferred from 25 to 75 wt%, most preferred 30 to 70 wt%. It has been found that the combination of a separate smooth first region and these high surfactant levels provide very good dispersing and cleaning properties to the tablet.
- the non-soap surfactants in the first region comprise a combination of anionic surfactants and non-ionic surfactants in a weight ratio of from 5 : 1 to 1 : 5, more preferred 3 : 1 to 1 : 3, more preferred 2 : 1 to 1: 2.
- Further surfactants for example cationic surfactants may equally be present for example at a level of 0.1 to 10 wt% based on the weight of the smooth part.
- the smooth region may comprise additional solid materials such as mineral salts, sugar or structuring soaps for example at a level of 2 to 90 wt% based on the weight of the smooth part, more preferred from 3 to 70 wt%, most preferred 5 to 40 wt%.
- suitable salts are for example soluble salts such as acetate, citrate, urea. The use of these materials can advantageously lead to improved structuring and/or improved dissolution properties of the smooth phase.
- the smooth region of the tablet may also contain diluent materials for example polyethyleneglycol, dipropyleneglycol, isopropanol or (mono-)propyleneglycol.
- diluent materials for example polyethyleneglycol, dipropyleneglycol, isopropanol or (mono-)propyleneglycol.
- the level of these diluents is from 0 to 40 wt%, more preferred 1 to 20, most preferred from 4 to 15 wt% based on the weight of the smooth phase.
- the smooth phase comprises no or only low levels of water.
- the level of water is less than 20 wt % based on the weight of the smooth phase, more preferred less than 15 wt%, most preferred from 5 to 12 wt%.
- the smooth phases are substantially free from water, which means that apart from low levels of moisture (e.g. for neutralisation or as crystal water) no additional added water is present.
- the total weight of surfactants in the smooth phase is from 2 to 20 grammes, more preferred from 3 to 10 grammes.
- the smooth phase comprises no or only low levels of ingredients such as builders, bleach activators and bleach materials.
- the level of these ingredients in the smooth phase is less than 5 wt%.
- the tablet may be a multi-phase tablet wherein the phases other than the smooth phase as described above comprise no or only low levels of surfactants.
- the level of surfactants in the other phases is less than 10 wt%(based on the total weight of said phases), more preferred from 0 to 9 wt%, most preferred from 1 to 8 wt%.
- the cleaning tablets comprise a first smooth region (as described above) in combination with a second region of the tablet which is a solid region, for example prepared by compression of a particulate composition.
- the second region may comprise surfactant materials
- this region preferably comprises ingredients of the tablet other than surfactants.
- these ingredients are for example builders, bleach system, enzymes etc.
- the builders in the tablet are predominantly present in the second region.
- the bleach system is predominantly present in the second region.
- the enzymes are predominantly present in the second region.
- the term "predominantly present” refers to a situation wherein at least 90 wt% of an ingredient is present in the second region, more preferred more than 98 wt%, most preferred substantially 100 wt%.
- each of the regions may be composed of a limited number of discrete regions.
- the first smooth region may be a single discrete part of the tablet but may also be a limited number (say 1-5) discrete smooth parts.
- each of these smooth parts are at least 1 gramme, also preferably each of these smooth parts is substantially of the same composition. If reference is made to the composition or weight of the first region it is understood that this concerns the total weight and composition of these smooth parts.
- the solid second region may be composed of a limited number (say 1-5) of solid parts e.g. separate layers in the tablet.
- each of these parts has a weight of at least 10 grammes, also preferably each of the solid parts is substantially of the same composition. If reference is made to the composition or weight of the second region it is understood that this concerns the total weight and composition of these solid parts.
- the cleaning tablets of the invention may optionally comprise further regions, for example the tablet may be partly or wholly coated.
- Cleaning tablets according to the invention are preferably manufactured by firstly preparing a smooth part.
- the preparation of the smooth phase may include the heating of the cleaning material followed by cooling.
- the preparation of the cleaning material may involve extrusion.
- Extrusion processes for washing articles are known, for example WO 01/02532 describes the extrusion of washing articles with a pressure of less than 10 bar.
- extrusion processes will involve the forming of an extrudable mass which is then subsequently extruded from an extrusion device and optionally then partitioned into parts of the desired size and weight.
- the smooth parts may then be hardened.
- the partitioning involves a high frequency cutting or jet cutting process.
- high frequency cutting processes are ultrasonic cutting and focused energy cutting for example by using focused laser light or ultrasound.
- jet cutting are air or water jet cutting.
- Ultrasonic cutting devices are for example described in EP 783 399 and US 6070509 and generally involve an oscillating cutting device e.g. a vibrating knife. Ultrasonic cutting machines may for example operate at oscillating frequencies of between 10 and 50 kHz, more preferred 20 to 40 kHz.
- Focused energy cutting generally uses focussed beams of high frequency radiation such as ultrasound or light (e.g. laser light such as for example from a CO 2 laser). Examples of laser devices for cutting are described in WO 00/48764, EP1083019 and WO 01/38242.
- Jet cutting processes involve the focused application of flows of liquid of gases for example air or other gases such as CO 2 or nitrogen or liquids such as for example water or propylene glycol.
- the pressure of the flow will be from 6.9 ⁇ 10 4 to 6.9 ⁇ 10 5 kPa (10000 to 100000 psi), more preferred 1.38 ⁇ 10 5 to 5.52 ⁇ 10 5 kPa (20000 to 80000 psi), most preferred from 2.07 ⁇ 10 5 to 3.45 ⁇ 10 5 kPa (30000 t0 50000 psi) (1 psi corresponds to 6.9 kPa).
- the diameter of the flow jets is from 0.025 mm to 0.25 mm, more preferred from 0.08 to 0.20 mm, most preferred from 0.1 to 0.15 mm.
- liquid cutting devices are for example described in WO00/69290 and US4640300.
- gas cutting devices are described in US 4471895.
- air or steam is used as the cutting gas it is used a elevated temperature of from 50 to 500°C, more preferred from 60 to 250 °C.
- the extrudable mass preferably has before extrusion an initial elevated temperature for example from 60 to 120°C, more preferred from 70 to 90°C.
- the extrudable mass is during the production of the smooth mass cooled e.g. to a final temperature of 20°C and then extruded. If extrusion is used this low temperature may for example be the temperature at the extrusion die for example from 10 to 40, preferably from 15 to 25, most preferred at ambient temperature (20°C).
- step (a) takes place before step (b).
- the particulate composition is pre-compressed at a force of 0.1 to 20 kN/cm 2 between steps (a) and (b) In another preferred embodiment the particulate composition is flattened between steps (a) and (b).
- the (co-)compression of the combination of the smooth and the solid region(s) takes place at a force of from 0.05 to 20 kN/cm 2 .
- the co-compression in step (c) can advantageously be at a force of 0.1- 10 kN/cm 2 , more preferred 0.5 to 5 kN/cm 2 .
- the co-compression preferably takes place at a force of 1- 100 kN/cm 2 , more preferred 2-50 kN/cm 2 ., most preferred 2-10 kN/cm 2 .
- One advantage of the method of the present invention is that the co-compression step of (c) leads to good adherence of the first region to the second region and avoids the need of applying an adhesive material between the smooth and solid region.
- Another advantage of the method of the invention is that it can be carried out in a normal tablet press without the need of adaptation of the shape of the pressing surfaces.
- a tablet of this invention may be intended for use in machine dishwashing.
- Such a tablet is likely to contain surfactant in a low concentration such as 0.5 to 2 wt% based on the whole tablet, although higher concentrations ranging up to 10 wt% may be used.
- Such will typically contain salts, such as over 60 wt%, often over 85 wt% of the tablet.
- Water soluble salts typically used in machine dishwashing compositions are phosphates (including condensed phosphates) carbonates and silicates, generally as alkali metal salts.
- Water soluble alkali metal salts selected from phosphates, carbonates and silicates may provide 60 wt% or more of a dishwashing composition.
- a tablet of this invention will be intended for fabric washing.
- the tablet will be likely to contain at least 2 wt%, probably at least 5 wt%, up to 40 or 50 wt% non-soap surfactant based on the whole tablet, and from 5 to 80 wt% detergency builder, based on the whole tablet.
- compositions which are used in tablets of the invention will contain one or more detergent surfactants.
- these preferably provide from 5 to 50% by weight of the overall tablet composition, more preferably from 8 or 9% by weight of the overall composition up to 40% or 50% by weight.
- Surfactant may be anionic (soap or non-soap), cationic, zwitterionic, amphoteric, nonionic or a combination of these.
- Anionic surfactant may be present in an amount from 0.5 to 50% by weight, preferably from 2% or 4% up to 30% or 40% by weight of the tablet composition.
- Synthetic (i.e. non-soap) anionic surfactants are well known to those skilled in the art.
- alkylbenzene sulphonates particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C 8 -C 15 ; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.
- Primary alkyl sulphate having the formula ROSO 3 - M + in which R is an alkyl or alkenyl chain of 8 to 18 carbon atoms especially 10 to 14 carbon atoms and M + is a solubilising cation, is commercially significant as an anionic surfactant.
- Linear alkyl benzene sulphonate of the formula where R is linear alkyl of 8 to 15 carbon atoms and M + is a solubilising cation, especially sodium, is also a commercially significant anionic surfactant.
- such linear alkyl benzene sulphonate or primary alkyl sulphate of the formula above, or a mixture thereof will be the desired anionic surfactant and may provide 75 to 100 wt% of any anionic non-soap surfactant in the composition.
- the amount of non-soap anionic surfactant lies in a range from 5 to 20 wt% of the tablet composition.
- Soaps for use in accordance to the invention are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from beef tallow.
- Suitable nonionic surfactant compounds which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide.
- Nonionic surfactant compounds are alkyl (C 8-22 ) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic C 8-20 primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene-diamine.
- the primary and secondary alcohol ethoxylates especially the C 9-11 and C 12-15 primary and secondary alcohols ethoxylated with an average of from 5 to 20 moles of ethylene oxide per mole of alcohol.
- the amount of nonionic surfactant lies in a range from 4 to 40%, better 4 or 5 to 30% by weight of the whole tablet.
- nonionic surfactants are liquids. These may be absorbed onto particles of the composition.
- the surfactant may be wholly nonionic, in an amount below 5 wt% of the whole tablet although it is known to include some anionic surfactant and to use up to 10 wt% surfactant in total.
- a composition which is used in tablets of the invention will usually contain from 5 to 80%, more usually 15 to 60% by weight of detergency builder. This may be provided wholly by water soluble materials, or may be provided in large part or even entirely by water-insoluble material with water-softening properties. Water-insoluble detergency builder may be present as 5 to 80 wt%, better 5 to 60 wt% of the composition.
- Alkali metal aluminosilicates are strongly favoured as environmentally acceptable water-insoluble builders for fabric washing.
- Alkali metal (preferably sodium) aluminosilicates may be either crystalline or amorphous or mixtures thereof, having the general formula: 0.8 - 1.5 Na 2 O.Al 2 O 3 . 0.8 - 6 SiO 2 . xH 2 O
- xH2O xH2O
- xH2O calcium ion exchange capacity
- the preferred sodium aluminosilicates contain 1.5-3.5 SiO 2 units (in the formula above). Both the amorphous and the crystalline materials can be prepared readily by reaction between sodium silicate and sodium aluminate, as amply described in the literature.
- Suitable crystalline sodium aluminosilicate ion-exchange detergency builders are described, for example, in GB 1429143 (Procter & Gamble).
- the preferred sodium aluminosilicates of this type are the well known commercially available zeolites A and X, the novel zeolite P described and claimed in EP 384070 (Unilever) and mixtures thereof.
- a water-insoluble detergency builder could be a layered sodium silicate as described in US 4664839.
- NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6").
- KSKS-6 has the delta-Na 2 SiO 5 morphology form of layered silicate. It can be prepared by methods such as described in DE-A-3,417,649 and DE-A-3,742,043.
- layered silicates such as those having the general formula NaMSi x O 2x+1 .yH 2 O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used.
- Water-soluble phosphorous-containing inorganic detergency builders include the alkali-metal orthophosphates, metaphosphates, pyrophosphates and polyphosphates.
- Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates.
- Non-phosphorous water-soluble builders may be organic or inorganic.
- Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates and hydroxyethyliminodiacetates.
- alkali metal generally sodium
- organic builders include polycarboxylate polymers, such as polyacrylates, acrylic/maleic copolymers, and acrylic phosphonates, monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono- di- and trisuccinates, carboxymethyloxysuccinates, carboxymethyloxymalonates, dip
- At least one region (preferably the second region) of a fabric washing tablet preferably include polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers which can function as builders and also inhibit unwanted deposition onto fabric from the wash liquor.
- Tablets according to the invention may contain a bleach system in at least one region of a tablet, preferably in the second region.
- This preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with activators to improve bleaching action at low wash temperatures. If any peroxygen compound is present, the amount is likely to lie in a range from 10 to 25% by weight of the composition.
- Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate, advantageously employed together with an activator.
- Bleach activators also referred to as bleach precursors
- Preferred examples include peracetic acid precursors, for example, tetraacetylethylene diamine (TAED), now in widespread commercial use in conjunction with sodium perborate; and perbenzoic acid precursors.
- TAED tetraacetylethylene diamine
- perbenzoic acid precursors perbenzoic acid precursors.
- the quaternary ammonium and phosphonium bleach activators disclosed in US 4751015 and US 4818426 are also of interest.
- bleach activator which may be used, but which is not a bleach precursor, is a transition metal catalyst as disclosed in EP-A-458397, EP-A-458398 and EP-A-549272.
- a bleach system may also include a bleach stabiliser (heavy metal sequestrant) such as ethylenediamine tetramethylene phosphonate and diethylenetriamine pentamethylene phosphonate.
- a bleach is present and is a water-soluble inorganic peroxygen bleach, the amount may well be from 10% to 25% by weight of the composition.
- the detergent tablets of the invention may also contain (preferably in the second region) one of the detergency enzymes well known in the art for their ability to degrade and aid in the removal of various soils and stains.
- Suitable enzymes include the various proteases, cellulases, lipases, amylases, and mixtures thereof, which are designed to remove a variety of soils and stains from fabrics.
- suitable proteases are Maxatase (Trade Mark), as supplied by Gist-Brocades N.V., Delft, Holland, and Alcalase (Trade Mark), and Savinase (Trade Mark), as supplied by Novo Industri A/S, Copenhagen, Denmark.
- Detergency enzymes are commonly employed in the form of granules or marumes, optionally with a protective coating, in amount of from about 0.1% to about 3.0% by weight of the composition; and these granules or marumes present no problems with respect to compaction to form a tablet.
- the detergent tablets of the invention may also contain (preferably in the second region) a fluorescer (optical brightener), for example, Tinopal (Trade Mark) DMS or Tinopal CBS available from Ciba-Geigy AG, Basel, Switzerland.
- a fluorescer optical brightener
- Tinopal DMS is disodium 4,4'bis-(2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene disulphonate
- Tinopal CBS is disodium 2,2'-bis-(phenyl-styryl) disulphonate.
- An antifoam material is advantageously included (preferably in the second region), especially if a detergent tablet is primarily intended for use in front-loading drum-type automatic washing machines.
- Suitable antifoam materials are usually in granular form, such as those described in EP 266863A (Unilever).
- Such antifoam granules typically comprise a mixture of silicone oil, petroleum jelly, hydrophobic silica and alkyl phosphate as antifoam active material, absorbed onto a porous absorbed water-soluble carbonate-based inorganic carrier material.
- Antifoam granules may be present in an amount up to 5% by weight of the composition.
- a detergent tablet of the invention includes an amount of an alkali metal silicate, particularly sodium ortho-, meta- or disilicate.
- an alkali metal silicate particularly sodium ortho-, meta- or disilicate.
- the presence of such alkali metal silicates at levels, for example, of 0.1 to 10 wt%, may be advantageous in providing protection against the corrosion of metal parts in washing machines, besides providing some measure of building and giving processing benefits in manufacture of the particulate material which is compacted into tablets.
- a tablet for fabric washing will generally not contain more than 15 wt% silicate.
- a tablet for machine dishwashing will often contain more than 20 wt% silicate.
- the silicate is present in the second region of the tablet.
- ingredients which can optionally be employed in a region of a fabric washing detergent of the invention tablet include anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents; heavy metal sequestrants such as EDTA; perfumes; and colorants or coloured speckles.
- anti-redeposition agents such as sodium carboxymethylcellulose, straight-chain polyvinyl pyrrolidone and the cellulose ethers such as methyl cellulose and ethyl hydroxyethyl cellulose, fabric-softening agents
- heavy metal sequestrants such as EDTA
- perfumes and colorants or coloured speckles.
- dispersing aids are water-swellable polymers (e.g. SCMC) highly soluble materials (e.g. sodium citrate, potassium carbonate or sodium acetate) or sodium tripolyphospate with preferably at least 40% of the anhydrous phase I form.
- SCMC water-swellable polymers
- highly soluble materials e.g. sodium citrate, potassium carbonate or sodium acetate
- sodium tripolyphospate preferably at least 40% of the anhydrous phase I form.
- the second region of a detergent tablet of this invention is a preferably a matrix of compacted particles.
- the particulate composition has an average particle size in the range from 200 to 2000 ⁇ m, more preferably from 250 to 1400 ⁇ m. Fine particles, smaller than 180 ⁇ m or 200 ⁇ m may be eliminated by sieving before tableting, if desired, although we have observed that this is not always essential.
- the starting particulate composition may in principle have any bulk density
- the present invention is especially relevant to tablets made by compacting powders of relatively high bulk density, because of their greater tendency to exhibit disintegration and dispersion problems.
- Such tablets have the advantage that, as compared with a tablet derived from a low bulk density powder, a given dose of composition can be presented as a smaller tablet.
- the starting particulate composition may suitably have a bulk density of at least 400 g/l, preferably at least 500 g/l, and perhaps at least 600 g/l.
- Tableting machinery able to carry out the manufacture of tablets of the invention is known, for example suitable tablet presses are available from Fette and from Korch.
- Tableting may be carried out at ambient temperature or at a temperature above ambient which may allow adequate strength to be achieved with less applied pressure during compaction.
- the particulate composition is preferably supplied to the tableting machinery at an elevated temperature. This will of course supply heat to the tableting machinery, but the machinery may be heated in some other way also.
- the size of a tablet will suitably range from 10 to 160 grams, preferably from 15 to 60 g, depending on the conditions of intended use, and whether it represents a dose for an average load in a fabric washing or dishwashing machine or a fractional part of such a dose.
- the tablets may be of any shape. However, for ease of packaging they are preferably blocks of substantially uniform cross-section, such as cylinders or cuboids.
- the overall density of a tablet preferably lies in a range from 1040 or 1050g/l up to 1600g/l.
- the mixture was pumped into a sequence of 2 stainless steel tubes by a Maag Sinox P7 pump or a piston pump, type SIBa HK 05016SST4000M000 ex Prominent, Vleuten (NL). Both tubes were double jacketed.
- the first tube was 2.5m long and had an inner diameter of 73mm.
- the second tube was 1.5m long and had an inner diameter of 45mm.
- the tubes were connected by a 10cm long pipe.
- the mixture was pumped into the tubes at a temperature of 85°C at a throughput of 4 kg/hr.
- the first tube was cooled using a water bath at 40°C.
- the second tube was cooled using a 50:50 weight mixture of ethylene glycol and water.
- the coolant temperature was -15°C.
- the material coming out of the second tube had a temperature of about 20°C and was collected and divided into bars of around 0.5m.
- the bars can for example be cut into slices of 5 grammes each by using a laser cutting device (CO 2 laser) an acoustic knife (oscillating at 25kHz) a water jet (operating at 25000 psi and with a diameter of 0.1 mm).
- a laser cutting device CO 2 laser
- an acoustic knife oscillating at 25kHz
- a water jet operating at 25000 psi and with a diameter of 0.1 mm.
- a detergent powder was made of the following composition by pregranulating the granule ingredients, followed by post-dosing the rest of the ingredients Ingredient Parts by weight Granules Na-las 1.1 Nonionic 7EO 0.5 C12 soap 0.1 NaAc.3aq 0.3 Zeolite A24 2.4 Light soda ash 0.4 Moisture/minors 0.4 Post-dose EAG (17% silicone) 3.0 Fluorescer (15%) 2.2 STP 62.4 Na-disilicate (80%) 3.8 TAED (83%) 4.3 Percarbonate 16.9 Dequest 2047 1.9 Minors/ enzymes/colour to 100
- the tablets were made in 2 different ways:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Claims (10)
- Verfahren zur Herstellung einer eine glatte Phase umfassenden Reinigungstablette, wobei die Herstellung der glatten Phase den Schritt von Hochfrequenzschneiden oder Strahlschneiden eines Reinigungsmaterials umfasst.
- Verfahren nach Anspruch 1, wobei das Reinigungsmaterial 10 bis 90 Gewichtsprozent Nichtseifentenside und 0 bis 20 Gewichtsprozent Wasser umfasst.
- Verfahren nach Anspruch 1, wobei die Reinigungstablette eine glatte Einphasentablette mit einem Gewicht von 5 bis 200 g, bevorzugter 10 bis 100 g, besonders bevorzugt 15 bis 35 g, ist.
- Verfahren nach Anspruch 1, wobei die Reinigungstablette eine Mehrphasentablette ist, die eine glatte Phase als einen unterscheidbaren Bereich mit einem Gewicht von 2 bis 20 g, bevorzugter 3 bis 10 g, umfasst.
- Verfahren nach Anspruch 1, wobei die Hochfrequenzschneideverfahren aus Ultraschallschneiden und gerichtetem Energieschneiden ausgewählt sind.
- Verfahren nach Anspruch 5, wobei die Ultraschallschneidevorrichtung bei Frequenzen zwischen 10 und 50 kHz, bevorzugter 20 bis 40 kHz, arbeitet.
- Verfahren nach Anspruch 5, wobei das gerichtete Energieschneiden gerichtete Strahlen von Ultraschall oder Licht, vorzugsweise Laserlicht, anwendet.
- Verfahren nach Anspruch 1, wobei das Strahlschneiden die gerichtete Anwendung von Flüssigkeitsströmen, wie beispielsweise Wasser oder Propylenglycol, beinhaltet.
- Verfahren nach Anspruch 1, wobei das Strahlschneiden die gerichtete Anwendung von Gasströmen, wie beispielsweise Luft, Dampf oder Stickstoff, beinhaltet.
- Verfahren nach Anspruch 8 oder 9, wobei der Druck des Stroms 6,9 · 104 bis 6,9 · 105 kPa (10000 bis 100000 psi), bevorzugter 1,38 · 105 bis 5,52 · 105 kPa (20000 bis 80000 psi), besonders bevorzugt 2,07 · 105 bis 3,45 · 105 kPa (30000 bis 50000 psi), ist, und der Durchmesser der Ströme 0,025 mm bis 0,25 mm, bevorzugter 0,08 bis 0,20 mm, besonders bevorzugt 0,1 bis 0,15 mm, ist.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02079186A EP1418224B1 (de) | 2002-10-09 | 2002-10-09 | Verfahren zur Herstellung einer Reinigungsmitteltablette |
ES02079186T ES2254602T3 (es) | 2002-10-09 | 2002-10-09 | Procedimiento de produccion de una pastilla de limpieza. |
AT02079186T ATE315077T1 (de) | 2002-10-09 | 2002-10-09 | Verfahren zur herstellung einer reinigungsmitteltablette |
DE60208493T DE60208493T2 (de) | 2002-10-09 | 2002-10-09 | Verfahren zur Herstellung einer Reinigungsmitteltablette |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02079186A EP1418224B1 (de) | 2002-10-09 | 2002-10-09 | Verfahren zur Herstellung einer Reinigungsmitteltablette |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1418224A1 EP1418224A1 (de) | 2004-05-12 |
EP1418224B1 true EP1418224B1 (de) | 2006-01-04 |
Family
ID=32103932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02079186A Expired - Lifetime EP1418224B1 (de) | 2002-10-09 | 2002-10-09 | Verfahren zur Herstellung einer Reinigungsmitteltablette |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1418224B1 (de) |
AT (1) | ATE315077T1 (de) |
DE (1) | DE60208493T2 (de) |
ES (1) | ES2254602T3 (de) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014079690A1 (en) * | 2012-11-23 | 2014-05-30 | Unilever N.V. | A method of cutting cosmetic articles using pressurised fluid |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1669438B1 (de) | 2004-12-08 | 2007-10-17 | Unilever N.V. | Wasch- und Reinigungsmitteltablette |
DE602005014328D1 (de) | 2005-01-04 | 2009-06-18 | Unilever Nv | Wasch- und Reinigungsmittelformkörper |
EP1705241B1 (de) | 2005-03-23 | 2008-08-13 | Unilever N.V. | Körperförmige Wasch- oder Reinigungsmittelzusammensetzungen |
EP1705240A1 (de) | 2005-03-23 | 2006-09-27 | Unilever N.V. | Wasch- oder Reinigungsmitteltabletten |
EP1746152A1 (de) | 2005-07-20 | 2007-01-24 | Unilever N.V. | Wasch- oder Reinigungsmittel |
EP1746151A1 (de) | 2005-07-20 | 2007-01-24 | Unilever N.V. | Wasch- und Reinigungsmitteltabletten |
DE102010051226A1 (de) | 2010-11-12 | 2012-05-31 | Dental Care Innovation Gmbh | Ausspültablete mit abrasiven Bestandteilen |
US10626350B2 (en) * | 2015-12-08 | 2020-04-21 | Ecolab Usa Inc. | Pressed manual dish detergent |
CN110505867A (zh) | 2017-02-02 | 2019-11-26 | 洁碧有限公司 | 用于牙齿清洁的包括研磨剂的片剂 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4011170A (en) * | 1974-07-10 | 1977-03-08 | John Harlan Pickin | Marbled detergent bars |
GB9124762D0 (en) * | 1991-11-21 | 1992-01-15 | Unilever Plc | Food cutting process |
US5225098A (en) * | 1992-03-20 | 1993-07-06 | The Procter & Gamble Company | Neutral pH freezer bar and process |
JP2001524590A (ja) * | 1997-11-26 | 2001-12-04 | ザ、プロクター、エンド、ギャンブル、カンパニー | 洗剤タブレット |
ATE276350T1 (de) * | 1997-11-26 | 2004-10-15 | Procter & Gamble | Verfahren zur herstellung einer waschmitteltablette |
-
2002
- 2002-10-09 EP EP02079186A patent/EP1418224B1/de not_active Expired - Lifetime
- 2002-10-09 ES ES02079186T patent/ES2254602T3/es not_active Expired - Lifetime
- 2002-10-09 DE DE60208493T patent/DE60208493T2/de not_active Expired - Lifetime
- 2002-10-09 AT AT02079186T patent/ATE315077T1/de not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014079690A1 (en) * | 2012-11-23 | 2014-05-30 | Unilever N.V. | A method of cutting cosmetic articles using pressurised fluid |
Also Published As
Publication number | Publication date |
---|---|
ATE315077T1 (de) | 2006-02-15 |
DE60208493D1 (de) | 2006-03-30 |
DE60208493T2 (de) | 2006-07-06 |
ES2254602T3 (es) | 2006-06-16 |
EP1418224A1 (de) | 2004-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1382668B1 (de) | Waschmitteltabletten | |
EP1705241B1 (de) | Körperförmige Wasch- oder Reinigungsmittelzusammensetzungen | |
EP1147172B1 (de) | Waschmittelformkörper | |
EP1511834B1 (de) | Waschmitteltabletten | |
EP1669438B1 (de) | Wasch- und Reinigungsmitteltablette | |
EP1418224B1 (de) | Verfahren zur Herstellung einer Reinigungsmitteltablette | |
EP1405901B1 (de) | Waschmittel | |
EP1239029B1 (de) | Wasch- oder Reinigungsmittel | |
EP1405902A1 (de) | Wasch- und Reinigungsmittel | |
EP1375636B1 (de) | Waschmitteltabletten | |
EP1866403B1 (de) | Mehrfasige wäschebehandlungstabletten | |
EP1405900B1 (de) | Waschmittelzusammensetzungen | |
EP1845153A1 (de) | Waschmitteltabletten | |
EP1574563B1 (de) | Verwendung von Waschmitteltabletten | |
EP1371720B1 (de) | Waschmitteltabletten | |
US6310028B1 (en) | Water-softening and detergent compositions containing partially hydrated Na acetate | |
EP1491622B1 (de) | Waschmittel | |
EP1746151A1 (de) | Wasch- und Reinigungsmitteltabletten | |
EP1469061B1 (de) | Verfahren zur Herstellung Mehrphasiger Reinigungstabletten mit einer glatten Phase | |
EP1650290A2 (de) | Verfahren zur Herstellung von Reinigungsmitteltabletten | |
EP1705240A1 (de) | Wasch- oder Reinigungsmitteltabletten | |
EP1522575B1 (de) | Waschmittelzusammensetzungen | |
EP1496105B1 (de) | Waschmittelzusammensetzungen | |
EP1676904B1 (de) | Wasch- und Reinigungsmittelformkörper | |
EP1516916A1 (de) | Waschmittelzusammensetzung |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL LT LV MK RO SI |
|
17P | Request for examination filed |
Effective date: 20040325 |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNILEVER N.V. Owner name: UNILEVER PLC |
|
RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: UNILEVER N.V. Owner name: UNILEVER PLC |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAC | Information related to communication of intention to grant a patent modified |
Free format text: ORIGINAL CODE: EPIDOSCIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LI LU MC NL PT SE SK TR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: IT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20060104 Ref country code: CH Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: LI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 60208493 Country of ref document: DE Date of ref document: 20060330 Kind code of ref document: P |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060404 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060404 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060404 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060605 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2254602 Country of ref document: ES Kind code of ref document: T3 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
ET | Fr: translation filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061031 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20061031 Year of fee payment: 5 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20061005 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060405 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060104 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20071009 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20141029 Year of fee payment: 13 Ref country code: FR Payment date: 20141017 Year of fee payment: 13 Ref country code: ES Payment date: 20141027 Year of fee payment: 13 Ref country code: GB Payment date: 20141027 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20141027 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60208493 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20151009 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20160503 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151009 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151102 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20170130 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151010 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151031 |