EP0871697A1 - Method of producing granular washing or cleaning agents or components therefor - Google Patents
Method of producing granular washing or cleaning agents or components thereforInfo
- Publication number
- EP0871697A1 EP0871697A1 EP96943030A EP96943030A EP0871697A1 EP 0871697 A1 EP0871697 A1 EP 0871697A1 EP 96943030 A EP96943030 A EP 96943030A EP 96943030 A EP96943030 A EP 96943030A EP 0871697 A1 EP0871697 A1 EP 0871697A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- granules
- acid
- premix
- cleaning agents
- 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.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000012459 cleaning agent Substances 0.000 title claims description 18
- 238000005406 washing Methods 0.000 title claims description 10
- 239000008187 granular material Substances 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 63
- 230000008569 process Effects 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 5
- 239000003599 detergent Substances 0.000 claims description 39
- 239000004094 surface-active agent Substances 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 239000000470 constituent Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 230000036961 partial effect Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000000306 component Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- -1 alkyl sulfate compound Chemical class 0.000 description 22
- 239000000314 lubricant Substances 0.000 description 22
- 239000004014 plasticizer Substances 0.000 description 20
- 239000010457 zeolite Substances 0.000 description 19
- 229910021536 Zeolite Inorganic materials 0.000 description 18
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 18
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 150000002191 fatty alcohols Chemical class 0.000 description 14
- 239000007844 bleaching agent Substances 0.000 description 13
- 239000003945 anionic surfactant Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002736 nonionic surfactant Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000004753 textile Substances 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 10
- 150000001298 alcohols Chemical class 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 108090000790 Enzymes Proteins 0.000 description 8
- 102000004190 Enzymes Human genes 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229940088598 enzyme Drugs 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 229920002472 Starch Polymers 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000003112 inhibitor Substances 0.000 description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 7
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- 239000000344 soap Substances 0.000 description 7
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
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- 229910019142 PO4 Inorganic materials 0.000 description 5
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- 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 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 102000035195 Peptidases Human genes 0.000 description 4
- 108091005804 Peptidases Proteins 0.000 description 4
- 239000004365 Protease Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
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- 238000009826 distribution Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 3
- 235000013162 Cocos nucifera Nutrition 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000013530 defoamer Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 150000004682 monohydrates Chemical class 0.000 description 3
- 229940055577 oleyl alcohol Drugs 0.000 description 3
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 150000003871 sulfonates Chemical class 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 229940120146 EDTMP Drugs 0.000 description 2
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 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 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000004435 Oxo alcohol Substances 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 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
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000001083 [(2R,3R,4S,5R)-1,2,4,5-tetraacetyloxy-6-oxohexan-3-yl] acetate Substances 0.000 description 2
- 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 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 239000011324 bead Substances 0.000 description 2
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- 239000001913 cellulose Substances 0.000 description 2
- 239000003240 coconut oil Substances 0.000 description 2
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- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical class CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 2
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 2
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- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
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- 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
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 108010005400 cutinase Proteins 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 235000011180 diphosphates Nutrition 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
- 238000006073 displacement reaction Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 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
- 239000000428 dust Substances 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical class COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 235000019426 modified starch 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
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 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
- 229920005615 natural polymer Polymers 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
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 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
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 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
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 235000019351 sodium silicates Nutrition 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
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length
-
- 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
-
- 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
Definitions
- the invention relates to a process for the production of almost spherical to cylindrical detergent or cleaning agent granules or components therefor, in which a gear pump is used, granules and detergents and cleaning agents thus obtainable.
- a process for the production of compacted granules of ingredients of detergents or cleaning agents is known.
- the granules are obtained from premixes of at least partially solid ingredients with the addition of water-soluble, water-emulsifiable or water-dispersible plasticizers and / or lubricants, which are processed to a homogeneous mass and at high pressures between 25 and 200 bar via perforated shapes Opening widths of the predetermined granule dimension are pressed in a rope shape.
- Conventional granulating devices for example pellet presses, extruders with one or two shafts, planetary roller extruders and other apparatus, can be used as the homogenizing device.
- a continuously operating twin-screw extruder is preferred.
- the premix, plasticized in the extruder emerges in the form of fine strands through a perforated die plate.
- the extrudate is then comminuted to almost spherical to cylindrical granules by means of a rotating knock-off knife, and these still plastic primary granules are preferably rounded off in a conventional rounding device, possibly with the use of small amounts of dry powder.
- further active ingredients in particular temperature-sensitive formulation constituents, can be added to the optionally dried-on granules, sprayed on and / or mixed in as a separately formed grain to form a multigrain mixture.
- the extrusion is carried out through a circular plate provided with nozzle bores.
- the hole nozzles can be arranged vertically or horizontally.
- the fine strands of about 0.5 to 5 mm, typically from 0.8 mm to 2.0 mm in diameter emerging through the hole shapes are converted in a hot cut from a single- or multi-bladed rotating cutter head into almost spherical to cylindrical granules crushed.
- the knife edges of the knock-off device either lie on the nozzle plate with a low contact pressure or form a gap with the plate which is very small compared to the diameter of the perforated nozzles.
- the homogeneous and solid, free-flowing premix must be of such a consistency that it is plastically softened and extrudable under the pressure or under the entry of specific work, but at the time of the exit from the hole shape, at which no shear forces on the system act, the viscosity of the system suddenly decreases so that the extruded strand can be cut and cut to predetermined dimensions.
- a disadvantage of this method is that energy losses occur in the form of temperature increases under the high working pressure, so that the extruder housing, including the extruder pelletizing head, normally has to be cooled in order to prevent the viscosity of the premix already during the extrusion sinks so much that an actual extrusion is no longer possible. Excessive temperature increases also lead to the fact that temperature-sensitive ingredients, for example bleaching agents such as perborate or percarbonate, could not be used without cooling the housing.
- temperature-sensitive ingredients for example bleaching agents such as perborate or percarbonate
- the object was therefore to modify the process described above in such a way that the premix can be pressed under more gentle conditions, for example also at lower pressures or without cooling, without the cutting ability of the extruded strands being lost after it emerges from the hole shape, or these high pressures can only be built up for a short time.
- This object is achieved according to the invention by a process for producing granular detergents or cleaning agents or components therefor, a plastifiable and solid, free-flowing premix being pressed by hole molds and a gear pump being connected upstream of these hole molds.
- Gear pumps of this type are commercially available. For example, they can be purchased from Witte GmbH, Federal Republic of Germany.
- the gear pumps used in the production process of granular detergents or cleaning agents according to the invention are generically a rotating displacement pump Depending on the viscosity of the material to be carried through, a throughput of 0.1 to 300 m 3 per hour, but preferably 1 to 20 m 3 per hour, can usually be achieved.
- the temperature in the gear pump can also be varied over wide ranges, for example from 0 ° C. to about 300 ° C, but it is preferably operated at usual operating temperatures of 30 to 70 ° C.
- the pre-mix to be compressed, plasticized, solid and free-flowing can either be drawn in directly or, for example, pre-plastified in an extruder upstream of the gear pump
- the premix does not remain in the gear pump and does not experience any mechanical energy input, but a plasticized premix is still required for the pressing, the plastification of the premix (material supply) must take place before the supply to the gear wheels.
- This plasticizing can be carried out using customary and known methods, for example in mixers, extruders, stuffing screws or devices made from mixers and kneaders
- a pressure of 6 to 200 bar, preferably 30 to 120 bar builds up within the gearwheels.
- the residence time of the premix to be pressed is only 1/10 to 1/3 of the time in the range of the aforementioned high pressure and the aforementioned temperature before the perforated plate, as is required according to the teaching of EP 486 592
- the knock-off device, in particular a doctor blade, at the outlet of the gear pump produces a granulate size of 0.5 to 10 mm, preferably 1 to 5 mm.
- the premix consists at least in part of solid, preferably finely divided, customary ingredients of detergents and cleaning agents, to which liquid constituents may have been added.
- the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
- liquid ingredients are added, if appropriate, and the plasticizer and / or lubricant selected according to the invention is then mixed in.
- aids are of polyfunctional importance in the context of the present invention.
- they enable the formation of the primary granulate granule by causing the premix to be converted into a mass pressed under high pressure and, if desired, subsequent subsequent shaping processing, which in particular results from the rounding off of the primary mär formed granules.
- they contribute to the stabilization of the granules, they maintain its predetermined spatial shape, in particular when mixing with other components, if necessary, during filling, during transport and storage of the granules, and in particular prevent the formation of undesirable, dust-like components.
- the auxiliaries discussed here can have an intrinsic effect in the washing and cleaning process, in particular in interaction with other mixture components.
- the plasticizers and / or lubricants used as auxiliaries can be solid, flowable, gel-like or pasty at room temperature without the need to use an additional liquid phase.
- Preferred plasticizers and / or lubricants are preparations based on surfactant components and / or on the basis of water-soluble or water-emulsifiable or water-dispersible polymer compounds. Examples of a plasticizer and / or lubricant which can be used without the use of an additional Liquid phase can be used, numerous types of the non-ionic surfactants commonly used in detergents and cleaning agents.
- Substances with a low melting point e.g. higher molecular weight polyethylene glycol ethers with molecular weights between 4,000 and 20,000
- plasticizers and / or lubricants which are solid at room temperature.
- plasticizers and / or lubricants are used which have been produced using limited amounts of auxiliary liquids.
- Organic liquid phases which are water-soluble or water-miscible are preferred here.
- aqueous preparations of the plasticizers and / or lubricants are preferred.
- the surfactants and / or polymer compounds used as plasticizers and / or lubricants are advantageously introduced into the process in such a concentrated form that the nature of the plastic, smoothly compressible mass can be adjusted even in small amounts of these auxiliaries.
- the pastes are preferably used in amounts not exceeding 12% by weight, in particular in amounts between 0.5 and 10% by weight, and with particular advantage between 3 and 8% by weight, based on the total mixture set. At least 30% by weight, preferably 40% by weight pastes and gels are particularly suitable.
- surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used.
- the present invention takes advantage of the fact that, in particular, these highly concentrated, aqueous surfactant mixtures show a state that can be described as a pasty or gel-like preparation form with a lubricant character.
- the surfactant components thus introduced form cover and intermediate layers which act like binders and which are jointly responsible for the grain cohesion.
- Anionic surfactant salts in particular sulfates and sulfonates, from the wide range of compounds proposed here for detergents and cleaners, optionally in admixture with customary, nonionic compounds, can be of particular importance.
- a mixture of at least two solid components spray-dried granulate / fatty alkyl sulfate compound
- sodium perborate monoohydrate and / or tetrahydrate
- a corresponding carrier bead can also be used instead of the fatty alkyl sulfate compound as described in European patent 0486592 B1.
- APG alkyl polyglycoside
- R is a primary straight-chain or in 2- Position means methyl-branched, aliphatic radical having 8 to 22, preferably 8 to 18 carbon atoms
- G is a symbol, which stands for a glycose unit with 5 or 6 carbon atoms
- the degree of oligomerization x is between 1 and 10.
- plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C 8 to C 18 fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated Fatty alcohol: water in the ratio of (0.5 - 1): 1: (1, 5 - 1), the content of APG in this case being calculated as an active substance and not as a paste.
- polymer compounds in numerous detergents and cleaning agents is common today, since the polymer compounds act, for example, as builders with the ability to bind the water hardness.
- polymers containing carboxyl groups which may be present in the salt form, for example as an alkali salt, such as the sodium or potassium salts of homopolymeric or copolymeric polycarboxylates, for example polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 10% maleic acid.
- the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
- Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, methyl esters, acrylamide and methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
- vinyl ethers such as vinyl methyl ethers, methyl esters, acrylamide and methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
- polymer compounds are also used to improve the dirt-carrying capacity of the aqueous washing liquor. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).
- aqueous preparation forms of these polymer compounds are distinguished by a pronounced lubricating character which gives the decisive processing aid in the processes according to the invention.
- these polymer components dry in the inventive Formation of the granulate to polymer films, which on the one hand promote the connection of the grain, on the other hand easily change back to the state of the solution or emulsification or dispersion when aqueous media are added. It is particularly preferred to use from 3 to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular a copolymer of acrylic acid and maleic acid in water as a plasticizer and / or lubricant. Mixtures of these polymer solutions and the surfactant, in particular anionic surfactant, plasticizers and / or lubricants are also advantageous.
- liquid phase (s) are used that, when mixed simply, a free-flowing, powdery structure of the premix is retained even after the addition of the plasticizer and / or lubricant.
- the content of the respective substance mixture in free water which is not bound as crystal water or in a comparable form is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to in this processing stage 8% by weight. Included in this amount is the amount of water that is entered via the plasticizing aids with a lubricating character. If desired, further solids can also be added to the premix after the addition of the plasticizer and / or lubricant. The total mass is briefly mixed in, a solid, free-flowing premix being obtained which is suitable for feeding the gear pump used according to the invention.
- the granules can then be fed to a rounding step as in international patent application WO-A-91/02047.
- Usual rounding devices such as Marumerizer, but also sieve mills, as are commercially available from Bepex GmbH, for example, can be used here.
- Sieve mills of this type have the advantage that any coarse-grained fractions that may have occurred are reduced to a maximum grain size limit and the fractions of finer granules that are produced in this way can likewise be returned to the premix.
- the finally formed granulate is preferably fed to a drying step, for example a fluidized bed dryer, in which correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C. but then not be exceeded.
- a drying step for example a fluidized bed dryer, in which correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C. but then not be exceeded.
- the product is cooled, for example with cold air.
- Preferred residual contents of unbound water are about 1% by weight, preferably in the range of about 0.1 to 0.5% by weight.
- the resulting, very low-dust product can be classified, for example sieved, to remove small coarse particles that are formed.
- the proportion of grain to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material. In some cases it is also possible to carry out this drying step directly after the pressing the primary granulate and thus before the final shaping, if desired, to be carried out in a rounding device.
- the "internal drying" of the granules is also possible: by using moisture-binding components in the premix, the plasticizing effect of the liquid components presented can be exploited in the short processing time: Then at least partial components are found by binding of these liquid components due to the mixed-in constituents, the granules are dried "from the inside", so that the external drying can be shortened or omitted entirely.
- Constituents which are able to bind water in the form of water of crystallization are, for example, sodium sulfate and / or sodium carbonate in anhydrous or low-water form or else a zeolite partially freed from water of crystallization.
- the primarily formed and still plastic granules can be applied before, during and / or after any rounding off of the further active ingredients.
- sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, e.g. B. sprayed and / or mixed as a separately formed grain to form a multigrain mixture.
- the invention encompasses both the area of ready-to-use multi-substance mixtures in the form of uniform granulate bodies and also partial products which, in order to complete the recipe, require mixing of further constituents of the particular detergent and cleaning agent concerned.
- more than 60% by weight and in particular more than 70% by weight of the total mixture are granules obtained by the process according to the invention with a highly compressed and solid grain structure.
- granule systems are used which represent a combination of granules of different compositions.
- the storage-stable combination of potentially reactive or at least only partially compatible components succeeds.
- An example of this are conventional textile detergents, which, however, now use at least two types of granules in a mixture with one another in this preparation form.
- the bleaching agent component in particular perborate or sodium carbonate containing water of crystallization, is pelletized with the use of a proportion of the plasticizers and / or lubricants, in a separate second granulate the zeolite, if used as detergent builder, in particular zeolite NaA and / or zeolite P, pressed with the rest of the detergent components.
- the storage stability of the mixed product which has a substantially influencing interaction between peroxy bleaching agent and zeolite - as must be taken into account in powdery preparations - is excluded in this way. With this possibility of using granulate systems of differently composed granules, use can be made in almost any combination.
- the granules according to the invention can be recycled, ie. that is, they can be used in the first process step in combination with other steps to produce the plasticized premix.
- the material densities in the grain and thus also the bulk density of the granules are decisively determined by the working pressures used in pressing the homogenized material through the perforated plates.
- z. B. with conventional textile detergent formulations bulk densities well above 700 g / l, preferably above 750 g / l and in particular in the range from about 800 to approximately 1,000 g / l.
- Bulk densities in the range from 850 to 980 g / l can be adjusted on the basis of commercially available textile detergent formulations with good free-flowing properties and a preferably high, uniform, spherical grain structure.
- free-flowing granules are in the dry state with uniform bulk densities of 950 to 980 g / l an average particle size of the spherical granules in the range of, for example, about 1 mm.
- the method according to the invention is characterized by a very low proportion of returned goods.
- This portion of the return material after sieving the granules through a 1.6 mm sieve was in each case in the range of at most 7% by weight.
- sensitive formulation constituents for example activators for bleaching agents, enzymes, defoamers, in particular Silicone defoamers, perfume and the like are added to the granules. Even then, detergent products with bulk densities in the range of about 900 g / l are still obtained.
- the textile detergents which are customary in the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic surfactant and nonionic surfactant detergent components.
- the anionic surfactant components make up the largest proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture.
- Textile detergent concentrates with surfactant contents for example, of up to 35% by weight and preferably in the range of about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as is the case in the commercially available powdery formulations Mixtures occur with such increases in the surfactant content.
- the goal of space-saving and low-packaging detergent preparations is optimally achieved without the area of free-flowing, storage-stable and all other requirements having to leave fulfilling detergent preparations.
- the preparation of detergents and cleaning agents in the process type of granulation according to the invention to the predetermined particle size brings a number of advantages: It has been shown that in the process according to the invention the bleaching agent, in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate, can already be processed in the raw material to be classified and then pressed without substantial losses of perborate occurring . Each granulate thus contains the predetermined proportion of granules of peroxy bleach.
- the use of spray-dried powders / granules with variable admixture is possible.
- neither spray-dried powders / granules nor pre-formed powders with a bead structure are required to produce the raw materials to be pressed.
- nonionic surfactants commonly used in detergents and cleaning agents are no problem, and the pluming effects that occur in spray drying, see definition in Römpp Chemielexikon, 4th edition, volume 5, p. 3488, are eliminated.
- the nonionic surfactants are added without problems by incorporation into the mixture of substances before the pressing step; they can even provide valuable process help in the manner described here as a highly concentrated, aqueous gel or paste.
- defoamers in liquid form saves a process for the separate production of defoamer solid carrier concentrates. This eliminates the need to add defoamer granules to the detergent preparation. It has proven to be particularly advantageous to mix the defoamer directly into the plasticizer and / or lubricant.
- the invention relates to universal detergents for textiles which are present in this form of the free-flowing granules with bulk densities above 750 g / l, in particular above 800 g / l, for example in the range from 850 to 950 g / l and in one particularly important embodiment are characterized by a uniform particle shape and size.
- the preferred particle shape is spherical.
- Preferred particle sizes here are in the range from 0.5 to 10 mm ball diameter, in particular in the range from approximately 1 to 5 mm.
- the type and quantity of the formulation components can correspond to that of today's textile detergents containing builder substances.
- Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
- Suitable surfactants of the sulfonate type are alkylbenzene sulfonates (C 9 to C 13 alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates of the type obtained, for example, from C 12 to C 18 monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates which are obtainable from C 12 to C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for .
- esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates)
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, in particular from fatty alcohols, e.g. B. from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 - C 2 o-oxo alcohols, and those secondary alcohols of this chain length.
- the sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-C- * •, alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
- Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals is 30 to 70% by weight on C 12 to 18 to 30% by weight on C 14> 5 to 15% by weight find a preferred use. are distributed on C 16 , less than 3% by weight on C 10 and 0 to 40% by weight on C 18. Sulfated fatty acid monoglycides are also suitable
- anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8 - C 18 -fatty alcohol residues or mixtures of these, in particular preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants.
- sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols derive narrowed homogeneous distribution, particularly preferred
- Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 5% by weight.
- Saturated fatty acid soaps such as the salts of lauric acid, mypinsic acid, palmitic acid or stearic acid, and in particular from natural fat, are suitable ⁇ acidic, eg coconut, palm kernel or tallow fatty acids, derived soap mixtures
- anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tetrahanolamine.
- the anionic surfactants are preferably present in the form of their sodium or potassium salts before the content of detergents according to the invention anionic surfactants or anionic surfactant mixtures is preferably 5 to 40% by weight, in particular 8 to 30% by weight
- Addition products of 1-40, preferably 2-20 moles of ethylene oxide to one mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides can be used as nonionic surfactants
- the preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of alkylene oxide, in which the alcohol residue can be linear or methyl-branched in the 2-position, or can contain linear or methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. from Ko ⁇ kos-, tallow or oleyl alcohol.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE).
- NRE narrow range ethoxylates
- alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
- alkylpolyglycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position means and G is the symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides or oligoglycosides, is any number between 1 and 10.
- Other suitable surfactants are polyhydroxy fatty acid amides of the general formula
- R 2 - CO for an aliphatic acyl radical with 6 to 22 carbon atoms
- R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
- [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides in which R 3 is hydrogen or an alkyl group, R 2 - CO is the acyl radical of a saturated or unsaturated fatty acid and [Z] is a glucose radical.
- bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing hydrogen peroxide, such as perbenzoates, peroxophthalates, diperazelaic acid or dimerododecanedioic acid.
- the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate or percarbonate advantageously being used.
- bleach activators can be incorporated into the preparations.
- these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
- the bleaching agent content of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular in particular between 2 and 8% by weight.
- bleach activators are N, N, N ', N'-tetraacetylethylenediamine, 1,4-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, also carboxylic anhydrides and esters of polyols, such as Glucose pentaacetate.
- water-soluble polyglycol ethers with 2 to 7 ethylene glycol residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
- Suitable and, in particular, ecologically harmless substances such as finely crystalline, synthetic water-containing zeolites of the NaA type and / or zeolite P, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) a preferred use.
- Their average particle size is usually in the range from 1 to 10 micrometers (measurement method: Coulter Counter; volume distribution).
- Their content is generally 0-40, preferably 10-30% by weight, based on the anhydrous substance.
- Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents.
- Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 micrometers and preferably consist of at least 80% particles smaller than 10 micrometers.
- Zeolite A and zeolite P are particularly suitable, as are zeolite X and mixtures of A and X and / or P. Quantities and weight ratios that affect the builders are based on the anhydrous active substance in the context of the present invention, unless stated otherwise .
- Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered silicates of the general formula NaMSi x ⁇ 2 X + ⁇ • VH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20 is.
- layer silicates are described, for example, in European patent application 0164514.
- ⁇ - and ⁇ -sodium disilicates Na2Si2 ⁇ 5 • yH 2 O are preferred.
- Other builder substances are amorphous silicates with secondary washing power, for example those according to DE-P44 00 024.3, DE-P44 19 745.4 and DE-P44 46 363.4.
- zeolite and / or the crystalline layered silicate and / or the amorphous silicate are preferably used either alone or with a zeolite to crystalline layered silicate or amorphous silicate weight ratio with secondary washability of 10: 1 to 1: 3 and in particular 3: 1 to 1: 1.
- Usable organic builders are, for example, polycarboxylates, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these and (co) -polymeric polycarboxylic acids and polycarboxylates, such as the sodium salts of polyacrylic acids or polymethacrylic acids, for example those with a relative molecular weight of 800 to 150,000 (based on acid) and in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained.
- polycarboxylates the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriace
- Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
- Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000, and in particular more 5000 to 100000.
- biodegradable terpolymers for example those which, according to DE-A-43 00 772, as salts of acrylic acid and maleic acid as well as vinyl alcohols or vinyl alcohol derivatives or according to DE-C- 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
- copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
- phosphate can also be used, in particular pentasodium triphosphate, possibly also pyrophosphates such as orthophosphates, which act primarily as precipitants for lime salts.
- pentasodium triphosphate possibly also pyrophosphates such as orthophosphates, which act primarily as precipitants for lime salts.
- the phosphate content based on pentasodium triphosphate, is below 30% by weight.
- agents without a phosphate content are preferably used here.
- Suitable inorganic, non-complexing salts are the bicarbonates, also known as washing alkalis, carbonates, borates or silicates of the alkalis.
- the alkali silicates especially the sodium silicates with a ratio Na2 ⁇ : Si ⁇ 2 such as 1: 1 to 1: 3.5 usable (see above).
- the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts.
- Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
- Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch and cellulose, ether sulfonic acids or salts of acidic sulfuric acid esters of cellulose or starch.
- water soluble, Acid-containing polyamides are suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starches, aldehyde starches, etc.
- Polyvinylpyrrolidone can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose are preferred and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition
- the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants, a reduction can also be achieved by adding non-surfactant-like substances.
- a reduced foaming power which is desirable when working in machines, can be achieved in many cases by combining different tenants sidtypes, for example sulfates and / or sulfonates with nonionic tensides and / or with soaps. In the case of soaps, the foam-dampening effect increases with the degree of saturation and the C number of the fatty acid salt.
- foam-inhibiting soaps a high proportion of C ⁇ "C 24 -Fettsauren have Suitable non-active foam inhibitors are beispiels ⁇ , organopolysiloxanes and mixtures thereof with microfine, if appropriate silanized silica and also paraffins, waxes, waxes Mikrokristallin ⁇ and mixtures thereof with silanized silica also of C
- Mixtures of different foam inhibitors are also advantageously used, for example those made of silicones, paraffins or waxes.
- the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or who ⁇ added to the plasticizers and / or lubricants
- the agents can contain enzyme stabilizers.
- enzyme stabilizers For example, 0.5 to 1% by weight of sodium formate can be used.
- proteases containing soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme are stabilized but the use is particularly advantageous boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 0 7 ).
- the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
- salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triacin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable, which instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyamino group.
- Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; for example the compounds 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
- Enzymes from the class of proteases, lipases, cutinases, cellulases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subiii, Bacillus licheniformis or Streptomyces griseus are particularly suitable. Proteases of the subtilis type and in particular proteases which are obtained from Bacillus lentus are preferably used in a mixture with other enzymes. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. Their proportion can be about 0.2 to 2% by weight.
- the salts of polyphosphonic acids, hydroxyethane-1,1-diphosphonic acid (HEDP) and ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) are suitable as stabilizers, in particular for per-compounds or enzymes.
- the present invention also relates to granules which, according to the have been obtained, which are characterized in that they have a bulk density of above 700 g / l, preferably 750 to 1,000 g / l and in particular 850 to 980 g / l, and as a ready-to-use multi-substance mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product which, in order to complete the recipe, still requires mixing with other constituents of conventional washing and cleaning agents
- the present invention relates to detergents and cleaners containing granules of the aforementioned type, which are characterized in that they contain a surfactant content of up to 40% by weight, preferably 15 to 25% by weight
- a plastifiable, solid, free-flowing premix was obtained by reacting 61.6% by weight of a spray-dried granulate, 5% by weight of an alkyl sulfate compound, 20.7 % By weight sodium perborate monohydrate, 3.5% by weight C 12 -C 18 fatty alcohol with 7 EO, 1.7% by weight polyethylene glycol (PEG 400), 1.8% by weight
- the powder components were placed in a batch mixer of 130 l, which was equipped with a cutter head comminutor, and then with the mixer running, the premixed nonionic surfactant / PEG 400 mixture and then the carboxylate solution were added and the mixture was mixed for 30 seconds .
- the premix obtained was free-flowing and could be fed to feed the granulating system according to the invention, the hole shapes of which were preceded by an extruder with a gear pump connected to it.
- an extruder from Lei ⁇ stritz, Federal Republic of Germany, with the designation LSM 30.34 GL was used.
- a perforated disk with a diameter of 3 mm for pre-plasticizing the premix.
- the gear pump according to the invention used in the granulation was a model available from Witte GmbH, Federal Republic of Germany, under the name VAH 2.78 M, with a typical throughput of 4 kg per hour for a typical hole Nozzle diameter of 1.5 mm is carried out, product outlet and discharge temperatures of 60 ° C. being used. It was not necessary to cool the apparatus.
- the subsequent batch rounding was carried out optimally within a batch time of 1 min at a rotor peripheral speed of 8 m / s in the presence of 3.2% by weight of zeolite NaA powder. After sieving through a 1.6 mm sieve, a granulate with a granular bulk density of about 800 g / l was obtained in a granulate yield of 93%.
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Abstract
The aim is to specify a process for compressing solid pourable initial mixtures which allows operation under less harsh conditions than were hitherto customary. This was achieved by connecting a gear pump upstream of the perforated moulds through which the granules are compressed.
Description
„Verfahren zur Herstellung von granulären Wasch- oder Reinigungsmit¬ teln oder Komponenten hierfür" "Process for the production of granular washing or cleaning agents or components therefor"
Die Erfindung betrifft ein Verfahren zur Herstellung von nahezu kugelför¬ migen bis zylindrischen Wasch- oder Reinigungsmittelgranuiaten oder Komponenten hierfür, bei denen eine Zahnradpumpe eingesetzt wird, so erhältliche Granulate sowie Wasch- und Reinigungsmittel.The invention relates to a process for the production of almost spherical to cylindrical detergent or cleaning agent granules or components therefor, in which a gear pump is used, granules and detergents and cleaning agents thus obtainable.
Aus den internationalen Patentanmeldungen WO-A-91/02047 und WO-A- 91/13678 sowie aus dem europäischen Patent 486 592 ist ein Verfahren zur Herstellung verdichteter Granulate von Inhaltsstoffen von Wasch- oder Reinigungsmitteln bekannt. Die Granulate werden aus Vorgemischen von wenigstens anteilsweise festen Inhaltsstoffen unter Zusatz von wasserlös¬ lichen, wasseremulgierbaren oder wasserdispergierbaren Plastifizier- und/oder Gleitmitteln erhalten, welche zu einer homogenen Masse verar¬ beitet und unter hohen Drücken zwischen 25 und 200 bar über Lochfor¬ men mit Öffnungsweiten der vorbestimmten Granulatdimension strang- förmig verpreßt werden. Als Homogenisiervorrichtung können übliche Granuliereinrichtungen, beispielsweise Pelletpressen, Extruder mit ein oder zwei Wellen, Planetwalzenextruder und andere Apparate eingesetzt werden. Ein kontinuierlich arbeitender Zwei-Schnecken-Extruder ist dabei bevorzugt. Das im Extruder plastifizierte Vorgemisch tritt in Form feiner Stränge durch eine Lochdüsenplatte aus. Das Extrudat wird dann mittels eines rotierenden Abschlagmessers zu nahezu kugelförmigen bis zylindri¬ schen Granulaten zerkleinert und dieses noch plastische Primärgranulat vorzugsweise in einem üblichen Rondiergerät ggf. unter Mitverwendung geringer Mengen an Trockenpulver abgerundet. Zur Rezepturvervollstän¬ digung können weitere Wirkstoffe, insbesondere temperaturempfindliche Rezepturbestandteile, dem ggf. aufgetrockneten Granulat zugegeben, aufgesprüht und/oder als getrennt ausgebildetes Korn unter Ausbildung eines Mehrkorngemisches zugemischt werden.From international patent applications WO-A-91/02047 and WO-A-91/13678 and from European patent 486 592 a process for the production of compacted granules of ingredients of detergents or cleaning agents is known. The granules are obtained from premixes of at least partially solid ingredients with the addition of water-soluble, water-emulsifiable or water-dispersible plasticizers and / or lubricants, which are processed to a homogeneous mass and at high pressures between 25 and 200 bar via perforated shapes Opening widths of the predetermined granule dimension are pressed in a rope shape. Conventional granulating devices, for example pellet presses, extruders with one or two shafts, planetary roller extruders and other apparatus, can be used as the homogenizing device. A continuously operating twin-screw extruder is preferred. The premix, plasticized in the extruder, emerges in the form of fine strands through a perforated die plate. The extrudate is then comminuted to almost spherical to cylindrical granules by means of a rotating knock-off knife, and these still plastic primary granules are preferably rounded off in a conventional rounding device, possibly with the use of small amounts of dry powder. To complete the formulation, further active ingredients, in particular temperature-sensitive formulation constituents, can be added to the optionally dried-on granules, sprayed on and / or mixed in as a separately formed grain to form a multigrain mixture.
In der technischen Ausführungsform wird die Extrusion durch eine kreis¬ förmige, mit Düsenbohrungen versehene Platte vorgenommen. Die Loch-
düsen können vertikal oder horizontal angeordnet sein. Die durch die Lochformen austretenden feinen Stränge von etwa 0,5 bis 5 mm, typi¬ scherweise von 0,8 mm bis 2,0 mm Durchmesser werden in einem Hei߬ abschlag von einem ein- oder mehrflügeligen rotierenden Messerkopf zu nahezu kugelförmigen bis zylindrischen Granulaten zerkleinert. Die Mes¬ serschneiden der Abschlagvorrichtung liegen entweder an der Düsenplat¬ te mit einer geringen Anpreßkraft auf oder bilden mit der Platte einen Spalt, der sehr klein gegenüber dem Durchmesser der Lochdüsen ist.In the technical embodiment, the extrusion is carried out through a circular plate provided with nozzle bores. The hole nozzles can be arranged vertically or horizontally. The fine strands of about 0.5 to 5 mm, typically from 0.8 mm to 2.0 mm in diameter emerging through the hole shapes are converted in a hot cut from a single- or multi-bladed rotating cutter head into almost spherical to cylindrical granules crushed. The knife edges of the knock-off device either lie on the nozzle plate with a low contact pressure or form a gap with the plate which is very small compared to the diameter of the perforated nozzles.
Das homogene und feste, rieselfähige Vorgemisch muß von derartiger Konsistenz sein, daß es zwar unter dem Druck bzw. unter dem Eintrag spezifischer Arbeit plastisch erweicht und extrudierbar wird, daß aber zum Zeitpunkt des Austritts aus der Lochform, zu dem keine Scherkräfte mehr auf das System einwirken, sich die Viskosität des Systems schlagartig derart verringert, daß der extrudierte Strang geschnitten und zwar auf vorherbestimmbare Dimensionen geschnitten werden kann.The homogeneous and solid, free-flowing premix must be of such a consistency that it is plastically softened and extrudable under the pressure or under the entry of specific work, but at the time of the exit from the hole shape, at which no shear forces on the system act, the viscosity of the system suddenly decreases so that the extruded strand can be cut and cut to predetermined dimensions.
Ein Nachteil dieses Verfahrens besteht darin, daß unter dem hohen Ar¬ beitsdruck Energieverluste in Form von Temperatursteigerungen auftre¬ ten, so daß das Extrudergehäuse einschließlich des Extruder- Granulierkopfes normalerweise gekühlt werden muß, um zu verhindern, daß die Viskosität des Vorgemisches bereits während der Extrusion so stark absinkt, daß eine eigentliche Extrusion gar nicht mehr möglich ist. Ebenso führen zu starke Temperaturerhöhungen dazu, daß temperatu¬ rempfindliche Inhaltsstoffe, beispielsweise Bleichmittel wie Perborat oder Percarbonat, ohne Kühlung des Gehäuses nicht eingesetzt werden könnten.A disadvantage of this method is that energy losses occur in the form of temperature increases under the high working pressure, so that the extruder housing, including the extruder pelletizing head, normally has to be cooled in order to prevent the viscosity of the premix already during the extrusion sinks so much that an actual extrusion is no longer possible. Excessive temperature increases also lead to the fact that temperature-sensitive ingredients, for example bleaching agents such as perborate or percarbonate, could not be used without cooling the housing.
Es bestand daher die Aufgabe, das oben beschriebene Verfahren derart zu modifizieren, daß ein Verpressen des Vorgemisches unter schonende¬ ren Bedingungen, beispielsweise auch bei geringeren Drücken oder ohne Kühlung erlaubt, ohne daß die Schneidfähigkeit der extrudierten Stränge nach dem Austritt aus der Lochform verlorengeht oder diese hohen Drük- ke nur kurzfristig aufgebaut werden.
Diese Aufgabe wird erfindungsgemaß durch ein Verfahren zur Herstellung von granulären Wasch- oder Reinigungsmitteln oder Komponenten hierfür gelost, wobei ein plastifizierbares und festes, rieselfähiges Vorgemisch durch Lochformen verpreßt wird und diesen Lochformen eine Zahn¬ radpumpe vorgeschaltet ist.The object was therefore to modify the process described above in such a way that the premix can be pressed under more gentle conditions, for example also at lower pressures or without cooling, without the cutting ability of the extruded strands being lost after it emerges from the hole shape, or these high pressures can only be built up for a short time. This object is achieved according to the invention by a process for producing granular detergents or cleaning agents or components therefor, a plastifiable and solid, free-flowing premix being pressed by hole molds and a gear pump being connected upstream of these hole molds.
Derartige Zahnradpumpen sind im Handel erhältlich Beispielsweise können sie von der Witte GmbH, Bundesrepublik Deutschland, erworben werden Bei den im Rahmen des erfindungsgemäßen Herstellungsverfah¬ rens von granulären Wasch- oder Reinigungsmitteln eingesetzten Zahn¬ radpumpen handelt es sich gattungsmäßig um eine rotierende Verdrän¬ gerpumpe Derartige Zahnradpumpen können je nach Viskosität des durchzusetzenden Gutes üblicherweise einen Durchsatz von 0,1 bis 300 m3 pro Stunde, vorzugsweise aber 1 bis 20 m3 pro Stunde durchsetzen Die Temperatur in der Zahnradpumpe kann auch über große Bereiche variiert werden, beispielsweise von 0 °C bis etwa 300 °C, vorzugsweise wird sie aber bei üblichen Betriebstemperaturen von 30 bis 70 °C betrie¬ ben Das zu verpressende, plastifizierbare, feste und rieselfähige Vorge¬ misch kann sowohl direkt eingezogen werden oder beispielsweise in ei¬ nem der Zahnradpumpe vorgeschalteten Extruder vorplastifiziert werdenGear pumps of this type are commercially available. For example, they can be purchased from Witte GmbH, Federal Republic of Germany. The gear pumps used in the production process of granular detergents or cleaning agents according to the invention are generically a rotating displacement pump Depending on the viscosity of the material to be carried through, a throughput of 0.1 to 300 m 3 per hour, but preferably 1 to 20 m 3 per hour, can usually be achieved. The temperature in the gear pump can also be varied over wide ranges, for example from 0 ° C. to about 300 ° C, but it is preferably operated at usual operating temperatures of 30 to 70 ° C. The pre-mix to be compressed, plasticized, solid and free-flowing can either be drawn in directly or, for example, pre-plastified in an extruder upstream of the gear pump
Da das Vorgemisch in der Zahnradpumpe nicht verweilt und keinen me¬ chanischen Energieeintrag erfährt, für das Verpressen aber nach wie vor ein plastifiziertes Vorgemisch erforderlich ist, muß die Plastifizierung des Vorgemisches (Matenalzufuhr) vor der Zuführung zu den Zahnradern er¬ folgen. Diese Plastifizierung kann nach üblichen und bekannten Metho¬ den, beispielsweise in Mischern, Extrudern, Stopfschnecken oder Vorrich¬ tungen aus Mischern und Knetern vorgenommen werdenSince the premix does not remain in the gear pump and does not experience any mechanical energy input, but a plasticized premix is still required for the pressing, the plastification of the premix (material supply) must take place before the supply to the gear wheels. This plasticizing can be carried out using customary and known methods, for example in mixers, extruders, stuffing screws or devices made from mixers and kneaders
Nach einer bevorzugten Ausführungsform des vorliegenden Verfahrens baut sich innerhalb der Zahnräder ein Druck von 6 bis 200 bar, vorzugs¬ weise 30 bis 120 bar auf. Die Verweilzeit des zu verpressenden Vorgemi¬ sches betragt erfindungsgemäß im Bereich des vorgenannten hohen Druckes und der vorgenannten Temperatur vor der Lochplatte nur 1/10 bis 1/3 der Zeit, wie sie nach der Lehre der EP 486 592 erforderlich ist
Die am Ausgang der Zahnradpumpe vorhandene Abschlagvorrichtung, insbesondere Abstreifmesser, erzeugt auf diese Weise ein Granulatkorn von 0,5 bis 10 mm, vorzugsweise 1 bis 5 mm.According to a preferred embodiment of the present method, a pressure of 6 to 200 bar, preferably 30 to 120 bar, builds up within the gearwheels. According to the invention, the residence time of the premix to be pressed is only 1/10 to 1/3 of the time in the range of the aforementioned high pressure and the aforementioned temperature before the perforated plate, as is required according to the teaching of EP 486 592 In this way, the knock-off device, in particular a doctor blade, at the outlet of the gear pump produces a granulate size of 0.5 to 10 mm, preferably 1 to 5 mm.
Das Vorgemisch besteht wenigstens anteilsweise aus festen, vorzugswei¬ se feinteiligen, üblichen Inhaltsstoffen von Wasch- und Reinigungsmitteln, denen gegebenenfalls flüssige Bestandteile zugemischt sind. Die festen Inhaltsstoffe können durch Sprühtrocknung gewonnene Turmpulver, aber auch Agglomerate, die jeweils gewählten Mischungsbestandteile als reine Stoffe, die im feinteiligen Zustand miteinander vermischt werden, sowie Mischungen aus diesen sein.The premix consists at least in part of solid, preferably finely divided, customary ingredients of detergents and cleaning agents, to which liquid constituents may have been added. The solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
Im Anschluß daran werden gegebenenfalls die flüssigen inhaltsstoffe zu¬ gegeben und dann das erfindungsgemäß ausgewählte Plastifizier- und/oder Gleitmittel eingemischt.Subsequently, the liquid ingredients are added, if appropriate, and the plasticizer and / or lubricant selected according to the invention is then mixed in.
Diesen Hilfsmitteln kommt im Rahmen der vorliegenden Erfindung eine polyfunktionelle Bedeutung zu. Bei der Granulatherstellung ermöglichen sie die Ausbildung des primär entstehenden Granulatkoms, in dem sie bewirken, daß das Vorgemisch in eine unter hohem Druck verpreßte Mas¬ se überführt wird, und deren gewünschtenfalls anschließende, formge¬ bende Weiterverarbeitung, die insbesondere aus der Abrundung des pri¬ mär gebildeten Granulatkorns besteht. Weiterhin tragen sie zur Stabilisie¬ rung des Granulatkorns bei, sie bewahren seine vorbestimmte Raumform insbesondere bei der gegebenenfalls erforderlichen Abmischung mit wei¬ teren Bestandteilen, bei der Abfüllung, beim Transport und der Lagerung des Granulats und verhindern insbesondere die Bildung unerwünschter, staubförmiger Anteile. Im praktischen Einsatz des granulären Wasch- und Reinigungsmittels ermöglichen sie dann umgekehrt wieder die rasche Auflösung des Granulatkorns, da sie den Lösungs-, Emulgierungs- bzw. Dispergierungsvorgang begünstigen. Schließlich können die hier diskutier¬ ten Hilfsstoffe in insbesondere wichtigen Ausführungsformen der vorlie¬ genden Erfindung eine Eigenwirkung im Wasch- und Reinigungsprozeß, insbesondere in Wechselwirkung mit anderen Mischungskomponenten, besitzen.
Die als Hilfsmittel eingesetzten Plastifizier- und/oder Gleitmittel können bei Raumtemperatur fest, fließfähig, gelartig oder pastös sein, ohne daß die Mitverwendung einer zusätzlichen Flüssigphase erforderlich ist. Bevorzug¬ te Plastifizier- und/oder Gleitmittel stellen Zubereitungen auf Basis tensidi- scher Komponenten und/oder auf Basis wasserlöslicher oder wassere- mulgierbarer bzw. wasserdispergierbarer Polymerverbindungen dar. Bei¬ spiele für ein Plastifizier- und/oder Gleitmittel, das ohne Mitverwendung einer zusätzlichen Flüssigphase eingesetzt werden kann, sind zahlreiche Typen der in Wasch- und Reinigungsmitteln üblicherweise eingesetzten, nichtionischen Tenside.These aids are of polyfunctional importance in the context of the present invention. In the production of granules, they enable the formation of the primary granulate granule by causing the premix to be converted into a mass pressed under high pressure and, if desired, subsequent subsequent shaping processing, which in particular results from the rounding off of the primary mär formed granules. Furthermore, they contribute to the stabilization of the granules, they maintain its predetermined spatial shape, in particular when mixing with other components, if necessary, during filling, during transport and storage of the granules, and in particular prevent the formation of undesirable, dust-like components. Conversely, in practical use of the granular detergent and cleaning agent, they enable the granules to dissolve quickly, since they promote the dissolving, emulsifying or dispersing process. Finally, the auxiliaries discussed here, in particularly important embodiments of the present invention, can have an intrinsic effect in the washing and cleaning process, in particular in interaction with other mixture components. The plasticizers and / or lubricants used as auxiliaries can be solid, flowable, gel-like or pasty at room temperature without the need to use an additional liquid phase. Preferred plasticizers and / or lubricants are preparations based on surfactant components and / or on the basis of water-soluble or water-emulsifiable or water-dispersible polymer compounds. Examples of a plasticizer and / or lubricant which can be used without the use of an additional Liquid phase can be used, numerous types of the non-ionic surfactants commonly used in detergents and cleaning agents.
Als bei Raumtemperaturen feste Plastifizier- und/oder Gleitmittel können Substanzen mit niedrigem Schmelzpunkt (z.B. höhermolekulare Polyethy- lenglykolether mit Molekülmassen zwischen 4000 und 20000) eingesetzt werden.Substances with a low melting point (e.g. higher molecular weight polyethylene glycol ethers with molecular weights between 4,000 and 20,000) can be used as plasticizers and / or lubricants which are solid at room temperature.
In einer bevorzugten Ausführungsform werden jedoch Plastifizier- und/oder Gleitmittel eingesetzt, die unter Mitverwendung begrenzter Men¬ gen an Hilfsflüssigkeiten hergestellt worden sind. Hier kommen vorzugs¬ weise organische Flüssigphasen in Betracht, die wasserlöslich bzw. was¬ sermischbar sind. Aus Gründen der Verfahrenssicherheit kann es zweck¬ mäßig sein, vergleichsweise hochsiedende organische Flüssigkeiten, ge¬ gebenenfalls in Abmischung mit Wasser, einzusetzen. Beispiele hierfür sind höhersiedende, gegebenenfalls polyfunktionelle Alkohole, bei Raumtemperatur oder mäßig erhöhten Temperaturen fließfähige Polyal- koxylate und dergleichen. Insbesondere sind jedoch wäßrige Zubereitun¬ gen der Plastifizier- und/oder Gleitmittel bevorzugt.In a preferred embodiment, however, plasticizers and / or lubricants are used which have been produced using limited amounts of auxiliary liquids. Organic liquid phases which are water-soluble or water-miscible are preferred here. For reasons of process reliability, it may be expedient to use comparatively high-boiling organic liquids, if appropriate in a mixture with water. Examples of these are higher-boiling, optionally polyfunctional alcohols, polyalkoxylates which flow at room temperature or moderately elevated temperatures and the like. In particular, however, aqueous preparations of the plasticizers and / or lubricants are preferred.
Die als Plastifizier- und/oder Gleitmittel eingesetzten Tenside und/oder Polymerverbindungen werden vorteilhaft in derart konzentrierter Form in das Verfahren eingebracht, daß die Beschaffenheit der plastischen, glei¬ tend verpreßbaren Masse schon in geringen Mengen dieser Hilfsstoffe eingestellt werden kann.
Vorzugsweise werden die Pasten in Mengen nicht über 12 Gew.-%, ins¬ besondere in Mengen zwischen 0,5 und 10 Gew.-%, und mit besonderem Vorteil zwischen 3 und 8 Gew.-%, bezogen auf die Gesamtmischung, ein¬ gesetzt. Geeignet sind insbesondere wenigstens 30 Gew.-%ige, vorzugs¬ weise 40 Gew.-%ige Pasten und Gele.The surfactants and / or polymer compounds used as plasticizers and / or lubricants are advantageously introduced into the process in such a concentrated form that the nature of the plastic, smoothly compressible mass can be adjusted even in small amounts of these auxiliaries. The pastes are preferably used in amounts not exceeding 12% by weight, in particular in amounts between 0.5 and 10% by weight, and with particular advantage between 3 and 8% by weight, based on the total mixture set. At least 30% by weight, preferably 40% by weight pastes and gels are particularly suitable.
Nach einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung werden Tensidzubereitungen mit einem Tensidgehalt von we¬ nigstens 50 Gew.-%, insbesondere von 50 bis 70 Gew.-%, verwendet. Die vorliegende Erfindung macht sich dabei die Tatsache zunutze, daß insbe¬ sondere diese hochkonzentrierten, wäßrigen Tensidmischungen ein Zu- standsbild zeigen, das als pastenförmige oder gelartige Zubereitungsform mit Schmiermittelcharakter bezeichnet werden kann. Zusätzlich bilden die so eingetragenen Tensidanteile in einer weiteren Ausführungsform, in der die primär gebildeten Granulate aufgetrocknet werden, bindemittelartig wirkende Deck- und Zwischenschichten aus, die mitverantwortlich für den Kornzusammenhalt sind. Anionischen Tensidsalzen, insbesondere Sulfa¬ ten und Sulfonaten, aus der breiten Palette der für Wasch- und Reini¬ gungsmittel hier vorgeschlagenen Verbindungen, gegebenenfalls in Ab¬ mischung mit üblichen, nichtionischen Verbindungen, kann dabei beson¬ dere Bedeutung zukommen. Als Beispiel sei bei der Herstellung von Tex- tilwaschmitteln ein Einsatzgemisch aus mindestens zwei festen Kompo¬ nenten (sprühgetrocknetes Granulat/Fettalkylsulfat-Compound) mit oder ohne Zusatz von Natriumperborat (Monohydrat und/oder Tetrahydrat) unter Zusatz von 2 bis 5 Gew.-% Wasser und 4 bis 8 Gew.-% einer 55 bis 65 %igen C9 bis C13-Alkylbenzolsulfonat-Paste (ABS-Paste) genannt. Anstelle der vorgenannten Kombination eines sprühgetrockneten Granu¬ lats und eines Fettalkylsulfat-Compounds mit weiteren Komponenten kann auch ein entsprechendes Trägerbead anstelle des Fettalkylsulfat- Compounds, wie es im europäischen Patent 0486592 B1 beschrieben ist, eingesetzt werden. Gleichermaßen bevorzugt ist der Einsatz von 3 bis 8 Gew.-% einer 50 bis 60 Gew.-%igen wäßrigen Paste eines Alkylpolygly- kosids (APG) der allgemeinen Formel RO(G)x, in der R einen primären geradkettigen oder in 2-Stellung methylverzweigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 8 bis 18 C-Atomen bedeutet, G ein Symbol ist,
das für eine Glykose-Einheit mit 5 oder 6 C-Atomen steht, und der Oligo¬ merisierungsgrad x zwischen 1 und 10 liegt. Weitere bevorzugte Plastifi¬ zier- und/oder Gleitmittel auf tensidischer Basis sind Mischungen aus ABS und APG-Pasten, sowie Mischungen aus ABS-Pasten und ethoxylierten C8 bis C18-Fettalkoholen, Mischungen aus ethoxylierten Fettalkoholen und Wasser sowie Mischungen aus APG : ethoxylierter Fettalkohol : Wasser im Verhältnis von (0,5 - 1) : 1 : (1 ,5 - 1), wobei der Gehalt an APG in die¬ sem Fall als Aktivsubstanz und nicht als Paste gerechnet wird.According to a particularly preferred embodiment of the present invention, surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used. The present invention takes advantage of the fact that, in particular, these highly concentrated, aqueous surfactant mixtures show a state that can be described as a pasty or gel-like preparation form with a lubricant character. In addition, in a further embodiment, in which the primarily formed granules are dried, the surfactant components thus introduced form cover and intermediate layers which act like binders and which are jointly responsible for the grain cohesion. Anionic surfactant salts, in particular sulfates and sulfonates, from the wide range of compounds proposed here for detergents and cleaners, optionally in admixture with customary, nonionic compounds, can be of particular importance. As an example in the manufacture of textile detergents, use a mixture of at least two solid components (spray-dried granulate / fatty alkyl sulfate compound) with or without the addition of sodium perborate (monohydrate and / or tetrahydrate) with the addition of 2 to 5% by weight. Water and 4 to 8 wt .-% of a 55 to 65% C 9 to C 13 alkyl benzene sulfonate paste (ABS paste) called. Instead of the aforementioned combination of a spray-dried granulate and a fatty alkyl sulfate compound with further components, a corresponding carrier bead can also be used instead of the fatty alkyl sulfate compound as described in European patent 0486592 B1. Equally preferred is the use of 3 to 8% by weight of a 50 to 60% by weight aqueous paste of an alkyl polyglycoside (APG) of the general formula RO (G) x , in which R is a primary straight-chain or in 2- Position means methyl-branched, aliphatic radical having 8 to 22, preferably 8 to 18 carbon atoms, G is a symbol, which stands for a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10. Further preferred plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C 8 to C 18 fatty alcohols, mixtures of ethoxylated fatty alcohols and water and mixtures of APG: ethoxylated Fatty alcohol: water in the ratio of (0.5 - 1): 1: (1, 5 - 1), the content of APG in this case being calculated as an active substance and not as a paste.
Ebenso wie der Einsatz von Tensiden ist heute die Mitverwendung von Polymerverbindungen in zahlreichen Wasch- und Reinigungsmitteln üb¬ lich, da die Polymerverbindungen beispielsweise als Gerüstsubstanzen mit der Fähigkeit zur Bindung der Wasserhärte wirken. Beispiele hierfür sind Polymere mit einem Gehalt an Carboxylgruppen, die in der Salzform beispielsweise als Alkalisalz vorliegen können, wie die Natrium- oder Kali¬ umsalze homopolymerer oder copolymerer Polycarboxylate, beispielswei¬ se Polyacrylate, Polymethacrylate und insbesondere Copolymere der Acrylsäure mit Maleinsäure, vorzugsweise solche aus 50 % bis 10 % Maleinsäure. Das Molekulargewicht der Homopolymeren liegt im allge¬ meinen zwischen 1.000 und 100.000, das der Copolymeren zwischen 2.000 und 200.000, vorzugsweise 50.000 bis 120.000, bezogen auf die freie Säure. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethem, wie Vinylmethylethern, Methylestern, Acrylamid und Methacrylamid, Ethylen, Propylen und Styrol, bei denen der Anteil der Säure mindestens 50 % beträgt. Aber auch zur Verbesserung des Schmutztragevermögens der wäßrigen Waschflotte werden Polymerver¬ bindungen eingesetzt. Beispiele hierfür sind Carboxymethyl-cellulose (CMC) und/oder Methylcellulose (MC).Just like the use of surfactants, the use of polymer compounds in numerous detergents and cleaning agents is common today, since the polymer compounds act, for example, as builders with the ability to bind the water hardness. Examples of these are polymers containing carboxyl groups, which may be present in the salt form, for example as an alkali salt, such as the sodium or potassium salts of homopolymeric or copolymeric polycarboxylates, for example polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those made from 50% to 10% maleic acid. The molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on the free acid. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, methyl esters, acrylamide and methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%. But polymer compounds are also used to improve the dirt-carrying capacity of the aqueous washing liquor. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).
Insbesondere hochkonzentrierte, wäßrige Zubereitungsformen dieser Po¬ lymerverbindungen zeichnen sich wie die tensidischen Zubereitungen durch einen ausgeprägten Schmiercharakter aus, der in den erfindungs¬ gemäßen Verfahren die entscheidende Verarbeitungshilfe gibt. Gleichzei¬ tig trocknen diese Polymerkomponenten bei der erfindungsgemäßen
Ausbildung des Granulatkorns zu Polymerfilmen auf, die einerseits den Zusammenhang des Korns fördern, andererseits bei Zugabe insbesonde¬ re wäßriger Medien leicht wieder in den Zustand der Lösung bzw. Emul¬ gierung oder Dispergierung übergehen. Besonders bevorzugt ist der Ein¬ satz von 3 bis 8 Gew.-% einer 30 bis 50 Gew.-%igen Lösung eines Poly¬ mers, insbesondere eines Copolymers von Acrylsäure und Maleinsäure in Wasser als Plastifizier- und/oder Gleitmittel. Vorteilhaft sind ebenso Mi¬ schungen aus diesen Polymerlösungen und den tensidischen, insbeson¬ dere aniontensidischen Plastifizier- und/oder Gleitmitteln.In particular, highly concentrated, aqueous preparation forms of these polymer compounds, like the surfactant preparations, are distinguished by a pronounced lubricating character which gives the decisive processing aid in the processes according to the invention. At the same time, these polymer components dry in the inventive Formation of the granulate to polymer films, which on the one hand promote the connection of the grain, on the other hand easily change back to the state of the solution or emulsification or dispersion when aqueous media are added. It is particularly preferred to use from 3 to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular a copolymer of acrylic acid and maleic acid in water as a plasticizer and / or lubricant. Mixtures of these polymer solutions and the surfactant, in particular anionic surfactant, plasticizers and / or lubricants are also advantageous.
Die Praxis kennt zahlreiche weitere natürliche oder synthetische Polymer¬ typen, die hier ebenso erfindungsgemäß als Plastifizier- und/oder Gleitmit¬ tel Verwendung finden können. Lediglich als Beispiele seien hier Gelatine, Stärke und Stärkederivate sowie Polyvinylalkohol genannt.Practice knows numerous other natural or synthetic polymer types, which can also be used here according to the invention as plasticizers and / or lubricants. Gelatin, starch and starch derivatives as well as polyvinyl alcohol may only be mentioned here as examples.
Aus Gründen der hinreichenden Durchfeuchtung bzw. um ein Stauben des Vorgemisches zu vermeiden, können geringfügig größere Flüssig¬ keitsmengen benötigt werden. Im allgemeinen ist es zweckmäßig, diese zusätzlichen Anteile als solche dem Vorgemisch und nicht etwa die als Gleitmittel eingesetzten Tensidpasten und/oder Polymerlösungen stärker zu verdünnen. Die Einführung solcher Flüssigkeitsmengen kann vor, wäh¬ rend und/oder nach der Verarbeitung des Plastifizier- und/oder Gleitmitteis erfolgen, wobei der Zusatz vor der Verarbeitung des Plastifizier- und/oder Gleitmittels bevorzugt ist. Es kommen jedoch nur derartig beschränkte Mengen an Flüssigphase(n) zum Einsatz, daß zunächst beim einfachen Vermischen eine rieselfähige, pulverförmige Struktur des Vorgemisches auch nach der Zugabe des Plastifizier- und/oder Gleitmittels erhalten bleibt. Der Gehalt des jeweiligen Stoffgemisches an freiem, nicht als Kri¬ stallwasser oder in vergleichbarer Form gebundenen Wassers liegt in die¬ ser Verarbeitungsstufe vorzugsweise bei bis 12 Gew.-%, vorzugsweise bis zu 10 Gew.-% und insbesondere im Bereich von etwa 4 bis 8 Gew.-%. Eingeschlossen ist in diesem Betrag der Wasseranteil, der über die Plasti- fizierungshilfsmittel mit Schmiercharakter eingetragen wird.
Gewünschtenfalls können nach der Zugabe des Plastifizier- und/oder Gleitmittels auch noch weitere Feststoffe zu dem Vorgemisch zugegeben werden. Die Gesamtmasse wird kurz nachgemischt, wobei ein festes, rie¬ selfähiges Vorgemisch anfällt, das zur Beschickung der erfindungsgemäß eingesetzten Zahnradpumpe geeignet ist.For reasons of sufficient moisture penetration or to avoid dusting the premix, slightly larger amounts of liquid may be required. In general, it is advisable to dilute these additional portions as such to the premix and not, for example, the surfactant pastes and / or polymer solutions used as lubricants. Such amounts of liquid can be introduced before, during and / or after the processing of the plasticizer and / or lubricant, the addition before processing of the plasticizer and / or lubricant being preferred. However, only such limited amounts of liquid phase (s) are used that, when mixed simply, a free-flowing, powdery structure of the premix is retained even after the addition of the plasticizer and / or lubricant. The content of the respective substance mixture in free water which is not bound as crystal water or in a comparable form is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to in this processing stage 8% by weight. Included in this amount is the amount of water that is entered via the plasticizing aids with a lubricating character. If desired, further solids can also be added to the premix after the addition of the plasticizer and / or lubricant. The total mass is briefly mixed in, a solid, free-flowing premix being obtained which is suitable for feeding the gear pump used according to the invention.
Anschließend können die Granulate wie in der internationalen Patentan¬ meldung W0-A-91/02047 einem Verrundungsschritt zugeführt werden. Hier können übliche Rondiergeräte wie Marumerizer, aber auch Siebmühlen, wie sie im Handel beispielsweise ebenfalls von der Bepex GmbH erhältlich sind, eingesetzt werden. Derartige Siebmühlen besitzen den Vorteil, daß eventuell aufgetretene Grobkornanteile auf eine maxima¬ le Kornobergrenze verkleinert werden und die dabei entstandenen Anteile an feineren Granulaten ebenfalls wieder in das Vorgemisch rückgeführt werden können. Gleichzeitig ist es auch möglich, die Granulate in dieser Verfahrensstufe in an sich üblicher Weise mit festen Stoffen abzupudern oder mit flüssigen bis wachsartigen Substanzen wie Niotensiden, Schauminhibitoren, insbesondere Silikonölen und Paraffinen, sowie Tex- tilweichmachem oder Parfümölen zu besprühen.The granules can then be fed to a rounding step as in international patent application WO-A-91/02047. Usual rounding devices such as Marumerizer, but also sieve mills, as are commercially available from Bepex GmbH, for example, can be used here. Sieve mills of this type have the advantage that any coarse-grained fractions that may have occurred are reduced to a maximum grain size limit and the fractions of finer granules that are produced in this way can likewise be returned to the premix. At the same time, it is also possible in this process step to powder the granules in a conventional manner with solid substances or to spray them with liquid to wax-like substances such as nonionic surfactants, foam inhibitors, in particular silicone oils and paraffins, and textile softeners or perfume oils.
Im Anschluß daran wird das abschließend geformte Granulatkorn vor¬ zugsweise einem Trocknungsschritt, beispielsweise einem Wirbelschicht¬ trockner, zugeführt, in dem bei mäßig angehobenen Zulufttemperaturen, insbesondere bis maximal 80 °C entsprechend mäßige Produkt- Endtemperaturen von beispielsweise zwischen 55 bis 60 °C eingestellt, dann aber nicht überschritten werden. Nach hinreichender Trocknung er¬ folgt die Kühlung des Produkts beispielsweise mit Kaltluft. Hier kann der Gehalt an freiem Wasser im Granulat abgesenkt werden. Bevorzugte Restgehalte von nicht gebundenem Wasser liegen bei Werten von etwa 1 Gew.-%, vorzugsweise im Bereich von etwa 0,1 bis 0,5 Gew.-%. Das an¬ fallende, sehr staubarme Produkt kann zur Entfernung geringer mitgebil¬ deter Grobanteile klassiert, beispielsweise abgesiebt werden. Der erfin¬ dungsgemäß einzustellende Kornanteil liegt dabei in aller Regel oberhalb 90 %, vorzugsweise oberhalb 95 % des granulierten Materials. Teilweise ist es möglich, diesen Trockenschritt auch direkt im Anschluß an die Ver-
pressung des Primärgranulats und damit zeitlich vor der gewünschtenfalls vorgenommenen, abschließenden Formgebung in einem Rondiergerät durchzuführen.Subsequently, the finally formed granulate is preferably fed to a drying step, for example a fluidized bed dryer, in which correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C. but then not be exceeded. After sufficient drying, the product is cooled, for example with cold air. Here the content of free water in the granulate can be reduced. Preferred residual contents of unbound water are about 1% by weight, preferably in the range of about 0.1 to 0.5% by weight. The resulting, very low-dust product can be classified, for example sieved, to remove small coarse particles that are formed. The proportion of grain to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material. In some cases it is also possible to carry out this drying step directly after the pressing the primary granulate and thus before the final shaping, if desired, to be carried out in a rounding device.
Wenigstens anteilsweise ist aber auch die „innere Trocknung" der Granu¬ late möglich: Durch die Mitverwendung von feuchtigkeitsbindenden Be¬ standteilen im Vorgemisch kann in der kurzen Verarbeitungszeitspanne der plastifizierende Effekt der vorgelegten Flüssiganteile ausgenutzt wer¬ den: Dann findet durch die Bindung wenigstens partieller Anteile dieser Flüssiganteile durch die eingemischten Bestandteile eine Trocknung des Granulats „von innen heraus" statt, so daß die äußere Trocknung abge¬ kürzt werden kann oder ganz entfällt. Bestandteile, die in der Lage sind, Wasser in Form von Kristallwasser zu binden, sind beispielsweise Natri¬ umsulfat und/oder Natriumcarbonat in wasserfreier oder wasserarmer Form oder auch ein vom Kristallwasser anteilsweise befreites Zeolith.At least partially, however, the "internal drying" of the granules is also possible: by using moisture-binding components in the premix, the plasticizing effect of the liquid components presented can be exploited in the short processing time: Then at least partial components are found by binding of these liquid components due to the mixed-in constituents, the granules are dried "from the inside", so that the external drying can be shortened or omitted entirely. Constituents which are able to bind water in the form of water of crystallization are, for example, sodium sulfate and / or sodium carbonate in anhydrous or low-water form or else a zeolite partially freed from water of crystallization.
In einer weiteren bevorzugten Ausführungsform können die primär gebil¬ deten und noch plastischen Granulatkörner vor, während und/oder nach einer gegebenenfalls vorgenommenen Abrundung der weiteren Wirkstoffe beaufschlagt werden. Vorzugsweise können aber auch beispielsweise empfindliche, insbesondere temperaturempfindliche Rezepturbestandteile dem aufgetrockneten Granulat zugegeben, z. B. aufgesprüht und/oder als getrennt ausgebildetes Korn unter Ausbildung eines Mehrkorngemisches zugemischt werden. Die Erfindung erfaßt dabei sowohl den Bereich ge¬ brauchsfertiger Mehrstoffgemische in Form einheitlicher Granulatkörper als auch Teilprodukte, die zur Rezepturvervollständigung nach der Ab¬ mischung mit weiteren Bestandteilen des jeweiligen betroffenen Wasch- und Reinigungsmittels bedürfen. Vorteilhafterweise sind mehr als 60 Gew.-% und insbesondere mehr als 70 Gew.-% des Gesamtstoffgemi¬ sches nach dem erfindungsgemäßen Verfahren gewonnene Granulate mit hochverdichteter und fester Kornstruktur.In a further preferred embodiment, the primarily formed and still plastic granules can be applied before, during and / or after any rounding off of the further active ingredients. Preferably, however, sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, e.g. B. sprayed and / or mixed as a separately formed grain to form a multigrain mixture. The invention encompasses both the area of ready-to-use multi-substance mixtures in the form of uniform granulate bodies and also partial products which, in order to complete the recipe, require mixing of further constituents of the particular detergent and cleaning agent concerned. Advantageously, more than 60% by weight and in particular more than 70% by weight of the total mixture are granules obtained by the process according to the invention with a highly compressed and solid grain structure.
Nach einer besonders wichtigen Ausführungsform der vorliegenden Erfin¬ dung werden Granulatsysteme eingesetzt, die eine Kombination von Gra¬ nulaten unterschiedlicher Zusammensetzung darstellen. Auf diese Weise
gelingt die lagerstabile Vereinigung potentiell reaktiver oder zumindest nur begrenzt verträglicher Komponenten. Ein Beispiel hierfür sind übliche Textilwaschmittel, die in dieser Aufbereitungsform jetzt jedoch wenigstens zwei Granulattypen in Mischung miteinander einsetzen. In einer ersten, beispielsweise kugelförmigen Granulattype wird die Bleichmittelkompo¬ nente, insbesondere kristallwasserhaltiges Perborat oder Natriumcarbonat unter Mitverwendung eines Anteils der Plastifizier- und/oder Gleitmittel pelletiert, in einem getrennten zweiten Granulatkorn wird der gegebenen¬ falls als Waschmittelbuildersubstanz eingesetzte Zeolith, insbesondere Zeolith NaA und/oder Zeolith P, mit dem Rest der Waschmittelbestandteile verpreßt. Die Lagerstabilität des Mischproduktes substantiell beeinflus¬ sende Interaktion zwischen Peroxybleichmittel und Zeolith - wie sie in pul¬ verförmigen Zubereitungen zu berücksichtigen sind - sind auf diese Weise ausgeschlossen. Bei dieser Möglichkeit des Einsatzes von Granulatsy¬ stemen aus unterschiedlich zusammengesetzten Granulaten kann in na¬ hezu beliebiger Kombination Gebrauch gemacht werden.According to a particularly important embodiment of the present invention, granule systems are used which represent a combination of granules of different compositions. In this way the storage-stable combination of potentially reactive or at least only partially compatible components succeeds. An example of this are conventional textile detergents, which, however, now use at least two types of granules in a mixture with one another in this preparation form. In a first, for example spherical type of granulate, the bleaching agent component, in particular perborate or sodium carbonate containing water of crystallization, is pelletized with the use of a proportion of the plasticizers and / or lubricants, in a separate second granulate the zeolite, if used as detergent builder, in particular zeolite NaA and / or zeolite P, pressed with the rest of the detergent components. The storage stability of the mixed product, which has a substantially influencing interaction between peroxy bleaching agent and zeolite - as must be taken into account in powdery preparations - is excluded in this way. With this possibility of using granulate systems of differently composed granules, use can be made in almost any combination.
In einer weiteren bevorzugten Ausführungsform können die erfindungs¬ gemäße Granulate recycliert werden, d. h., sie können im ersten Verfah¬ rensschritt in Kombination mit anderen Schritten zur Herstellung des pla¬ stifizierten Vorgemischs eingesetzt werden.In a further preferred embodiment, the granules according to the invention can be recycled, ie. that is, they can be used in the first process step in combination with other steps to produce the plasticized premix.
Die Materialdichten im Korn und somit auch die Schüttdichte des Granu¬ lats werden durch die bei dem Verpressen des homogenisierten Materials durch die Lochplatten eingesetzten Arbeitsdrücke maßgeblich mitbe¬ stimmt. Durch den Aufbau einer hinreichend verdichteten Grundstruktur der zu verpressenden Masse und Einsatz entsprechend hoher Dichtdruk- ke lassen sich z. B. bei üblichen Textilwaschmittel-Rezepturen Schüttdich¬ ten deutlich oberhalb 700 g/l, vorzugsweise oberhalb 750 g/l und insbe¬ sondere im Bereich von etwa 800 bis annähernd 1.000 g/l verwirklichen. So sind auf Basis handelsüblicher Textilwaschmittelformulierungen Schüttdichten im Bereich von 850 bis 980 g/l bei gleichzeitig guter Riesel¬ fähigkeit und einer bevorzugt hohen, einheitlichen, kugelförmigen Korn¬ struktur einstellbar. In ähnlichen Einsätzen sind rieselfähige Granulate im Trockenzustand mit einheitlichen Schüttdichten von 950 bis 980 g/l bei
einer durchschnittlichen Teilchengröße der kugelförmigen Granulate im Bereich von beispielsweise etwa 1 mm verwirklicht worden.The material densities in the grain and thus also the bulk density of the granules are decisively determined by the working pressures used in pressing the homogenized material through the perforated plates. By building up a sufficiently compacted basic structure of the mass to be pressed and using correspondingly high sealing pressures, z. B. with conventional textile detergent formulations bulk densities well above 700 g / l, preferably above 750 g / l and in particular in the range from about 800 to approximately 1,000 g / l. Bulk densities in the range from 850 to 980 g / l can be adjusted on the basis of commercially available textile detergent formulations with good free-flowing properties and a preferably high, uniform, spherical grain structure. In similar applications, free-flowing granules are in the dry state with uniform bulk densities of 950 to 980 g / l an average particle size of the spherical granules in the range of, for example, about 1 mm.
Wie bereits vorstehend erörtert, zeichnet sich das erfindungsgemäßen Verfahren durch einen sehr geringen Rückgut-Anteil aus. Dieser Rückgut- Anteil nach der Siebung des Granulats über ein 1 ,6 mm-Sieb lag jeweils im Bereich von höchstens 7 Gew.-% Analog zur konventionellen Waschmittelaufbereitung können empfindliche Rezepturbestandteile, bei¬ spielsweise Aktivatoren für Bleichmittel, Enzyme, Entschäumer, insbeson¬ dere Silikonentschäumer, Parfüm und dergleichen, dem Granulat zuge¬ setzt werden. Selbst dann werden noch immer Waschmittelprodukte mit Schüttdichten im Bereich von etwa 900 g/l erhalten.As already discussed above, the method according to the invention is characterized by a very low proportion of returned goods. This portion of the return material after sieving the granules through a 1.6 mm sieve was in each case in the range of at most 7% by weight. Analogous to conventional detergent preparation, sensitive formulation constituents, for example activators for bleaching agents, enzymes, defoamers, in particular Silicone defoamers, perfume and the like are added to the granules. Even then, detergent products with bulk densities in the range of about 900 g / l are still obtained.
Die heute marktüblichen Textilwaschmittel in Form rieselfähiger Pulver und/oder Granulate enthalten in aller Regel eine Kombination von anion- tensidischen und niotensidischen Waschaktivkomponenten. Im allgemei¬ nen machen die Aniontensidkomponenten den größten Anteil und die Niotenside den kleineren Anteil des Tensidgemisches aus. So können Textilwaschmittelkonzentrate mit Tensidgehalten beispielsweise bis 35 Gew.-% und vorzugsweise im Bereich von etwa 15 bis 25 Gew.-% herge¬ stellt werden, ohne daß Verklebungen und/oder Produkterweichungen zu befürchten sind, wie sie in den marktgängigen, pulverförmigen Ab¬ mischungen bei solchen Anhebungen des Tensidgehalts auftreten. Durch die Kombination der Maßnahmen der Verdichtung der Stoffgemische zu hohen Schüttdichten und einer gleichzeitigen Anhebung der waschaktiven Inhaltsstoffe, insbesondere der Tenside in ihrem Mengenanteil im Waschmittelgemisch wird das Ziel raumsparender und verpackungsarmer Waschmittelzubereitungen optimal verwirklicht, ohne den Bereich riesel¬ fähiger, lagerstabiler und alle sonstige Anforderungen erfüllender Waschmittelzubereitungen verlassen zu müssen.The textile detergents which are customary in the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic surfactant and nonionic surfactant detergent components. In general, the anionic surfactant components make up the largest proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture. Textile detergent concentrates with surfactant contents, for example, of up to 35% by weight and preferably in the range of about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as is the case in the commercially available powdery formulations Mixtures occur with such increases in the surfactant content. By combining the measures of compression of the substance mixtures to high bulk densities and a simultaneous increase in the detergent ingredients, especially the surfactants in their proportion in the detergent mixture, the goal of space-saving and low-packaging detergent preparations is optimally achieved without the area of free-flowing, storage-stable and all other requirements having to leave fulfilling detergent preparations.
Die Aufbereitung von Wasch- und Reinigungsmitteln im erfindungsgemä¬ ßen Verfahrenstyp der Granulation zur vorbestimmten Teilchengröße bringt eine Vielzahl von Vorteilen:
Es hat sich gezeigt, daß im erfindungsgemäßen Verfahren das Bleichmit¬ tel, insbesondere Natriumperborat in Form des Monohydrats und/oder des Tetrahydrats schon in der zu klassifizierenden und dann zu verpressen¬ den Rohmasse mitverarbeitet werden kann, ohne daß substantielle Ver¬ luste an Perborat auftreten. Damit enthält jedes Granulatkorn den vorbe¬ stimmten Granulatanteil an Peroxybleichmittel. Der Einsatz von sprühge¬ trockneten Pulvern/Granulaten mit variabler Zumischung ist möglich. Auf der anderen Seite sind zur Herstellung der zu verpressenden Rohmassen weder sprühgetrocknete Pulver/Granulate noch vorgebildete Pulver mit Bead-Struktur erforderlich. Der Einsatz bzw. Zusatz von Schwerpulvern der einzelnen Rohstoffe ist nicht erforderlich. Die Verarbeitung der in Wasch- und Reinigungsmitteln üblicherweise eingesetzten Niotenside wird problemlos, die in der Sprühtrocknung hier auftretenden Pluming-Effekte, siehe Definition in Römpp Chemielexikon, 4. Auflage, Band 5, S. 3488, entfallen. Die Niotenside werden durch Einarbeitung in das Stoffgemisch vor dem Preßschritt problemlos zugeführt, sie können hier sogar als hoch¬ konzentriertes, wäßriges Gel bzw. Paste wertvolle Verfahrenshilfe in der geschilderten Weise leisten.The preparation of detergents and cleaning agents in the process type of granulation according to the invention to the predetermined particle size brings a number of advantages: It has been shown that in the process according to the invention the bleaching agent, in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate, can already be processed in the raw material to be classified and then pressed without substantial losses of perborate occurring . Each granulate thus contains the predetermined proportion of granules of peroxy bleach. The use of spray-dried powders / granules with variable admixture is possible. On the other hand, neither spray-dried powders / granules nor pre-formed powders with a bead structure are required to produce the raw materials to be pressed. The use or addition of heavy powder of the individual raw materials is not necessary. The processing of the nonionic surfactants commonly used in detergents and cleaning agents is no problem, and the pluming effects that occur in spray drying, see definition in Römpp Chemielexikon, 4th edition, volume 5, p. 3488, are eliminated. The nonionic surfactants are added without problems by incorporation into the mixture of substances before the pressing step; they can even provide valuable process help in the manner described here as a highly concentrated, aqueous gel or paste.
Die mögliche Einarbeitung von Entschäumern in flüssiger Form erspart ein Verfahren zur getrennten Herstellung von Entschäumer-Feststoffträger- Konzentraten. Hierdurch entfällt die Zumischung von Entschäumer- Granulat bei der Waschmittelaufbereitung. Als besonders vorteilhaft hat sich erwiesen, den Entschäumer direkt in das Plastifizier- und/oder Gleitmittel einzumischen.The possible incorporation of defoamers in liquid form saves a process for the separate production of defoamer solid carrier concentrates. This eliminates the need to add defoamer granules to the detergent preparation. It has proven to be particularly advantageous to mix the defoamer directly into the plasticizer and / or lubricant.
Die Erfindung betrifft in einer besonderen Ausführungsform Universal¬ waschmittel für Textilien, die in dieser Angebotsform der gut rieselfähigen Granulate mit Schüttdichten oberhalb 750 g/l, insbesondere oberhalb 800 g/l, beispielsweise im Bereich von 850 bis 950 g/l vorliegen und in einer besonders wichtigen Ausführungsform durch eine einheitliche Teilchen¬ form und -große gekennzeichnet sind. Die bevorzugte Teilchenform ist die Kugelform. Bevorzugte Teilchengrößen liegen hier im Bereich von 0,5 bis 10 mm Kugeldurchmesser, insbesondere im Bereich von etwa 1 bis 5 mm.
Die Rezepturbestandteile können dabei in Art und Menge den heute übli¬ chen buildersubstanzhaltigen Textilwaschmitteln entsprechen.In a particular embodiment, the invention relates to universal detergents for textiles which are present in this form of the free-flowing granules with bulk densities above 750 g / l, in particular above 800 g / l, for example in the range from 850 to 950 g / l and in one particularly important embodiment are characterized by a uniform particle shape and size. The preferred particle shape is spherical. Preferred particle sizes here are in the range from 0.5 to 10 mm ball diameter, in particular in the range from approximately 1 to 5 mm. The type and quantity of the formulation components can correspond to that of today's textile detergents containing builder substances.
Es folgen allgemeine Angaben zur Zusammensetzung geeigneter Wirk- stoffgemische, wobei hier insbesondere heute übliche Bestandteile von Textilwaschmitteln zusammengefaßt sind.The following is general information on the composition of suitable active substance mixtures, with components of textile detergents customary today being summarized here.
Als anionische Tenside eigenen sich beispielsweise solche vom Typ der Sulfonate und Sulfate. Als Tenside vom Sulfonattyp kommen Alkylbenzol¬ sulfonate (C9 bis C13-Alkyl), Olefinsulfonate, d. h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispiels¬ weise aus C12-bis C18-Monoolefιnen mit end- oder innenständiger Dop¬ pelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und an¬ schließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch die Alkansulfonate, die aus C12-bis C18-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation bzw. durch Bisulfitaddition an Olefine er¬ hältlich sind, sowie insbesondere die Ester von α-Sulfofettsäuren (Estersulfonate), z. B. die α-sulfonierten Methylester der hydrierten Kokos- , Palmkern- oder Taigfettsäuren.Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type. Suitable surfactants of the sulfonate type are alkylbenzene sulfonates (C 9 to C 13 alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates of the type obtained, for example, from C 12 to C 18 monoolefins with terminal or internal ones Double bond obtained by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are the alkanesulfonates which are obtainable from C 12 to C 18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of α-sulfofatty acids (ester sulfonates), for . B. the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
Geeignete sind Tenside vom Sulfattyp sind die Schwefelsäuremonoester aus primären Alkoholen natürlichen oder synthetischen Ursprungs, insbe¬ sondere aus Fettalkoholen, z. B. aus Kokosfettalkohol, Taigfettalkohol, Oleylalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder den C10- C2o-Oxoalkoholen, und diejenigen sekundärer Alkohole dieser Kettenlän¬ ge. Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten Alkohole, wie 2-Methyl-verzweigte Cg-C-* •, -Alkohole mit dem Durchschnitt 3,5 Mol Ethylenoxid, sind geeignet. Bevorzugte Fettalkylsul- fate leiten sich von aus Kokosöl, Palm- und Palmkernöl gewonnenen Fettalkoholgemischen, die zusätzlich noch Anteile an ungesättigten Alko¬ holen, z. B. an Oleylalkohol, enthalten können, ab. Eine bevorzugte Ver¬ wendung finden dabei Gemische, in denen der Anteil der Alkylreste zu 30 bis 70 Gew.-% auf C12 zu 18 bis 30 Gew.-% auf C14> zu 5 bis 15 Gew.-%
auf C16, unter 3 Gew -% auf C10 und 0 bis 40 Gew -% auf C18 verteilt sind Ebenso eignen sich sulfatierte FettsauremonoglyceπdeSuitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, in particular from fatty alcohols, e.g. B. from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 - C 2 o-oxo alcohols, and those secondary alcohols of this chain length. The sulfuric acid monoesters of alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched Cg-C- * •, alcohols with an average of 3.5 moles of ethylene oxide, are also suitable. Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals is 30 to 70% by weight on C 12 to 18 to 30% by weight on C 14> 5 to 15% by weight find a preferred use. are distributed on C 16 , less than 3% by weight on C 10 and 0 to 40% by weight on C 18. Sulfated fatty acid monoglycides are also suitable
Ebenso bevorzugte Aniontenside sind die Salze der Alkylsulfobernstein- saure, die auch als Sulfosuccinate oder als Sulfobernstemsaureester be¬ zeichnet werden und die Monoester und/oder Diester der Sulfobernstein- saure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen Bevorzugte Sulfosuccinate enthal¬ ten C8- bis C18-Fettalkoholreste oder Mischungen aus diesen Insbeson¬ dere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nicht ioni¬ sche Tenside darstellen Dabei sind wiederum Sulfosuccinate, deren Fet¬ talkoholreste sich von ethoxylierten Fettalkoholen mit eingeengter Homo- logenverteilung ableiten, besonders bevorzugtLikewise preferred anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 - C 18 -fatty alcohol residues or mixtures of these, in particular preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants. In turn, sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols derive narrowed homogeneous distribution, particularly preferred
Als weitere anionische Tenside kommen insbesondere Seifen, vorzugs¬ weise in Mengen von 0,5 bis 5 Gew -% in Betracht Geeignet sind gesat¬ tigte Fettsaureseifen, wie die Salze der Laurinsaure, Myπstinsaure, Pal- mitinsaure oder Stearinsaure, sowie insbesondere aus natürlichen Fett¬ sauren, z B Kokos-, Palmkern- oder Talgfettsauren, abgeleitete Seifen- gemischeOther suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 5% by weight. Saturated fatty acid soaps, such as the salts of lauric acid, mypinsic acid, palmitic acid or stearic acid, and in particular from natural fat, are suitable ¬ acidic, eg coconut, palm kernel or tallow fatty acids, derived soap mixtures
Die anionischen Tenside können in Form ihrer Natrium-, Kalium- oder Ammomumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Tπethanolamin vorliegen Vorzugsweise liegend die anionischen Tenside in Form ihrer Natrium- oder Kahumsalze vor Der Gehalt erfin- dungsgemaßer Waschmittel an anionischen Tensiden bzw an anioni- schen Tensidgemischen betragt vorzugweise 5 bis 40 Gew -%, insbeson¬ dere 8 - 30 Gew-%The anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tetrahanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts before the content of detergents according to the invention anionic surfactants or anionic surfactant mixtures is preferably 5 to 40% by weight, in particular 8 to 30% by weight
Als nichtionische Tenside sind Anlagungsprodukte von 1 - 40, vorzugs¬ weise von 2 - 20 Mol Ethylenoxid an ein Mol einer aliphatischen Verbin¬ dung mit im wesentlichen 10 - 20 Kohlenstoffatomen aus der Gruppe der Alkohole, Carbonsauren, Fettamine, Carbonsäureamide und Alkansul- fonamide verwendbar
Als nichtionische Tenside dienen vorzugsweise flüssige ethoxylierte und/oder propoxylierte Alkohole, die sich von primären Alkoholen mit vor¬ zugsweise 8 bis 18 Kohlenstoffatomen und durchschnittlich 1 bis 12 Mol Alkylenoxid ableiten, in denen der Alkoholrest linear oder in 2-Stellung methylverzweigt sein kann, bzw. lineare oder methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch lineare Reste aus Alkoholen nativen Ursprungs mit 12 bis 18 Kohlenstoffatomen bevorzugt, wie z. B. aus Ko¬ kos-, Taigfett- oder Oleylalkohol. Insbesondere werden C12-C14-Alkohole mit drei Mol Ethylenoxid oder vier Mol Ethylenoxid, C9-Cι rAlkohol mit 7 Mol Ethylenoxid, C13-C15-Alkohole mit drei Mol Ethylenoxid, fünf Mol Ethylenoxid, sieben Mol Ethylenoxid oder acht Mol Ethylenoxid, C12-C18- Alkoholen mit drei Mol Ethylenoxid, fünf Mol Ethylenoxid oder sieben Mol Ethylenoxid oder Mischungen aus diesen, wie Mischungen aus C12- bis C14-Alkohol mit drei Mol Ethylenoxid und C12- bis C18-Alkohol mit fünf Mol Ethylenoxid eingesetzt.Addition products of 1-40, preferably 2-20 moles of ethylene oxide to one mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides can be used as nonionic surfactants The preferred nonionic surfactants are liquid ethoxylated and / or propoxylated alcohols derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of alkylene oxide, in which the alcohol residue can be linear or methyl-branched in the 2-position, or can contain linear or methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. from Ko¬ kos-, tallow or oleyl alcohol. In particular, C 12 -C 14 alcohols with three moles of ethylene oxide or four moles of ethylene oxide, C 9 -C ι r alcohol with 7 moles of ethylene oxide, C 13 -C 15 alcohols with three moles of ethylene oxide, five moles of ethylene oxide, seven moles of ethylene oxide or Eight moles of ethylene oxide, C 12 -C 18 alcohols with three moles of ethylene oxide, five moles of ethylene oxide or seven moles of ethylene oxide or mixtures thereof, such as mixtures of C 12 to C 14 alcohol with three moles of ethylene oxide and C 12 to C 18 -Alcohol used with five moles of ethylene oxide.
Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homolo¬ genverteilung auf (Narrow Range Ethoxylates, NRE). Insbesondere sind Alkoholethoxylate bevorzugt, die durchschnittlich 2 bis 8 Ethylenoxidgrup- pen aufweisen.The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrowed homolog distribution (narrow range ethoxylates, NRE). In particular, alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
Außerdem können als weitere nichtionische Tenside auch Alkylpolyglyco- side der allgemeinen Formel RO (G)x eingesetzt werden, in der R einen primären, geradkettigen oder in 2-Stellung methylverzweigten aliphati¬ schen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glucoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglycosiden oder Oligoglycosiden angibt, ist eine be¬ liebige Zahl zwischen 1 und 10.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der allgemei¬ nen FormelIn addition, alkylpolyglycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position means and G is the symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides or oligoglycosides, is any number between 1 and 10. Other suitable surfactants are polyhydroxy fatty acid amides of the general formula
R3 R 3
R2 - CO - N - [Z],R 2 - CO - N - [Z],
in der R2 - CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffa¬ tomen, R3 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Po- lyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxyl¬ gruppen steht. Vorzugsweise werden als Polyhydroxyfettsäureamide Fett- säure-N-alkylglucamide eingesetzt, in der R3 für Wasserstoff oder eine Alkylgruppe, R2 - CO für den Acylrest einer gesättigten oder ungesättigten Fettsäure und [Z] für einen Glucoserest steht.in the R 2 - CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides in which R 3 is hydrogen or an alkyl group, R 2 - CO is the acyl radical of a saturated or unsaturated fatty acid and [Z] is a glucose radical.
Unter den als Bleichmittel dienenden, in Wasser Wasserstoffperoxid lie¬ fernden Verbindungen haben das Natriumperborattetrahydrat, Natrium- perboratmonohydrat und das Natriumpercarbonat Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Peroxypyrophosphate, Citrat- perhydrate sowie Wasserstoffperoxid liefernde persaure Salze oder Per¬ säuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure oder Di- perdodekandisäure. Der Gehalt der Mittel an Bleichmittel beträgt vor¬ zugsweise 5 bis 25 Gew.-% und insbesondere 10 bis 20 Gew.-%, wobei vorteilhafterweise Perboratmonohydrat oder Percarbonat eingesetzt wer¬ den.Among the compounds which serve as bleaching agents and which are hydrogen peroxide in water, sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of importance. Further bleaching agents that can be used are, for example, peroxypyrophosphates, citrate perhydrates and peracid salts or peracids providing hydrogen peroxide, such as perbenzoates, peroxophthalates, diperazelaic acid or dimerododecanedioic acid. The bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate or percarbonate advantageously being used.
Um beim Waschen bei einer Temperatur von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren in die Präparate eingearbeitet werden. Beispiele hierfür sind mit Wasserstoff¬ peroxid organische Persäuren bildende N-Acyl- bzw. O-Acyl- Verbindungen, vorzugsweise N,N'-tetraacylierte Diamine, ferner Carbon¬ säureanhydride und Ester von Polyolen wie Glucosepentaacetat. Der Ge¬ halt der bleichmittelhaltigen Mittel an Bleichmittelaktivatoren liegt in dem üblichen Bereich, vorzugsweise zwischen 1 und 10 Gew.-% und insbe-
sondere zwischen 2 und 8 Gew.-%. Besonders bevorzugte Bleichaktivato¬ ren sind N,N,N',N'-Tetraacetylethylendiamin, 1 ,4-Diacetyl-2,4-dioxo- hexahydro-1 ,3,5-triazin, ferner Carbonsäureanhydride und Ester von Po¬ lyolen, wie Glucosepentaacetat.In order to achieve an improved bleaching effect when washing at a temperature of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. The bleaching agent content of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular in particular between 2 and 8% by weight. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine, 1,4-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, also carboxylic anhydrides and esters of polyols, such as Glucose pentaacetate.
Neben den wasserlöslichen Nonionics sind auch nicht beziehungsweise nicht vollständig wasserlösliche Polyglykolether mit 2 bis 7 Ethylenglykole¬ therresten im Molekül von Interesse, insbesondere, wenn sie zusammen mit wasserlöslichen, nichtionischen oder anionischen Tensiden eingesetzt werden.In addition to the water-soluble nonionics, not or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
Als organische oder anorganische Gerüstsubstanzen eignen sich schwach sauer, neutral oder alkalisch reagierende lösliche und/oder un¬ lösliche Komponenten, die Calciumionen ausfällen oder komplex zu bin¬ den vermögen. Geeignete und insbesondere ökologisch unbedenkliche Substanzen, wie feinkristalline, synthetische wasserhaltige Zeolithe vom Typ NaA und/oder Zeolith P, die ein Calciumbindevermögen im Bereich von 100 - 200 mg CaO/g (gemäß den Angaben der DE 24 12 837) auf¬ weisen, findet eine bevorzugte Verwendung. Ihre mittlere Teilchengröße liegt üblicherweise im Bereich von 1 - 10 Mikrometer (Meßmethode: Coulter Counter; Volumenverteilung). Ihr Gehalt beträgt im allgemeinen 0 - 40, vorzugsweise 10 - 30 Gew.-%, bezogen auf die wasserfreie Sub¬ stanz. Zeolith NaA fällt bei seiner Herstellung als wasserhaltiger Slurry (Masterbatch) an, der nach heute üblichen Verfahren der Herstellung von Textilwaschmitteln einer Trocknung, insbesondere einer Sprühtrocknung unterworfen wird. Ihr Wassergehalt liegt vorzugsweise zwischen 19 und 22 Gew.-%. Sie weisen praktisch keine Teilchen größer als 30 Mikrometer auf und bestehen vorzugsweise aus wenigstens 80 % Teilchen einer Grö¬ ße kleiner als 10 Mikrometer. Geeignet sind insbesondere Zeolith A und Zeolith P, ferner auch Zeolith X sowie Mischungen aus A und X und/oder P. Mengenangaben und Gewichtsverhältnisse, die den Gerüststoff treffen, werden im Rahmen der vorliegenden Erfindung - sofern nichts anderes angegeben ist - auf wasserfreie Aktivsubstanz bezogen.
Geeignete Substitute beziehungsweise Teilsubstitute für Phosphate und Zeolith sind einmal kristalline, schichtförmige Silikate der allgemeinen Formel NaMSixθ2X+ι • VH2O, wobei M Natrium oder Wasserstoff bedeu¬ tet, x eine Zahl von 1,9 - 4, y eine Zahl von 0 - 20 ist. Derartige Schichtsili¬ kate werden beispielsweise in der europäischen Patentanmeldung 0164514 beschrieben. Insbesondere sind sowohl ß- als auch δ- Natriumdisilikate Na2Si2θ5 • yH2O bevorzugt. Weitere Builder-Substanzen sind amorphe Silikate mit Sekundärwaschvermögen, beispielsweise sol¬ che gemäß DE-P44 00 024.3, DE-P44 19 745.4 und DE-P44 46 363.4. Erfindungsgemäß wird es auch möglich sein, Zeolith und/oder das kri¬ stalline Schichtsilikat und/oder das amorphe Silikat als Mischungen einzu¬ setzen, wobei das Mischungsverhältnis beliebig ist. Vorzugsweise wird jedoch Zeolith entweder allein oder mit einem Gewichtsverhältnis Zeolith zu kristallinem Schichtsilikat oder amorphem Silikat mit Sekundär¬ waschvermögen von 10 : 1 bis 1 : 3 und insbesondere 3 : 1 bis 1 : 1 ein¬ gesetzt. Erfindungsgemäß ist es weiter möglich, den Zeolith oder wenig¬ stens Zeolithanteile in Form des nicht getrockneten Masterbatch oder ei¬ nes nur anteilsweise angettrockneten und damit lediglich beschränkt in Wassergehalt abgereicherten Materials der Vormischung zuzuführen.Weakly acidic, neutral or alkaline-reacting soluble and / or insoluble components which precipitate or bind calcium ions in a complex manner are suitable as organic or inorganic builders. Suitable and, in particular, ecologically harmless substances, such as finely crystalline, synthetic water-containing zeolites of the NaA type and / or zeolite P, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 24 12 837) a preferred use. Their average particle size is usually in the range from 1 to 10 micrometers (measurement method: Coulter Counter; volume distribution). Their content is generally 0-40, preferably 10-30% by weight, based on the anhydrous substance. Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents. Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 micrometers and preferably consist of at least 80% particles smaller than 10 micrometers. Zeolite A and zeolite P are particularly suitable, as are zeolite X and mixtures of A and X and / or P. Quantities and weight ratios that affect the builders are based on the anhydrous active substance in the context of the present invention, unless stated otherwise . Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered silicates of the general formula NaMSi x θ2 X + ι • VH2O, where M is sodium or hydrogen, x is a number from 1.9 to 4, y is a number from 0 to 20 is. Such layer silicates are described, for example, in European patent application 0164514. In particular, both β- and δ-sodium disilicates Na2Si2θ 5 • yH 2 O are preferred. Other builder substances are amorphous silicates with secondary washing power, for example those according to DE-P44 00 024.3, DE-P44 19 745.4 and DE-P44 46 363.4. According to the invention, it will also be possible to use zeolite and / or the crystalline layered silicate and / or the amorphous silicate as mixtures, the mixing ratio being arbitrary. However, zeolite is preferably used either alone or with a zeolite to crystalline layered silicate or amorphous silicate weight ratio with secondary washability of 10: 1 to 1: 3 and in particular 3: 1 to 1: 1. According to the invention, it is further possible to add the zeolite or at least zeolite fractions in the form of the undried masterbatch or only partially dried and thus only water-depleted material to the premix.
Brauchbare organische Gerüstsubstanzen sind beispielsweise Polycar- boxylate, die vorzugsweise in Form ihrer Natriumsalze eingesetzten Poly¬ carbonsäuren, wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutar- säure, Aminocarbonsäure, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mi¬ schungen aus diesen und (co)-polymeren Polycarbonsäuren und Polycar- boxylaten, wie die Natriumsalze der Polyacrylsäuren oder Polymethacryl- säuren, beispielsweise solche mit einer relativen Molekulmasse von 800 bis 150000 (auf Säure bezogen) sowie insbesondere solche der Acrylsäu¬ re mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Mal¬ einsäure bevorzugt sind, zusätzlich enthalten. Als besonders gut geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allge¬ meinen 5000 bis 200000, vorzugsweise 10000 bis 120000 und insbeson-
dere 50000 bis 100000. Insbesondere bevorzugt sind auch biologisch ab¬ baubare Terpolymere, beispielsweise solche, die gemäß der DE-A-43 00 772 als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohole bzw. Vinylalkohol-Derivate oder gemäß der DE-C-42 21 381 als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A-43 03 320 und P 44 17 734.8 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Usable organic builders are, for example, polycarboxylates, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons. and mixtures of these and (co) -polymeric polycarboxylic acids and polycarboxylates, such as the sodium salts of polyacrylic acids or polymethacrylic acids, for example those with a relative molecular weight of 800 to 150,000 (based on acid) and in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid are preferred, additionally contained. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000, and in particular more 5000 to 100000. Also particularly preferred are biodegradable terpolymers, for example those which, according to DE-A-43 00 772, as salts of acrylic acid and maleic acid as well as vinyl alcohols or vinyl alcohol derivatives or according to DE-C- 42 21 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives. Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
In Fällen, in denen ein Phosphatgehalt toleriert wird, können auch Phos¬ phat mitverwendet werden, insbesondere Pentanatriumtriphosphat, gege¬ benenfalls auch Pyrophosphate wie Orthophosphate, die in der ersten Linie als Fällungsmittel für Kalksalze wirken. Der Gehalt an Phosphaten, bezogen auf Pentanatriumtriphosphat liegt unter 30 Gew -%. Es werden hier jedoch bevorzugt Mittel ohne Phosphatgehalt eingesetzt.In cases where a phosphate content is tolerated, phosphate can also be used, in particular pentasodium triphosphate, possibly also pyrophosphates such as orthophosphates, which act primarily as precipitants for lime salts. The phosphate content, based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used here.
Geeignete anorganische, nicht komplexbildende Salze sind die - auch als Waschalkalien bezeichneten - Bicarbonate, Carbonate, Borate oder Silika¬ te der Alkalien, von den Alkalisilikaten sind vor allem die Natriumsilikate mit einem Verhältnis Na2θ:Siθ2 wie 1 : 1 bis 1 : 3,5 brauchbar (siehe oben).Suitable inorganic, non-complexing salts are the bicarbonates, also known as washing alkalis, carbonates, borates or silicates of the alkalis. Of the alkali silicates, especially the sodium silicates with a ratio Na2θ: Siθ2 such as 1: 1 to 1: 3.5 usable (see above).
Zu den sonstigen Waschmittelbestandteilen zählen Vergrauungsinhibito- ren (Schmutzträger), Schauminhibitoren, optische Aufheller, Enzyme, textiiweichmachende Stoffe, Färb- und Duftstoffe sowie Neutralsalze.The other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts.
Vergrauungsinhibitoren haben die Aufgabe, den von der Faser abgelösten Schmutz in der Flotte suspendiert zu halten und so das Vergrauen zu verhindern. Hierfür sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise die wasserlöslichen Salze polymerer Carbonsäu¬ ren, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke und der Cellulose, Ethersulfonsäuren oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche,
saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet Weiterhin lassen sich losliche Starkepraparate und andere als die oben¬ genannten Starkeprodukte verwenden, z B abgebaute Starke, Aldehyd¬ starken usw Auch Polyvinylpyrrolidon ist brauchbar Bevorzugt werden jedoch Carboxymethylcellulose (Natriumsalz), Methylcellulose, Methyl- hydroxyethylcellulose und deren Gemische sowie Polyvinylpyrrolidon, bei¬ spielsweise in Mengen von 0,1 bis 5 Gew -%, bezogen auf die Mittel, ein¬ gesetztGraying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying. Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch and cellulose, ether sulfonic acids or salts of acidic sulfuric acid esters of cellulose or starch. Also water soluble, Acid-containing polyamides are suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starches, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose are preferred and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition
Das Schaumvermogen der Tenside laßt sich durch Kombination geeigne¬ ter Tensidtypen steigern oder verringern, eine Verringerung laßt sich ebenfalls durch Zusätze nicht-tensidartiger Substanzen erreichen Ein verringertes Schaumvermogen, das beim Arbeiten in Maschinen er¬ wünscht ist, erreicht man vielfach durch Kombination verschiedener Ten¬ sidtypen, z B von Sulfaten und/oder Sulfonaten mit nichionischen Tensi¬ den und/oder mit Seifen Bei Seifen steigt die schaumdampfende Wirkung mit dem Sättigungsgrad und der C-Zahl des Fettsauresalzes an Als schauminhibierende Seifen eignen sich daher solche Seifen naturlicher oder synthetischer Herkunft, die einen hohen Anteil an C ιβ"C24-Fettsauren aufweisen Geeignete nichttensidartige Schauminhibitoren sind beispiels¬ weise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebe¬ nenfalls silanierter Kieselsaure sowie Paraffine, Wachse, Mikrokristallin¬ wachse und deren Gemische mit silanierter Kieselsaure Auch von C-|2-bιs C2o-Alkylamιnen und C2-bιs Ce.Dicarbonsauren abgeleitete Bisacylamide sind brauchbar Mit Vorteil werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, z B solche aus Silikonen, Paraffinen oder Wachsen Vorzugsweise sind die Schauminhibitoren auf eine granuläre, in Wasser lösliche bzw dispergierbare Tragersubstanz gebunden oder wer¬ den dem Plastifizien und/oder Gleitmittel beigemischtThe foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants, a reduction can also be achieved by adding non-surfactant-like substances. A reduced foaming power, which is desirable when working in machines, can be achieved in many cases by combining different tenants sidtypes, for example sulfates and / or sulfonates with nonionic tensides and / or with soaps. In the case of soaps, the foam-dampening effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin are therefore suitable as foam-inhibiting soaps, a high proportion of C ιβ "C 24 -Fettsauren have Suitable non-active foam inhibitors are beispiels¬, organopolysiloxanes and mixtures thereof with microfine, if appropriate silanized silica and also paraffins, waxes, waxes Mikrokristallin¬ and mixtures thereof with silanized silica also of C | 2-bιs C2o-alkylamines and C2-bis Ce.Dicarboxylic acids derived bisacylamides can be used. Mixtures of different foam inhibitors are also advantageously used, for example those made of silicones, paraffins or waxes. The foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or who ¬ added to the plasticizers and / or lubricants
Zusätzlich können die Mittel Enzymstabilisatoren enthalten Beispielswei¬ se können 0,5 bis 1 Gew -% Natπumformiat eingesetzt werden Möglich ist auch der Einsatz von Proteasen, die mit löslichen Calciumsalzen und einem Calciumgehalt von vorzugsweise etwa 1 ,2 Gew -%, bezogen auf das Enzym, stabilisiert sind Besonders vorteilhaft ist jedoch der Einsatz
von Borverbindungen, beispielsweise von Borsäure, Boroxid, Borax und anderen Alkalimetallboraten, wie den Salzen der Orthoborsäure (H3BO3), der Metaborsäure (HBO2) und der Pyroborsäure (Tetraborsäure H2B407).In addition, the agents can contain enzyme stabilizers. For example, 0.5 to 1% by weight of sodium formate can be used. It is also possible to use proteases containing soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme , are stabilized but the use is particularly advantageous boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates, such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 0 7 ).
Die Waschmittel können als optische Aufheller Derivate der Diaminostil- bendisulfonsäure bzw. deren Alkalisalze enthalten.The detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
Geeignet sind beispielsweise Salze der 4,4'-Bis(2-anilino-4-morpholino- 1 ,3,5-triacin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufge¬ baute Verbindungen, die anstelle der Morpholinogruppe eine Diethano- laminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2- Methoxyaminogruppe tragen. Weiterhin können Aufheller des Typs des substituierten 4,4'-Distyryl-diphenyls anwesend sein; beispielsweise die Verbindungen 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyl. Auch Gemische der vorgenannten Aufheller können verwendet werden.For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triacin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure are suitable, which instead of the morpholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyamino group. Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; for example the compounds 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Cuti- nasen, Cellulasen und Amylasen bzw. deren Gemische in Frage. Beson¬ ders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtiiis, Bacillus licheniformis oder Streptomyces griseus gewonnene en¬ zymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilis-Typ und insbesondere Proteasen, die aus Bacillus Lentus gewonnen werden, vorteilhaft im Gemisch mit anderen Enzymen eingesetzt. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebet¬ tet sein, um sie gegen vorzeitige Zersetzung zu schützen. Ihr Anteil kann etwa 0.2 bis 2 Gew-% betragen.Enzymes from the class of proteases, lipases, cutinases, cellulases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subiii, Bacillus licheniformis or Streptomyces griseus are particularly suitable. Proteases of the subtilis type and in particular proteases which are obtained from Bacillus lentus are preferably used in a mixture with other enzymes. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. Their proportion can be about 0.2 to 2% by weight.
Als Stabilisatoren insbesondere für Perverbindungen oder Enzyme kom¬ men die Salze der Polyphosphonsäuren, Hydroxyethan-1 ,1- diphosphonsäure (HEDP) und Ethylendiamintetramethylenphosphonsäure (EDTMP) oder Diethylentriamin-pentamethylenphosphonsäure (DTPMP bzw. DETPMP) in Betracht.The salts of polyphosphonic acids, hydroxyethane-1,1-diphosphonic acid (HEDP) and ethylenediaminetetramethylenephosphonic acid (EDTMP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) are suitable as stabilizers, in particular for per-compounds or enzymes.
Nach einer weiteren bevorzugten Ausführungsform sind daher Gegen¬ stand der vorliegenden Erfindung ebenso Granulate, die nach der vorge-
nannten Art erhalten worden sind, die dadurch gekennzeichnet sind, daß sie eine Schüttdichte von oberhalb 700 g/l, vorzugsweise 750 bis 1.000 g/l und insbesondere 850 bis 980 g/l, aufweisen und als gebrauchsfertiges Mehrstoffgemisch in Form einheitlicher Granulate oder als Kombination von Granulaten unterschiedlicher Zusammensetzung oder als Teilprodukt, das zur Rezepturvervollständigung noch der Abmischung mit weiteren Bestandteilen üblicher Wasch- und Reinigungsmittel bedarf, darstelltAccording to a further preferred embodiment, the present invention also relates to granules which, according to the have been obtained, which are characterized in that they have a bulk density of above 700 g / l, preferably 750 to 1,000 g / l and in particular 850 to 980 g / l, and as a ready-to-use multi-substance mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product which, in order to complete the recipe, still requires mixing with other constituents of conventional washing and cleaning agents
Gegenstand der vorliegenden Erfindung sind schließlich Wasch- und Rei¬ nigungsmittel, enthaltend Granulate der vorgenannten Art, die dadurch gekennzeichnet sind, daß sie einen Gehalt an Tensiden von bis zu 40 Gew -%, vorzugsweise 15 bis 25 Gew -% enthalten
Finally, the present invention relates to detergents and cleaners containing granules of the aforementioned type, which are characterized in that they contain a surfactant content of up to 40% by weight, preferably 15 to 25% by weight
Beispielexample
Zur Herstellung von Textilwaschmitteln in Form der erfindungsgemäßen lagerstabilen, rieselfähigen Granulate wurde zunächst ein plastifizierbares, festes, rieselfähiges Vorgemisch durch Umsetzung von 61 ,6 Gew. -% ei¬ nes sprühgetrockneten Granulats, 5 Gew.-% eines Alkylsulfatcom- pounds, 20,7 Gew.-% Natriumperboratmonohydrat, 3,5 Gew -% C12-C18- Fettalkohol mit 7 EO, 1 ,7 Gew.-% Polyethylenglykol (PEG 400), 1 ,8 Gew.-To produce textile detergents in the form of the storage-stable, free-flowing granules according to the invention, first a plastifiable, solid, free-flowing premix was obtained by reacting 61.6% by weight of a spray-dried granulate, 5% by weight of an alkyl sulfate compound, 20.7 % By weight sodium perborate monohydrate, 3.5% by weight C 12 -C 18 fatty alcohol with 7 EO, 1.7% by weight polyethylene glycol (PEG 400), 1.8% by weight
% Soda (wasserfrei) und 5,6 Gew -% einer 30 %-igen, wäßrigen Polycar-% Soda (anhydrous) and 5.6% by weight of a 30% aqueous polycar
® boxylat-Lösung (Sokalan CP5) vermischt und aufgearbeitet. Zusam¬ mensetzung des sprühgetrockneten Granulats:® boxylat solution (Sokalan CP5) mixed and worked up. Composition of the spray-dried granules:
- 27,4 Gew.-% eines Tensidgemisches aus Natrium- Dodecylbenzolsulfonat (ABS) und aus mit 5 Ethylenoxidgruppen (EO) umgesetzten Taigfettalkohol im Verhältnis 24 : 1 ;27.4% by weight of a surfactant mixture of sodium dodecylbenzenesulfonate (ABS) and of tallow fatty alcohol reacted with 5 ethylene oxide groups (EO) in a ratio of 24: 1;
- 9,4 Gew.-% einer calcinierten Soda,9.4% by weight of a calcined soda,
- 39,4 Gew.-% Zeolith NaA als wasserfreie Substanz,39.4% by weight of zeolite NaA as an anhydrous substance,
- 4 Gew.-% eines Acrylsäurecopolymers (Sokalan " CP5 der BASF AG),4% by weight of an acrylic acid copolymer (Sokalan "CP5 from BASF AG),
- 9,9 Gew.-% gebundenes Wasser,9.9% by weight of bound water,
- 3,6 Gew.-% freies Wasser und- 3.6% by weight of free water and
- auf 100 Gew.-% Natriumsulfat und Salze aus Rohstoffen- on 100 wt .-% sodium sulfate and salts from raw materials
Bei der Vorgemischherstellung wurden in einem Chargenmischer von 130 I, welcher mit einem Messerkopfzerkleinerer ausgerüstet war, die Pulver¬ komponenten vorgelegt und anschließend bei laufendem Mischer zu¬ nächst das vorgemischte Niotensid/PEG 400-Gemisch und im Anschluß daran die Carboxylatlösung zugegeben und 30 Sekunden nachgemischt.In the premix production, the powder components were placed in a batch mixer of 130 l, which was equipped with a cutter head comminutor, and then with the mixer running, the premixed nonionic surfactant / PEG 400 mixture and then the carboxylate solution were added and the mixture was mixed for 30 seconds .
Das erhaltene Vorgemisch war rieselfähig und konnte zur Beschickung der erfindungsgemäßen Granulieranlage, deren Lochformen ein Extruder mit daran angeschlossener Zahnradpumpe vorgeschaltet war, zugeführt werden.
Im Rahmen des Ausführungsbeispiels wurde ein Extruder der Firma Lei¬ stritz, Bundesrepublik Deutschland, der Bezeichnung LSM 30,34 GL ein¬ gesetzt. Im Verbindungsstück zwischen dem Extruder und der Zahn¬ radpumpe befand sich eine Lochscheibe mit einem Durchmesser von 3 mm zum Vorplastifizieren des Vorgemisches.The premix obtained was free-flowing and could be fed to feed the granulating system according to the invention, the hole shapes of which were preceded by an extruder with a gear pump connected to it. Within the scope of the exemplary embodiment, an extruder from Lei¬stritz, Federal Republic of Germany, with the designation LSM 30.34 GL, was used. In the connecting piece between the extruder and the gear pump there was a perforated disk with a diameter of 3 mm for pre-plasticizing the premix.
Für das Verpressen des plastifizierbaren, festen und rieselfähigen Vor- gemischs durch Lochformen waren folgende Granulierbedingungen ein¬ zuhalten:The following granulation conditions had to be observed for pressing the plastifiable, solid and free-flowing premix by hole shapes:
Die im Rahmen der Granulierung eingesetzte erfindungsgemäße Zahn¬ radpumpe war ein von der Firma Witte GmbH, Bundesrepublik Deutsch¬ land, unter der Bezeichnung VAH 2,78 M erhältliches Modell, wobei typi¬ scherweise ein Durchsatz von 4 kg pro Stunde bei einem typischen Loch¬ düsendurchmesser von 1 ,5 mm durchgeführt wird, wobei Produkt-Auslaß bzw. Austragstemperaturen von 60°C eingesetzt wurden. Eine Kühlung der Apparatur war nicht erforderlich. Die optimal hieran anschließende Chargenrondierung wurde innerhalb einer Chargenzeit von 1 min bei einer Rotorumfangsgeschwindigkeit von 8 m/s in Gegenwart von 3,2 Gew.-% Zeolith NaA-Pulver durchgeführt. Nach der Siebung über ein 1 ,6 mm-Sieb erhielt man hieraus in einer Granulatausbeute von 93 % ein Granulat mit einer Granulatschüttdichte von etwa 800 g/l.
The gear pump according to the invention used in the granulation was a model available from Witte GmbH, Federal Republic of Germany, under the name VAH 2.78 M, with a typical throughput of 4 kg per hour for a typical hole Nozzle diameter of 1.5 mm is carried out, product outlet and discharge temperatures of 60 ° C. being used. It was not necessary to cool the apparatus. The subsequent batch rounding was carried out optimally within a batch time of 1 min at a rotor peripheral speed of 8 m / s in the presence of 3.2% by weight of zeolite NaA powder. After sieving through a 1.6 mm sieve, a granulate with a granular bulk density of about 800 g / l was obtained in a granulate yield of 93%.
Claims
1. Verfahren zur Herstellung von granulären Wasch- oder Reinigungsmit¬ teln oder Komponenten hierfür durch das Verpressen eines plastifi¬ zierbares, festen, rieselfähigen Vorgemisches durch Lochformen, da¬ durch gekennzeichnet, daß diesen Lochformen eine Zahnradpumpe vorgeschaltet ist.1. Process for the production of granular detergents or cleaning agents or components therefor by pressing a plastifiable, solid, free-flowing premix by hole molds, characterized in that a gear pump is connected upstream of these hole molds.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß die aus den Lochdüsen der Zahnradpumpe austretenden Stränge durch Ab¬ schlagvorrichtungen, insbesondere rotierende Messer, geschnitten werden.2. The method according to claim 1, characterized in that the strands emerging from the perforated nozzles of the gear pump are cut by knock-off devices, in particular rotating knives.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß der Druck in der Zahnradpumpe zwischen 6 und 200 bar, insbesondere 30 bis 120 bar beträgt und die Preßdüse ein Granulatkorn von 0,5 bis 10 mm, vorzugsweise 1 bis 5 mm, erzeugt.3. The method according to claim 1 or 2, characterized in that the pressure in the gear pump is between 6 and 200 bar, in particular 30 to 120 bar and the press nozzle produces a granulate of 0.5 to 10 mm, preferably 1 to 5 mm .
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeich¬ net, daß die Zahnradpumpe mit einem Durchsatz von 0,1 bis 300 m3/h, vorzugsweise 1 bis 20 m3/h betrieben wird.4. The method according to any one of claims 1 to 3, characterized gekennzeich¬ net that the gear pump is operated with a throughput of 0.1 to 300 m 3 / h, preferably 1 to 20 m 3 / h.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeich¬ net, daß das zu verpressende Vorgemisch im Pumpeneinlaß Tempe¬ raturen von 20 bis 80 °C, vorzugsweise 30 bis 60 °C und im Auslaß 40 bis 100 °C, vorzugsweise 45 bis 75 °C aufweist.5. The method according to any one of claims 1 to 4, characterized gekennzeich¬ net that the premix to be compressed in the pump inlet temperatures from 20 to 80 ° C, preferably 30 to 60 ° C and in the outlet 40 to 100 ° C, preferably 45 up to 75 ° C.
6. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeich¬ net, daß das Vorgemisch in den Zahnradpumpen vorgeschalteten Mi¬ schern, Extrudern oder Vorrichtungen aus Mischern und Knetern plastifiziert wird. 6. The method according to any one of claims 1 to 5, characterized gekennzeich¬ net that the premix in the gear pumps upstream mixers, extruders or devices from mixers and kneaders is plasticized.
7 Verfahren nach einem der Ansprüche 1 bis 6 dadurch gekennzeich¬ net, daß ein Verrundungsschritt nachgeschaltet wird7 The method according to one of claims 1 to 6, characterized in that a rounding step is followed
8. Granulat, erhalten nach einem der Ansprüche 1 bis 7, dadurch ge¬ kennzeichnet, daß es eine Schüttdichte von oberhalb 700 g/l, vor¬ zugsweise 750 bis 1000 g/l und insbesondere 850 bis 980 g/l aufweist und als gebrauchsfertiges Mehrstoffgemisch in Form einheitlicher Granulate oder als Kombination von Granulaten unterschiedlicher Zu¬ sammensetzung oder als Teilprodukt, das zur Rezepturvervollstandi- gung noch die Abmischung mit weiteren Bestandteilen üblicher Wasch- und Reinigungsmittel bedarf, darstellt.8. Granules obtained according to one of claims 1 to 7, characterized ge indicates that it has a bulk density of above 700 g / l, preferably 750 to 1000 g / l and in particular 850 to 980 g / l and as ready-to-use Multicomponent mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product which, in order to complete the recipe, still requires mixing with other constituents of conventional washing and cleaning agents.
9 Wasch- und Reinigungsmittel, enthaltend Granulate gemäß Anspruch 8, dadurch gekennzeichnet, daß sie einen Gehalt an Tensiden bis zu 40 Gew -%, vorzugsweise zwischen 15 und 25 Gew -% enthalten 9 washing and cleaning agents containing granules according to claim 8, characterized in that they contain a surfactant content of up to 40% by weight, preferably between 15 and 25% by weight
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19546465 | 1995-12-13 | ||
DE1995146465 DE19546465A1 (en) | 1995-12-13 | 1995-12-13 | Process for the production of granular washing or cleaning agents or components therefor |
PCT/EP1996/005409 WO1997021798A1 (en) | 1995-12-13 | 1996-12-04 | Method of producing granular washing or cleaning agents or components therefor |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0871697A1 true EP0871697A1 (en) | 1998-10-21 |
Family
ID=7779959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96943030A Withdrawn EP0871697A1 (en) | 1995-12-13 | 1996-12-04 | Method of producing granular washing or cleaning agents or components therefor |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP0871697A1 (en) |
JP (1) | JP2000501759A (en) |
DE (1) | DE19546465A1 (en) |
WO (1) | WO1997021798A1 (en) |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2767437A (en) * | 1952-02-11 | 1956-10-23 | Donald E Marshall | Method of amalgamating and extruding soap |
GB1603640A (en) * | 1977-07-20 | 1981-11-25 | Gist Brocades Nv | Enzyme particles |
JPS5887013A (en) * | 1981-11-18 | 1983-05-24 | Japan Steel Works Ltd:The | Continuous kneading and granulating apparatus |
-
1995
- 1995-12-13 DE DE1995146465 patent/DE19546465A1/en not_active Withdrawn
-
1996
- 1996-12-04 JP JP9521702A patent/JP2000501759A/en active Pending
- 1996-12-04 WO PCT/EP1996/005409 patent/WO1997021798A1/en not_active Application Discontinuation
- 1996-12-04 EP EP96943030A patent/EP0871697A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO9721798A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO1997021798A1 (en) | 1997-06-19 |
JP2000501759A (en) | 2000-02-15 |
DE19546465A1 (en) | 1997-06-19 |
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