WO1996011254A1 - Procede de production d'extrudats a effet detergent ou nettoyant - Google Patents
Procede de production d'extrudats a effet detergent ou nettoyant Download PDFInfo
- Publication number
- WO1996011254A1 WO1996011254A1 PCT/EP1995/003815 EP9503815W WO9611254A1 WO 1996011254 A1 WO1996011254 A1 WO 1996011254A1 EP 9503815 W EP9503815 W EP 9503815W WO 9611254 A1 WO9611254 A1 WO 9611254A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- weight
- extrudate
- acid
- extrudates
- zeolite
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005406 washing Methods 0.000 title abstract description 13
- 238000004140 cleaning Methods 0.000 title abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 238000000227 grinding Methods 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 17
- 238000007493 shaping process Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000012545 processing Methods 0.000 claims abstract description 13
- 229920003023 plastic Polymers 0.000 claims abstract description 5
- 239000004033 plastic Substances 0.000 claims abstract description 5
- 238000005520 cutting process Methods 0.000 claims abstract description 4
- 239000004014 plasticizer Substances 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000010457 zeolite Substances 0.000 claims description 38
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 24
- 239000000194 fatty acid Substances 0.000 claims description 24
- 229930195729 fatty acid Natural products 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 18
- 239000008187 granular material Substances 0.000 claims description 11
- 239000000428 dust Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 5
- 239000010419 fine particle Substances 0.000 claims description 3
- 239000000314 lubricant Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 3
- 239000012748 slip agent Substances 0.000 abstract 1
- 229910021536 Zeolite Inorganic materials 0.000 description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 32
- -1 olefin sulfonates Chemical class 0.000 description 29
- 239000002253 acid Substances 0.000 description 17
- 102000004190 Enzymes Human genes 0.000 description 13
- 108090000790 Enzymes Proteins 0.000 description 13
- 229940088598 enzyme Drugs 0.000 description 13
- 150000002191 fatty alcohols Chemical class 0.000 description 12
- 239000002736 nonionic surfactant Substances 0.000 description 12
- 239000007844 bleaching agent Substances 0.000 description 11
- 108091005804 Peptidases Proteins 0.000 description 10
- 239000004365 Protease Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 10
- 239000012459 cleaning agent Substances 0.000 description 10
- 239000000344 soap Chemical class 0.000 description 10
- 239000003112 inhibitor Substances 0.000 description 9
- 239000003760 tallow Substances 0.000 description 9
- 239000003945 anionic surfactant Substances 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 102000004882 Lipase Human genes 0.000 description 6
- 239000004367 Lipase Substances 0.000 description 6
- 108090001060 Lipase Proteins 0.000 description 6
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 235000019421 lipase Nutrition 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 108010059892 Cellulase Proteins 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- 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 5
- 239000004115 Sodium Silicate Substances 0.000 description 5
- 229940106157 cellulase Drugs 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 5
- 235000019419 proteases Nutrition 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 4
- 235000013162 Cocos nucifera Nutrition 0.000 description 4
- 102000035195 Peptidases Human genes 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 238000006277 sulfonation reaction Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004382 Amylase Substances 0.000 description 3
- 102000013142 Amylases Human genes 0.000 description 3
- 108010065511 Amylases Proteins 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 3
- 235000019418 amylase Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 235000019351 sodium silicates Nutrition 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 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 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 239000004200 microcrystalline wax Substances 0.000 description 2
- 235000019808 microcrystalline wax Nutrition 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- 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 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical class CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- REJHVSOVQBJEBF-OWOJBTEDSA-N 5-azaniumyl-2-[(e)-2-(4-azaniumyl-2-sulfonatophenyl)ethenyl]benzenesulfonate Chemical class OS(=O)(=O)C1=CC(N)=CC=C1\C=C\C1=CC=C(N)C=C1S(O)(=O)=O REJHVSOVQBJEBF-OWOJBTEDSA-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
- DHMQDGOQFOQNFH-UHFFFAOYSA-M Aminoacetate Chemical compound NCC([O-])=O DHMQDGOQFOQNFH-UHFFFAOYSA-M 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 241000193422 Bacillus lentus Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910003544 H2B4O7 Inorganic materials 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 108090000787 Subtilisin Proteins 0.000 description 1
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 1
- UAOKXEHOENRFMP-ZJIFWQFVSA-N [(2r,3r,4s,5r)-2,3,4,5-tetraacetyloxy-6-oxohexyl] acetate Chemical compound CC(=O)OC[C@@H](OC(C)=O)[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](OC(C)=O)C=O UAOKXEHOENRFMP-ZJIFWQFVSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229960002645 boric acid Drugs 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 229920003064 carboxyethyl cellulose Polymers 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 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
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 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
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 239000003248 enzyme activator Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PMYUVOOOQDGQNW-UHFFFAOYSA-N hexasodium;trioxido(trioxidosilyloxy)silane Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])O[Si]([O-])([O-])[O-] PMYUVOOOQDGQNW-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- SXLLDUPXUVRMEE-UHFFFAOYSA-N nonanediperoxoic acid Chemical compound OOC(=O)CCCCCCCC(=O)OO SXLLDUPXUVRMEE-UHFFFAOYSA-N 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004967 organic peroxy acids Chemical class 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical class OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 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
- 235000019353 potassium silicate Nutrition 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- BXNRKCXZILSQHE-UHFFFAOYSA-N propane-1,2,3-triol;sulfuric acid Chemical class OS(O)(=O)=O.OCC(O)CO BXNRKCXZILSQHE-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 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
- 239000000600 sorbitol Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical class CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 239000002888 zwitterionic surfactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- 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
- C11D11/00—Special methods for preparing compositions containing mixtures of detergents
- C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
Definitions
- the invention relates to a method for producing known extrudates which are active in washing and cleaning.
- the invention accordingly relates to a process for the production of extrudates with high density which are active in washing or cleaning, a homogeneous, solid and free-flowing premix which has been produced with the addition of a plasticizer and / or lubricant being extruded at high pressures of up to 200 bar and the strand after exiting the hole shape is cut to the predetermined granule size by means of a cutting device, the still plastic, moist raw extrudate is optionally fed to a further shaping processing step and then dried.
- dry powders are added as powdering agents either during the drying step or immediately before the crude extrudate is transferred to the dryer, but in any case after the shaping processing step which may have been carried out.
- finely divided dry powders which are common ingredients of detergents or cleaning agents, are suitable as powdering agents.
- Zeolites in particular zeolites of type A and / or P, silicas, in particular microfine, silanized silica, salts of fatty acids, in particular calcium stearate, finely divided alkyl sulfates, neutral salts, in particular sodium sulfate, or mixtures of these, are preferred, mixtures of zeolite and Silicas or mixtures of zeolite and calcium stearate or mixtures of zeolite, silicas and calcium stearate are particularly preferred.
- the further shaping processing step after the extrusion is carried out in a rounding device. It is then further preferred that after the completion of the shaping processing step, at least partially dust or fine particles which have accumulated during the shaping processing step are used as the powdering agent.
- the amount of dust or fine fraction which is used as the powdering agent should advantageously not exceed 5% by weight, in particular 3% by weight, based in each case on the extrudate still to be dried.
- the powdering agents can be used in amounts of up to about 8% by weight. Depending on the recipe, however, in the preferred cases 0.2 to 5% by weight, based on the extrudate to be dried, of powdering agent is sufficient to prevent the extrudates from sticking together in the drying step. Amounts in excess of this are therefore not preferred.
- powdering agents both before and during the drying step, it being preferred to use a maximum of 50% by weight, based on the powdering agent, before the drying step.
- powdering agents during the further shaping processing step. It is only essential to the invention that further powdering agents are added in the manner according to the invention after the rounding step.
- the premix is preferably fed continuously to a 2-screw extruder with a co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extruder temperature.
- the premix is compressed, plasticized, in the form of fine strands by means of pressure, which is preferably at least 25 bar, but at extremely high throughputs depending on the apparatus used Hole die plate extruded in the extruder head and finally reduced the extrudate by means of a rotating knives preferably to approximately spherical to cylindrical granules.
- the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
- granules of an essentially uniformly predeterminable particle size can be produced, and in particular the absolute particle sizes can be adapted to the intended use. In general, particle diameters of up to at most 0.8 cm are preferred.
- Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
- the length / diameter ratio of the chipped primary extrudates (crude extrudates) is in an important embodiment in the range from about 1: 1 to about 3: 1.
- the extrudates are then fed to a drying step, for example a fluidized bed dryer.
- the extruded granules which contain peroxy bleaching agents, for example perborate monohydrate, can be dried at supply air temperatures between 80 and 150 ° C. without loss of active oxygen.
- the premix can contain all the usual ingredients of detergents or cleaning agents, such as anionic, nonionic, cationic, amphoteric or zwitterionic surfactants, inorganic and organic builders, alkali carbonates and alkali silicates, bleaches, optical brighteners, graying inhibitors and, if appropriate, foam inhibitors, bleaching enzymes, enzyme activators, Textile calibrating substances, dyes and fragrances and neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- Preferred surfactants of the sulfonate type are Cg-Ci3-alkylbenzenesulfonates, olefin sulfonates, dg mixtures of alkene and hydroxyalkalsulfonates and disulfonates, such as are obtained, for example, from Ci2-Ci8 * monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, or the disalts of the corresponding ⁇ -sulfofatty acids.
- Other suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
- the sulfonation products represent a complex mixture which contains mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
- sulfonated fatty acid salts, glyceride sulfates, glycerine sulfates, glycerin and soaps are formed. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol esters, the proportion of the ⁇ -sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.
- Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
- the alk (en) yl sulfates here are the sulfuric acid half-esters of the C 16 -C 16 -alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from the corresponding oxo alcohols, and those secondary alcohols of this chain length prefers.
- alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and have an analogous degradation behavior like the appropriate compounds based on fettchemis raw materials.
- Ci6-Cj8-Alk (en) ylsul are particularly preferred from the point of view of washing technology.
- the alk (en) yl sulfates and, in particular, tallow fatty alkyl sulfates can be introduced into the Ver in any form.
- Powders, pastes, granular compounds, for example, are also conceivable, for example those which are likewise obtained according to the L of the international patent application WO-A-93/04162.
- D granular compounds are preferred which have a high content of alkyl sulfates, in particular a content of above 70% by weight of alkyl sulfates.
- detergents or cleaning agents are prepared which contain 5 to% by weight of C8-Ci8-alk (en) yl sulfates and preferably Ci2-Ci8-alk (en) yl sulfate.
- Soaps in particular in quantities of 0.5 to 5% by weight, are particularly suitable as further anionic components.
- Suitable fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, P mitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap genes.
- the anionic surfactants and soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mon di- or triethanola in.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of sodium salts.
- Preferred detergents or cleaning agents contain 5 40% by weight of surfactants, which may optionally consist entirely of anionic surfactants and in particular of alk (en) yl sulfates of the type specified above and in the amounts specified above.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably up to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per alcohol, in which the alcohol radical can be linear or preferably methyl-branched or linear and can contain methyl-branched Re in the mixture, as is usually the case in oxo alcohols O 96/11254 PCI7EP95 / 0
- alcohol ethoxyates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- Preferred ethoxylated alcohols include, for example, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn-Alkonol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Ci4 alcohol rr 3 EO and Ci2-Ci8 alcohol with 5 EO.
- ide represent statistical averages, which can be a whole for a special Prouukt or a broken Zah '.
- Preferred alcohol ethoxylates have a narrow homolc distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, C. -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycos and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid of the formula (I),
- the polyhydroxy fatty acid ides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the preferred polyhydroxy fatty acid amides are fatty acid N-alkylglucamides.
- Preferred washing or cleaning agents contain 2 to 25% by weight of non-ionic surfactants.
- embodiments can be advantageous which contain anionic and nonionic surfactants in a weight ratio of 2: 1 to 1: 2 and in particular around 1: 1 to 1: 1.5.
- the nonionic surfactants and in particular ethoxylated fatty alcohols are used in combination with constituents which improve the solubility of the extrudates.
- constituents which improve the solubility of the extrudates are described, for example, in international patent applications WO-A-93/02176 and WO-A-93/15180.
- the preferred ingredients include, in particular, fatty alcohols with 20 to 80 moles of ethylene oxide per mole of fatty alcohol, for example tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0, but also fatty alcohols with for example 14 E0 and polyethylene glycols with a relative molecular weight between 200 and 2000 .
- Phosphates and in particular zeolites are suitable as builder substances.
- the fine-crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
- zeolite X or P and mixtures of A, X and / or P are also suitable.
- the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
- the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite ethoxylated Ci2-Ci8 fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 ⁇ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the formula Na Si ⁇ 2 ⁇ + ⁇ * yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline sheet silicates are those in which M represents sodium and x assumes the values 2 or 3.
- both ⁇ - and Üf sodium disilicate Na2Si2 ⁇ 5 * yH2 ⁇ are preferred.
- Washing or cleaning agents which are preferably produced contain 15 to 60% by weight, in particular at least 20% by weight, of inorganic builder substances of the type specified above.
- Useful organic builders are, for example, preferably in the form of their sodium salts polycarboxylic acids used, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such a r domestic set for ecological reasons not objectionable , as well as mixed: n from these.
- Preferred salts are the salts of the polycarboxylic acids wit tronic acid, adipic acid, succinic acid, glutaric acid, tartaric acid, zuc acids and mixtures of these.
- Their content in the washing / cleaning agents is preferably 0 to 20% by weight.
- the polycarboxylic acids, in particular citric acid can also be used in highly toxic agents. AO
- Suitable polymeric polycarboxylates are, for example, the sodium salt of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
- Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which have 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable contain.
- Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution, 2 to 55% by weight. % aqueous solutions are preferred. Also particularly preferred are biodegradable terpolymers or quadropolymers, for example those which, according to DE-A-4300772, are salts of acrylic acid and de-maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives or DE-C-4221 381 are monomers of acrylic acid salts and the 2-A1 contain kylallylsulfonic acid as well as sugar derivatives.
- the content of (co) polymeric polycarboxylates in the middle is preferably 2 to 8% by weight.
- polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
- Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures thereof;
- alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
- the content of sodium carbonate in the agent is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
- the content of sodium silicate in the compositions is generally up to 15% by weight and preferably between 2 and 10% by weight.
- the alkali silicates into the process at least partially in the form of an aqueous solution, for example in the form of a 10 to 45% by weight aqueous water glass solution.
- alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and amino acids and / or their salts.
- the alkali metal carbonates it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.
- the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
- Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing H2O2, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
- the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
- bleach activators can be incorporated into the preparations.
- N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
- Other known bleach activators are cetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239.
- the content of lead activators in the bleach-containing compositions is in the customary range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
- bleach activators are N, N, N '.N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dicxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitoi-mannitol mixtures (S0RMAN).
- TAED N, N, N '.N'-tetraacetylethylene diamine
- DADHT 1,5-diacetyl-2,4-dicxo-hexahydro-1,5,5-triazine
- S0RMAN acetylated sorbitoi-mannitol mixtures
- a reduced foaming power which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. of sulfates and / or sulfonates with nonionic surfactants and / or with soaps.
- surfactants e.g. of sulfates and / or sulfonates
- nonionic surfactants and / or with soaps the foam-suppressing effect increases with the degree of saturation and the C number of the fatty acid residue.
- Soaps of natural or synthetic origin that contain a high proportion of Ci8-C24 fatty acids are therefore suitable as foam-inhibiting soaps.
- Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.
- the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
- Enzymes from the class of proteases, lipases, aylases, Ce11ulases or mixtures thereof are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniform and Strepto yces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
- Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
- Peroxides or oxidases have also proven to be suitable in some cases.
- the enzymes can be adsorbed on carriers and / or embedded in Hü11 substances to protect them against premature decomposition.
- the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
- the salts of polyphosphonic acids come as stabilizers, in particular for per-compounds and enzymes.
- Phonic acid (HEDP) and Diethylerr iaminpentamethylenphosphonat into consideration. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
- boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H2B4O7), is particularly advantageous.
- Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed onto the fiber.
- water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid ester cellulose or starch. Also contain water-soluble, acidic groups.
- de Polyamides are suitable for this purpose.
- soluble starch preparations and starch products other than those mentioned above can be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
- cellulose ethers such as carboxyethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrole, for example in amounts of 0.1 to 5% by weight, based on the Means used.
- the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which contain an replace the morpholino group with a diethanola ino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
- the type of the substituted diphenylstyryls can be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro- J- sulfostyryl) diphenyl , or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
- Mixtures of the aforementioned brighteners can also be used.
- premixes which contain 10 to 30% by weight and in particular 15 to 25% by weight of anionic and nonionic surfactants, 20 to 40% by weight of zeolite, 2 to 15% by weight of sodium carbonate, 0 to 10% by weight sodium citrate, 1 to 5% by weight polymeric polycarboxylates and 0 to 20% by weight peroxy bleaching agent.
- the finished washing or cleaning agents can be built up uniformly from extrudates which have the above-mentioned ingredients.
- the extrudates are prepared with further ingredients of washing or cleaning agents. This can be such that the washing or cleaning agents are obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component.
- Bleach activators for example N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine, enzyme granules containing enzymes, in particular protease and / or lipase and / or cellulase and / or amylase, are preferred, blends consisting of 2 or 3 enzymes can be particularly advantageous, and perfume added afterwards.
- N, N'-tetraacylated diamines such as N, N, N ', N'-tetraacetylethylenediamine
- enzyme granules containing enzymes in particular protease and / or lipase and / or cellulase and / or amylase
- blends consisting of 2 or 3 enzymes can be particularly advantageous, and perfume added afterwards.
- the extrudates can also be prepared with further finely divided dry powders before enzymes and the other ingredients are added.
- examples include zeolite, silicas and salts of fatty acids, for example calcium stearate, bleach activator or mixtures of zeolite with one of the other powders mentioned.
- the foaming behavior for detergents can be positively influenced if the foam inhibitor, for example organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide, at least in part is not extruded, but is subsequently mixed with the extrudate.
- the surface of the extrudate according to the invention is first covered, for example, with zeolite or a zeolite-containing mixture and then with a foam inhibitor. Such measures make it possible to further improve the flushing behavior of the extrudates.
- the bulk density of the extrudates produced according to the invention is preferably between 600 and 1200 g / 1, bulk densities between 700 and 1000 g / 1 and in particular between 750 and 950 g / 1 being particularly preferred.
- a premix was prepared which was 7 parts by weight of alkylbenzenesulfonate and 6.5 parts by weight of C12-Ci8-alkyl sulfate. 2 parts by weight of Ci2-Ci8 fatty acid soap, 9 parts by weight of with 5 ethylene oxide groups, 37 parts by weight of zeolite, based on anhydrous active substance, 7.5 parts by weight of sodium citrate, 5.4 parts by weight of copolymeric salt of acrylic acid and maleic acid, 7 parts by weight .-% parts of sodium carbonate, 2 parts by weight of sodium sulfate, 0.4 parts by weight of salts from solutions and 11.2 parts by weight of water.
- V4 Zeolite 5.5 Rounder does not stick 0.0 before dryer 0.0 in dryer
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)
Abstract
L'invention concerne un procédé d'extrusion pour produire des extrudats à effet détergent ou nettoyant, qui ont une masse volumique élevée. Un prémix homogène, solide et coulant, obtenu par adjonction d'un plastifiant et/ou d'un lubrifiant, est soumis à des pressions élevées allant jusqu'à 200 bar pour former un jonc. A sa sortie de la filière, le jonc est découpé à l'aide d'un dispositif de coupe, à la dimension de granulé prédéterminée. L'extrudat brut humide à l'état encore plastique est éventuellement acheminé jusqu'à une autre étape de traitement de formage, puis est séché. Une éventuelle adhérence de l'extrudat au cours du séchage peut être réduite par adjonction de poudres sèches faisant office d'agents de poudrage soit pendant le séchage, soit directement avant le transfert de l'extrudat brut dans le sécheur, en tout cas, après que l'éventuelle étape de formage ait été accomplie.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4435742.7 | 1994-10-06 | ||
DE19944435742 DE4435742A1 (de) | 1994-10-06 | 1994-10-06 | Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1996011254A1 true WO1996011254A1 (fr) | 1996-04-18 |
Family
ID=6530116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1995/003815 WO1996011254A1 (fr) | 1994-10-06 | 1995-09-27 | Procede de production d'extrudats a effet detergent ou nettoyant |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE4435742A1 (fr) |
WO (1) | WO1996011254A1 (fr) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6169899A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
WO1991002047A1 (fr) * | 1989-08-09 | 1991-02-21 | Henkel Kommanditgesellschaft Auf Aktien | Fabrication de granules comprimes pour produits de lavage |
WO1994001526A1 (fr) * | 1992-07-02 | 1994-01-20 | Henkel Kommanditgesellschaft Auf Aktien | Preparation detergente solide ayant un meilleur comportement au rinçage |
DE4235646A1 (de) * | 1992-10-22 | 1994-04-28 | Henkel Kgaa | Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate |
-
1994
- 1994-10-06 DE DE19944435742 patent/DE4435742A1/de not_active Withdrawn
-
1995
- 1995-09-27 WO PCT/EP1995/003815 patent/WO1996011254A1/fr active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6169899A (ja) * | 1984-09-14 | 1986-04-10 | 花王株式会社 | 流動性の改良された高密度の粒状洗剤の製法 |
WO1991002047A1 (fr) * | 1989-08-09 | 1991-02-21 | Henkel Kommanditgesellschaft Auf Aktien | Fabrication de granules comprimes pour produits de lavage |
WO1994001526A1 (fr) * | 1992-07-02 | 1994-01-20 | Henkel Kommanditgesellschaft Auf Aktien | Preparation detergente solide ayant un meilleur comportement au rinçage |
DE4235646A1 (de) * | 1992-10-22 | 1994-04-28 | Henkel Kgaa | Verfahren zur Herstellung wasch- und reinigungsaktiver Extrudate |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Section Ch Week 8621, Derwent World Patents Index; Class A81, AN 86-133906 * |
Also Published As
Publication number | Publication date |
---|---|
DE4435742A1 (de) | 1996-04-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0746599A1 (fr) | Produit de lavage a adjuvants au silicate amorphes | |
EP0665879B1 (fr) | Procede de preparation d'extrudats a action lavante et nettoyante | |
WO1996006156A1 (fr) | Procede de production de produits de lavage et de nettoyage en comprimes | |
EP0804529B1 (fr) | Compose silicate alcalin amorphe | |
EP0674700B1 (fr) | Detergents et nettoyants granulaires a haute teneur en tensioactifs | |
EP0814152A2 (fr) | Procédé de préparation des détergents solides | |
EP0828818A1 (fr) | Produit de lavage ou detergent en granules a densite en vrac elevee | |
EP0724620B1 (fr) | Procede de production d'extrudes de lavage ou de nettoyage a pouvoir ameliore de redispersion | |
EP0793708B1 (fr) | Procede de preparation par extrusion d' agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles | |
EP0840780B1 (fr) | Produit granule de lavage ou de nettoyage a masse volumique apparente elevee | |
EP0746601B1 (fr) | Produit detergent ou nettoyant granulaire | |
WO1995000629A1 (fr) | Procede de fabrication de produits d'extrusion ayant un effet nettoyant et detergent | |
EP0845028B1 (fr) | Procede de production d'un silicate alcalin amorphe soumis a une impregnation | |
EP0814149A2 (fr) | Procédé de préparation des détergents solides | |
WO1996011254A1 (fr) | Procede de production d'extrudats a effet detergent ou nettoyant | |
EP0711338A1 (fr) | Procede de fabrication d'un produit extrude a activite detergente ou nettoyante | |
DE19644591A1 (de) | Verfahren zur Herstellung enzym- und bleichmittelhaltiger Wasch- und Reinigungsmittel | |
WO1994009110A1 (fr) | Procede de fabrication d'un detergent-nettoyant granulaire | |
DE19752388A1 (de) | Verfahren zur Herstellung von Wasch- und Reinigungsmitteln mit hoher Schüttdichte | |
WO1997018290A1 (fr) | Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CZ FI HU JP KR PL SK US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
122 | Ep: pct application non-entry in european phase |