EP1195429A1 - Automatic dishwashing process and automatic dishwashing compositions having improved anti-corrosion characteristics - Google Patents
Automatic dishwashing process and automatic dishwashing compositions having improved anti-corrosion characteristics Download PDFInfo
- Publication number
- EP1195429A1 EP1195429A1 EP01123093A EP01123093A EP1195429A1 EP 1195429 A1 EP1195429 A1 EP 1195429A1 EP 01123093 A EP01123093 A EP 01123093A EP 01123093 A EP01123093 A EP 01123093A EP 1195429 A1 EP1195429 A1 EP 1195429A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- surfactant
- agents
- cleaning
- weight
- 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.)
- Granted
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- 238000005260 corrosion Methods 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000004851 dishwashing Methods 0.000 title claims abstract description 22
- 239000000203 mixture Substances 0.000 title claims description 53
- 239000004094 surface-active agent Substances 0.000 claims abstract description 75
- 239000003599 detergent Substances 0.000 claims abstract description 43
- 230000007797 corrosion Effects 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- -1 transition metal salts Chemical class 0.000 claims description 76
- 239000003795 chemical substances by application Substances 0.000 claims description 51
- 238000004140 cleaning Methods 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 30
- 239000012459 cleaning agent Substances 0.000 claims description 28
- 239000004615 ingredient Substances 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000001565 benzotriazoles Chemical class 0.000 claims description 6
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- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 5
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical class NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- JSIAIROWMJGMQZ-UHFFFAOYSA-N 2h-triazol-4-amine Chemical class NC1=CNN=N1 JSIAIROWMJGMQZ-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003852 triazoles Chemical class 0.000 claims description 3
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002541 furyl group Chemical group 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 2
- 125000004076 pyridyl group Chemical group 0.000 claims description 2
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 2
- 125000000719 pyrrolidinyl group Chemical group 0.000 claims description 2
- 125000001302 tertiary amino group Chemical group 0.000 claims description 2
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 claims description 2
- 125000001544 thienyl group Chemical group 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 238000005406 washing Methods 0.000 abstract description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 62
- 239000002736 nonionic surfactant Substances 0.000 description 43
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- 239000000126 substance Substances 0.000 description 26
- 239000001913 cellulose Substances 0.000 description 24
- 239000011734 sodium Substances 0.000 description 24
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- 239000007844 bleaching agent Substances 0.000 description 21
- 150000007513 acids Chemical class 0.000 description 19
- 235000014113 dietary fatty acids Nutrition 0.000 description 19
- 239000000194 fatty acid Substances 0.000 description 19
- 229930195729 fatty acid Natural products 0.000 description 19
- 150000002191 fatty alcohols Chemical class 0.000 description 18
- 150000001298 alcohols Chemical class 0.000 description 17
- 235000019832 sodium triphosphate Nutrition 0.000 description 17
- 102000004190 Enzymes Human genes 0.000 description 16
- 108090000790 Enzymes Proteins 0.000 description 16
- 229940088598 enzyme Drugs 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 238000002844 melting Methods 0.000 description 15
- 230000008018 melting Effects 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 15
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- 150000001875 compounds Chemical class 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- 150000004665 fatty acids Chemical class 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 239000003205 fragrance Substances 0.000 description 12
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- 229920002245 Dextrose equivalent Polymers 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 10
- 108091005804 Peptidases Proteins 0.000 description 9
- 239000004365 Protease Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012190 activator Substances 0.000 description 9
- 229920005646 polycarboxylate Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000003945 anionic surfactant Substances 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 8
- 150000003254 radicals Chemical class 0.000 description 8
- 239000003760 tallow Substances 0.000 description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- 239000002535 acidifier Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 150000004760 silicates Chemical class 0.000 description 7
- 229910019142 PO4 Inorganic materials 0.000 description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 6
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 6
- 239000011976 maleic acid Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 229920001451 polypropylene glycol Polymers 0.000 description 6
- 235000019419 proteases Nutrition 0.000 description 6
- 239000001488 sodium phosphate Substances 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- 239000001226 triphosphate Substances 0.000 description 6
- 108010065511 Amylases Proteins 0.000 description 5
- 102000013142 Amylases Human genes 0.000 description 5
- 229920001353 Dextrin Polymers 0.000 description 5
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- 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 5
- 108090001060 Lipase Proteins 0.000 description 5
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 5
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- 229910052783 alkali metal Inorganic materials 0.000 description 5
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- 238000006243 chemical reaction Methods 0.000 description 5
- 235000019425 dextrin Nutrition 0.000 description 5
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
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- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 4
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- LTUGGBOPBQPPGK-UHFFFAOYSA-A octadecasodium;hexaphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LTUGGBOPBQPPGK-UHFFFAOYSA-A 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 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
- RUVINXPYWBROJD-UHFFFAOYSA-N para-methoxyphenyl Natural products COC1=CC=C(C=CC)C=C1 RUVINXPYWBROJD-UHFFFAOYSA-N 0.000 description 1
- XCRBXWCUXJNEFX-UHFFFAOYSA-N peroxybenzoic acid Chemical compound OOC(=O)C1=CC=CC=C1 XCRBXWCUXJNEFX-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PATMLLNMTPIUSY-UHFFFAOYSA-N phenoxysulfonyl 7-methyloctanoate Chemical compound CC(C)CCCCCC(=O)OS(=O)(=O)OC1=CC=CC=C1 PATMLLNMTPIUSY-UHFFFAOYSA-N 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 229940093916 potassium phosphate Drugs 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 239000010670 sage oil Substances 0.000 description 1
- 239000010671 sandalwood oil Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 150000003388 sodium compounds Chemical class 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 239000012418 sodium perborate tetrahydrate Substances 0.000 description 1
- 229940045872 sodium percarbonate Drugs 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 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
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229940012831 stearyl alcohol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 239000010679 vetiver oil Substances 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- ZFNVDHOSLNRHNN-UHFFFAOYSA-N xi-3-(4-Isopropylphenyl)-2-methylpropanal Chemical compound O=CC(C)CC1=CC=C(C(C)C)C=C1 ZFNVDHOSLNRHNN-UHFFFAOYSA-N 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/28—Heterocyclic compounds containing nitrogen in the ring
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3281—Heterocyclic compounds
-
- 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
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
Definitions
- the present invention relates to agents for the mechanical cleaning of metallic surfaces as well as the use of these agents in household dishwashers and a cleaning process using these means.
- Detergent compositions for cleaning soiled dishes in dishwashers are widely described in the prior art.
- a disadvantage that these funds often have is however the cleaning performance on metal surfaces, for example tarnished silver surfaces. Since machine dishwashing detergent both with regard to the substrates to be treated as well as a variety of requirements with regard to the contamination that occurs certain task fields are not to the complete satisfaction of the user solved.
- corrosion inhibitors which is another Prevent tarnishing, but tarnished silver surfaces cannot clean.
- silver cleaning agents should be used which contain alkaline electrolyte, metal and at least 1% by weight of builder and nonionic surfactant.
- the metal must have a more negative standard potential than silver.
- the agents can also be incorporated as a component in conventional MGSM.
- a mechanical silver cleaning process is also claimed in this document.
- the proposed solutions of the prior art have the disadvantage that they can only be used as pure cleaning agents for metallic objects (hereinafter referred to as silver cleaning agents for short). However, since the consumer rarely provides an entire dishwasher filling only from metallic surfaces, the machine either has to run partially loaded, or one accepts poor cleaning performance on other objects, such as baking dishes, plates, tea cups, etc.
- the object of the present invention was to provide a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher.
- a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher.
- Detergents for household dishwashers are provided, which improve the cleaning performance achieved conventional means and improved the performance on metallic surfaces, so that comparable results are achieved with special cleaners. For cost reasons, these should Results can be achieved with the same or reduced use of corrosion inhibitors.
- the present invention relates to a method for the mechanical cleaning of dishes in a domestic dishwasher using a detergent composition which contains anticorrosive agents and surfactant (s), the anticorrosive agent (s) being released before the surfactant (s) into the application liquor ,
- a detergent composition which contains anticorrosive agents and surfactant (s)
- the anticorrosive agent (s) being released before the surfactant (s) into the application liquor
- surfactants are part of most automatic dishwashing detergents and that their use can be desired for a variety of reasons.
- Corresponding agents according to the invention contain representatives of both classes of substances (corrosion inhibitors and surfactants) and have suitable measures for realizing the above-mentioned release sequence.
- the aqueous application liquor for step a) of the cleaning process according to the invention is required in the household dishwasher by adding water to the Interior in which there is a detergent composition in addition to the dirty dishes which contains anti-corrosion agents.
- a detergent composition in addition to the anti-corrosion agent (s) as ingredient (s) surfactant (s), so these Protected against early release by suitable measures to create a surfactant-free application fleet to ensure for step a).
- the concentration of the anti-corrosion agent (s) in The application fleet depends on the one hand on the amount of water that goes into the dishwasher flows, on the other hand according to the amount of detergent composition and the concentration the anti-corrosion agents herein.
- the concentration of the corrosion protection agent (s) in the application liquor is 0.0001 to 1 g / l, preferably 0.001 to 0.5 g / l, particularly preferably 0.002 to 0.25 g / l and in particular 0.005 up to 0.1 g / l.
- Corrosion inhibitors are used, with silver protection agents in particular Machine dishwashing have a special meaning. They can be used known substances of the prior art.
- silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used.
- Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- Zinc compounds can also be used to prevent corrosion be used on the wash ware.
- 1,2,4-triazoles substituted in the 5-position are again particularly preferred.
- Processes according to the invention which are characterized in that the application liquor substituted in the 5-position 3-amino-1,2,4-triazoles of the formula (I) or their mixtures and / or their salts, preferably with hydrochloric acid, sulfuric acid, phosphoric acid, Contains carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid or mixtures thereof in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, furyl, te
- those substituted in the 5-position are 3-amino-1,2,4-triazoles selected from the group of 5-propyl, butyl, pentyl, heptyl, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2- furyl) -, - (5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazoles.
- 5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles are very particularly effective as well as mixtures of these substances.
- preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic carboxylic acids such as vinegar, glycol, citric, Succinic acid.
- the alkylamino-1,2,4-triazoles or their physiological compatible salts usually in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, in each case based on the means used. Under normal household conditions, these quantities lead to the above concentrations mentioned in the application fleet.
- the application liquor can be used in the first step of the
- the cleaning method according to the invention naturally also contains other ingredients of cleaning agents included, wherein surfactant (s) are not present according to the invention in this step.
- further possible ingredients of the application liquor in the first process step are Builders, cobuilders, complexing agents, bleaches, bleach activators, enzymes, dyes, To name fragrances etc.
- the application liquor in step a) contains the application liquor in step a) in addition to the corrosion inhibitor (s) builders and / or cobuilders, polymers and / or complexing agents. It is also preferred if the Application liquor in step a) is free of bleaching agents and bleach activators.
- the crockery parts are also contacted a cleaning agent containing surfactant, which of course contains other ingredients from Cleaning agents, such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc., may contain.
- cleaning agents such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc.
- the surfactant component which is in the second step in the application liquor, come Anionic, nonionic, cationic and / or amphoteric surfactants into consideration, with nonionic Surfactants are preferred because of their foaming power.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
- Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.
- Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
- the anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
- nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
- 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 be suitable.
- the amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in The presence of an alkoxide as a catalyst is converted into the desired polyhydroxy fatty acid amides become.
- the application liquor in step b) of the cleaning process according to the invention particularly preferably contains nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- step b) contains a nonionic surfactant which has a melting point above room temperature having.
- preferred cleaning methods are characterized in that the Application liquor in step b) nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C included.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
- Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- the is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.
- a particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
- the application liquors in step b) is particularly preferred inventive cleaning method ethoxylated (s) nonionic surfactant (s), which / from C 6-20 monohydroxyalkanols or C 6- 20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- ethoxylated (s) nonionic surfactant (s) which / from C 6-20 monohydroxyalkanols or C 6- 20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
- the nonionic surfactant which is solid at room temperature, preferably has additional propylene oxide units in the Molecule.
- Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 % By weight of the total molecular weight of such nonionic surfactants.
- Preferred cleaning methods are characterized in that the application liquor in step b) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-%, preferred up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
- nonionic surfactants to be used with particular preference with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.
- nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.
- a further preferred cleaning method according to the invention is characterized in that the application liquor nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ] contains, in which R 1 represents a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1, 5 and y represents a value of at least 15.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
- H, -CH 3 or -CH 2 CH 3 are particularly preferred for the radical R 3 .
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula can be different if x ⁇ 2.
- the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
- step b) end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 contains in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to
- surfactant preferably nonionic (s) Surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated Contain alcohols.
- Step a) and step b) of the method according to the invention can be further described below in the description of agents according to the invention.
- Another object of the present invention is the use of surfactant-free aqueous Corrosion protection solutions for machine washing of dishes.
- the cleaning method according to the invention can be used, among other things by performing specially made cleaning agents in a household dishwasher brings in and runs a cleaning program.
- the Cleaning according to the invention dispenses with surfactants as intentionally added ingredients in the agents, thereby achieving essentially surfactant-free application liquors and the inventive ones Benefits are used.
- Substantially free from surfactants means that the agents are free from intentionally added surfactants are. Contamination of raw materials or manufacturing equipment can, however, result in small quantities of surfactants in agents that release them into the application liquor when used. A previous level can also result in a residual content with cleaning agents containing surfactants Stick surfactants to the crockery baskets or the spray arms of the dishwasher the application fleet of a subsequent cleaning process according to the invention is slight contaminated with surfactants.
- Another object of the present invention is therefore a dishwasher detergent, containing builders, corrosion inhibitors and possibly other ingredients of cleaning agents, which - based on its weight - contains a maximum of 0.5% by weight of surfactant (s).
- the residual content of surfactants on average can - as already mentioned - through contaminated manufacturing equipment or by raw materials that contain small amounts of surfactants. So be some raw materials are granulated or coated with the addition of small amounts of surfactant, resulting in a The product is exposed to tensides.
- agents according to the invention are preferred, the maximum 0.25% by weight, preferably at most 0.1% by weight, particularly preferably at most 0.05% by weight and in particular contain a maximum of 0.01% by weight (in each case based on the weight of the composition) of surfactants.
- Agents according to the invention which are free from surfactant (s) are particularly preferred.
- both automatic dishwashing detergents are the Builders, corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents included and are characterized in that they the surfactant (s) in dissolving Contain form, as well as machine dishwashing detergent, containing builders, corrosion inhibitors, Surfactants and possibly other ingredients of cleaning agents that contain the corrosion inhibitor (s) in accelerated form, other items of present invention.
- a delay in the dissolution of surfactants can be achieved, for example, by coating surfactant compounds, by compounding alone or by embedding in dissolution-delayed matrices respectively.
- a release acceleration of corrosion inhibitors takes place, for example, by assembly with disintegration aids, shower systems, dissolving accelerators (easily soluble Substances) etc.
- the physical packaging can also accelerate or slow down the solution act, for example by a dishwasher detergent body, which surfactant (s) contains and is coated or "powdered” on its surface with corrosion inhibitor (s) dissolve before the molded body goes into solution.
- multi-phase moldings in which whole Phases are delayed in release (for example due to ingredients, high pressure and thus high compression with poor solubility, through coating etc.), while others accelerate dissolution are (for example, by using disintegration aids, by low Pressing pressure and thus low compression with better solubility, etc.) are used to carry out the Teaching according to the invention can be easily produced.
- the corrosion inhibitors are preferably released and can have their effect via a unfold for a certain period of time before surfactants enter the fleet.
- Another subject of The present invention is therefore a machine dishwashing detergent containing builders, Corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents, which is characterized in that the surfactant (s) wholly or partially with a coating material coated or compounded or so physically made up that they are in the cleaning liquor after a period t1 of 10 s to 5 min. at most 10% and after t1 plus 1 minute up to 30 min. is at least 90% released, while the corrosion inhibitor (s) are so is compounded or physically assembled, that these are in the cleaning liquor a period t1 from 10 s to 5 min. is / are released to at least 90%.
- the surfactant or the surfactants are / are preferably in a period t1 of 10 s to 5 min. and especially preferably from 1 min. up to 5 min. at most 10% and preferably after t1 plus 5 min. to 15 minute and particularly preferably from t1 plus 7 min. up to 10 min. released at least 90%.
- the time t1 can be the start of the wash cycle be in the case of specially made-up agents (for example in the case of coated moldings)
- t1 can also mean the time of dissolution of the assembly (here: coating). It is crucial that there is a fixed time "starting point" from which to start First dissolve the corrosion inhibitors and then the surfactants in the application liquor. The the exact location of this point in time t1 in the washing program is not important.
- Enveloping materials fatty alcohols or fatty acids, which may be mixed with other enveloping substances can be mixed.
- a mixture of fatty alcohols and aluminum stearate is an example called.
- envelope materials known from the prior art are as follows summarized in key words: magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and silicate, water glass and sodium polyphosphate, Sodium sulfate and silicate, or sodium bicarbonate, borax and magnesium sulfate, Boric acid, but also some organic components such as fat derivatives, paraffins and waxes (Melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters of which with a molecular weight of 300 to 1,700, combinations with magnesium oxide, Vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene methacrylate copolymer emulsions. Polycarboxylates or other water-soluble polymers.
- the coating materials can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation.
- Application as a fine powder for example by electrostatic techniques, is also possible, although this method leads to irregular and poorly adhering coatings.
- the coating materials can be applied to particles in agitators, mixers and granulators. However, it is preferred to apply the coating materials in a fluidized bed, it being possible for the particles to be sized at the same time. If the coating materials lead to sticky products under certain circumstances, it can make sense to apply fine particles to the coated particles ("powdering"). All fine-particle substances can be used as powdering agents, although other detergent components such as builder substances can also be used.
- Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives etc. are preferably used as additional powdering agents. Part of an existing buffer system can also be used for powdering.
- the coating materials for particles containing surfactants are used in such amounts that an optimal interaction of the individual components and thus an exactly controlled release is made possible. Depending on the period within which the release is to be largely suppressed and depending on the size of the coated particles, the amount of coating material will be measured. Preferred embodiments use less than 20% by weight of shell material, based on the amount of the coated particles, in particular less than 10% by weight of shell material is preferred.
- a preferred "physical" way to delay the release of surfactants is to use them in compared to the other ingredients of poorly soluble form. For example can be achieved by varying the particle size of surfactant-containing particles, since Dissolve finely divided detergent ingredients faster due to the larger surface.
- the combination of differently densified ingredients is also preferred Way to realize different solubilities.
- powdered ingredients with more compressed, for example extruded, and thus more slowly soluble Surfactant particles can be combined.
- the "physical release delay" is particularly preferred to be realized within a molded body.
- detergent tablets can be produced are made up of several phases, one phase being less compressed as a different phase. The more easily compressed phase disintegrates faster in the cleaning process previously compressed premix, which increases solubility compared to a harder compressed phase is increased.
- particular preference is given to two-layer tablets in which one layer is softer pressed than the other, the harder pressed layer containing the surfactant (s) contains.
- the retardation of a phase can also have a lower content a de-integration aid contained in it can be achieved.
- the agents according to the invention generally contain one or more builders, in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates.
- builders in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates.
- the latter are particularly in detergent tablets for machine dishwashing preferred builders.
- the builders mentioned are also suitable as alkalizing agents.
- Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
- the delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compaction, by overdrying or by coating.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments.
- This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons.
- the alkali metal phosphates are among particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
- Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
- NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
- Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
- Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
- Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
- Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction.
- Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
- the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
- Potassium diphosphate potassium pyrophosphate
- K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
- Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
- pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
- sodium tripolyphosphate sodium tripolyphosphate
- n 3
- Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
- sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
- Polycarboxylates in particular can be used as organic cobuilders in the agents according to the invention /
- Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.
- Usable organic builders are, for example, those that can be used in the form of their sodium salts
- Polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function.
- these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these.
- Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids have a builder effect typically also the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents.
- the acids are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.
- Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.
- copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid.
- Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become.
- the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 up to 20% by weight, in particular 3 to 10% by weight.
- the polymers can also allylsulfonic acids, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, contained as a monomer.
- biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
- copolymers are those which preferably use acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their To name salts or their precursors.
- Polyaspartic acids are particularly preferred or their salts and derivatives.
- polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained.
- Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches.
- the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium molecular weights in the range from 400 to 500000 g / mol.
- a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
- the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Ethylene diamine N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts.
- EDDS Ethylene diamine N, N'-disuccinate
- glycerol disuccinate and glycerol trisuccinate are 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
- HEDP hydroxyalkane-1,1-diphosphonate
- Preferred aminoalkane phosphonates are Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B.
- the class of phosphonates preferably HEDP used.
- the aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
- all compounds that are able to form complexes with alkaline earth metal ions can be used as a cobuilder.
- the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the entire agent according to the invention.
- the invention contain Agents organic and / or in particular inorganic bleaching agents.
- Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water.
- Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate peroxypyrophosphate, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
- Bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxyacidoxy (PAP), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydalsoxyperiperyl
- the bleaching agent content of the agents can be 1 to 40% by weight and in particular 10 to 20% by weight. amount, advantageously using percarbonate or perborate mono- or tetrahydrate becomes.
- bleach activators can be incorporated.
- bleach activators compounds those under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 up to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
- Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Tri
- Bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are as Bleaching catalysts are suitable, preference being given to using compounds which are used in the DE 197 09 284 A1 are described.
- the cleaning agent according to the invention can be further conventional ingredients, in particular enzymes, Sequestering agents, electrolytes, and other auxiliary substances, such as foam regulators, additional Contain bleach activators, colors and fragrances.
- Enzymes in the agents according to the invention include in particular those from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry for the removal of stains such as stains containing protein, fat or starch. to Bleach can also be used with oxidoreductases.
- Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants obtained enzymatic active ingredients.
- proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used.
- enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or mixtures containing lipase or mixtures with lipolytically active enzymes of particular importance Interest.
- Known cutinases are examples of such lipolytically active enzymes.
- Peroxidases or oxidases have also proven to be suitable in some cases.
- suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.
- the enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition.
- the percentage of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight be.
- Agents preferred in the context of the present invention are characterized in that that they contain protease and / or amylase.
- Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product.
- perfume oils or fragrances individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons are used. Fragrance compounds of the ester type are e.g.
- the ethers include, for example Benzyl ethyl ether, to the aldehydes e.g.
- the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, ⁇ -isomethylionon and methylcedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance.
- perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- fragrances can be incorporated directly into the cleaning agents according to the invention can also be advantageous to apply the fragrances on carriers.
- the agents according to the invention In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes.
- Preferred dyes the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as glass, ceramic or Plastic dishes so as not to stain them.
- the agents according to the invention can be provided in all known forms of offer, in particular powdered cleaners and detergent tablets being of particular importance. If detergent tablets are produced, they can contain disintegration aids, so-called tablet disintegrants, in order to facilitate the disintegration of highly compressed moldings and to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt “Textbook of pharmaceutical technology” (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
- Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, the information given relates only to the weight of the basic tablet. Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- CMC carboxymethyl cellulose
- the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
- the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
- the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed.
- Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
- the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
- the above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
- microcrystalline cellulose As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged.
- a subsequent disaggregation of the The hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the primary particle sizes of about 5 ⁇ m and for example to granules with a medium Particle size of 200 microns can be compacted.
- Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- a disintegration aid preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
- Shaped detergent tablets according to the invention can also be a gas-evolving shower system included.
- the gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is particular to name the magnesium peroxide, which releases oxygen when in contact with water.
- the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a variety of systems is conceivable and executable, which will release nitrogen, oxygen or hydrogen, for example the bubble system used in the detergent tablets according to the invention Choose both from an economic and an ecological point of view to let.
- Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts to release carbon dioxide in aqueous solution.
- the alkali metal carbonates or bicarbonates the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.
- shaped detergent bodies 2 to 20% by weight, preferably, are used as the shower system 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of one Acidifying agent, based in each case on the entire molded body.
- alkali metal dihydrogen phosphates and other inorganic salts can be used.
- organic acidifying agents are preferred used, the citric acid being a particularly preferred acidifying agent.
- the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group, tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
- Organic sulfonic acids such as amidosulfonic acid can also be used.
- Sokalan® DCS trademark from BASF
- agents are preferred in which the corrosion inhibitor content of the agents is 0.001 to 10% by weight, preferably 0.0025 to 2 % By weight and in particular 0.01 to 0.04% by weight, in each case based on the total cleaning agent, is.
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Abstract
Description
Die vorliegende Erfindung betrifft Mittel zum maschinellen Reinigen von metallischen Oberflächen sowie die Verwendung dieser Mittel in haushaltsüblichen Geschirrspülmaschinen und ein Reinigungsverfahren unter Einsatz dieser Mittel.The present invention relates to agents for the mechanical cleaning of metallic surfaces as well as the use of these agents in household dishwashers and a cleaning process using these means.
Reinigungsmittelzusammensetzungen für die Reinigung verschmutzten Geschirrs in Geschirrspülmaschinen sind im Stand der Technik breit beschrieben. Ein Nachteil, den diese Mittel oft aufweisen, ist allerdings die Reinigungsleistung an Metalloberflächen, beispielsweise angelaufenen Silberoberflächen. Da maschinelle Geschirrspülmittel sowohl hinsichtlich der zu behandelnden Substrate als auch hinsichtlich der auftretenden Verschmutzungen eine Vielzahl von Anforderungen erfüllen müssen, werden bestimmte Aufgabenfelder nicht zur vollständigen Zufriedenheit des Anwenders gelöst. Im Falle der Reinigung von metallischen, insbesondere silbernen oder versilberten Oberflächen begnügt man sich daher meist mit dem Zusatz von Korrosionsinhibitoren, die ein weiteres Anlaufen verhindern, aber angelaufene Silberoberflächen nicht zu reinigen vermögen.Detergent compositions for cleaning soiled dishes in dishwashers are widely described in the prior art. A disadvantage that these funds often have is however the cleaning performance on metal surfaces, for example tarnished silver surfaces. Since machine dishwashing detergent both with regard to the substrates to be treated as well as a variety of requirements with regard to the contamination that occurs certain task fields are not to the complete satisfaction of the user solved. In the case of cleaning metallic, especially silver or silver-plated Surfaces are therefore mostly satisfied with the addition of corrosion inhibitors, which is another Prevent tarnishing, but tarnished silver surfaces cannot clean.
Für die Reinigung von Silber werden spezielle Reinigungsmittel angeboten, die zum Teil auch in Geschirrspülmaschinen anwendbar sind. In Anlehnung an die altbekannte Methode, die silbernen Gegenstände auf Aluminiumfolie zu legen und mit einer Elektrolytlösung zu bedecken, schlägt die US 3,701,736 (Colgate) maschinelle Geschirrspülmittel (MGSM) vor, welche Buildersalze und mindestens 3,25 Gew.-% Aluminium in Form des reinen Metalls oder von Aluminiumlegierungen enthalten.Special cleaning agents are available for cleaning silver, some of which can also be used in dishwashers. Based on the well-known method of placing the silver objects on aluminum foil and covering them with an electrolyte solution, US Pat. No. 3,701,736 (Colgate) suggests automatic dishwashing detergent (MGSM) which contains builder salts and at least 3.25% by weight aluminum in the form of the contain pure metal or aluminum alloys.
Ein ähnliches Produkt für die nicht-maschinelle Reinigung wird in der EP 039 193 (Crown & And-rews) beschrieben.A similar product for non-machine cleaning is described in EP 039 193 (Crown & And-rews).
Ein neuerer Ansatz für die Silberreinigung in Geschirrspülmaschinen geht aus der WO98/51769
(Procter&Gamble) hervor. Nach der Lehre dieser Schrift sollen Silberreinigungsmittel eingesetzt
werden, welche alkalischen Elektrolyt, Metall sowie jeweils mindestens 1 Gew.-% Builder und
nichtionisches Tensid enthalten. Das Metall muß dabei ein negativeres Standardpotential als Silber
aufweisen. Die Mittel können auch als Komponente in herkömmliche MGSM inkorporiert werden.
Ein maschinelles Silberreinigungsverfahren wird in dieser Schrift ebenfalls beansprucht.
Die Lösungsvorschläge des Standes der Technik besitzen den Nachteil, daß sie nur als reine Reinigungsmittel
für metallische Gegenstände (nachfolgend kurz als Silberreinigungsmittel bezeichnet)
benutzt werden können. Da der Verbraucher aber selten eine gesamte Spülmaschinenfüllung
nur aus metallischen Oberflächen bereitstellt, muß die Maschine entweder teilbeladen laufen, oder
man nimmt eine mangelhafte Reinigungsleistung an anderen Gegenständen, beispielsweise Auflaufformen,
Tellern, Teetassen usw. in Kauf.A newer approach to silver cleaning in dishwashers can be found in WO98 / 51769 (Procter & Gamble). According to the teaching of this document, silver cleaning agents should be used which contain alkaline electrolyte, metal and at least 1% by weight of builder and nonionic surfactant. The metal must have a more negative standard potential than silver. The agents can also be incorporated as a component in conventional MGSM. A mechanical silver cleaning process is also claimed in this document.
The proposed solutions of the prior art have the disadvantage that they can only be used as pure cleaning agents for metallic objects (hereinafter referred to as silver cleaning agents for short). However, since the consumer rarely provides an entire dishwasher filling only from metallic surfaces, the machine either has to run partially loaded, or one accepts poor cleaning performance on other objects, such as baking dishes, plates, tea cups, etc.
Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein Reinigungsmittel bereitzustellen, das einerseits metallische Gegenstände gut reihigt und auch an angelaufenen Oberflächen eine gute Reinigungsleistung aufweist, das andererseits aber auch ein "vollwertiges" Reinigungsmittel für den normalen Mischbeladungszustand der Geschirrspülmaschine ist. Mit anderen Worten sollte ein Reinigungsmittel für Haushaltsgeschirrspülmaschinen bereitgestellt werden, das die Reinigungsleistung herkömmlicher Mittel erreicht und die Leistung an metallischen Oberflächen verbessert, so daß mit Spezialreinigern vergleichbare Ergebnisse erzielt werden. Aus Kostengründen sollten diese Ergebnisse mit gleichem oder reduziertem Einsatz an Korrosionsinhibitoren erzielt werden.The object of the present invention was to provide a cleaning agent which on the one hand, metallic objects well lined up and also good on tarnished surfaces Has cleaning performance, but on the other hand also a "full" cleaning agent for the normal mixed load condition of the dishwasher. In other words, one should Detergents for household dishwashers are provided, which improve the cleaning performance achieved conventional means and improved the performance on metallic surfaces, so that comparable results are achieved with special cleaners. For cost reasons, these should Results can be achieved with the same or reduced use of corrosion inhibitors.
Es wurde nun gefunden, daß die Zeitpunkte der Freisetzung einzelner Inhaltsstoffe einen entscheidenden Einfluß auf die Leistung des Mittels haben. Dabei kommt es darauf an, daß vorhandene Korrosionsinhibitoren (nachfolgend auch als "Silberschutzmittel" bezeichnet) in möglichst tensidarmen Lösungen zur Anwendung gelangen. Enthalten maschinelle Geschirrspülmittel Tenside, so sollten diese erst nach den Korrosionsinhibitoren in die Anwendungsflotte freigesetzt werden. Dabei sind die positiven Effekte umso ausgeprägter, je tensidärmer die Flotte bei der Einwirkung der Silberschutzmittel ist. Erfindungsgemäße Mittel lassen sich daher entweder tensidarm bzw. völlig tensidfrei formulieren, oder weisen Konfektionierungsmaßnahmen auf, um die geregelte Freisetzung der einzelnen Verbindungsklassen zu gewährleisten.It has now been found that the timing of the release of individual ingredients is crucial Influence the performance of the product. It is important that existing Corrosion inhibitors (hereinafter also referred to as "silver protection agents") in as few surfactants as possible Solutions are used. Contain automatic dishwashing detergents, so these should only be released into the application fleet after the corrosion inhibitors. there the positive effects are more pronounced, the lower the surfactant the fleet is exposed to Silver protection is. Agents according to the invention can therefore either be low in surfactants or completely Formulate free of surfactants, or have packaging measures to ensure controlled release of the individual connection classes.
In einer ersten Ausführungsform betrifft die vorliegende Erfindung ein Verfahren zur maschinellen
Reinigung von Geschirr in einer Haushaltsgeschirrspülmaschine unter Verwendung einer Reinigungsmittelzusammensetzung,
welche Korrosionsschutzmittel und Tensid(e) enthält, wobei das/die
Korrosionsschutzmittel vor dem/den Tensid(en) in die Anwendungsflotte freigesetzt werden.
Diese Ausführungsform berücksichtigt, daß Tenside Bestandteil der meisten maschinellen Geschirrspülmittel
sind und ihr Einsatz aus den unterschiedlichsten Gründen gewünscht sein kann.
Entsprechende erfindungsgemäße Mittel (siehe weiter unten) enthalten Vertreter beider Substanzklassen
(Korrosionsinhibitoren und Tenside) und verfügen über geeignete Maßnahmen, um die
vorstehend genannte Freisetzungsreihenfolge zu verwirklichen.In a first embodiment, the present invention relates to a method for the mechanical cleaning of dishes in a domestic dishwasher using a detergent composition which contains anticorrosive agents and surfactant (s), the anticorrosive agent (s) being released before the surfactant (s) into the application liquor ,
This embodiment takes into account that surfactants are part of most automatic dishwashing detergents and that their use can be desired for a variety of reasons. Corresponding agents according to the invention (see below) contain representatives of both classes of substances (corrosion inhibitors and surfactants) and have suitable measures for realizing the above-mentioned release sequence.
Das erfindungsgemäße Reinigungsverfahren umfaßt die Freisetzung von Korrosionsinhibitor in
eine tensidfreie Umgebung und die zeitlich nachgeordnete Freisetzung von Tensid(en) in die Anwendungsflotte.
In einer weiteren Ausführungsform betrifft die vorliegende Erfindung daher ein
Verfahren zur maschinellen Reinigung von Geschirr in einer Haushaltsgeschirr-spülmaschine, das
durch die Schritte
Die wäßrige Anwendungsflotte, die für Schritt a) des erfindungsgemäßen Reinigungsverfahrens benötigt wird, entsteht in der Haushaltsgeschirrspülmaschine durch Zugabe von Wasser in den Innenraum, in dem sich neben dem verschmutztem Geschirr eine Reinigungsmittelzusammensetzung befindet, welche Korrosionsschutzmittel enthält. Enthält diese Reinigungsmittelzusammensetzung neben dem/den Korrosionsschutzmittel(n) als Inhaltsstoff(e) Tensid(e), so werden diese durch geeignete Maßnahmen vor frühzeitiger Freisetzung geschützt, um eine tensidfreie Anwendungsflotte für Schritt a) zu gewährleisten. Die Konzentration des/der Korrosionsschutzmittel(s) in der Anwendungsflotte richtet sich einerseits nach der Wassermenge, die in die Geschirrspülmaschine einfließt, andererseits nach der Menge an Reinigungsmittelzusammensetzung und der Konzentration der Korrosionsschutzmittel hierin. In erfindungsgemäß bevorzugten Reinigungsverfahren beträgt die Konzentration des/der Korrosionsschutzmittel(s) in der Anwendungsflotte 0,0001 bis 1 g/l, vorzugsweise 0,001 bis 0,5 g/l, besonders bevorzugt 0,002 bis 0,25 g/l und insbesondere 0,005 bis 0,1 g/l.The aqueous application liquor for step a) of the cleaning process according to the invention is required in the household dishwasher by adding water to the Interior in which there is a detergent composition in addition to the dirty dishes which contains anti-corrosion agents. Contains this detergent composition in addition to the anti-corrosion agent (s) as ingredient (s) surfactant (s), so these Protected against early release by suitable measures to create a surfactant-free application fleet to ensure for step a). The concentration of the anti-corrosion agent (s) in The application fleet depends on the one hand on the amount of water that goes into the dishwasher flows, on the other hand according to the amount of detergent composition and the concentration the anti-corrosion agents herein. In cleaning methods preferred according to the invention the concentration of the corrosion protection agent (s) in the application liquor is 0.0001 to 1 g / l, preferably 0.001 to 0.5 g / l, particularly preferably 0.002 to 0.25 g / l and in particular 0.005 up to 0.1 g / l.
Im erfindungsgemäßen Reinigungsverfahren können sämtliche aus dem Stand der Technik bekannten Korrosionsinhibitoren zur Anwendung kommen, wobei besonders Silberschutzmittel im Bereich des maschinellen Geschirrspülens eine besondere Bedeutung haben. Einsetzbar sind die bekannten Substanzen des Standes der Technik. Allgemein können vor allem Silberschutzmittel ausgewählt aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder -komplexe eingesetzt werden. Besonders bevorzugt zu verwenden sind Benzotriazol und/oder Alkylaminotriazol. Erfindungsgemäße Verfahren, bei denen die Anwendungsflotte ein oder mehrere Korrosionsschutzmittel aus der Gruppe der Triazole, der Benzotriazole, der Bisbenzotriazole, der Aminotriazole, der Alkylaminotriazole und der Übergangsmetallsalze oder -komplexe enthält, wobei Benzotriazole und/oder Alkylaminotriazole bevorzugt sind, sind daher bevorzugte Ausführungsformen der vorliegenden Erfindung.In the cleaning process according to the invention, all known from the prior art can Corrosion inhibitors are used, with silver protection agents in particular Machine dishwashing have a special meaning. They can be used known substances of the prior art. In general, silver protection agents in particular selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Benzotriazole and / or alkylaminotriazole are particularly preferably to be used. invention Processes in which the application liquor contains one or more anti-corrosion agents Group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and which contains transition metal salts or complexes, with benzotriazoles and / or alkylaminotriazoles are preferred are therefore preferred embodiments of the present invention.
Man findet in Reinigerformulierungen darüberhinaus häufig aktivchlorhaltige Mittel, die das Korrodieren der Silberoberfläche deutlich vermindern können. In chlorfreien Reinigern werden besonders Sauerstoff- und stickstoffhaltige organische redoxaktive Verbindungen, wie zwei- und dreiwertige Phenole, z. B. Hydrochinon, Brenzkatechin, Hydroxyhydrochinon, Gallussäure, Phloroglucin, Pyrogallol bzw. Derivate dieser Verbindungsklassen. Auch salz- und komplexartige anorganische Verbindungen, wie Salze der Metalle Mn, Ti, Zr, Hf, V, Co und Ce finden häufig Verwendung. Bevorzugt sind hierbei die Übergangsmetallsalze, die ausgewählt sind aus der Gruppe der Mangan und/oder Cobaltsalze und/oder -komplexe, besonders bevorzugt der Cobalt(ammin)-Komplexe, der Cobalt(acetat)-Komplexe, der Cobalt-(Carbonyl)-Komplexe, der Chloride des Cobalts oder Mangans und des Mangansulfats. Ebenfalls können Zinkverbindungen zur Verhinderung der Korrosion am Spülgut eingesetzt werden.In addition, active chlorine-containing agents that corrode are often found in detergent formulations significantly reduce the silver surface. Chlorine-free cleaners are special Organic and redox-active compounds containing oxygen and nitrogen, such as divalent and trivalent Phenols, e.g. B. hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds. Also salt and complex inorganic Compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers are the transition metal salts selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the Cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Zinc compounds can also be used to prevent corrosion be used on the wash ware.
Unter den bevorzugt im erfindungsgemäßen Verfahren angewendeten Korrosionsinhibitoren aus den Gruppen der Benzotriazole bzw. Alkylaminotriazole sind wiederum in 5-Stellung substituierte 1,2,4-triazole besonders bevorzugt. Erfindungsgemäße Verfahren, die dadurch gekennzeichnet sind, daß die Anwendungsflotte in 5-Stellung substituierte 3-Amino-1,2,4-triazole der Formel (I) bzw. deren Gemische und/oder deren Salze, bevorzugt mit Salzsäure, Schwefelsäure, Phosphorsäure, Kohlensäure, schwefliger Säure, organischen Carbonsäuren wie Essig-, Glykol-, Citronen-, Bernsteinsäure bzw. deren Gemische enthält in der R für einen linearen oder verzweigten, gesättigten oder ungesättigten, gegebenenfalls durch Hydroxy- oder Alkoxylgruppen substituierten Alkylrest mit 1 bis 15 C-Atomen oder eine gegebenenfalls durch Hydroxy-, primäre, sekundäre, tertiäre Aminogruppen, Alkoxy- Alkylthio- oder Thiolgruppen substituierte Aryl-, Furyl-, Tetrahydrofuryl, Thienyl-, Pyridyl-, Pyrrolidinyl-, 5-Oxo-2-pyrrolidinyl-, Pyrryl-, Imidazolyl-, Pyrimidylgruppe steht, sind daher ebenfalls besonders bevorzugt.Among the corrosion inhibitors from the groups of benzotriazoles or alkylaminotriazoles which are preferably used in the process according to the invention, 1,2,4-triazoles substituted in the 5-position are again particularly preferred. Processes according to the invention which are characterized in that the application liquor substituted in the 5-position 3-amino-1,2,4-triazoles of the formula (I) or their mixtures and / or their salts, preferably with hydrochloric acid, sulfuric acid, phosphoric acid, Contains carbonic acid, sulfurous acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid or mixtures thereof in the R for a linear or branched, saturated or unsaturated, optionally substituted by hydroxyl or alkoxyl groups, alkyl radical having 1 to 15 carbon atoms or an aryl optionally substituted by hydroxyl, primary, secondary, tertiary amino groups, alkoxy, alkylthio or thiol groups -, furyl, tetrahydrofuryl, thienyl, pyridyl, pyrrolidinyl, 5-oxo-2-pyrrolidinyl, pyrryl, imidazolyl, pyrimidyl group are therefore also particularly preferred.
In besonders bevorzugten erfindungsgemäßen Reinigungsverfahren sind die in 5-Stellung substituierten 3-Amino-1,2,4-triazole ausgewählt aus der Gruppe der 5-Propyl-, -Butyl-, -Pentyl-, -Heptyl-, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-säurealkyl-, -Phenyl-, -p-Tolyl-, -(4-tert. Butylphenyl)-, -(4-Methoxyphenyl)-, -(2-, -3-, -4-Pyridyl)-, -(2-Thienyl)-, -(5-Methyl-2-furyl)-, -(5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazole.In particularly preferred cleaning processes according to the invention, those substituted in the 5-position are 3-amino-1,2,4-triazoles selected from the group of 5-propyl, butyl, pentyl, heptyl, -Octyl-, -Nonyl-, -Decyl-, -Undecyl-, -Dodecyl-, -Isononyl-, -Versatic-10-acid alkyl-, -Phenyl-, -p-tolyl-, - (4-tert.butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-thienyl) -, - (5-methyl-2- furyl) -, - (5-Oxo-2-pyrrolidinyl) -3-amino-1,2,4-triazoles.
Ganz besonders wirksam sind 5-Pentyl-, 5-Heptyl-, 5-Nonyl-, 5-Undecyl-, 5-Isononyl-, 5-Versatic-10-säurealkyl-3-amino-1,2,4-triazole sowie Mischungen dieser Substanzen.5-Pentyl-, 5-heptyl-, 5-nonyl-, 5-undecyl-, 5-isononyl-, 5-versatic-10-acid-alkyl-3-amino-1,2,4-triazoles are very particularly effective as well as mixtures of these substances.
Bevorzugte Säuren für die Salzbildung sind wie bereits erwähnt Salzsäure, Schwefelsäure, Phosphorsäure, Kohlensäure, schweflige Säure, organische Carbonsäuren wie Essig-, Glykol-, Citronen-, Bernsteinsäure. In Geschirrspülmitteln werden die Alkyl-amino-1,2,4-triazole bzw. ihre physiologisch verträglichen Salze üblicherweise in einer Konzentration von 0,001 bis 10 Gew.-%, vorzugsweise 0,0025 bis 2 Gew.-%, besonders bevorzugt 0,01 bis 0,04 Gew.-%, jeweils bezogen auf das Mittel, eingesetzt. Diese Mengen führen unter haushaltsüblichen Bedingungen zu den vorstehend genannten Konzentrationen in der Anwendungsflotte.As already mentioned, preferred acids for salt formation are hydrochloric acid, sulfuric acid, phosphoric acid, Carbonic acid, sulphurous acid, organic carboxylic acids such as vinegar, glycol, citric, Succinic acid. In dishwashing detergents, the alkylamino-1,2,4-triazoles or their physiological compatible salts usually in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2% by weight, particularly preferably 0.01 to 0.04% by weight, in each case based on the means used. Under normal household conditions, these quantities lead to the above concentrations mentioned in the application fleet.
Neben dem/den Korrosionsschutzmittel(n) kann die Anwendungsflotte im ersten Teilschritt des erfindungsgemäßen Reinigungsverfahrens selbstverständlich noch andere Inhaltsstoffe von Reinigungsmitteln enthalten, wobei Tensid(e) erfindungsgemäß in diesem Schritt nicht zugegen sind. Als weitere mögliche Inhaltsstoffe der Anwendungsflotte im ersten Verfahrensschritt sind insbesondere Gerüststoffe, Cobuilder, Komplexbildner, Bleichmittel, Bleichaktivatoren, Enzyme, Farbstoffe, Duftstoffe usw. zu nennen. In besonders bevorzugten erfindungsgemäßen Reinigungsverfahren enthält die Anwendungsflotte in Schritt a) neben dem/den Korrosionsinhibitor(en) Gerüststoffe und/oder Cobuilder, Polymere und/oder Komplexbildner. Bevorzugt ist es auch, wenn die Anwendungsflotte in Schritt a) frei von Bleichmitteln und Bleichaktivatoren ist.In addition to the anti-corrosion agent (s), the application liquor can be used in the first step of the The cleaning method according to the invention naturally also contains other ingredients of cleaning agents included, wherein surfactant (s) are not present according to the invention in this step. In particular, further possible ingredients of the application liquor in the first process step are Builders, cobuilders, complexing agents, bleaches, bleach activators, enzymes, dyes, To name fragrances etc. In particularly preferred cleaning processes according to the invention contains the application liquor in step a) in addition to the corrosion inhibitor (s) builders and / or cobuilders, polymers and / or complexing agents. It is also preferred if the Application liquor in step a) is free of bleaching agents and bleach activators.
Im zweiten Schritt des erfindungsgemäßen Reinigungsverfahrens werden die Geschirrteile mit einer tensidhaltigen Reinigungsflotte kontaktiert, die selbstverständlich weitere Inhaltsstoffe von Reinigungsmitteln, wie beispielsweise Bleichmittel, Bleichaktivatoren, Gerüststoffe, Enzyme, Duftstoffe, Farbstoffe, usw., enthalten kann.In the second step of the cleaning process according to the invention, the crockery parts are also contacted a cleaning agent containing surfactant, which of course contains other ingredients from Cleaning agents, such as bleaches, bleach activators, builders, enzymes, fragrances, Dyes, etc., may contain.
Als Tensidkomponente, die sich im zweiten Teilschritt in der Anwendungsflotte befindet, kommen anionische, nichtionische, kationische und/oder amphotere Tenside in Betracht, wobei nichtionische Tenside aufgrund ihres Schaumvermögens bevorzugt sind.The surfactant component, which is in the second step in the application liquor, come Anionic, nonionic, cationic and / or amphoteric surfactants into consideration, with nonionic Surfactants are preferred because of their foaming power.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten 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 Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren geeignet.Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside.Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO, sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische.Soaps are particularly suitable as further anionic surfactants. Saturated ones are suitable Fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated Erucic acid and behenic acid and in particular from natural fatty acids, e.g. Coconut-, Palm kernel or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Außerdem können als weitere nichtionische Tenside auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4.In addition, alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette.Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Also 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 be suitable. The amount of these nonionic surfactants is preferably no longer than that of ethoxylated fatty alcohols, especially not more than half of them.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (II), in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (III), in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can be reacted with fatty acid methyl esters in The presence of an alkoxide as a catalyst is converted into the desired polyhydroxy fatty acid amides become.
Als bevorzugte Tenside werden schwachschäumende nichtionische Tenside eingesetzt. Mit besonderem Vorzug enthält die Anwendungsflotte in Schritt b) des erfindungsgemäßen Reinigungsverfahrens nichtionische Tenside, insbesondere nichtionische Tenside aus der Gruppe der alkoxylierten Alkohole. Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.Low-foaming nonionic surfactants are used as preferred surfactants. The application liquor in step b) of the cleaning process according to the invention particularly preferably contains nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Insbesondere bevorzugt sind erfindungsgemäße Reinigungsverfahren, in denen die Anwendungsflotte in Schritt b) ein nichtionisches Tensid enthält, das einen Schmelzpunkt oberhalb Raumtemperatur aufweist. Demzufolge sind bevorzugte Reinigungsverfahren dadurch gekennzeichnet, daß die Anwendungsflotte in Schritt b) nichtionische(s) Tensid(e) mit einem Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C, enthalten.Cleaning processes according to the invention in which the application liquor is particularly preferred in step b) contains a nonionic surfactant which has a melting point above room temperature having. Accordingly, preferred cleaning methods are characterized in that the Application liquor in step b) nonionic surfactant (s) with a melting point above 20 ° C, preferably above 25 ° C, particularly preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C included.
Geeignete nichtionische Tenside, die Schmelz- bzw. Erweichungspunkte im genannten Temperaturbereich
aufweisen, sind beispielsweise schwachschäumende nichtionische Tenside, die bei
Raumtemperatur fest oder hochviskos sein können. Werden bei Raumtemperaturhochviskose Niotenside
eingesetzt, so ist bevorzugt, daß diese eine Viskosität oberhalb von 20 Pas, vorzugsweise
oberhalb von 35 Pas und insbesondere oberhalb 40 Pas aufweisen. Auch Niotenside, die bei
Raumtemperatur wachsartige Konsistenz besitzen, sind bevorzugt.
Bevorzugt als bei Raumtemperatur feste einzusetzende Niotenside stammen aus den Gruppen der
alkoxylierten Niotenside, insbesondere der ethoxylierten primären Alkohole und Mischungen dieser
Tenside mit strukturell komplizierter aufgebauten Tensiden wie Polyoxypropylen/Polyoxyethylen/Polyoxypropylen
(PO/EO/PO)-Tenside. Solche (PO/EO/PO)-Niotenside zeichnen sich
darüberhinaus durch gute Schaumkontrolle aus.Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
In einer bevorzugten Ausführungsform der vorliegenden Erfindung ist das nichtionische Tenside mit einem Schmelzpunkt oberhalb Raumtemperatur ein ethoxyliertes Niotensid, das aus der Reaktion von einem Monohydroxyalkanol oder Alkylphenol mit 6 bis 20 C-Atomen mit vorzugsweise mindestens 12 Mol, besonders bevorzugt mindestens 15 Mol, insbesondere mindestens 20 Mol Ethylenoxid pro Mol Alkohol bzw. Alkylphenol hervorgegangen ist. In a preferred embodiment of the present invention, the is nonionic surfactant with a melting point above room temperature an ethoxylated nonionic surfactant resulting from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms with preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles Ethylene oxide per mole of alcohol or alkylphenol has emerged.
Ein besonders bevorzugtes bei Raumtemperatur festes, einzusetzendes Niotensid wird aus einem geradkettigen Fettalkohol mit 16 bis 20 Kohlenstoffatomen (C16-20-Alkohol), vorzugsweise einem C18-Alkohol und mindestens 12 Mol, vorzugsweise mindestens 15 Mol und insbesondere mindestens 20 Mol Ethylenoxid gewonnen. Hierunter sind die sogenannten "narrow range ethoxylates" (siehe oben) besonders bevorzugt.A particularly preferred nonionic surfactant which is solid at room temperature is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol, of ethylene oxide , Among these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.
Demnach enthalten die Anwendungsflotten in Schritt b) besonders bevorzugter erfindungsgemäßer Reinigungsverfahren ethoxylierte(s) Niotensid(e), das/die aus C6-20-Monohydroxyalkanolen oder C6- 20-Alkylphenolen oder C16-20-Fettalkoholen und mehr als 12 Mol, vorzugsweise mehr als 15 Mol und insbesondere mehr als 20 Mol Ethylenoxid pro Mol Alkohol gewonnen wurde(n).Accordingly, the application liquors in step b) is particularly preferred inventive cleaning method ethoxylated (s) nonionic surfactant (s), which / from C 6-20 monohydroxyalkanols or C 6- 20 -alkylphenols or C 16-20 fatty alcohols and more than 12 mole , preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
Das bei Raumtemperatur feste Niotensid besitzt vorzugsweise zusätzlich Propylenoxideinheiten im Molekül. Vorzugsweise machen solche PO-Einheiten bis zu 25 Gew.-%, besonders bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids aus. Besonders bevorzugte nichtionische Tenside sind ethoxylierte Monohydroxyalkanole oder Alkylphenole, die zusätzlich Polyoxyethylen-Polyoxypropylen Blockcopolymereinheiten aufweisen. Der Alkohol- bzw. Alkylphenolteil solcher Niotensidmoleküle macht dabei vorzugsweise mehr als 30 Gew.-%, besonders bevorzugt mehr als 50 Gew.-% und insbesondere mehr als 70 Gew.-% der gesamten Molmasse solcher Niotenside aus. Bevorzugte Reinigungsverfahren sind dadurch gekennzeichnet, daß die Anwendungsflotte in Schritt b) ethoxylierte und propoxylierte Niotenside enthalten, bei denen die Propylenoxideinheiten im Molekül bis zu 25 Gew.-%, bevorzugt bis zu 20 Gew.-% und insbesondere bis zu 15 Gew.-% der gesamten Molmasse des nichtionischen Tensids ausmachen, enthalten.The nonionic surfactant, which is solid at room temperature, preferably has additional propylene oxide units in the Molecule. Such PO units preferably make up to 25% by weight, particularly preferably up to up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the nonionic Surfactants. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules is preferred more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70 % By weight of the total molecular weight of such nonionic surfactants. Preferred cleaning methods are characterized in that the application liquor in step b) ethoxylated and propoxylated nonionic surfactants contain, in which the propylene oxide units in the molecule up to 25 wt .-%, preferred up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic Make up surfactants.
Weitere besonders bevorzugt einzusetzende Niotenside mit Schmelzpunkten oberhalb Raumtemperatur enthalten 40 bis 70% eines Polyoxypropylen/Polyoxyethylen/Polyoxypropylen-Blockpolymerblends, der 75 Gew.-% eines umgekehrten Block-Copolymers von Polyoxyethylen und Polyoxypropylen mit 17 Mol Ethylenoxid und 44 Mol Propylenoxid und 25 Gew.-% eines Block-Copolymers von Polyoxyethylen und Polyoxypropylen, initiiert mit Trimethylolpropan und enthaltend 24 Mol Ethylenoxid und 99 Mol Propylenoxid pro Mol Trimethylolpropan.Other nonionic surfactants to be used with particular preference with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with and containing trimethylolpropane 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylol propane.
Nichtionische Tenside, die mit besonderem Vorzug eingesetzt werden können, sind beispielsweise unter dem Namen Poly Tergent® SLF-18 von der Firma Olin Chemicals erhältlich.Examples of nonionic surfactants that can be used with particular preference are available under the name Poly Tergent® SLF-18 from Olin Chemicals.
Ein weiter bevorzugtes erfindungsgemäßes Reinigungsverfahren ist dadurch gekennzeichnet, daß
die Anwendungsflotte nichtionische Tenside der Formel
Weitere bevorzugt einsetzbare Niotenside sind die endgruppenverschlossenen Poly(oxyalkylierten)
Niotenside der Formel
Wie vorstehend beschrieben, kann jedes R3 in der obenstehenden Formel unterschiedlich sein, falls x ≥ 2 ist. Hierdurch kann die Alkylenoxideinheit in der eckigen Klammer variiert werden. Steht x beispielsweise für 3, kann der Rest R3 ausgewählt werden, um Ethylenoxid- (R3 = H) oder Propylenoxid- (R3 = CH3) Einheiten zu bilden, die in jedweder Reihenfolge aneinandergefügt sein können, beispielsweise (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) und (PO)(PO)(PO). Der Wert 3 für x ist hierbei beispielhaft gewählt worden und kann durchaus größer sein, wobei die Variationsbreite mit steigenden x-Werten zunimmt und beispielsweise eine große Anzahl (EO)-Gruppen, kombiniert mit einer geringen Anzahl (PO)-Gruppen einschließt, oder umgekehrt.As described above, each R 3 in the above formula can be different if x ≥ 2. This allows the alkylene oxide unit in the square brackets to be varied. For example, if x is 3, the radical R 3 can be selected to form ethylene oxide (R 3 = H) or propylene oxide (R 3 = CH 3 ) units which can be joined together in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
Insbesondere bevorzugte endgruppenverschlossenen Poly(oxyalkylierte) Alkohole der obenstehenden
Formel weisen Werte von k = 1 und j = 1 auf, so daß sich die vorstehende Formel zu
Faßt man die letztgenannten Aussagen zusammen, sind erfindungsgemäße Reinigungsverfahren
bevorzugt, bei denen die Anwendungsflotte in Schritt b) endgruppenverschlossene Poly(oxyalkylierten)
Niotenside der Formel
An Stelle der genannten Tenside oder in Verbindung mit ihnen können auch kationische und/oder amphotere Tenside eingesetzt werden. Zusammenfassend sind erfindungsgemäße Reinigungsverfahren bevorzugt, bei denen die Anwendungsflotte in Schritt b) Tensid(e), vorzugsweise nichtionische(s) Tensid(e) und insbesondere nichtionische(s) Tensid(e) aus der Gruppe der alkoxylierten Alkohole enthalten.Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants are used. In summary, cleaning methods according to the invention preferred, in which the application liquor in step b) surfactant (s), preferably nonionic (s) Surfactant (s) and in particular nonionic surfactant (s) from the group of the alkoxylated Contain alcohols.
Die weiteren Inhaltsstoffe von Reinigungsmitteln, die sowohl Bestandteil der Reinigungsflotte in Schritt a) als auch in Schritt b) des erfindungsgemäßen Verfahrens sein können, werden weiter unten bei der Beschreibung erfindungsgemäßer Mittel beschrieben.The other ingredients of cleaning agents that are part of the cleaning fleet in Step a) and step b) of the method according to the invention can be further described below in the description of agents according to the invention.
Ein weiterer Gegenstand der vorliegenden Erfindung ist die Verwendung von tensidfreien wäßrigen Lösungen von Korrosionsschutzmitteln zur maschinellen Reinigung von Geschirr.Another object of the present invention is the use of surfactant-free aqueous Corrosion protection solutions for machine washing of dishes.
Wie bereits vorstehend erwähnt, läßt sich das erfindungsgemäße Reinigungsverfahren unter anderem dadurch ausführen, daß man speziell konfektionierte Reinigungsmittel in eine Haushaltsgeschirrspülmaschine einbringt und ein Reinigungsprogramm ablaufen läßt. Im einfachsten Fall der erfindungsgemäßen Reinigung verzichtet man auf Tenside als intentionell zugesetzte Inhaltsstoffe in den Mitteln, wodurch im wesentlichen tensidfreie Anwendungsflotten erzielt und die erfindungsgemäßen Vorteile genutzt werden.As already mentioned above, the cleaning method according to the invention can be used, among other things by performing specially made cleaning agents in a household dishwasher brings in and runs a cleaning program. In the simplest case, the Cleaning according to the invention dispenses with surfactants as intentionally added ingredients in the agents, thereby achieving essentially surfactant-free application liquors and the inventive ones Benefits are used.
"Im wesentlichen tensidfrei" bedeutet, daß die Mittel frei von intentionell zugesetzten Tensiden sind. Durch Verunreinigung von Rohstoffen oder Herstellapparaten können jedoch geringe Mengen von Tensiden in Mittel gelangen, die diese bei der Anwendung in die Anwendungsflotte freisetzen. Auch kann durch vorhergehende Reinigungsgänge mit tensidhaltigen Reinigern ein Restgehalt an Tensiden an den Geschirrkörben oder den Sprüharmen der Geschirrspülmaschine anhaften, der die Anwendungsflotte eines nachfolgenden erfindungsgemäßen Reinigungsverfahrens geringfügig mit Tensiden verunreinigt."Substantially free from surfactants" means that the agents are free from intentionally added surfactants are. Contamination of raw materials or manufacturing equipment can, however, result in small quantities of surfactants in agents that release them into the application liquor when used. A previous level can also result in a residual content with cleaning agents containing surfactants Stick surfactants to the crockery baskets or the spray arms of the dishwasher the application fleet of a subsequent cleaning process according to the invention is slight contaminated with surfactants.
Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, das - bezogen auf sein Gewicht - maximal 0,5 Gew.-% Tensid(e) enthält.Another object of the present invention is therefore a dishwasher detergent, containing builders, corrosion inhibitors and possibly other ingredients of cleaning agents, which - based on its weight - contains a maximum of 0.5% by weight of surfactant (s).
Der Restgehalt an Tensiden im Mittel kann - wie bereits erwähnt - durch kontaminierte Herstellapparate oder durch Rohstoffe erfolgen, die geringe Mengen an Tensiden enthalten. So werden manche Rohstoffe unter Zusatz geringer Tensidmengen granuliert oder beschichtet, was zu einer Tensidbelastung des Produkts führt. In bevorzugten Ausführungsformen dieses teils der vorliegenden Erfindung achtet man aber bei der Auswahl der Rohstoffe und der Herstellapparate auf einen geringstmögliche Kontamination, so daß erfindungsgemäße Mittel bevorzugt sind, die maximal 0,25 Gew.-%, vorzugsweise maximal 0,1 Gew.-%, besonders bevorzugt maximal 0,05 Gew.-% und insbesondere maximal 0,01 Gew.-% (jeweils bezogen auf das Gewicht des Mittels) Tenside enthalten. Insbesondere sind dabei erfindungsgemäße Mittel bevorzugt, die frei von Tensid(en) sind.The residual content of surfactants on average can - as already mentioned - through contaminated manufacturing equipment or by raw materials that contain small amounts of surfactants. So be some raw materials are granulated or coated with the addition of small amounts of surfactant, resulting in a The product is exposed to tensides. In preferred embodiments of this part of the present However, one pays particular attention to the invention when selecting the raw materials and the manufacturing apparatus lowest possible contamination, so that agents according to the invention are preferred, the maximum 0.25% by weight, preferably at most 0.1% by weight, particularly preferably at most 0.05% by weight and in particular contain a maximum of 0.01% by weight (in each case based on the weight of the composition) of surfactants. Agents according to the invention which are free from surfactant (s) are particularly preferred.
Eine weitere Möglichkeit, erfindungsgemäße Reinigungsverfahren durch Zugabe eines einzigen Mittels in die Geschirrspülmaschine zu ermöglichen besteht darin, die Mittel derart zu konfektionieren, daß die Korrosionsinhibitoren in die Anwendungsflotte freigesetzt werden, bevor die Tenside in das Anwendungsmedium freigesetzt werden. Dies kann durch eine Löseverzögerung der Tenside oder durch eine Lösebeschleunigung der Korrosionsinhibitoren erfolgen, wobei auch eine Kombination beider Möglichkeiten möglich ist. Daher sind sowohl maschinelle Geschirrspülmittel, die Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln enthalten und dadurch gekennzeichnet sind, daß sie das/die Tensid(e) in löseverzögerter Form enthalten, als auch maschinelle Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, die den/die Korrosionsinhibitor(en) in lösebeschleunigter Form enthalten, weitere Gegenstände der vorliegenden Erfindung.Another possibility, cleaning method according to the invention by adding a single To enable means in the dishwasher is to assemble the means in such a way that the corrosion inhibitors are released into the application liquor before the surfactants in the application medium are released. This can be caused by a delay in the dissolution of the surfactants or by accelerating the release of the corrosion inhibitors, a combination of which both options is possible. Therefore, both automatic dishwashing detergents are the Builders, corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents included and are characterized in that they the surfactant (s) in dissolving Contain form, as well as machine dishwashing detergent, containing builders, corrosion inhibitors, Surfactants and possibly other ingredients of cleaning agents that contain the corrosion inhibitor (s) in accelerated form, other items of present invention.
Eine Löseverzögerung von Tensiden kann dabei beispielsweise durch Beschichtung von Tensidcompounds, durch alleinige Compoundierung oder durch Einbettung in löseverzögerte Matrizes erfolgen. Eine Lösbeschleunigung von Korrosionsinhibitoren erfolgt beispielsweise durch Konfektionierung mit Desintegrationshilfsmitteln, Brausesystemen, Lösebeschleunigern (leicht löslichen Substanzen) usw.. Auch die physikalische Konfektionierung kann lösebeschleunigend oderverzögernd wirken, beispielsweise durch einen Geschirrspülmittelformkörper, welcher Tensid(e) enthält und auf seiner Oberfläche mit Korrosionsinhibitor(en) beschichtet bzw. "abgepudert" ist, die sich lösen, bevor der Formkörper in Lösung geht. Auch mehrphasige Formkörper, bei denen ganze Phasen löseverzögert sind (beispielsweise durch Inhaltsstoffe, durch hohen Preßdruck und damit hohe Verdichtung mit schlechterer Löslichkeit, durch Beschichtung usw.), während andere lösebesschleunigt sind (beispielsweise durch Einsatz von Desintegrationshilfsmitteln, durch niedrigen Preßdruck und damit geringe Verdichtung mit besser Löslichkeit usw.), sind zur Ausführung der erfindungsgemäßen Lehre problemlos herstellbar.A delay in the dissolution of surfactants can be achieved, for example, by coating surfactant compounds, by compounding alone or by embedding in dissolution-delayed matrices respectively. A release acceleration of corrosion inhibitors takes place, for example, by assembly with disintegration aids, shower systems, dissolving accelerators (easily soluble Substances) etc. The physical packaging can also accelerate or slow down the solution act, for example by a dishwasher detergent body, which surfactant (s) contains and is coated or "powdered" on its surface with corrosion inhibitor (s) dissolve before the molded body goes into solution. Also multi-phase moldings, in which whole Phases are delayed in release (for example due to ingredients, high pressure and thus high compression with poor solubility, through coating etc.), while others accelerate dissolution are (for example, by using disintegration aids, by low Pressing pressure and thus low compression with better solubility, etc.) are used to carry out the Teaching according to the invention can be easily produced.
Vorzugsweise werden die Korrosionsinhibitoren freigesetzt und können ihre Wirkung über einen gewissen Zeitraum enflalten, bevor Tenside in die Flotte gelangen. Ein weiterer Gegenstand der vorliegenden Erfindung ist daher ein maschinelles Geschirrspülmittel, enthaltend Gerüststoffe, Korrosionsinhibitoren, Tenside sowie gegebenenfalls weitere Inhaltsstoffe von Reinigungsmitteln, das dadurch gekennzeichnet ist, daß das/die Tensid(e) ganz oder teilweise mit einem Hüllmaterial beschichtet oder so compoundiert bzw. physikalisch konfektioniert ist/sind, daß diese(s) in der Reinigungsflotte nach einem Zeitraum t1 von 10 s bis 5 min. zu höchstens 10% und nach t1 plus 1 min. bis 30 min. zu mindestens 90% freigesetzt ist, während der/die Korrosionsinhibitor(en) so compoundiert bzw. physikalisch konfektioniert ist/sind, daß diese(r) in der Reinigungsflotte nach einem Zeitraum t1 von 10 s bis 5 min. zu mindestens 90% freigesetzt ist/sind.The corrosion inhibitors are preferably released and can have their effect via a unfold for a certain period of time before surfactants enter the fleet. Another subject of The present invention is therefore a machine dishwashing detergent containing builders, Corrosion inhibitors, surfactants and possibly other ingredients of cleaning agents, which is characterized in that the surfactant (s) wholly or partially with a coating material coated or compounded or so physically made up that they are in the cleaning liquor after a period t1 of 10 s to 5 min. at most 10% and after t1 plus 1 minute up to 30 min. is at least 90% released, while the corrosion inhibitor (s) are so is compounded or physically assembled, that these are in the cleaning liquor a period t1 from 10 s to 5 min. is / are released to at least 90%.
Diese erfindungsgemäßen Mittel führen zu den gewünschten Anwendungsflotten zur Durchführung des erfindungsgemäßen Reinigungsverfahrens in Haushaltsgeschirrspülmaschinen. Das Tensid bzw. die Tenside wird/werden vorzugsweise in einem Zeitraum t1 von 10 s bis 5 min. und besonders bevorzugt von 1 min. bis 5 min. zu höchstens 10% und bevorzugt nach t1 plus 5 min. bis 15 min. und besonders bevorzugt von t1 plus 7 min. bis 10 min. zu mindestens 90% freigesetzt. Auf diese Weise gelangen die Tenside erst später in die Anwendungsflotte, während die Korrosionsinhibitoren schon in der Anwendungsflotte sind. Der Zeitpunkt t1 kann dabei der Beginn des Spülgangs sein, bei speziell konfektionierten Mitteln (beispielsweise bei beschichteten Formkörpern) kann t1 aber auch den Zeitpunkt der Auflösung der Konfektionierung (hier: Beschichtung) bedeuten. Entscheidend ist, daß ein festgelegter zeitlicher "Startpunkt" existiert, von dem ausgehend sich erst die Korrrosionsinhibitoren und nachfolgend die Tenside in die Anwendungsflotte lösen. Die genaue Lage dieses Zeitpunkts t1 im Spülprogramm ist dabei nicht von Bedeutung.These agents according to the invention lead to the desired application fleets for implementation of the cleaning method according to the invention in household dishwashers. The surfactant or the surfactants are / are preferably in a period t1 of 10 s to 5 min. and especially preferably from 1 min. up to 5 min. at most 10% and preferably after t1 plus 5 min. to 15 minute and particularly preferably from t1 plus 7 min. up to 10 min. released at least 90%. On this way the surfactants only reach the application liquor later, while the corrosion inhibitors are already in the application fleet. The time t1 can be the start of the wash cycle be in the case of specially made-up agents (for example in the case of coated moldings) t1 can also mean the time of dissolution of the assembly (here: coating). It is crucial that there is a fixed time "starting point" from which to start First dissolve the corrosion inhibitors and then the surfactants in the application liquor. The the exact location of this point in time t1 in the washing program is not important.
Um die Freisetzung der Tenside auf den erfindungsgemäß definierten Zeitraum einzustellen, hat es sich als geeignet erwiesen diese Mittel (bzw. sie enthaltende Compounds) mit Hüllmaterialien zu versehen, die sich in der Reinigungsflotte mit einer definierten Kinetik auflösen. Bevorzugt sind als Hüllmaterialien Fettalkohole oder Fettsäuren, die gegebenenfalls in Mischung mit anderen Hüllstoffen gemischt sein können. Beispielhaft sei hier eine Mischung aus Fettalkoholen und Aluminiumstearat genannt. Andere aus dem Stand der Technik bekannte Hüllmaterialien sind nachfolgend stichwortartig zusammengefaßt: Magnesiumsulfat und Natriumhexaphosphat, Dihydrogenphosphat oder Pyrophosphate, Phosphonsäuren, Natriummetaborat und -Silikat, Wasserglas und Natriumpolyphosphat, Natriumsulfat, und -silikat, oder Natriumbicarbonat, Borax und Magnesiumsulfat, Borsäure, aber auch zum Teil organische Komponenten wie Fettderivate, Paraffine und Wachse (Schmelztemperatur der Verbindungen zwischen 25 und 90°C), Polyethylenglykole und Fettsäureester davon mit einem Molekulargewicht von 300 bis 1.700, Kombinationen mit Magnesiumoxid, Vinylchlorid-Ethylencopolymeremulsionen oder Vinylchlorid-Ethylen-Methacrylat-copolymeremulsionen. Polycarboxylate oder andere wasserlösliche Polymere.In order to adjust the release of the surfactants to the period defined according to the invention, it has these agents (or compounds containing them) with coating materials proved to be suitable provided that dissolve in the cleaning fleet with a defined kinetics. Are preferred as Enveloping materials fatty alcohols or fatty acids, which may be mixed with other enveloping substances can be mixed. A mixture of fatty alcohols and aluminum stearate is an example called. Other envelope materials known from the prior art are as follows summarized in key words: magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and silicate, water glass and sodium polyphosphate, Sodium sulfate and silicate, or sodium bicarbonate, borax and magnesium sulfate, Boric acid, but also some organic components such as fat derivatives, paraffins and waxes (Melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters of which with a molecular weight of 300 to 1,700, combinations with magnesium oxide, Vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene methacrylate copolymer emulsions. Polycarboxylates or other water-soluble polymers.
Das Aufbringen der Hüllmaterialien kann aus der Schmelze oder aus Lösungen oder Dispersionen
erfolgen, wobei das Lösungs- bzw. Emulgiermittel durch Verdampfen entfernt wird. Auch ein Aufbringen
als feines Pulver, beispielsweise durch elektrostatische Techniken, ist möglich, wenngleich
diese Methode zu unregelmäßigen und schlecht haftenden Beschichtungen führt. Die Hüllmaterialien
können dabei in Rühr-, Misch- und Granulierapparaten auf Partikel aufgebracht werden. Bevorzugt
ist aber eine Aufbringung der Hüllmaterialien in einer Wirbelschicht, wobei gleichzeitig eine
Größenklassierung der Teilchen erfolgen kann. Sollten die Hüllmaterialien unter bestimmten Umständen
zu klebrigen Produkten führen, kann es sinnvoll sein, die umhüllten Partikel zusätzlich
noch mit feinteiligen Stoffen zu beaufschlagen ("Abpudern"). Als Abpuderungsmittel kommen sämtliche
feinteiligen Stoffe in Frage, wobei auch andere Waschmittelbestandteile wie Buildersubstanzen
verwendet werden können. Bevorzugt werden als zusätzliche Abpuderungsmittel Zeolithe,
Silikate, polymere Polycarboxylate, Carbonate, Citrate, Stärke, Cellulosederivate usw. benutzt.
Auch ein Teil eines ggf. vorhandenen Puffersystems kann zur Abpuderung eingesetzt werden.
Die Hüllmaterialien für tensidhaltige Teilchen werden in solchen Mengen eingesetzt, daß ein optimales
Zusammenspiel der einzelnen Komponenten und somit eine exakt gesteuerte Freisetzung
ermöglicht wird. Je nach dem Zeitraum, innerhalb dessen die Freisetzung weitgehend unterdrückt
werden soll und je nach Größe de beschichteten Teilchen wird man die Menge an Hüllmaterial
bemessen. Bevorzugte Ausführungsformen verwenden weniger als 20 Gew.-% Hüllmaterial, bezogen
auf die Menge der beschichteten Teilchen, insbesondere sind weniger als 10 Gew.-% Hüllmaterialien
bevorzugt.The coating materials can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation. Application as a fine powder, for example by electrostatic techniques, is also possible, although this method leads to irregular and poorly adhering coatings. The coating materials can be applied to particles in agitators, mixers and granulators. However, it is preferred to apply the coating materials in a fluidized bed, it being possible for the particles to be sized at the same time. If the coating materials lead to sticky products under certain circumstances, it can make sense to apply fine particles to the coated particles ("powdering"). All fine-particle substances can be used as powdering agents, although other detergent components such as builder substances can also be used. Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives etc. are preferably used as additional powdering agents. Part of an existing buffer system can also be used for powdering.
The coating materials for particles containing surfactants are used in such amounts that an optimal interaction of the individual components and thus an exactly controlled release is made possible. Depending on the period within which the release is to be largely suppressed and depending on the size of the coated particles, the amount of coating material will be measured. Preferred embodiments use less than 20% by weight of shell material, based on the amount of the coated particles, in particular less than 10% by weight of shell material is preferred.
Neben der vorstehend beschriebenen stofflichen ("chemischen") Konfektionierung der Tenside zur Einstellung der definierten Freisetzung innerhalb eines bestimmten Zeitraums kann auch eine "physikalische" Konfektionierung vorgenommen werden. Selbstverständlich sind auch Kombinationen aus stofflichen und verfahrenstechnischen Maßnahmen zur erfindungsgemäßen Einstellung des Freisetzungszeitpunkts geeignet.In addition to the material ("chemical") packaging of the surfactants described above Setting the defined release within a certain period of time can also "physical" assembly can be made. Combinations are of course also possible from material and procedural measures for the setting according to the invention the time of release.
Eine bevorzugte "physikalische" Methode, um Tenside verzögert freizusetzen, besteht darin, sie in gegenüber den anderen Inhaltsstoffen schlechter löslicher Form bereitzustellen. Dies kann beispielsweise durch die Variation der Teilchengröße tensidhaltiger Partikel erreicht werden, da sich feinteilige Reinigungsmittel-Inhaltsstoffe aufgrund der größeren Oberfläche schneller auflösen. A preferred "physical" way to delay the release of surfactants is to use them in compared to the other ingredients of poorly soluble form. For example can be achieved by varying the particle size of surfactant-containing particles, since Dissolve finely divided detergent ingredients faster due to the larger surface.
Auch die Kombination von unterschiedlich stark verdichteten Inhaltsstoffen ist ein bevorzugter Weg, unterschiedliche Löslichkeiten zu realisieren. So können beispielsweise pulverförmige Inhaltsstoffe mit stärker verdichteten, beispielsweise extrudierten, und damit langsamer löslichen Tensidpartikeln kombiniert werden.The combination of differently densified ingredients is also preferred Way to realize different solubilities. For example, powdered ingredients with more compressed, for example extruded, and thus more slowly soluble Surfactant particles can be combined.
Besonders bevorzugt ist im Rahmen der vorliegenden Erfindung die "physikalische Löseverzögerung" innerhalb eines Formkörpers zu realisieren. Hierzu können Reinigungsmittelformkörper hergestellt werden, die aus mehreren Phasen bestehen, wobei eine Phase weniger stark verpreßt ist als eine andere Phase. Die leichter verpreßte Phase zerfällt im Reinigungsgang schneller in das vorher verpreßte Vorgemisch, wodurch die Löslichkeit gegenüber einer härter verpreßten Phase erhöht wird. Erfindungsgemäß besonders bevorzugt sind hierbei Zweischichttabletten, bei denen eine Schicht weicher verpreßt ist als die andere, wobei die härter verpreßte Schicht das/die Tensid(e) enthält. Alternativ kann die Retardierung einer Phase auch über einen niedrigeren Gehalt an einem in ihr enthaltenen Deintegrationshilfsmittel erreicht werden.In the context of the present invention, the "physical release delay" is particularly preferred to be realized within a molded body. For this purpose, detergent tablets can be produced are made up of several phases, one phase being less compressed as a different phase. The more easily compressed phase disintegrates faster in the cleaning process previously compressed premix, which increases solubility compared to a harder compressed phase is increased. According to the invention, particular preference is given to two-layer tablets in which one layer is softer pressed than the other, the harder pressed layer containing the surfactant (s) contains. Alternatively, the retardation of a phase can also have a lower content a de-integration aid contained in it can be achieved.
Neben der Zweischichttablette bietet sich auch ein System zweier separater Tabletten mit unterschiedlicher Zerfallszeit an, die z.B. in einem gemeinsamen Beutel verpackt sein können. Die Retardierung einer dieser Tabletten kann auf die gleiche Weise vorgenommen werden, wie oben bei der Zweischichttablette beschrieben.In addition to the two-layer tablet, there is also a system of two separate tablets with different ones Decay time, e.g. can be packed in a common bag. The retardation one of these tablets can be made in the same way as above of the two-layer tablet.
Die erfindungsgemäßen Mittel enthalten in der Regel einen oder mehrere Builder, insbesondere Zeolithe, Silikate, Carbonate, organische Cobuilder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Letztere sind insbesondere in Reinigungsmitteltabletten für das maschinelle Geschirrspülen bevorzugt einzusetzende Gerüststoffe. Die im folgenden genannten Gerüststoffe sind auch als Alkalisierungsmittel geeignet.The agents according to the invention generally contain one or more builders, in particular Zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use persists - including the phosphates. The latter are particularly in detergent tablets for machine dishwashing preferred builders. The following The builders mentioned are also suitable as alkalizing agents.
Geeignete kristalline, schichtförmige Natriumsilikate besitzen die allgemeine Formel NaMSixO2x+1 H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5 · yH2O bevorzugt.Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung, durch Übertrocknung oder durch Beschichtung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compaction, by overdrying or by coating. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist vorzugsweise
Zeolith A und/oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt der Firma Crosfield)
besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen aus A, X
und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden Erfindung bevorzugt einsetzbar
ist beispielsweise auch ein Co-Kristallisat aus Zeolith X und Zeolith A (ca. 80 Gew.-% Zeolith
X), das von der Firma CONDEA Augusta S.p.A. unter dem Markennamen VEGOBOND AX® vertrieben
wird und durch die Formel
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Unter der Vielzahl der kommerziell erhältlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat) in der Wasch- und Reinigungsmittel-Industrie die größte Bedeutung.It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. Among the large number of commercially available phosphates, the alkali metal phosphates are among particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) of greatest importance in the detergent and cleaning agent industry.
Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) -Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei.Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
Natriumdihydrogenphosphat, NaH2PO4, existiert als Dihydrat (Dichte 1,91 gcm-3, Schmelzpunkt 60°) und als Monohydrat (Dichte 2,04 gcm-3). Beide Salze sind weiße, in Wasser sehr leicht lösliche Pulver, die beim Erhitzen das Kristallwasser verlieren und bei 200°C in das schwach saure Diphosphat (Dinatriumhydrogendiphosphat, Na2H2P2O7), bei höherer Temperatur in Natiumtrimetaphosphat (Na3P3O9) und Maddrellsches Salz (siehe unten), übergehen. NaH2PO4 reagiert sauer; es entsteht, wenn Phosphorsäure mit Natronlauge auf einen pH-Wert von 4,5 eingestellt und die Maische versprüht wird. Kaliumdihydrogenphosphat (primäres oder einbasiges Kaliumphosphat, Kaliumbiphosphat, KDP), KH2PO4, ist ein weißes Salz der Dichte 2,33 gcm-3, hat einen Schmelzpunkt 253° [Zersetzung unter Bildung von Kaliumpolyphosphat (KPO3)x] und ist leicht löslich in Wasser.Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below). NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
Dinatriumhydrogenphosphat (sekundäres Natriumphosphat), Na2HPO4, ist ein farbloses, sehr leicht wasserlösliches kristallines Salz. Es existiert wasserfrei und mit 2 Mol. (Dichte 2,066 gcm-3, Wasserverlust bei 95°), 7 Mol. (Dichte 1,68 gcm-3, Schmelzpunkt 48° unter Verlust von 5 H2O) und 12 Mol. Wasser (Dichte 1,52 gcm-3, Schmelzpunkt 35° unter Verlust von 5 H2O), wird bei 100° wasserfrei und geht bei stärkerem Erhitzen in das Diphosphat Na4P2O7 über. Dinatriumhydrogenphosphat wird durch Neutralisation von Phosphorsäure mit Sodalösung unter Verwendung von Phenolphthalein als Indikator hergestellt. Dikaliumhydrogenphosphat (sekundäres od. zweibasiges Kaliumphosphat), K2HPO4, ist ein amorphes, weißes Salz, das in Wasser leicht löslich ist.Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
Trinatriumphosphat, tertiäres Natriumphosphat, Na3PO4, sind farblose Kristalle, die als Dodecahydrat eine Dichte von 1,62 gcm-3 und einen Schmelzpunkt von 73-76°C (Zersetzung), als Decahydrat (entsprechend 19-20% P2O5) einen Schmelzpunkt von 100°C und in wasserfreier Form (entsprechend 39-40% P2O5) eine Dichte von 2,536 gcm-3 aufweisen. Trinatriumphosphat ist in Wasser unter alkalischer Reaktion leicht löslich und wird durch Eindampfen einer Lösung aus genau 1 Mol Dinatriumphosphat und 1 Mol NaOH hergestellt. Trikaliumphosphat (tertiäres oder dreibasiges Kaliumphosphat), K3PO4, ist ein weißes, zerfließliches, körniges Pulver der Dichte 2,56 gcm-3, hat einen Schmelzpunkt von 1340° und ist in Wasser mit alkalischer Reaktion leicht löslich. Es entsteht z.B. beim Erhitzen von Thomasschlacke mit Kohle und Kaliumsulfat. Trotz des höheren Preises werden in der Reinigungsmittel-Industrie die leichter löslichen, daher hochwirksamen, Kaliumphosphate gegenüber entsprechenden Natrium-Verbindungen vielfach bevorzugt.Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
Tetranatriumdiphosphat (Natriumpyrophosphat), Na4P2O7, existiert in wasserfreier Form (Dichte 2,534 gcm-3, Schmelzpunkt 988°, auch 880° angegeben) und als Decahydrat (Dichte 1,815-1,836 gcm-3, Schmelzpunkt 94° unter Wasserverlust). Bei Substanzen sind farblose, in Wasser mit alkalischer Reaktion lösliche Kristalle. Na4P2O7 entsteht beim Erhitzen von Dinatriumphosphat auf >200° oder indem man Phosphorsäure mit Soda im stöchiometrischem Verhältnis umsetzt und die Lösung durch Versprühen entwässert. Das Decahydrat komplexiert Schwermetall-Salze und Härtebildner und verringert daher die Härte des Wassers. Kaliumdiphosphat (Kaliumpyrophosphat), K4P2O7, existiert in Form des Trihydrats und stellt ein farbloses, hygroskopisches Pulver mit der Dichte 2,33 gcm-3 dar, das in Wasser löslich ist, wobei der pH-Wert der 1%igen Lösung bei 25° 10,4 beträgt.Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
Durch Kondensation des NaH2PO4 bzw. des KH2PO4 entstehen höhermol. Natrium- und Kaliumphosphate, bei denen man cyclische Vertreter, die Natrium- bzw. Kaliummetaphosphate und kettenförmige Typen, die Natrium- bzw. Kaliumpolyphosphate, unterscheiden kann. Insbesondere für letztere sind eine Vielzahl von Bezeichnungen in Gebrauch: Schmelz- oder Glühphosphate, Grahamsches Salz, Kurrolsches und Maddrellsches Salz. Alle höheren Natrium- und Kaliumphosphate werden gemeinsam als kondensierte Phosphate bezeichnet.Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
Das technisch wichtige Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat), ist ein wasserfrei
oder mit 6 H2O kristallisierendes, nicht hygroskopisches, weißes, wasserlösliches Salz der
allgemeinen Formel NaO-[P(O)(ONa)-O]n-Na mit n=3. In 100 g Wasser lösen sich bei Zimmertemperatur
etwa 17 g, bei 60° ca. 20 g, bei 100° rund 32 g des kristallwasserfreien Salzes; nach
zweistündigem Erhitzen der Lösung auf 100° entstehen durch Hydrolyse etwa 8% Orthophosphat
und 15% Diphosphat. Bei der Herstellung von Pentanatriumtriphosphat wird Phosphorsäure mit
Sodalösung oder Natronlauge im stöchiometrischen Verhältnis zur Reaktion gebracht und die Lsg.
durch Versprühen entwässert. Ähnlich wie Grahamsches Salz und Natriumdiphosphat löst Pentanatriumtriphosphat
viele unlösliche Metall-Verbindungen (auch Kalkseifen usw.). Pentakaliumtriphosphat,
K5P3O10 (Kaliumtripolyphosphat), kommt beispielsweise in Form einer 50 Gew.-%-igen
Lösung (> 23% P2O5, 25% K2O) in den Handel. Die Kaliumpolyphosphate finden in der
Wasch- und Reinigungsmittel-Industrie breite Verwendung. Weiter existieren auch Natriumkaliumtripolyphosphate,
welche ebenfalls im Rahmen der vorliegenden Erfindung einsetzbar sind.
Diese entstehen beispielsweise, wenn man Natriumtrimetaphosphat mit KOH hydrolysiert:
Diese können genau wie Natriumtripolyphosphat, Kaliumtripolyphosphat oder Mischungen aus diesen beiden eingesetzt werden; auch Mischungen aus Natriumtripolyphosphat und Natriumkaliumtripolyphosphat oder Mischungen aus Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat oder Gemische aus Natriumtripolyphosphat und Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat sind erfindungsgemäß einsetzbar.These can be made just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures these two are used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
Als organische Cobuilder können in den erfindungsgemäßen Mitteln insbesondere Polycarboxylate / Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder (siehe unten) sowie Phosphonate eingesetzt werden. Diese Stoffklassen werden nachfolgend beschrieben. Polycarboxylates in particular can be used as organic cobuilders in the agents according to the invention / Polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, others organic cobuilders (see below) and phosphonates are used. These substance classes are described below.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen.Usable organic builders are, for example, those that can be used in the form of their sodium salts Polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function. For example, these are citric acid, adipic acid, Succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use from ecological Reasons is not objectionable, as well as mixtures of these. Preferred salts are the salts polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, Sugar acids and mixtures of these.
Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and are therefore also used for Setting a lower and milder pH value for detergents or cleaning agents. In particular are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and to name any mixtures of these.
Als Builder sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol.Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 500 to 70,000 g / mol.
Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Schrift angegebenen Molmassen.For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 have up to 20,000 g / mol. Because of their superior solubility, this group can again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol. Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol, and in particular 30,000 to 40,000 g / mol.
Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden. Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 3 bis 10 Gew.-%.The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution become. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 up to 20% by weight, in particular 3 to 10% by weight.
Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie beispielsweise Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten.To improve the water solubility, the polymers can also allylsulfonic acids, such as Allyloxybenzenesulfonic acid and methallylsulfonic acid, contained as a monomer.
Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid as monomers and the 2-alkylallylsulfonic acid and sugar derivatives.
Weitere bevorzugte Copolymere sind solche, die als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Further preferred copolymers are those which preferably use acrolein and acrylic acid / acrylic acid salts as monomers or acrolein and vinyl acetate.
Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate.Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, can be obtained. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000 g/mol.Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes be performed. They are preferably hydrolysis products with medium molecular weights in the range from 400 to 500000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, are preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100 is. Both maltodextrins with a DE between 3 can be used and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Ebenfalls geeignet ist ein oxidiertes Oligosaccharid, z. B. ein am C6 des Saccharidrings oxidiertes Produkt.The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. An oxidized oligosaccharide, e.g. B. a product oxidized at C 6 of the saccharide ring.
Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat, sind weitere geeignete Cobuilder. Dabei wird Ethylendiamin-N,N'-disuccinat (EDDS) bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate. Geeignete Einsatzmengen liegen in zeolithhaltigen und/oder silicathaltigen Formulierungen bei 3 bis 15 Gew.-%.Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred used in the form of its sodium or magnesium salts. Are further preferred in this Connection also glycerol disuccinate and glycerol trisuccinate. Suitable quantities in formulations containing zeolite and / or silicate are 3 to 15% by weight.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten.Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.
Eine weitere Substanzklasse mit Cobuildereigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden.Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, the disodium salt being neutral and the tetrasodium salt is alkaline (pH 9). Preferred aminoalkane phosphonates are Ethylene diamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in shape the neutral sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and Octa sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
Darüber hinaus können alle Verbindungen, die in der Lage sind, Komplexe mit Erdalkaliionen auszubilden, als Cobuilder eingesetzt werden.In addition, all compounds that are able to form complexes with alkaline earth metal ions can can be used as a cobuilder.
Die Menge an Gerüststoff beträgt üblicherweise zwischen 10 und 70 Gew.-%, vorzugsweise zwischen 15 und 60 Gew.-% und insbesondere zwischen 20 und 50 Gew.-%, jeweils bezogen auf das gesamte erfindungsgemäße Mittel.The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%, each based on the entire agent according to the invention.
In einer möglichen Ausführungsform der vorliegenden Erfindung enthalten die erfindungsgemäßen Mittel organische und/oder insbesondere anorganische Bleichmittel. In a possible embodiment of the present invention, the invention contain Agents organic and / or in particular inorganic bleaching agents.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen hat das Natriumpercarbonat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise, das Natriumperborattetrahydrat und das Natriumperboratmonohydrat Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Es können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind (a) die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkylperoxybenzoesäuren, aber auch Peroxy-α-Naphtoesäure und Magnesium-monoperphthalat, (b) die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimidoperoxycapronsäure [Phthaloiminoperoxyhexansäure (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipinsäure und N-nonenylamidopersuccinate, und (c) aliphatische und araliphatische Peroxydicarbonsäuren, wie 1,12-Diperoxycarbonsäure, 1,9-Diperoxyazelainsäure, Diperoxysebacinsäure, Diperoxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyldiperoxybutan-1,4-disäure, N,N-Terephthaloyl-di(6-aminopercapronsäue) können eingesetzt werden.Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and produce H 2 O 2 in water. Other useful bleaching agents are, for example, sodium perborate tetrahydrate and sodium perborate monohydrate peroxypyrophosphate, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoxyacidoxy (PAP), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydalsoxyperiperyldoxybutyldiacyldiperbutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacid-diperoxybiperyl-doxy-oxy-oxy-doxy-oxy-oxy-oxyacetate, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.
Der Gehalt der Mittel an Bleichmitteln kann 1 bis 40 Gew.-% und insbesondere 10 bis 20 Gew.-% betragen, wobei vorteilhafterweise Percarbonat oder Perboratmono- oder tetrahydrat eingesetzt wird.The bleaching agent content of the agents can be 1 to 40% by weight and in particular 10 to 20% by weight. amount, advantageously using percarbonate or perborate mono- or tetrahydrate becomes.
Um beim Reinigen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren eingearbeitet werden. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden.To improve the bleaching effect when cleaning at temperatures of 60 ° C and below reach, bleach activators can be incorporated. As bleach activators, compounds those under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 up to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid result, are used.
Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0 525 239 (Ausimont SPA) beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfructose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626 (alle Procter & Gamble), WO 95/14759 (Warwick) und WO 95/17498 (Procter & Gamble) bekannt sind. Die aus der internationalen Patentanmeldung WO 95/14075 (Degussa) beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE 44 43 177 (Henkel) bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren sind in Mengen von 0,5 Gew.-% bis 15 Gew.-%, bezogen auf gesamtes Mittel, enthalten.Substances containing O- and / or N-acyl groups of the number of carbon atoms mentioned and / or are suitable optionally substituted benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, in particular Triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and Mannitol or their in European patent application EP 0 525 239 (Ausimont SPA) described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-Benzoylcaprolactam resulting from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626 (all Procter & Gamble), WO 95/14759 (Warwick) and WO 95/17498 (Procter & Gamble) are known. The from the international patent application Acyl lactams described in WO 95/14075 (Degussa) are also preferably used. The combinations known from German patent application DE 44 43 177 (Henkel) conventional bleach activators can be used. Such bleach activators are contained in amounts of 0.5 wt .-% to 15 wt .-%, based on the total agent.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren enthalten sein. Bei diesen Stoffen handelt es sich um bleichverstärkende Ü-bergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren geeignet, wobei solche Verbindungen bevorzugt eingesetzt werden, die in der DE 197 09 284 A1 beschrieben sind.In addition to the conventional bleach activators or in their place, so-called Bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru amine complexes are as Bleaching catalysts are suitable, preference being given to using compounds which are used in the DE 197 09 284 A1 are described.
Das erfindungsgemäße Reinigungsmittel kann als weitere übliche Inhaltsstoffe insbesondere Enzyme, Sequestrierungsmittel, Elektrolyte, und weitere Hilfsstoffe, wie Schaumregulatoren, zusätzliche Bleichaktivatoren, Farb- und Duftstoffe enthalten.The cleaning agent according to the invention can be further conventional ingredients, in particular enzymes, Sequestering agents, electrolytes, and other auxiliary substances, such as foam regulators, additional Contain bleach activators, colors and fragrances.
Als Enzyme kommen in den erfindungsgemäßen Mitteln insbesondere solche aus der Klassen der Hydrolasen wie der Proteasen, Esterasen, Lipasen bzw. lipolytisch wirkende Enzyme, Amylasen, Glykosylhydrolasen und Gemische der genannten Enzyme in Frage. Alle diese Hydrolasen tragen zur Entfernung von Anschmutzungen wie protein-, fett- oder stärkehaltigen Verfleckungen bei. Zur Bleiche können auch Oxidoreduktasen eingesetzt werden. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen wie Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus und Humicola insolens sowie aus deren gentechnisch modifizierten Varianten gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase bzw. lipolytisch wirkenden Enzymen oder aus Protease, Amylase und Lipase bzw. lipolytisch wirkenden Enzymen oder Protease, Lipase bzw. lipolytisch wirkenden Enzymen, insbesondere jedoch Protease und/oder Lipase-haltige Mischungen bzw. Mischungen mit lipolytisch wirkenden Enzymen von besonderem Interesse. Beispiele für derartige lipolytisch wirkende Enzyme sind die bekannten Cutinasen. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Zu den geeigneten Amylasen zählen insbesondere alpha-Amylasen, Iso-Amylasen, Pullulanasen und Pektinasen. Enzymes in the agents according to the invention include in particular those from the classes of Hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases carry for the removal of stains such as stains containing protein, fat or starch. to Bleach can also be used with oxidoreductases. Bacterial strains are particularly suitable or mushrooms such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus Cinereus and Humicola insolens and their genetically modified variants obtained enzymatic active ingredients. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic acting enzymes or from protease, amylase and lipase or lipolytically acting enzymes or protease, lipase or lipolytic enzymes, but especially protease and / or mixtures containing lipase or mixtures with lipolytically active enzymes of particular importance Interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. To The suitable amylases include in particular alpha-amylases, iso-amylases, pullulanases and Pectinases.
Die Enzyme können an Trägerstoffe adsorbiert oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,5 bis etwa 4,5 Gew.-% betragen. Im Rahmen der vorliegenden Erfindung bevorzugte Mittel sind dadurch gekennzeichnet, daß sie Protease und/oder Amylase enthalten.The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The percentage of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.5 to about 4.5% by weight be. Agents preferred in the context of the present invention are characterized in that that they contain protease and / or amylase.
Farb- und Duftstoffe können den erfindungsgemäßen maschinellen Geschirrspülmitteln zugesetzt werden, um den ästhetischen Eindruck der entstehenden Produkte zu verbessern und dem Verbraucher neben der Leistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzylcarbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenylglycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, α-Isomethylionon und Methylcedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl.Dyes and fragrances can be added to the automatic dishwashing detergents according to the invention to improve the aesthetic impression of the resulting products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. As perfume oils or fragrances, individual fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde, ketone, alcohol type and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, among the Ketones e.g. the Jonone, α-isomethylionon and methylcedryl ketone, to the alcohols anethole, Citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons mainly include the terpenes like limes and pinene. However, mixtures are preferred different fragrances are used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures such as those from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, Cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
Die Duftstoffe können direkt in die erfindungsgemäßen Reinigungsmittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen.The fragrances can be incorporated directly into the cleaning agents according to the invention can also be advantageous to apply the fragrances on carriers.
Um den ästhetischen Eindruck der erfindungsgemäßen Mittel zu verbessern, kann es (oder Teile davon) mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber den mit den Mitteln zu behandelnden Substraten wie Glas, Keramik oder Kunststoffgeschirr, um diese nicht anzufärben.In order to improve the aesthetic impression of the agents according to the invention, it (or parts of which) are dyed with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and insensitivity compared to the other ingredients of the agents and against light and no pronounced Substantivity towards the substrates to be treated with the agents such as glass, ceramic or Plastic dishes so as not to stain them.
Die erfindungsgemäßen Mittel können in sämtlichen bekannten Angebotsformen bereitgestellt werden, wobei insbesondere pulverförmige Reiniger und Reinigungsmitteltabletten besondere Bedeutung haben. Werden Reinigungsmitteltabletten hergestellt, so können diese Desintegrationshilfsmittel, sogenannte Tablettensprengmittel, enthalten, um den Zerfall hochverdichteter Formkörper zu erleichtern und die Zerfallszeiten zu verkürzen. Unter Tablettensprengmitteln bzw. Zerfallsbeschleunigern werden gemäß Römpp (9. Auflage, Bd. 6, S. 4440) und Voigt "Lehrbuch der pharmazeutischen Technologie" (6. Auflage, 1987, S. 182-184) Hilfsstoffe verstanden, die für den raschen Zerfall von Tabletten in Wasser oder Magensaft und für die Freisetzung der Pharmaka in resorbierbarer Form sorgen.The agents according to the invention can be provided in all known forms of offer, in particular powdered cleaners and detergent tablets being of particular importance. If detergent tablets are produced, they can contain disintegration aids, so-called tablet disintegrants, in order to facilitate the disintegration of highly compressed moldings and to shorten the disintegration times. According to Römpp (9th edition, vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184), tablet disintegrants or accelerators of decay are understood as auxiliary substances which are necessary for rapid disintegration of tablets in water or gastric juice and ensure the release of the pharmaceuticals in absorbable form.
Diese Stoffe, die auch aufgrund ihrer Wirkung als "Spreng"mittel bezeichnet werden, vergrößern bei Wasserzutritt ihr Volumen, wobei einerseits das Eigenvolumen vergrößert (Quellung), andererseits auch über die Freisetzung von Gasen ein Druck erzeugt werden kann, der die Tablette in kleinere Partikel zerfallen läßt. Altbekannte Desintegrationshilfsmittel sind beispielsweise Carbonat/Citronensäure-Systeme, wobei auch andere organische Säuren eingesetzt werden können. Quellende Desintegrationshilfsmittel sind beispielsweise synthetische Polymere wie Polyvinylpyrrolidon (PVP) oder natürliche Polymere bzw. modifizierte Naturstoffe wie Cellulose und Stärke und ihre Derivate, Alginate oder Casein-Derivate.These substances, which are also called "explosives" due to their effect, enlarge their volume when water enters, the volume on the one hand increasing (swelling) and on the other a pressure can also be generated via the release of gases, which the tablet in lets smaller particles disintegrate. Well-known disintegration aids are, for example, carbonate / citric acid systems, other organic acids can also be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.
Bevorzugte Reinigungsmittelformkörper enthalten 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-%
und insbesondere 4 bis 6 Gew.-% eines oder mehrerer Desintegrationshilfsmittel, jeweils bezogen
auf das Formkörpergewicht. Enthält nur der Basisformkörper Desintegratzionshilfsmittel, so
beziehen sich die genannten Angaben nur auf das Gewicht des Basisformkörpers.
Als bevorzugte Desintegrationsmittel werden im Rahmen der vorliegenden Erfindung Desintegrationsmittel
auf Cellulosebasis eingesetzt, so daß bevorzugte Reinigungsmittelformkörper ein solches
Desintegrationsmittel auf Cellulosebasis in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7
Gew.-% und insbesondere 4 bis 6 Gew.-% enthalten. Reine Cellulose weist die formale Bruttozusammensetzung
(C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose
dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei
aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von
50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der
vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose
erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte
aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert
wurden. Aber auch Cellulosen, in denen die Hydroxy-Gruppen gegen funktionelle Gruppen, die
nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate
einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose
(CMC), Celluloseester und -ether sowie Aminocellulosen. Die genannten Cellulosederivate
werden vorzugsweise nicht allein als Desintegrationsmittel auf Cellulosebasis eingesetzt,
sondern in Mischung mit Cellulose verwendet. Der Gehalt dieser Mischungen an Cellulosederivaten
beträgt vorzugsweise unterhalb 50 Gew.-%, besonders bevorzugt unterhalb 20 Gew.-%,
bezogen auf das Desintegrationsmittel auf Cellulosebasis. Besonders bevorzugt wird als Desintegrationsmittel
auf Cellulosebasis reine Cellulose eingesetzt, die frei von Cellulosederivaten ist.Preferred detergent tablets contain 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight of one or more disintegration auxiliaries, in each case based on the weight of the tablet. If only the basic tablet contains disintegration aids, the information given relates only to the weight of the basic tablet.
Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight .-% contain. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
Die als Desintegrationshilfsmittel eingesetzte Cellulose wird vorzugsweise nicht in feinteiliger Form eingesetzt, sondern vor dem Zumischen zu den zu verpressenden Vorgemischen in eine gröbere Form überführt, beispielsweise granuliert oder kompaktiert. Wasch- und Reinigungsmittelformkörper, die Sprengmittel in granularer oder gegebenenfalls cogranulierter Form enthalten, werden in den deutschen Patentanmeldungen DE 197 09 991 (Stefan Herzog) und DE 197 10 254 (Henkel) sowie der internationalen Patentanmeldung WO98/40463 (Henkel) beschrieben. Diesen Schriften sind auch nähere Angaben zur Herstellung granulierter, kompaktierter oder cogranulierter Cellulosesprengmittel zu entnehmen. Die Teilchengrößen solcher Desintegrationsmittel liegen zumeist oberhalb 200 µm, vorzugsweise zu mindestens 90 Gew.-% zwischen 300 und 1600 µm und insbesondere zu mindestens 90 Gew.-% zwischen 400 und 1200 µm. Die vorstehend genannten und in den zitierten Schriften näher beschriebenen gröberen Desintegrationshilfsmittel auf Cellulosebasis sind im Rahmen der vorliegenden Erfindung bevorzugt als Desintegrationshilfsmittel einzusetzen und im Handel beispielsweise unter der Bezeichnung Arbocel® TF-30-HG von der Firma Rettenmaier erhältlich.The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be compressed. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose which are described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from the company Rettenmaier.
Als weiteres Desintegrationsmittel auf Cellulosebasis oder als Bestandteil dieser Komponente kann mikrokristalline Cellulose verwendet werden. Diese mikrokristalline Cellulose wird durch partielle Hydrolyse von Cellulosen unter solchen Bedingungen erhalten, die nur die amorphen Bereiche (ca. 30% der Gesamt-Cellulosemasse) der Cellulosen angreifen und vollständig auflösen, die kristallinen Bereiche (ca. 70%) aber unbeschadet lassen. Eine nachfolgende Desaggregation der durch die Hydrolyse entstehenden mikrofeinen Cellulosen liefert die mikrokristallinen Cellulosen, die Primärteilchengrößen von ca. 5 µm aufweisen und beispielsweise zu Granulaten mit einer mittleren Teilchengröße von 200 µm kompaktierbar sind.As a further disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial Hydrolysis of celluloses obtained under conditions that only the amorphous areas (approx. Attack 30% of the total cellulose mass) of the celluloses and completely dissolve the crystalline ones Leave areas (approx. 70%) undamaged. A subsequent disaggregation of the The hydrolysis of the microfine celluloses produces the microcrystalline celluloses, the primary particle sizes of about 5 µm and for example to granules with a medium Particle size of 200 microns can be compacted.
Im Rahmen der vorliegenden Erfindung bevorzugte Reinigungsmittelformkörper enthalten zusätzlich ein Desintegrationshilfsmittel, vorzugsweise ein Desintegrationshilfsmittel auf Cellulosebasis, vorzugsweise in granularer, cogranulierter oder kompaktierter Form, in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise von 3 bis 7 Gew.-% und insbesondere von 4 bis 6 Gew.-%, jeweils bezogen auf das Formkörpergewicht.Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 % By weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the molded body weight.
Erfindungsgemäße Reinigungsmittelformkörper können darüber hinaus ein gasentwickelndes Brausesystem enthalten. Das gasentwickelnde Brausesystem kann aus einer einzigen Substanz bestehen, die bei Kontakt mit Wasser ein Gas freisetzt. Unter diesen Verbindungen ist insbesondere das Magnesiumperoxid zu nennen, das bei Kontakt mit Wasser Sauerstoff freisetzt. Üblicherweise besteht das gasfreisetzende Sprudelsystem jedoch seinerseits aus mindestens zwei Bestandteilen, die miteinander unter Gasbildung reagieren. Während hier eine Vielzahl von Systemen denk- und ausführbar ist, die beispielsweise Stickstoff, Sauerstoff oder Wasserstoff freisetzen, wird sich das in den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern eingesetzte Sprudelsystem sowohl anhand ökonomischer als auch anhand ökologischer Gesichtspunkte auswählen lassen. Bevorzugte Brausesysteme bestehen aus Alkalimetallcarbonat und/oder hydrogencarbonat sowie einem Acidifizierungsmittel, das geeignet ist, aus den Alkalimetallsalzen in wäßrige Lösung Kohlendioxid freizusetzen.Shaped detergent tablets according to the invention can also be a gas-evolving Shower system included. The gas-developing shower system can consist of a single substance exist, which releases a gas on contact with water. Among these connections is particular to name the magnesium peroxide, which releases oxygen when in contact with water. Usually however, the gas-releasing bubble system itself consists of at least two components, that react with each other to form gas. While here a variety of systems is conceivable and executable, which will release nitrogen, oxygen or hydrogen, for example the bubble system used in the detergent tablets according to the invention Choose both from an economic and an ecological point of view to let. Preferred shower systems consist of alkali metal carbonate and / or hydrogen carbonate and an acidifying agent which is suitable from the alkali metal salts to release carbon dioxide in aqueous solution.
Bei den Alkalimetallcarbonaten bzw. -hydrogencarbonaten sind die Natrium- und Kaliumsalze aus Kostengründen gegenüber den anderen Salzen deutlich bevorzugt. Selbstverständlich müssen nicht die betreffenden reinen Alkalimetallcarbonate bzw. -hydrogencarbonate eingesetzt werden; vielmehr können Gemische unterschiedlicher Carbonate und Hydrogencarbonate bevorzugt sein.In the case of the alkali metal carbonates or bicarbonates, the sodium and potassium salts are out Cost reasons clearly preferred over the other salts. Needless to say the pure alkali metal carbonates or bicarbonates concerned are not used; rather, mixtures of different carbonates and hydrogen carbonates may be preferred.
In bevorzugten Reinigungsmittelformkörper werden als Brausesystem 2 bis 20 Gew.-%, vorzugsweise 3 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% eines Alkalimetallcarbonats oder-hydrogencarbonats sowie 1 bis 15, vorzugsweise 2 bis 12 und insbesondere 3 bis 10 Gew.-% eines Acidifizierungsmittels, jeweils bezogen auf den gesamten Formkörper, eingesetzt.In preferred shaped detergent bodies, 2 to 20% by weight, preferably, are used as the shower system 3 to 15% by weight and in particular 5 to 10% by weight of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 and in particular 3 to 10% by weight of one Acidifying agent, based in each case on the entire molded body.
Als Acidifizierungsmittel, die aus den Alkalisalzen in wäßriger Lösung Kohlendioxid freisetzen, sind beispielsweise Borsäure sowie Alkalimetallhydrogensulfate, Alkalimetalldihydrogenphosphate und andere anorganische Salze einsetzbar. Bevorzugt werden allerdings organische Acidifizierungsmittel verwendet, wobei die Citronensäure ein besonders bevorzugtes Acidifizierungsmittel ist. Einsetzbar sind aber auch insbesondere die anderen festen Mono-, Oligo- und Polycarbonsäuren. Aus dieser Gruppe wiederum bevorzugt sind Weinsäure, Bernsteinsäure, Malonsäure, Adipinsäure, Maleinsäure, Fumarsäure, Oxalsäure sowie Polyacrylsäure. Organische Sulfonsäuren wie Amidosulfonsäure sind ebenfalls einsetzbar. Kommerziell erhältlich und als Acidifizierungsmittel im Rahmen der vorliegenden Erfindung ebenfalls bevorzugt einsetzbar ist Sokalan® DCS (Warenzeichen der BASF), ein Gemisch aus Bernsteinsäure (max. 31 Gew.-%), Glutarsäure (max. 50 Gew.-%) und Adipinsäure (max. 33 Gew.-%).As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution for example boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, organic acidifying agents are preferred used, the citric acid being a particularly preferred acidifying agent. However, the other solid mono-, oligo- and polycarboxylic acids can also be used in particular. From this group, tartaric acid, succinic acid, malonic acid, adipic acid, Maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifier in Sokalan® DCS (trademark from BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
Bevorzugt sind im Rahmen der vorliegenden Erfindung Reingungsmittelformkörper, bei denen als Acidifizierungsmittel im Brausesystem ein Stoff aus der Gruppe der organischen Di-, Tri- und Oligocarbonsäuren bzw. Gemische aus diesen eingesetzt werden.In the context of the present invention, preference is given to detergent tablets in which Acidifying agent in the effervescent system a substance from the group of organic di-, tri- and oligocarboxylic acids or mixtures of these are used.
Unabhängig von der Angebotsform der erfindungsgemäßen Mittel sind Mittel bevorzugt, bei denen der Gehalt der Mittel an Korrosionsinhibitor 0,001 bis 10 Gew.-%, vorzugsweise 0,0025 bis 2 Gew.-% und insbesondere 0,01 bis 0,04 Gew.-%, jeweils bezogen auf das gesamte Reinigungsmittel, beträgt.Regardless of the form of the agents according to the invention, agents are preferred in which the corrosion inhibitor content of the agents is 0.001 to 10% by weight, preferably 0.0025 to 2 % By weight and in particular 0.01 to 0.04% by weight, in each case based on the total cleaning agent, is.
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE10049657A DE10049657C2 (en) | 2000-10-07 | 2000-10-07 | Machine dishwashing method and machine dishwashing detergent with improved corrosion protection |
DE10049657 | 2000-10-07 |
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EP1195429A1 true EP1195429A1 (en) | 2002-04-10 |
EP1195429B1 EP1195429B1 (en) | 2006-06-07 |
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EP01123093A Expired - Lifetime EP1195429B1 (en) | 2000-10-07 | 2001-09-27 | Automatic dishwashing process and automatic dishwashing compositions having improved anti-corrosion characteristics |
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Country | Link |
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EP (1) | EP1195429B1 (en) |
AT (1) | ATE328997T1 (en) |
DE (2) | DE10049657C2 (en) |
ES (1) | ES2266066T3 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004055144A1 (en) * | 2002-12-17 | 2004-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Silver protection for dishwasher-proof dishes |
WO2008104240A1 (en) * | 2007-02-28 | 2008-09-04 | Henkel Ag & Co. Kgaa | Active ingredient carrier systems |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0928828A1 (en) * | 1997-12-31 | 1999-07-14 | Henkel KGaA | Alkylaminotriazole-containing granular components for automatic dishwashing compositions and process for preparing them |
GB2335434A (en) * | 1998-03-19 | 1999-09-22 | Mcbride Robert Ltd | Encapsulated liquid incorporation in tableted compositions |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5480576A (en) * | 1993-10-14 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | 1,3-N azole containing detergent compositions |
DE4338626A1 (en) * | 1993-11-12 | 1995-05-18 | Henkel Kgaa | Additive for glass bottle cleaning and its use to reduce glass corrosion |
DE19501645A1 (en) * | 1995-01-20 | 1996-07-25 | Henkel Kgaa | Silver corrosion inhibitors |
DE19518693A1 (en) * | 1995-05-22 | 1996-11-28 | Henkel Kgaa | Automatic dishwashing detergent with silver corrosion inhibitor |
DE19631787C2 (en) * | 1996-08-07 | 2000-06-29 | Henkel Kgaa | Granular component containing benzotriazole for use in machine dishwashing detergents (MGSM) and process for its production |
DE19701031C2 (en) * | 1997-01-15 | 1998-12-10 | Henkel Kgaa | Use of 3-amino-5-alkyl-1,2,4-triozoles as silver protection agents |
GB2325243A (en) * | 1997-05-13 | 1998-11-18 | Procter & Gamble | Removing tarnish from tarnished silverware |
DE19860670A1 (en) * | 1998-12-29 | 2000-08-10 | Benckiser Nv | Water-soluble glass as corrosion protection in a dishwasher |
-
2000
- 2000-10-07 DE DE10049657A patent/DE10049657C2/en not_active Expired - Fee Related
-
2001
- 2001-09-27 AT AT01123093T patent/ATE328997T1/en not_active IP Right Cessation
- 2001-09-27 DE DE50110017T patent/DE50110017D1/en not_active Expired - Fee Related
- 2001-09-27 ES ES01123093T patent/ES2266066T3/en not_active Expired - Lifetime
- 2001-09-27 EP EP01123093A patent/EP1195429B1/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0928828A1 (en) * | 1997-12-31 | 1999-07-14 | Henkel KGaA | Alkylaminotriazole-containing granular components for automatic dishwashing compositions and process for preparing them |
GB2335434A (en) * | 1998-03-19 | 1999-09-22 | Mcbride Robert Ltd | Encapsulated liquid incorporation in tableted compositions |
Non-Patent Citations (1)
Title |
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DATABASE WPI Section Ch Derwent World Patents Index; Class A97, AN 1973-01235U, XP002187399 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004055144A1 (en) * | 2002-12-17 | 2004-07-01 | Henkel Kommanditgesellschaft Auf Aktien | Silver protection for dishwasher-proof dishes |
WO2008104240A1 (en) * | 2007-02-28 | 2008-09-04 | Henkel Ag & Co. Kgaa | Active ingredient carrier systems |
Also Published As
Publication number | Publication date |
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DE50110017D1 (en) | 2006-07-20 |
ATE328997T1 (en) | 2006-06-15 |
EP1195429B1 (en) | 2006-06-07 |
ES2266066T3 (en) | 2007-03-01 |
DE10049657C2 (en) | 2003-02-27 |
DE10049657A1 (en) | 2002-04-25 |
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