EP0576479B1 - Liquid or paste-like washing product - Google Patents
Liquid or paste-like washing product Download PDFInfo
- Publication number
- EP0576479B1 EP0576479B1 EP92906453A EP92906453A EP0576479B1 EP 0576479 B1 EP0576479 B1 EP 0576479B1 EP 92906453 A EP92906453 A EP 92906453A EP 92906453 A EP92906453 A EP 92906453A EP 0576479 B1 EP0576479 B1 EP 0576479B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- detergent
- sodium
- formula
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
Links
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000005406 washing Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- 150000004760 silicates Chemical class 0.000 claims abstract description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 150000002334 glycols Chemical class 0.000 claims abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 239000003599 detergent Substances 0.000 claims description 38
- -1 glycol ethers Chemical class 0.000 claims description 21
- 239000002736 nonionic surfactant Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- 150000002978 peroxides Chemical class 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 2
- 229910021527 natrosilite Inorganic materials 0.000 claims description 2
- XSVSPKKXQGNHMD-UHFFFAOYSA-N 5-bromo-3-methyl-1,2-thiazole Chemical compound CC=1C=C(Br)SN=1 XSVSPKKXQGNHMD-UHFFFAOYSA-N 0.000 claims 1
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 claims 1
- 229940045872 sodium percarbonate Drugs 0.000 claims 1
- 235000019351 sodium silicates Nutrition 0.000 abstract description 9
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 235000011187 glycerol Nutrition 0.000 abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 description 22
- 150000003839 salts Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 150000004665 fatty acids Chemical class 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 235000011837 pasties Nutrition 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- 239000003945 anionic surfactant Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- 150000001447 alkali salts Chemical class 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 239000003760 tallow Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004435 Oxo alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 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
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 150000003138 primary alcohols Chemical class 0.000 description 3
- 150000003333 secondary alcohols Chemical class 0.000 description 3
- 239000003352 sequestering agent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910000503 Na-aluminosilicate Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229920003086 cellulose ether Polymers 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940096386 coconut alcohol Drugs 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229930182478 glucoside Natural products 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical class CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 2
- CIOXZGOUEYHNBF-UHFFFAOYSA-N (carboxymethoxy)succinic acid Chemical compound OC(=O)COC(C(O)=O)CC(O)=O CIOXZGOUEYHNBF-UHFFFAOYSA-N 0.000 description 1
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N 1-Tetradecanol Natural products CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 1
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NSMMFSKPGXCMOE-UHFFFAOYSA-N 2-[2-(2-sulfophenyl)ethenyl]benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=CC1=CC=CC=C1S(O)(=O)=O NSMMFSKPGXCMOE-UHFFFAOYSA-N 0.000 description 1
- JBVOQKNLGSOPNZ-UHFFFAOYSA-N 2-propan-2-ylbenzenesulfonic acid Chemical class CC(C)C1=CC=CC=C1S(O)(=O)=O JBVOQKNLGSOPNZ-UHFFFAOYSA-N 0.000 description 1
- ZMPRRFPMMJQXPP-UHFFFAOYSA-N 2-sulfobenzoic acid Chemical class OC(=O)C1=CC=CC=C1S(O)(=O)=O ZMPRRFPMMJQXPP-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 241000194108 Bacillus licheniformis Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 102000005701 Calcium-Binding Proteins Human genes 0.000 description 1
- 108010045403 Calcium-Binding Proteins Proteins 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
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- 108090001060 Lipase Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
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- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
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- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
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- 239000011777 magnesium Substances 0.000 description 1
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- 125000004492 methyl ester group Chemical group 0.000 description 1
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- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
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- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl 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])=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])[H] 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000019832 sodium triphosphate 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
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 239000013042 solid detergent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- DIORMHZUUKOISG-UHFFFAOYSA-N sulfoformic acid Chemical class OC(=O)S(O)(=O)=O DIORMHZUUKOISG-UHFFFAOYSA-N 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- 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
- C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
- C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
Definitions
- the present invention relates to liquid to pasty detergents which contain silicates and nonionic surfactants.
- a recent proposal relates to crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH2O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 (EP 164 514, EP 337 217 and EP 337 219).
- Layer silicates of this general formula, in which x is preferably a number from 1.5 to 4 and y is less than 2x, are, according to EP 263 520, in a detergent together with polyoxyethylated, long-chain alcohols used.
- the invention relates to liquid to pasty detergents, the crystalline, layered sodium silicate of the general formula NaMSi x O2 x + 1 .yH2O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 mean, wherein this silicate is suspended in a liquid phase, the nonionic surfactants, the formula R- (O-CH2-CH2-) n OH (I), in which R is a long-chain primary or secondary alkyl radical with 8 to 20 C.
- -Atoms and n are a number between 3 and 20, and optionally organic solvents from the group of glycols and glycol ethers, and not more than 30% by weight, based on the total composition, of water.
- Agents in which the liquid phase contains not more than 20% by weight, in particular not more than 10% by weight, of water are particularly preferred.
- the decomposition of the crystalline, layered sodium silicates has been suppressed to such an extent that it no longer interferes with the storage times customary for detergents.
- the builder effect remains at the level necessary for the washing process.
- Another advantage is that inorganic peroxides can be stably incorporated into these detergents.
- the crystalline, layered sodium silicates used according to the invention can be naturally occurring minerals, for example kanemite. However, preference is given to using synthetically produced, layered silicates which have been described in various forms in the literature.
- the silicates of the formula NaMSi2O5 ⁇ yH2O are particularly preferred, of which in turn the beta and delta modifications of Na2Si2O5 are particularly preferred.
- the crystalline, layered Sodium silicates are preferably contained in the liquid to pasty detergents in amounts between 10 and 50% by weight and in particular in amounts between 20 and 40% by weight, based on the total agent.
- the crystalline, layered sodium silicates are preferably used in the compositions in the form of very small particles, which are preferably smaller than 100 »m, in particular smaller than 30» m.
- the essential components of the liquid phase in which the crystalline, layered sodium silicates are suspended, contain nonionic surfactants of the formula (I) and optionally organic solvents from the group of glycols and glycol ethers and up to 30% by weight, based on the total Medium, in water.
- the water content is preferably between 0.5 and 20% by weight, in particular not more than 10% by weight, based on the total composition.
- the water that is introduced into the medium in the form of water of hydration of solid salts or in a similarly bound form must be included in the calculation. Otherwise, the composition of the liquid phase is preferably chosen so that the pour point of this phase is below 15 ° C., in particular below 10 ° C.
- the nonionic surfactants of the formula (I) which can be used according to the invention are the addition products of 3 to 20 mol of ethylene oxide (EO) and long-chain primary and secondary alcohols having 8 to 20 C atoms, preferably 10 to 18 C atoms. These are preferably addition products of 4 to 10 mol EO and 1 mol saturated or unsaturated fatty alcohols with 12 to 18 carbon atoms or oxo alcohols of this chain length. Examples of such surfactants are coconut alcohol C 12/14 + 3 EO, coconut alcohol C 12/18 + 5 EO and oleyl cetyl alcohol + 10 EO, and oxo alcohol C 11/13 + 7 EO.
- the nonionic surfactants of the formula (I) are preferably present in the agents according to the invention in amounts between 10 and 60% by weight, in particular in amounts between 10 and 40% by weight.
- the liquid phase of can form agents according to the invention primarily water-soluble glycols and glycol ethers and glycerol come into consideration; preferably no other organic solvents are used in addition.
- the glycols are preferably those having 2 to 6 carbon atoms in the molecule, and the di- and oligomers of propylene glycol and, preferably, ethylene glycol which are liquid at room temperature.
- the monoethers from methanol, ethanol, propanol or butanol and mono-, di- or triglycols are preferably used.
- the ethers contain no more than 10 carbon atoms per molecule.
- the organic solvent content is preferably not more than 30% by weight, in particular between 0.5 and 10% by weight, based on the detergent as a whole.
- inorganic peroxides which are effective as bleaching agents.
- an equal weight of hydrogen peroxide can be used instead of part of the water present in the liquid phase.
- solid inorganic peroxides which on average are then predominantly also in undissolved, i.e. suspended form.
- Perborate tetrahydrate, perborate monohydrate and the adduct of H2O2 with sodium carbonate, which is also referred to as percarbonate are very particularly preferred.
- the solid inorganic peroxides like the crystalline, layered sodium silicates, are preferably used in the compositions in very finely divided form.
- Their content in the agents according to the invention can be up to 30% by weight, preferably between 5 and 30% by weight and in particular between 10 and 25% by weight.
- the detergents according to the invention can contain further active ingredients and auxiliaries as are customary in liquid and pasty detergents, provided that these further ingredients do not impair the stability of the detergents.
- the following are primarily mentioned as such constituents: surfactants of other types, in particular nonionic and anionic surfactants, further organic or inorganic builders and sequestering agents, foam regulators, graying inhibitors and bleach activators.
- auxiliaries and additives are optical brighteners, detergency boosters, enzymes, dyes, perfumes, inorganic salts and preservatives.
- the total content of the abovementioned active substances and auxiliaries in the agents according to the invention is generally not more than 50% by weight, preferably between 0.5 and 20% by weight, it being possible for the individual components to be present in the agents in dissolved or suspended form.
- Additional nonionic surfactants include primarily the addition products of ethylene oxide with polypropylene oxide or with fatty acids, fatty acid amides or alkylphenols with 12 to 18 carbon atoms, and the alkyl glycosides, for example the alkyl glucosides or alkyl polyglucosides available from glucose and long-chain primary alcohols. These alkyl glucosides preferably contain 10 to 14 carbon atoms in the alcohol part and 1 to 3 glucose units per molecule.
- Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
- the amount of these nonionic surfactants is generally not more than that of the nonionic surfactants of the formula (I), preferably not more than half of them.
- Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.
- surfactants of the sulfonate type come alkylbenzenesulfonates with a C9-15-alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products into consideration.
- alkanesulfonates which are obtainable from C12-C18 alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of ⁇ -sulfofatty acids, such as, for. B. the ⁇ -sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
- Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural or synthetic origin, ie of fatty alcohols such as, for example, coconut oil, tallow oil, oleyl, lauryl, myristyl, palmityl or stearyl alcohol or the C10-C20 oxo alcohols or secondary alcohols of this chain length.
- the sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol EO are also suitable.
- Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable.
- the anionic surfactants based on natural raw materials are in particular the wash-active soaps, ie the salts of C12 ⁇ C18 fatty acids.
- the anionic surfactants are present in the agents according to the invention preferably in the form of their sodium salts or in the form of the soluble salts with organic bases, in particular mono-, di- and triethanolamine.
- the amount of anionic surfactants in the agents according to the invention is preferably not greater than the total amount of nonionic surfactants, in particular it is less than half of the nonionic surfactants.
- a preferred content is between 5 and 20% by weight, based on the total agent.
- Cationic surfactants include, in particular, the quaternary ammonium compounds which, in addition to three shorter alkyl radicals, each with no more than 2 carbon atoms, have a long-chain alkyl radical with 10 to 18 carbon atoms on the nitrogen. Two or three of the shorter alkyl chains can also be closed to form a ring, for example a pyridine ring.
- Examples of such compounds are N, N, N-trimethyl-N-tetradecylammonium chloride and N, N-dimethyl-N-hydroxyethyl-N-dodecylammonium hydrogen sulfate.
- the betaine surfactants are predominantly long-chain quaternary ammonium compounds in which one of the shorter alkyl substituents contains an anionic group, usually a carboxyl group.
- An example of a betaine surfactant is N, N-dimethyl-N-cocoalkylaminoacetate.
- the agents according to the invention preferably contain only the crystalline, layered sodium silicates as builders, the agents may also contain further organic and / or inorganic, soluble or insoluble builders.
- the amount of these additional builder substances is generally not more than the amount of layered silicates and is preferably less than half these silicates; in particular the amount is between 0.1 and 5% by weight, based on the total agent.
- alkaline salts in particular alkali salts, which not only precipitate or complexly bind calcium ions, but also, as far as possible, bring about a synergistic increase in washing power and have dirt-carrying capacity, should be mentioned as an additional framework substance.
- the water-soluble alkali metal or alkali polyphosphates especially pentasodium triphosphate, are still of importance.
- Organic builder substances include sequestering agents of the aminopolycarboxylic acid type, such as, for example. Nitrilotriacetic acid, ethylenediaminetetraacetic acid, and higher homologues.
- Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids, such as. B. the compounds methanediphosphonic acid, dimethylaminomethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid. These sequestering agents can also be present in smaller amounts as stabilizers for per-compounds.
- the N- and P-free polycarboxylic acids that form complex salts with calcium ions are of particular importance.
- these include low molecular weight compounds, such as. As citric acid, 2,2'-oxydisuccinic acid or carboxymethyloxy succinic acid, and polymeric polycarboxylic acids with a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts.
- Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000. These include compounds such as, for. B.
- polyacrylic acid poly-alphahydoxyacrylic acid and polymaleic acid
- copolymers of the corresponding monomeric carboxylic acids with one another for example from acrylic acid and maleic acid, or with other ethylenically unsaturated compounds, such as. B. with vinyl methyl ether.
- water-soluble salts of polyglyoxylic acid should also be mentioned.
- Particularly suitable water-insoluble inorganic builders are the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 24 12 837 as phosphate substitutes for detergents and cleaning agents.
- the cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i.e. H. they have practically no particles larger than 30 »m and preferably consist at least 80% of particles smaller than 10» m.
- Their calcium binding capacity which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g.
- the zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX.
- the zeolites are preferably only used in the agents according to the invention if no inorganic peroxides, in particular perborate, are present.
- Suitable inorganic, non-complexing salts are the bicarbonates, also known as "washing alkalis", carbonates, borates, sulfates or amorphous silicates of the alkalis.
- Other structural substances that are also used because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids, of sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.
- foam regulators are the salts of fatty acids with 20 to 24 carbon atoms or long-chain N-alkylaminotriazines with essentially 8 to 18 carbon atoms in the alkyl radical or aliphatic C18-C40 ketones.
- Paraffin and silicone oil dispersions are preferred, which can optionally be made up with microfine silica.
- the content can be, for example in the case of soaps, up to 5% by weight of the total composition, in the case of the paraffins and silicone oils it is usually much less, for example 0.05 to 0.5% by weight.
- Graying inhibitors include, above all, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as Mention should be made of methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose, furthermore mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose.
- cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as Mention should be made of methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose, furthermore mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose.
- bleach activators in addition to inorganic peroxide.
- These are acylating agents which react with hydrogen peroxide in the wash liquor to form peroxycarboxylic acids or their salts.
- Examples of common bleach activators are tetraacetylethylenediamine, pentaacetylglucose and diacetyldioxohexahydrotriazine.
- anhydrides can also be used.
- Bleach activators are preferably used which remain largely undissolved in the liquid portion of the detergent and are therefore predominantly in suspended form.
- the amounts of bleach activators are preferably not more than 6% by weight, in particular between 2 and 5% by weight, based on the total agent.
- Optical brighteners which are particularly suitable for detergents are alkali salts of 4,4-bis (2 '' - anilino-4 '' - morpholino-1,3,5-triazinyl-6 '' - amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group instead of the morpholino group. Furthermore, brighteners of the type of the substituted diphenylstyryl come into question, e.g. B.
- Detergent boosters are polar long-chain compounds that do not themselves have any surface-active properties, but are able to increase the cleaning effect of the surfactants contained in the detergents. Examples of such compounds are coconut amine + 2 EO and the addition products of glycerol and long-chain ⁇ -olefin epoxide.
- Enzymes from the class of proteases, lipases and amylases or their mixtures are possible.
- Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and are particularly suitable Streptomyces griseus enzymatic substances obtained.
- the enzymes can be embedded in coating substances to protect them against premature decomposition.
- the preparation of the agents according to the invention presents no difficulties.
- it is carried out by mixing all the components, the components which later form the liquid phase are advantageously first premixed and then the components to be suspended are introduced into this liquid and mixed homogeneously therewith.
- the solid constituents of the composition are preferably already based on particle sizes as they are later to be present in the finished composition, but it is also possible to further reduce the size of the suspended solid particles by wet grinding the finished composition.
- the viscosity of the finished product depends primarily on the solid / liquid ratio in the finished product and on the viscosity of the liquid phase. This in turn can be varied within wide limits by choosing suitable components.
- the viscosity can be reduced by adding organic solvents and the viscosity can be increased by adding constituents with a thickening effect, such as soaps.
- Liquid agents according to the invention preferably have viscosities between about 1,000 and about 5,000 mPas, in particular between about 2,000 and about 4,000 mPas, the viscosity being measured using a Brookfield viscometer at 20 ° C.
- the viscosities of the detergent in paste form which are preferred because of their particularly high physical stability, go far beyond.
- the agents according to the invention are primarily intended for use in textile washing. Depending on the content of active ingredients, they can be used as stand-alone detergents or as detergent additives. However, if the active ingredients are selected appropriately, they are also suitable for cleaning hard surfaces in the home or in the commercial sector. Due to the stability of the suspensions, the agents can also be dosed automatically.
- the paste-like detergents A and B described below were prepared in batches of 50 g each by weighing all the components together and homogenizing the mixtures in a ceramic ball mill (running time 5 minutes).
- ingredients Percentage by weight A B Crystalline layered disilicate (delta form) (SKS 6, Hoechst AG) 19.1 21.1 Nonionic surfactant Dehydol LST 80/20 (Henkel) 10.5 18.0 Polyethylene glycol 400 5.3 5.4 C 12/13 alkylbenzenesulfonate Na (55% aqueous paste) 33.3 14.5 Sodium perborate tetrahydrate 31.8 22.0 sodium - 9.0
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- Engineering & Computer Science (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
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Abstract
Description
Die vorliegende Erfindung betrifft flüssige bis pastenförmige Waschmittel, die Silikate und nichtionische Tenside enthalten.The present invention relates to liquid to pasty detergents which contain silicates and nonionic surfactants.
Seit langer Zeit ist man bemüht, die früher in nahezu allen Waschmitteln als Gerüstsubstanzen (Builder) enthaltenen Phosphate durch andere gleichwirkende Stoffe zu ersetzen, da Phosphate für die Eutrophierung von Oberflächengewässern verantwortlich sein können. Obwohl mit den Zeolithen in den 70iger Jahren Austauschstoffe gefunden wurden, die praktisch alle Ansprüche an derartige Substanzen befriedigten, so daß sie inzwischen die Phosphate weitgehend aus Waschmitteln verdrängt haben, ist man auch weiterhin bemüht, alternative Austauschstoffe für Phosphat zu finden. Ein Vorschlag aus jüngerer Zeit betrifft kristalline, schichtförmige Natriumsilikate der allgemeinen Formel NaMSixO2x+1.yH₂O, in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten (EP 164 514, EP 337 217 und EP 337 219). Schichtsilikate dieser allgemeinen Formel, in der x vorzugsweise eine Zahl von 1,5 bis 4 und y kleiner als 2x bedeuten, werden gemäß EP 263 520 in einem Waschmittel zusammen mit polyoxyethylierten, langkettigen Alkoholen eingesetzt. Im Unterschied zu amorphen Silikaten, die schon immer in Waschmitteln, zum Teil allein oder auch neben Phosphat, verwendet wurden, besitzen diese dort vorgestellten kristallinen, schichtförmigen Silikate ein ausgeprägtes Bindevermögen für Calcium- und Magnesiumionen. Sie wurden deshalb in den oben genannten Patentanmeldungen für den Einsatz zur Wasserenthärtung und als Bestandteile von festen Waschmitteln vorgeschlagen.For a long time, efforts have been made to replace the phosphates previously contained in almost all detergents as builders (builders) with other substances having the same effect, since phosphates can be responsible for the eutrophication of surface waters. Although substitutes were found with the zeolites in the 1970s that met practically all requirements for such substances, so that they have largely displaced the phosphates from detergents, efforts are still being made to find alternative substitutes for phosphates. A recent proposal relates to crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH₂O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 (EP 164 514, EP 337 217 and EP 337 219). Layer silicates of this general formula, in which x is preferably a number from 1.5 to 4 and y is less than 2x, are, according to EP 263 520, in a detergent together with polyoxyethylated, long-chain alcohols used. In contrast to amorphous silicates, which have always been used in detergents, sometimes alone or in addition to phosphate, these crystalline, layered silicates presented there have a pronounced binding capacity for calcium and magnesium ions. They were therefore proposed in the above-mentioned patent applications for use in water softening and as components of solid detergents.
Von diesen kristallinen, schichtförmigen Silikaten war allerdings auch bekannt, daß sie in Gegenwart von polaren, protischen Flüssigkeiten unbeständig sind und sich in amorphe Silikate umwandeln. Mit dem Verlust der Schichtstruktur geht aber zwangsläufig ein Verlust an Calcium- und Magnesiumbindevermögen einher, so daß eine wesentliche Funktion, die ein Waschmittelbuilder aufweisen sollte, dann nicht mehr gegeben ist. Für den Einsatz in flüssigen oder pastenförmigen Waschmitteln schienen diese kristallinen, schichtförmigen Disilikate deshalb nicht in Betracht zukommen.These crystalline, layered silicates, however, were also known to be unstable in the presence of polar, protic liquids and to convert into amorphous silicates. With the loss of the layer structure, however, there is inevitably a loss of calcium and magnesium binding capacity, so that an essential function which a detergent builder should then no longer exist. For the These crystalline, layered disilicates therefore did not appear to be suitable for use in liquid or pasty detergents.
Überraschenderweise wurde jetzt gefunden, daß dieser Einsatz in flüssigen und pastösen Waschmitteln doch möglich ist, wenn diese Waschmittel eine flüssige Phase bestimmter Zusammensetzung enthalten und die kristallinen, schichtförmigen Disilikate in dieser flüssigen Phase zum überwiegenden Teil in suspendierter Form vorliegen.Surprisingly, it has now been found that this use in liquid and pasty detergents is nevertheless possible if these detergents contain a liquid phase of a certain composition and the crystalline, layered disilicates are predominantly in suspended form in this liquid phase.
Gegenstand der Erfindung sind flüssige bis pastöse Waschmittel, die kristallines, schichtförmiges Natriumsilikat der allgemeinen Formel NaMSixO2x+1.yH₂O, in der M Natrium oder Wasserstoff, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 bedeuten, enthalten, wobei dieses Silikat in einer flüssigen Phase suspendiert ist, die nichtionische Tenside, der Formel R-(O-CH₂-CH₂-)n OH (I), in der R einen langkettigen primären oder sekundären Alkylrest mit 8 bis 20 C-Atomen und n eine Zahl zwischen 3 und 20 bedeuten, sowie gegebenenfalls organische Lösungsmittel aus der Gruppe der Glykole und Glykolether, und nicht mehr als 30 Gew.-%, bezogen auf das gesamte Mittel, an Wasser enthält. Besonders bevorzugt werden solche Mittel, in denen die flüssige Phase nicht mehr als 20 Gew.-%, insbesondere nicht mehr als 10 Gew. -% an Wasser enthält.The invention relates to liquid to pasty detergents, the crystalline, layered sodium silicate of the general formula NaMSi x O2 x + 1 .yH₂O, in which M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 mean, wherein this silicate is suspended in a liquid phase, the nonionic surfactants, the formula R- (O-CH₂-CH₂-) n OH (I), in which R is a long-chain primary or secondary alkyl radical with 8 to 20 C. -Atoms and n are a number between 3 and 20, and optionally organic solvents from the group of glycols and glycol ethers, and not more than 30% by weight, based on the total composition, of water. Agents in which the liquid phase contains not more than 20% by weight, in particular not more than 10% by weight, of water are particularly preferred.
In den neuen Mitteln ist die Zersetzung der kristallinen, schichtförmigen Natriumsilikate soweit zurückgedrängt, daß sie innerhalb der für Waschmittel üblichen Lagerzeiten nicht mehr stört. Die Builderwirkung bleibt in der für den Waschvorgang notwendigen Höhe erhalten. Als weiterer Vorteil ist zu werten, daß sich anorganische Peroxide stabil in diese Waschmittel einarbeiten lassen.In the new compositions, the decomposition of the crystalline, layered sodium silicates has been suppressed to such an extent that it no longer interferes with the storage times customary for detergents. The builder effect remains at the level necessary for the washing process. Another advantage is that inorganic peroxides can be stably incorporated into these detergents.
Bei den erfindungsgemäß verwendeten kristallinen, schichtförmigen Natriumsilikaten kann es sich um natürlich vorkommende Mineralien, beispielsweise Kanemit, handeln. Bevorzugt werden aber synthetisch hergestellte, schichtförmige Silikate verwendet, die in verschiedenster Form in der Literatur beschrieben sind. Besonders bevorzugt werden die Silikate der Formel NaMSi₂O₅ · yH₂O, von denen wiederum die beta- und die delta-Modifikation des Na₂Si₂O₅ besonders bevorzugt sind. Die kristallinen, schichtförmigen Natriumsilikate sind in den flüssigen bis pastösen Waschmitteln vorzugsweise in Mengen zwischen 10 und 50 Gew.-% und insbesondere in Mengen zwischen 20 und 40 Gew.-%, bezogen auf das gesamte Mittel, enthalten. Vorzugsweise werden die kristallinen, schichtförmigen Natriumsilikate in den Mitteln in Form sehr kleiner Teilchen, die vorzugsweise kleiner als 100 »m, insbesondere kleiner als 30 »m sind, eingesetzt.The crystalline, layered sodium silicates used according to the invention can be naturally occurring minerals, for example kanemite. However, preference is given to using synthetically produced, layered silicates which have been described in various forms in the literature. The silicates of the formula NaMSi₂O₅ · yH₂O are particularly preferred, of which in turn the beta and delta modifications of Na₂Si₂O₅ are particularly preferred. The crystalline, layered Sodium silicates are preferably contained in the liquid to pasty detergents in amounts between 10 and 50% by weight and in particular in amounts between 20 and 40% by weight, based on the total agent. The crystalline, layered sodium silicates are preferably used in the compositions in the form of very small particles, which are preferably smaller than 100 »m, in particular smaller than 30» m.
Die flüssige Phase, in der die kristallinen, schichtförmigen Natriumsilikate suspendiert sind, enthält als wesentliche Bestandteile nichtionische Tenside der Formel (I), sowie gegebenenfalls organische Lösungsmittel aus der Gruppe der Glykole und Glykoläther und bis zu 30 Gew.-%, bezogen auf das gesamte Mittel, an Wasser. Vorzugsweise liegt der Wassergehalt zwischen 0,5 und 20 Gew.-%, insbesondere nicht über 10 Gew.-% bezogen auf das gesamte Mittel. Dabei ist das Wasser, das in die Mittel in Form von Hydratwasser fester Salze oder in ähnlich gebundener Form eingebracht wird, mitzurechnen. Im übrigen wird die Zusammensetzung der flüssigen Phase vorzugsweise so gewählt, daß der Stockpunkt dieser Phase unterhalb von 15 °C, insbesondere unterhalb von 10 °C liegt. Diese Werte lassen sich ohne weiteres durch die Verwendung entsprechend flüssiger nichtionischer Tenside und/oder ausreichender Anteile an organischen Lösungsmitteln und/oder Wasser erreichen.The essential components of the liquid phase, in which the crystalline, layered sodium silicates are suspended, contain nonionic surfactants of the formula (I) and optionally organic solvents from the group of glycols and glycol ethers and up to 30% by weight, based on the total Medium, in water. The water content is preferably between 0.5 and 20% by weight, in particular not more than 10% by weight, based on the total composition. The water that is introduced into the medium in the form of water of hydration of solid salts or in a similarly bound form must be included in the calculation. Otherwise, the composition of the liquid phase is preferably chosen so that the pour point of this phase is below 15 ° C., in particular below 10 ° C. These values can easily be achieved by using appropriately liquid nonionic surfactants and / or sufficient proportions of organic solvents and / or water.
Bei den erfindungsgemäß brauchbaren nichtionischen Tensiden der Formel (I) handelt es sich um die Additionsprodukte aus 3 bis 20 Mol Ethylenoxid (EO) und langkettigen primären und sekundären Alkoholen mit 8 bis 20 C-Atomen, vorzugsweise 10 bis 18 C-Atomen. Vorzugsweise handelt es sich dabei um Additionsprodukte aus 4 bis 10 mol EO und 1 mol gesättigter oder ungesättigter Fettalkohole mit 12 bis 18 C-Atomen oder Oxoalkoholen dieser Kettenlänge. Beispiele für derartige Tenside sind Kokosalkohol C12/14 + 3 EO, Kokosalkohol C12/18 + 5 EO und Oleyl-Cetylalkohol + 10 EO, sowie Oxoalkohol C11/13 + 7 EO. Die nichtionischen Tenside der Formel (I) sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen zwischen 10 und 60 Gew.-%, insbesondere in Mengen zwischen 10 und 40 Gew.-% enthalten.The nonionic surfactants of the formula (I) which can be used according to the invention are the addition products of 3 to 20 mol of ethylene oxide (EO) and long-chain primary and secondary alcohols having 8 to 20 C atoms, preferably 10 to 18 C atoms. These are preferably addition products of 4 to 10 mol EO and 1 mol saturated or unsaturated fatty alcohols with 12 to 18 carbon atoms or oxo alcohols of this chain length. Examples of such surfactants are coconut alcohol C 12/14 + 3 EO, coconut alcohol C 12/18 + 5 EO and oleyl cetyl alcohol + 10 EO, and oxo alcohol C 11/13 + 7 EO. The nonionic surfactants of the formula (I) are preferably present in the agents according to the invention in amounts between 10 and 60% by weight, in particular in amounts between 10 and 40% by weight.
Als organische Lösungsmittel, die zusammen mit den nichtionischen Tensiden der Formel (I) und gegebenenfalls Wasser die flüssige Phase der erfindungsgemäßen Mittel bilden können, kommen in erster Linie wasserlösliche Glykole und Glykolether sowie Glycerin in Betracht; vorzugsweise werden keine anderen organischen Lösungsmittel zusätzlich verwendet. Bei den Glykolen handelt es sich vorzugsweise um solche mit 2 bis 6 C-Atomen im Molekül, sowie um die bei Raumtemperatur flüssigen Di- und Oligomeren von Propylenglykol und, vorzugsweise, Ethylenglykol. Bei den Glykolethern werden vorzugsweise die Monoether aus Methanol, Ethanol, Propanol oder Butanol und Mono-, Di- oder Triglykolen verwendet. Insbesondere enthalten die Ether nicht mehr als 10 C-Atome pro Molekül. Der Gehalt an organischen Lösungsmitteln beträgt vorzugsweise nicht mehr als 30 Gew.-%, insbesondere zwischen 0,5 und 10 Gew.-% bezogen auf das Waschmittel als Ganzes.As organic solvents, which together with the nonionic surfactants of formula (I) and optionally water, the liquid phase of can form agents according to the invention, primarily water-soluble glycols and glycol ethers and glycerol come into consideration; preferably no other organic solvents are used in addition. The glycols are preferably those having 2 to 6 carbon atoms in the molecule, and the di- and oligomers of propylene glycol and, preferably, ethylene glycol which are liquid at room temperature. For the glycol ethers, the monoethers from methanol, ethanol, propanol or butanol and mono-, di- or triglycols are preferably used. In particular, the ethers contain no more than 10 carbon atoms per molecule. The organic solvent content is preferably not more than 30% by weight, in particular between 0.5 and 10% by weight, based on the detergent as a whole.
Eine weitere bevorzugte Komponente der erfindungsgemäßen flüssigen bis pastenförmigen Waschmittel sind anorganische Peroxide, die als Bleichmittel wirksam sind. Im einfachsten Falle kann an Stelle eines Teils des in der flüssigen Phase vorhandenen Wassers eine gewichtsgleiche Menge an Wasserstoffperoxid eingesetzt werden. Vorzugsweise werden aber feste anorganische Peroxide eingesetzt, die sich dann im Mittel überwiegend auch in ungelöster, d.h. suspendierter Form befinden. Ganz besonders bevorzugt werden Perborat-Tetrahydrat, Perborat-Monohydrat und das Addukt von H₂O₂ an Natriumcarbonat, das auch als Percarbonat bezeichnet wird. Die festen anorganischen Peroxide werden wie die kristallinen, schichtförmigen Natriumsilikate in den Mitteln vorzugsweise in sehr feinteiliger Form eingesetzt. Ihr Gehalt in den erfindungsgemäßen Mitteln kann bis zu 30 Gew.-% betragen, vorzugsweise liegt er zwischen 5 und 30 Gew.-% und insbesondere zwischen 10 und 25 Gew.-%.Another preferred component of the liquid to pasty detergents according to the invention are inorganic peroxides, which are effective as bleaching agents. In the simplest case, an equal weight of hydrogen peroxide can be used instead of part of the water present in the liquid phase. However, preference is given to using solid inorganic peroxides, which on average are then predominantly also in undissolved, i.e. suspended form. Perborate tetrahydrate, perborate monohydrate and the adduct of H₂O₂ with sodium carbonate, which is also referred to as percarbonate, are very particularly preferred. The solid inorganic peroxides, like the crystalline, layered sodium silicates, are preferably used in the compositions in very finely divided form. Their content in the agents according to the invention can be up to 30% by weight, preferably between 5 and 30% by weight and in particular between 10 and 25% by weight.
Außer den bereits genannten Bestandteilen können die erfindungsgemäßen Waschmittel weitere Wirkstoffe und Hilfsstoffe enthalten, wie sie in flüssigen und pastösen Waschmitteln gebräuchlich sind, sofern diese weiteren Inhaltsstoffe die Stabilität der Mittel nicht beeinträchtigen. Als derartige Bestandteile sind in erster Linie folgende zu nennen: Tenside anderer Typen, insbesondere nichtionische und anionische Tenside, weitere organische oder anorganische Gerüstsubstanzen und Sequestriermittel, Schaumregulatoren, Vergrauungsinhibitoren und Bleichaktivatoren. Weitere Beispiele derartiger Hilfs- und Zusatzstoffe sind optische Aufheller, Waschkraftverstärker, Enzyme, Farbstoffe, Parfüme, anorganische Salze und Konservierungsmittel. Der Gesamtgehalt der vorgenannten Wirk- und Hilfsstoffe beträgt in den erfindungsgemäßen Mitteln im allgemeinen nicht mehr als 50 Gew.-%, vorzugweise zwischen 0,5 und 20 Gew.-%, wobei die einzelnen Komponenten gelöst oder suspendiert in den Mitteln vorliegen können.In addition to the constituents already mentioned, the detergents according to the invention can contain further active ingredients and auxiliaries as are customary in liquid and pasty detergents, provided that these further ingredients do not impair the stability of the detergents. The following are primarily mentioned as such constituents: surfactants of other types, in particular nonionic and anionic surfactants, further organic or inorganic builders and sequestering agents, foam regulators, graying inhibitors and bleach activators. Further Examples of such auxiliaries and additives are optical brighteners, detergency boosters, enzymes, dyes, perfumes, inorganic salts and preservatives. The total content of the abovementioned active substances and auxiliaries in the agents according to the invention is generally not more than 50% by weight, preferably between 0.5 and 20% by weight, it being possible for the individual components to be present in the agents in dissolved or suspended form.
Als weitere nichtionische Tenside sind in erster Linie die Additionsprodukte von Ethylenoxid an Polypropylenoxid oder an Fettsäuren, Fettsäureamide oder Alkylphenole mit 12 bis 18 C-Atomen, sowie die Alkylglykoside, beispielsweise die aus Glukose und langkettigen primären Alkoholen zugänglich Alkylglukoside bzw. Alkylpolyglukoside zu nennen. Vorzugsweise enthalten diese Alkylglukoside 10 bis 14 C-Atome im Alkoholteil und 1 bis 3 Glukoseeinheiten pro Molekül. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxiethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt im allgemeinen nicht mehr als die der nichtionischen Tenside der Formel (I), vorzugsweise nicht mehr als die Hälfte davon.Additional nonionic surfactants include primarily the addition products of ethylene oxide with polypropylene oxide or with fatty acids, fatty acid amides or alkylphenols with 12 to 18 carbon atoms, and the alkyl glycosides, for example the alkyl glucosides or alkyl polyglucosides available from glucose and long-chain primary alcohols. These alkyl glucosides preferably contain 10 to 14 carbon atoms in the alcohol part and 1 to 3 glucose units per molecule. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is generally not more than that of the nonionic surfactants of the formula (I), preferably not more than half of them.
Geeignete synthetische anionische Tenside sind insbesondere solche vom Typ der Sulfonate und Sulfate. Als Tenside vom Sulfonattyp kommen Alkylbenzolsulfonate mit einem C₉-₁₅-Alkylrest, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxialkansulfonaten, sowie Disulfonaten, wie man sie beispielsweise aus C₁₂-₁₈-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in betracht. Geeignet sind auch die Alkansulfonate, die aus C₁₂-C₁₈-Alkanen durch Sulfochlorierung oder Sulfoxidation und anschließende Hydrolyse bzw. Neutralisation oder durch Bisulfitaddition an Olefine erhältlich sind, sowie die Ester von α-Sulfofettsäuren, wie z. B. die α-sulfonierten Methyl- oder Ethylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren. Geeignete Tenside vom Sulfattyp sind die Schwefelsäuremonoester von primären Alkoholen natürlichen oder synthetischen Ursprungs, d. h. von Fettalkoholen wie z.B. Kokosfett-, Talgfett-, Oleyl-, Lauryl-, Myristyl-, Palmityl- oder Stearylalkohol oder den C₁₀-C₂₀-Oxoalkoholen oder sekundären Alkoholen dieser Kettenlänge. Auch die Schwefelsäuremonoester der mit 1 bis 6 mol EO ethoxylierten aliphatischen primären Alkohole bzw. ethoxylierten sekundären Alkoholen sind geeignet. Ferner eignen sich sulfatierte Fettsäurealkanolamide und sulfatierte Fettsäuremonoglyceride. Als anionische Tenside auf natürlicher Rohstoffbasis sind insbesondere die waschaktiven Seifen, d.h. die Salze der C₁₂₋C₁₈-Fettsäuren zu nennen. Die anionischen Tenside liegen in den erfindungsgemäßen Mitteln vorzugsweise in Form ihrer Natriumsalze oder in Form der löslichen Salze mit organischen Basen, insbesondere Mono-, Di- und Triethanolamin vor. Die Menge der anionischen Tenside ist in den erfindungsgemäßen Mitteln vorzugsweise nicht größer als die Menge der nichtionischen Tenside insgesamt, insbesondere beträgt sie weniger als die Hälfte der nichtionischen Tenside. Ein bevorzugter Gehalt liegt zwischen 5 und 20 Gew.-%, bezogen auf das gesamte Mittel.Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type. As surfactants of the sulfonate type come alkylbenzenesulfonates with a C₉-₁₅-alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C₁₂-₁₈ monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products into consideration. Also suitable are the alkanesulfonates which are obtainable from C₁₂-C₁₈ alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and the esters of α-sulfofatty acids, such as, for. B. the α-sulfonated methyl or ethyl esters of hydrogenated coconut, palm kernel or tallow fatty acids. Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural or synthetic origin, ie of fatty alcohols such as, for example, coconut oil, tallow oil, oleyl, lauryl, myristyl, palmityl or stearyl alcohol or the C₁₀-C₂₀ oxo alcohols or secondary alcohols of this chain length. The sulfuric acid monoesters of the aliphatic primary alcohols or ethoxylated secondary alcohols ethoxylated with 1 to 6 mol EO are also suitable. Sulfated fatty acid alkanolamides and sulfated fatty acid monoglycerides are also suitable. The anionic surfactants based on natural raw materials are in particular the wash-active soaps, ie the salts of C₁₂₋C₁₈ fatty acids. The anionic surfactants are present in the agents according to the invention preferably in the form of their sodium salts or in the form of the soluble salts with organic bases, in particular mono-, di- and triethanolamine. The amount of anionic surfactants in the agents according to the invention is preferably not greater than the total amount of nonionic surfactants, in particular it is less than half of the nonionic surfactants. A preferred content is between 5 and 20% by weight, based on the total agent.
Als kationische Tenside sind insbesondere die quartären Ammoniumverbindungen zu nennen, die am Stickstoff neben drei kürzeren Alkylresten mit jeweils nicht mehr als 2 C-Atomen einen langkettigen Alkylrest mit 10 bis 18 C-Atomen aufweisen. Dabei können zwei oder drei der kürzeren Alkylketten auch zu einem Ring, beispielsweise einem Pyridinring geschlossen sein. Beispiele derartiger Verbindungen sind N,N,N-Trimethyl-N-tetradecylammoniumchlorid und N,N-Dimethyl-N-hydroxyethyl-N-dodecylammoniumhydrogensulfat.Cationic surfactants include, in particular, the quaternary ammonium compounds which, in addition to three shorter alkyl radicals, each with no more than 2 carbon atoms, have a long-chain alkyl radical with 10 to 18 carbon atoms on the nitrogen. Two or three of the shorter alkyl chains can also be closed to form a ring, for example a pyridine ring. Examples of such compounds are N, N, N-trimethyl-N-tetradecylammonium chloride and N, N-dimethyl-N-hydroxyethyl-N-dodecylammonium hydrogen sulfate.
Bei den Betaintensiden handelt es sich vorwiegend um langkettige quartäre Ammoniumverbindungen, in denen einer der kürzeren Alkylsubstituenten eine anionische Gruppe, meist eine Carboxylgruppe, enthält. Ein Beispiel eines Betaintensids ist N,N-Dimethyl-N-kokosalkylaminoacetat.The betaine surfactants are predominantly long-chain quaternary ammonium compounds in which one of the shorter alkyl substituents contains an anionic group, usually a carboxyl group. An example of a betaine surfactant is N, N-dimethyl-N-cocoalkylaminoacetate.
Obwohl die erfindungsgemäßen Mittel vorzugsweise als Gerüstsubstanzen allein die kristallinen, schichtförmigen Natriumsilikate enthalten, können daneben in den Mitteln auch weitere organische und/oder anorganische, lösliche oder unlösliche Gerüstsubstanzen enthalten sein. Die Menge dieser zusätzlichen Gerüstsubstanzen liegt im allgemeinen nicht über der Menge an schichtförmigen Silikaten und beträgt vorzugsweise weniger als die Hälfte dieser Silikate; insbesondere liegt die Menge zwischen 0,1 und 5 Gew.-% bezogen auf das gesamte Mittel.Although the agents according to the invention preferably contain only the crystalline, layered sodium silicates as builders, the agents may also contain further organic and / or inorganic, soluble or insoluble builders. The amount of these additional builder substances is generally not more than the amount of layered silicates and is preferably less than half these silicates; in particular the amount is between 0.1 and 5% by weight, based on the total agent.
Als zusätzliche Gerüstsubstanz sind insbesondere die alkalisch reagierenden Salze, insbesondere Alkalisalze, die nicht nur Calciumionen auszufällen oder komplex zu binden vermögen, sondern möglichst auch mit den Tensiden eine synergistische Steigerung der Waschkraft bewirken und ein Schmutztragevermögen besitzen, zu erwähnen. Von den anorganischen Salzen sind die wasserlöslichen Alkalimeta- oder Alkalipolyphosphate, insbesondere das Pentanatriumtriphosphat, immer noch von Bedeutung. Zu den organischen Buildersubstanzen gehören Sequestiermittel vom Typ der Aminopolycarbonsäuren, wie z .B. Nitrilotriessigsäure, Ethylendiamintetraessigsäure, sowie höhere Homologe. Geeignete phosphorhaltige organische Komplexbildner sind die wasserlöslichen Salze der Alkanpolyphosphonsäuren, Amino- und Hydroxyalkanpolyphosphonsäuren und Phosphonopolycarbonsäuren, wie z. B. die Verbindungen Methandiphosphonsäure, Dimethylaminomethan-1,1-diphosphonsäure, Aminotrimethylenphosphonsäure, Ethylendiamintetramethylenphosphonsäure, Diethylentriaminpentamethylenphosphonsäure, 1-Hydroxyethan-1,1-diphosphonsäure, 2-Phosphonobutan-1,2,4-tricarbonsäure. Diese Sequestriermittel können auch in kleineren Mengen als Stabilisatoren für Perverbindungen enthalten sein. Unter den organischen Gerüstsubstanzen sind die N- und P-freien, mit Calciumionen Komplexsalze bildenden Polycarbonsäuren von besonderer Bedeutung. Dazu gehören niedermolekulare Verbindungen, wie z. B. Citronensäure, 2,2'-Oxydibernsteinsäure oder Carboxymethyloxybernsteinsäure, und polymere Polycarbonsäuren mit einem Molekulargewicht von 350 bis etwa 1 500 000 in Form der wasserlöslichen Salze. Besonders bevorzugte polymere Polycarboxylate haben ein Molekulargewicht im Bereich von 500 bis 175 000, und insbesondere im Bereich von 10 000 bis 100 000. Dazu gehören Verbindungen, wie z. B. Polyacrylsäure, Poly-alphahydoxyacrylsäure und Polymaleinsäure, sowie die Copoymerisate der entsprechenden monomeren Carbonsäuren untereinander, beispielsweise aus Acrylsäure und Maleinsäure, oder mit anderen ethylenisch ungesättigten Verbindungen, wie z. B. mit Vinylmethylether. Daneben sind auch die wasserlöslichen Salze der Polyglyoxylsäure zu erwähnen.The alkaline salts, in particular alkali salts, which not only precipitate or complexly bind calcium ions, but also, as far as possible, bring about a synergistic increase in washing power and have dirt-carrying capacity, should be mentioned as an additional framework substance. Of the inorganic salts, the water-soluble alkali metal or alkali polyphosphates, especially pentasodium triphosphate, are still of importance. Organic builder substances include sequestering agents of the aminopolycarboxylic acid type, such as, for example. Nitrilotriacetic acid, ethylenediaminetetraacetic acid, and higher homologues. Suitable phosphorus-containing organic complexing agents are the water-soluble salts of alkane polyphosphonic acids, amino and hydroxyalkane polyphosphonic acids and phosphonopolycarboxylic acids, such as. B. the compounds methanediphosphonic acid, dimethylaminomethane-1,1-diphosphonic acid, aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid. These sequestering agents can also be present in smaller amounts as stabilizers for per-compounds. Among the organic framework substances, the N- and P-free polycarboxylic acids that form complex salts with calcium ions are of particular importance. These include low molecular weight compounds, such as. As citric acid, 2,2'-oxydisuccinic acid or carboxymethyloxy succinic acid, and polymeric polycarboxylic acids with a molecular weight of 350 to about 1,500,000 in the form of the water-soluble salts. Particularly preferred polymeric polycarboxylates have a molecular weight in the range from 500 to 175,000, and in particular in the range from 10,000 to 100,000. These include compounds such as, for. B. polyacrylic acid, poly-alphahydoxyacrylic acid and polymaleic acid, and the copolymers of the corresponding monomeric carboxylic acids with one another, for example from acrylic acid and maleic acid, or with other ethylenically unsaturated compounds, such as. B. with vinyl methyl ether. The water-soluble salts of polyglyoxylic acid should also be mentioned.
Als wasserunlösliche anorganische Gerüstsubstanzen kommen vor allem die in der deutschen Patentanmeldung DE 24 12 837 als Phosphatsubstitute für Wasch- und Reinigungsmittel näher beschriebenen feinteiligen synthetischen, gebundenes Wasser enthaltenden Natriumalumosilikate vom Zeolith-A-Typ in Betracht. Die kationenaustauschenden Natriumalumosilikate kommen in der üblichen hydratisierten, feinkristallinen Form zum Einsatz, d. h. sie weisen praktisch keine Teilchen größer als 30 »m auf und bestehen vorzugsweise zu wenigstens 80 % aus Teilchen einer Größe von weniger als 10 »m. Ihr Calciumbindevermögen, das nach den Angaben der DE 24 12 837 bestimmt wird, liegt im Bereich von 100 bis 200 mg CaO/g. Brauchbar ist insbesondere der Zeolith NaA, ferner auch der Zeolith NaX und Mischungen aus NaA und NaX. Vorzugsweise werden die Zeolithe in den erfindungsgemäßen Mitteln aber nur dann eingesetzt, wenn keine anorganischen Peroxide, insbesondere Perborat, enthalten sind.Particularly suitable water-insoluble inorganic builders are the finely divided synthetic zeolite A-type sodium aluminosilicates containing bound water described in German patent application DE 24 12 837 as phosphate substitutes for detergents and cleaning agents. The cation-exchanging sodium aluminosilicates are used in the usual hydrated, finely crystalline form, i.e. H. they have practically no particles larger than 30 »m and preferably consist at least 80% of particles smaller than 10» m. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg CaO / g. The zeolite NaA can be used in particular, also the zeolite NaX and mixtures of NaA and NaX. However, the zeolites are preferably only used in the agents according to the invention if no inorganic peroxides, in particular perborate, are present.
Geeignete anorganische, nicht komplexbildende Salze sind die - auch als "Waschalkalien" bezeichneten - Bicarbonate, Carbonate, Borate, Sulfate oder amorphen Silikate der Alkalien. Weitere Gerüstsubstanzen, die auch wegen ihrer hydrotropen Eigenschaften eingesetzt werden, sind die Salze der nicht kapillaraktiven, 2 bis 9 C-Atome enthaltenden Sulfonsäuren, Carbonsäuren und Sulfocarbonsäuren, beispielsweise die Alkalisalze der Alkan-, Benzol-, Toluol-, Xylol- oder Cumolsulfonsäuren, der Sulfobenzoesäuren, Sulfophthalsäure, Sulfoessigsäure, Sulfobernsteinsäure sowie die Salze der Essigsäure oder Milchsäure.Suitable inorganic, non-complexing salts are the bicarbonates, also known as "washing alkalis", carbonates, borates, sulfates or amorphous silicates of the alkalis. Other structural substances that are also used because of their hydrotropic properties are the salts of the non-capillary-active sulfonic acids containing 2 to 9 carbon atoms, carboxylic acids and sulfocarboxylic acids, for example the alkali salts of alkanoic, benzene, toluene, xylene or cumene sulfonic acids, of sulfobenzoic acids, sulfophthalic acid, sulfoacetic acid, sulfosuccinic acid and the salts of acetic acid or lactic acid.
Als Schaumregulatoren sind beispielsweise die Salze von Fettsäuren mit 20 bis 24 C-Atomen oder langkettige N-Alkylaminotriazine mit im wesentlichen 8 bis 18 C-Atomen im Alkylrest oder aliphatische C₁₈-C₄₀-Ketone zu nennen. Bevorzugt werden Paraffin- und Siliconöldispersionen, die gegebenenfalls mit mikrofeiner Kieselsäure konfektioniert sein können. Der Gehalt kann, beispielsweise bei Seifen, bis zu 5 Gew.-% des gesamten Mittels betragen, bei den Paraffinen und Siliconölen üblicherweise wesentlich weniger, beispielsweise 0,05 bis 0,5 Gew.-%.Examples of foam regulators are the salts of fatty acids with 20 to 24 carbon atoms or long-chain N-alkylaminotriazines with essentially 8 to 18 carbon atoms in the alkyl radical or aliphatic C₁₈-C₄₀ ketones. Paraffin and silicone oil dispersions are preferred, which can optionally be made up with microfine silica. The content can be, for example in the case of soaps, up to 5% by weight of the total composition, in the case of the paraffins and silicone oils it is usually much less, for example 0.05 to 0.5% by weight.
Als Vergrauungsinhibitoren sind vor allem Celluloseether, wie Carboxymethylcellulose, Methylcellulose, Hydroxyalkylcellulosen und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose und Methyl-Carboxymethylcellulose zu erwähnen, ferner Gemische verschiedener Celluloseether, insbesondere Gemische aus Carboxymethylcellulose und Methylcellulose.Graying inhibitors include, above all, cellulose ethers, such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl celluloses and mixed ethers, such as Mention should be made of methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose and methyl carboxymethyl cellulose, furthermore mixtures of various cellulose ethers, in particular mixtures of carboxymethyl cellulose and methyl cellulose.
Zur Stärkung der Bleichwirksamkeit der erfindungsgemäßen Mittel können diese neben anorganischem Peroxid Bleichaktivatoren enthalten. Es handelt sich dabei um Acylierungsmittel, die mit Wasserstoffperoxid in der Waschlauge zu Peroxicarbonsäuren bzw. deren Salzen reagieren. Beispiele gebräuchlicher Bleichaktivatoren sind Tetraacetylethylendiamin, Pentaacetylglucose und Diacetyldioxohexahydrotriazin. Neben N-Acylverbindungen und O-Acylverbindungen können auch Anhydride zum Einsatz kommen. Vorzugsweise werden solche Bleichaktivatoren verwendet, die im flüssigen Anteil des Waschmittels weitgehend ungelöst bleiben und deshalb überwiegend in suspendierter Form vorliegen. Die Mengen an Bleichaktivatoren beträgt vorzugsweise nicht mehr als 6 Gew.-%, insbesondere zwischen 2 und 5 Gew.-%, bezogen auf das gesamte Mittel.To strengthen the bleaching effectiveness of the agents according to the invention, they can contain bleach activators in addition to inorganic peroxide. These are acylating agents which react with hydrogen peroxide in the wash liquor to form peroxycarboxylic acids or their salts. Examples of common bleach activators are tetraacetylethylenediamine, pentaacetylglucose and diacetyldioxohexahydrotriazine. In addition to N-acyl compounds and O-acyl compounds, anhydrides can also be used. Bleach activators are preferably used which remain largely undissolved in the liquid portion of the detergent and are therefore predominantly in suspended form. The amounts of bleach activators are preferably not more than 6% by weight, in particular between 2 and 5% by weight, based on the total agent.
Für Waschmittel besonders geeignete optische Aufheller sind Alkalisalze der 4,4-Bis-(2''-anilino-4''-morpholino-1,3,5-triazinyl-6''-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe tragen. Weiterhin kommen Aufheller vom Typ der substituierten Diphenylstyryle in Frage, z. B. die Alkalisalze des 4,4'-Bis-(2-sulfostyryl)-diphenyls, 4,4'-Bis-(4-chlor-3-sulfostyryl)-diphenyls und 4-(4-Chlorstyryl-4'-(2-sulfostyryl)-diphenyls.Optical brighteners which are particularly suitable for detergents are alkali salts of 4,4-bis (2 '' - anilino-4 '' - morpholino-1,3,5-triazinyl-6 '' - amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group instead of the morpholino group. Furthermore, brighteners of the type of the substituted diphenylstyryl come into question, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl and 4- (4-chlorostyryl-4 '- ( 2-sulfostyryl) diphenyl.
Bei Waschkraftverstärkern handelt es sich um polare langkettige Verbindungen, die selbst keine oberflächenaktiven Eigenschaften besitzen, aber in der Lage sind, die Reinigungswirkung der in den Waschmitteln enthaltenen Tenside zu erhöhen. Beispiele derartiger Verbindungen sind Kokosamin + 2 EO und die Additionsprodukte aus Glycerin und langkettigem α-Olefinepoxid.Detergent boosters are polar long-chain compounds that do not themselves have any surface-active properties, but are able to increase the cleaning effect of the surfactants contained in the detergents. Examples of such compounds are coconut amine + 2 EO and the addition products of glycerol and long-chain α-olefin epoxide.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen und Amylasen bzw. deren Gemische in Frage. Besonders geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Die Enzyme können in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen.Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and are particularly suitable Streptomyces griseus enzymatic substances obtained. The enzymes can be embedded in coating substances to protect them against premature decomposition.
Die Herstellung der erfindungsgemäßen Mittel bietet keine Schwierigkeiten. Sie erfolgt im einfachsten Falle durch Mischen sämtlicher Bestandteile, wobei man zweckmäßigerweise zunächst die Bestandteile, die später die flüssige Phase bilden, vormischt und dann die zu suspendierenden Bestandteile in diese Flüssigkeit einträgt und homogen damit vermischt. Vorzugsweise geht man bei den festen Bestandteilen des Mittels bereits von Teilchengrößen aus, wie sie später im fertigen Mittel vorliegen sollen, doch ist es auch möglich, die Größe der suspendierten festen Teilchen nachträglich durch Naßvermahlung des fertigen Mittels weiter zu verkleinern. Die Viskosität des fertigen Mittels hängt in erster Linie vom Verhältnis fest/flüssig im fertigen Mittel und von der Viskosität der flüssigen Phase ab. Diese wiederum läßt sich durch Wahl geeigneter Bestandteile in weiten Grenzen variieren. So kann beispielsweise durch Zusatz organischer Lösungsmittel die Viskosität erniedrigt und durch Zusatz verdickend wirkender Bestandteile, wie etwa Seifen, die Viskosität erhöht werden. Flüssige erfindungsgemäße Mittel haben vorzugsweise Viskositäten zwischen etwa 1 000 und etwa 5 000 mPas, insbesondere zwischen etwa 2 000 und etwa 4 000 mPas, wobei die Viskosität mit Hilfe eines Brookfield-Viskosimeters bei 20 °C gemessen wird. Die Viskositäten der Waschmittel in Pastenform, die wegen ihrer besonders hohen physikalischen Stabilität bevorzugt werden, gehen weit darüber hinaus.The preparation of the agents according to the invention presents no difficulties. In the simplest case, it is carried out by mixing all the components, the components which later form the liquid phase are advantageously first premixed and then the components to be suspended are introduced into this liquid and mixed homogeneously therewith. The solid constituents of the composition are preferably already based on particle sizes as they are later to be present in the finished composition, but it is also possible to further reduce the size of the suspended solid particles by wet grinding the finished composition. The viscosity of the finished product depends primarily on the solid / liquid ratio in the finished product and on the viscosity of the liquid phase. This in turn can be varied within wide limits by choosing suitable components. For example, the viscosity can be reduced by adding organic solvents and the viscosity can be increased by adding constituents with a thickening effect, such as soaps. Liquid agents according to the invention preferably have viscosities between about 1,000 and about 5,000 mPas, in particular between about 2,000 and about 4,000 mPas, the viscosity being measured using a Brookfield viscometer at 20 ° C. The viscosities of the detergent in paste form, which are preferred because of their particularly high physical stability, go far beyond.
Die erfindungsgemäßen Mittel sind in erster Linie für den Einsatz in der Textilwäsche bestimmt. Je nach Gehalt an Wirkstoffen können sie dabei als Alleinwaschmittel oder aber als Waschzusatzmittel eingesetzt werden. Sie eignen sich aber bei entsprechender Wahl der Wirkstoffe auch zur Reinigung von harten Oberflächen im Haushalt oder im gewerblichen Bereich. Bedingt durch die Stabilität der Suspensionen lassen sich die Mittel auch automatisch dosieren.The agents according to the invention are primarily intended for use in textile washing. Depending on the content of active ingredients, they can be used as stand-alone detergents or as detergent additives. However, if the active ingredients are selected appropriately, they are also suitable for cleaning hard surfaces in the home or in the commercial sector. Due to the stability of the suspensions, the agents can also be dosed automatically.
Die im folgenden beschriebenen pastenförmigen Waschmittel A und B wurden in Ansätzen von je 50 g durch zusammenwiegen aller Komponenten und Homogenisierung der Gemische in einer keramischen Kugelmühle (Laufzeit 5 Minuten) hergestellt.
Beide Waschmittel wurden 4 Wochen bei 40 °C in geschlossenen Polyethylenbeuteln gelagert. Nach dieser Zeit waren keinerlei Anzeichen für eine Phasentrennung zu erkennen. Der Erhalt der kristallinen schichtförmigen Struktur des Disilikats ließ sich mit Hilfe der Röntgenreflexe nachweisen. Ein Verlust an Aktivsauerstoff konnte durch manganometrische Titration nicht festgestellt werden.Both detergents were stored for 4 weeks at 40 ° C in closed polyethylene bags. No signs of phase separation were seen after this time. Obtaining the crystalline layered The structure of the disilicate was demonstrated with the help of the X-ray reflexes. A loss of active oxygen could not be determined by manganometric titration.
Claims (8)
- A liquid or paste-form detergent containing crystalline layer-form sodium silicate corresponding to general formula (I) NaMSixO2x+1·yH₂O, where M is sodium or hydrogen, x is a number of 1.9 to 4 and y is a number of 0 to 20, this silicate being suspended in a liquid phase containing nonionic surfactants corresponding to the formula R-(O-CH₂-CH₂-)n OH (I), in which R is a long-chain primary or secondary alkyl radical containing 8 to 20 C atoms and n is a number of 3 to 20, and optionally organic solvents from the group of glycols, glycol ethers and glycerol, and no more than 30% by weight, based on the detergent as a whole, of water.
- A detergent as claimed in claim 1, in which the crystalline layer-form sodium silicate corresponds to the formula NaMSiO₂O₅ · yH₂O.
- A detergent as claimed in claim 2, in which the beta- and/or delta-modification of Na₂Si₂O₅ is present as the crystalline layer-form sodium silicate.
- A detergent as claimed in any of claims 1 to 3, in which the water content is no more than 20% by weight and preferably no more than 10% by weight.
- A detergent as claimed in any of claims 1 to 3 containing
10 to 50 and preferably 20 to 40% by weight crystalline layer-form sodium silicate,
10 to 60 and preferably 10 to 40% by weight nonionic surfactant corresponding to formula (I),
5 to 30 and preferably 10 to 25% by weight inorganic peroxide,
0 to 30 and preferably 0.5 to 10% by weight organic solvent,
0 to 30 and preferably 0.5 to 20% by weight water and
0 to 50 and preferably 0.5 to 20% by weight other typical detergent ingredients. - A detergent as claimed in claim 5 in which the nonionic surfactant is selected from the group of adducts of 4 to 10 mol ethylene oxide and 1 mol long-chain alcohol containing 10 to 18 carbon atoms.
- A detergent as claimed in claim 5, in which the inorganlc peroxide is selected from the group consisting of sodium perborate monohydrate, sodium percarbonate and mixtures thereof.
- A detergent as claimed in claim 5 in paste form.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4109247 | 1991-03-21 | ||
| DE4109247A DE4109247A1 (en) | 1991-03-21 | 1991-03-21 | LIQUID OR PASTE-DETECTED DETERGENT |
| PCT/EP1992/000545 WO1992016608A1 (en) | 1991-03-21 | 1992-03-12 | Liquid or paste-like washing product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0576479A1 EP0576479A1 (en) | 1994-01-05 |
| EP0576479B1 true EP0576479B1 (en) | 1995-08-02 |
Family
ID=6427861
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92906453A Revoked EP0576479B1 (en) | 1991-03-21 | 1992-03-12 | Liquid or paste-like washing product |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0576479B1 (en) |
| JP (1) | JPH06506006A (en) |
| AT (1) | ATE125862T1 (en) |
| DE (2) | DE4109247A1 (en) |
| ES (1) | ES2075688T3 (en) |
| WO (1) | WO1992016608A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MY111592A (en) * | 1992-08-19 | 2000-09-27 | Colgate Palmolive Co | Automatic dishwashing detergent containing an organic compound having at least one hydroxyl group |
| ES2141138T3 (en) * | 1993-11-11 | 2000-03-16 | Procter & Gamble | SOFTENED THROUGH WASHING COMPOSITIONS. |
| DE19703364A1 (en) * | 1997-01-30 | 1998-08-06 | Henkel Ecolab Gmbh & Co Ohg | Paste-like detergent and cleaning agent |
| DE19854960A1 (en) | 1998-11-29 | 2000-05-31 | Clariant Gmbh | Dishwasher detergent |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409136A (en) * | 1977-01-31 | 1983-10-11 | Colgate Palmolive Company | Molecular sieve zeolite-built detergent paste |
| DE3615544A1 (en) * | 1986-05-09 | 1987-11-12 | Henkel Kgaa | METHOD FOR PRE-TREATING DIRTY TEXTILES |
| DE3634279A1 (en) * | 1986-10-08 | 1988-08-11 | Hoechst Ag | DETERGENT CONTAINING SOFTENER |
| DE3812556A1 (en) * | 1988-04-15 | 1989-10-26 | Hoechst Ag | DETERGENT WITH STORAGE-STABILIZED BLEACHING SYSTEM |
| DE3914504A1 (en) * | 1989-05-02 | 1990-11-08 | Henkel Kgaa | PASTOESES, PHOSPHATE-FREE, IN ESSENTIAL WATER-FREE DETERGENT |
-
1991
- 1991-03-21 DE DE4109247A patent/DE4109247A1/en not_active Withdrawn
-
1992
- 1992-03-12 JP JP4505807A patent/JPH06506006A/en active Pending
- 1992-03-12 DE DE59203122T patent/DE59203122D1/en not_active Revoked
- 1992-03-12 AT AT92906453T patent/ATE125862T1/en not_active IP Right Cessation
- 1992-03-12 EP EP92906453A patent/EP0576479B1/en not_active Revoked
- 1992-03-12 WO PCT/EP1992/000545 patent/WO1992016608A1/en not_active Application Discontinuation
- 1992-03-12 ES ES92906453T patent/ES2075688T3/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| WO1992016608A1 (en) | 1992-10-01 |
| DE59203122D1 (en) | 1995-09-07 |
| JPH06506006A (en) | 1994-07-07 |
| ES2075688T3 (en) | 1995-10-01 |
| EP0576479A1 (en) | 1994-01-05 |
| DE4109247A1 (en) | 1992-09-24 |
| ATE125862T1 (en) | 1995-08-15 |
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